•·�

lssUES IN TII
-E

CoNSEBVATION OF P1-10TOGBAP1-1s
 R e a d i n g s i n C o n s erv a t i o n

Issues in the
Conservation of Photographs

Edited by

DEBRA HESS NORRIS

JENNIFER jAE GUTIERREZ

T H E G E TTY C O N SE H V A TI O N I N STITU TE

L O S A N G E L E S
The Cellv Conservation Institute

Timothy P. Whalen, Director

Jea n ne Marie Teu lo n ico, Associate Director, Progrc11ns

The Celly Conservation I nstitute works i n ternationally to advance conservation practice

in the visual ;11·ts-broadly i n terpreted lo i n c l u de objects, coll ections, archi tect u re, a n d
s i t e s . The I n stitute serves the conservation com m u n ity t h rough scie ntific research, e d u ­
cation and t ra i n i ng, m o d e l fiel d projects, a n d the d isse m ination of t h e res u l ts of both its
own work a n d the work of others i n the flelcl. In all its e ndeavors, the C C I foc u ses on the
creation and del ivery of' knowledge that will benefit the professionals and orga n izations
responsible l'or the conservation o f the world's c u l t u ra l heritage.

© 2010 J. Paul G etty Trust

Published by the Getty Conservation I ns ti t ute

Getty Publ ications
1200 Getty Cente r Drive, S u i te 500

Los Angeles, C a l i fornia 90049-1682

\\'WW .gcll ypu hi ications.org

G regory M. Brillon. P11blis/1er

Tobi Lcvcnbcrg Kap l a n , Edit.or

Beat rice H o hcnegger, !Vla11uscript Editor
I D E M Tra nslations, I n c . and Sharon C reveL, Tra11slato1·s
Anita Keys, Product. ion Coordi1wt . o r
J i m Drobka, Designer
Ncwgen North America, Compositor

Pri nted in C h i n a a l Everbest Printing Company t hrough Four Colour Print C ro u p

Libra 1·y of' Congress Cataloging- i n- Pu b l i cation Data

Readi ngs i n conservation : issues in the conserva t i o n of photographs I edited by Debra

H ess Norris, Je n n iFer Jae G u t ierrez.
I " cm.
I nc l udes bibl iographical references and i ndex.
ISBN 97 8-1-60606-000- 1 (pbk.)
1. Photograp hs-Conservation and rcstorntion. I. Norris. Debra Hess. I I . G u t i e rrez,
Je n n i f'er Jae.
T!Lj65.1q 20 1 0

771'.46-de22

FIWNT covrn Sheldon K. N i chols (America n , act ive 1\Jorthern C a l i l'orn i a 1851 -1854).

Portrait of two girls recl.in ing on chnise lou uge (detail), 1851-5+ Dagucrrcolypc, hand­
colorcd, 8.3 X 1 1 cm (3 1 /, X 45/1<, i n .). Los Ange l es, J. Paul Getty M u seu 111 84.xr.1565.26

!MCI< COVEil 11esults oF tests at the East 111an Kodak Company in the la te 1970s, exa m i n­
ing Lhc useful ness oF Loners as protcclivc trcal mcnts l'or conventional pri nts. See Larry
1-1. Feldman " D i scoloration of' B l ack-and-vVh i tc Photograp h ic P ri n ts " ( Fig. 22, p. 201).
Repri nted with permission of' the I S&T: The Societv For Imagi ng Science a n d Technology
sole copyright O\\'ners of Jo u rn a l oF Appl ied Ph otographic E ngineering.

Every e!Ton has been made to contact the copyright holders of the materials i n this book
Lo obtain perm ission to p u b l i s h . J\ny om issions w i l l be corrected i n Future editions i[ the
p u b l isher is conLaeted in writi ng.
 Contents

Foreword xi
P reface xiii
Acknowledgments ;\,"!/

Note to the Reader xvii

Part I History of Photograph Conservation

H E A D 1 NG Thomas Frederick Hardwic h , Esq. I O n t h e Action of Da m p

A i r u p o n Posit ive Prints ( 1 856) 2

2 Eugene Ostroff I Preservation of P hotographs (1967) 8

3 Georgia O'Keeffe I Conditions For the Al fred Stiegl itz

Photographs and P h otogravu res ( 1 972 ) 21

4 Jose O rraca I P h i l osophy of Conservat i o n ( 1 974) 26

5 Wa l ter C lark I Conservation Center and Laboratory:

What Are the Objectives? ( 1 974) 34

6 Robert A. Weinstei n and Larry Booth I Col lection, Use

and C a re of H istorica l Photogra phs ( 1 978) 37

7 Ja mes M . Rei l ly I Stabil ity P roblems of 19th and 20th Cen t u ry

Photogra p h i c Materia l s ( 1 980)

8 I a n L. M oor and Angela M oor I The I m perfect Image ( 1 982)

9 Klaus B. Hendriks and Brian Lesser I D isaster Prepa redness

and Hecovery: P h otographic Materials (1983) 53

10 Anne Cartier- B resson I A New D i sc i p l i ne: Preservation

and Co nservation of Photogra phs ( 1 987)

11 Constance M c C abe and Lisha Deming G l i nsman I

U ndersta n d i ng A lfred S t iegl itz' P l a t i n u m a n d P a l l ad i u m Prints:
Exa m i nation by X-ray F l uorescence Spectrometry ( 1 995) 68

12 Nora Ke nnedy I The Com i n g of Age of Photograph

Co nservat ion ( 1 996) 88

11
 Paul Messier I Notes on Dating Photographic Paper (2006)

Grant B. Romer I What l s a Photograph? (2010) 107

Part II Silver Image Structure and Stability 111

HEADING 15 P h i l i p H . Delamotte, H ugh W. D i a mond, T. F re de ri c k

H ardwich , T. A. M alone, Joh n Percy, Henry Pollock, and
Geo. Shadbolt I First Report of the Committee Appoi nted to
Take i nto Consideration the Q uestion of the Fadi n g of Positive
Photographic Pictures upon Paper ( 1 855) 112

16 Thomas H. James I The Stabil ity of S i lver Filaments ( 1 965) u6

17 C a lvin S . M c C amy and C hester I . Pope I Redox Blem is hes-

Their Cause and Prevention ( 1 970) 139

18 Edith Weyde I A S imple Test to I dentify Gases W h i c h Destroy

S ilver I m ages ( 1 972) 148

19 Douglas W. N i s himura, James M. Re i l ly, and Pete r Adelstein I

I mprovements to the Photogra phic Activity Test i n A N S I
Standard I T9 . 2 ( 1 99 1 ) 1 55

20 Timothy F. Parsons, G l e n G . G ray, and Irwin H . Crawford I

To RC or Not to RC ( 1 979) 171

21 Larry H . Feldman I Discoloration o f B lack-and-White

Photograp h ic Prints ( 1 98 1 ) 188

22 M asaaki Torigoe, Kun ioki Ohmura, S hunzo Yagami, and

H aru hiko lwano I Long-Term Preservation of B lack-and-Wh ite
Photographs ( 1 984) 206

23 George T. Eaton I H istory of Processing and I mage

Stability ( 1 987) 212

24 Klaus B . H e n driks I On the M echanism of I mage S ilver

Degradation ( 1 99 1 ) 227

Part I I I Silver, Mercury, and Gold: Philosophical

and Practical Approaches in the Preservation
of Daguerreotypes 237

HEA D ING 2) Eugene Vai l lat I Process for Restoring Stained and Oxid ized
Old Prints to their Original Cond ition ( 1 850)
vi
 26 C harles van Ravenswaay I An I mp roved Method for the
RestorCJtion of Daguerreotypes ( 1 956)

Ruth K. Field I Cleaning of Daguerreotypes ( 1 958)

Irv i ng Pobboravsky I Daguerreotype Preservati o n : The

Problems of Tarn i s h Removal ( 1 978) 245

Alice Swan I The Preservation o f Daguerreotypes ( 1 98 1 )

30 Mogens S. Koch and Anker Sjogren I Treatment of

Daguerreotypes Using Hydrogen Plasma ( 1 984)

31 Grant B. Romer I G u idelines for the Ad m i n istration a n d Care

of Daguerreotype Col lections ( 1 989)

32 M. Susan Barger and William B. Wh i te I Corrosion R e mova l :

E l ectroc leaning ( 1 99 1 )

33 Thomas M . Edmondson and M . Susan Barger I The

Exa m i nation, S urface Analysis, and Retreatment of E ight
Daguerreotypes \Vh i c h \Vere Thi o u rea Cleaned i n
1 977 (1993) 284

Part IV Albumen Print Materials: Manufacture,

Structure, and Treatment 293

READING 34 M a thew Carey Lea I A n Exa m i n ation I n t o the C i rcu mstances

Under Which S ilver Is F o u n d in the Whi tes o f Albu men
Pri nts ( 1 866) 294

35 Gary E. Albright I The Conserva t i o n of A l b u m e n Prin ts ( 1 980) 297

36 James M . Reilly, Nora Ken n e dy, Donald B lack, and

Theodore Van Dam I I mage S t ru c t u re and Deterioration in
Albumen P rints ( 1 984 ) 306

37 Paul M essier and Timothy Vitale I Effects of Aqueous

Treatment on A l b u m e n Photographs ( 1 994) 320

Valerie Baas, C h ristopher Foster, and Karen Trentelman I

The Effects of F o u r D i fferent Wet Treatments on Albumen
Photographs ( 1 999)

vii
 Part V Photographic Negatives: Problems and Issues 337

H EA DING 39 Martine G i l let, Chantal Garnier, and Frani;:oise Flieder I

G lass Plate Negatives: P reservation and Hestoration ( 1 986) 338

40 Mark J-1. McCorm ick-Goodhart I f\n Analysis of I mage

Deteriorat ion in \Net-plate N egatives Fro m the M a t hew Brady
S t u d ios ( 1 992) 35 1
41 John M . Calhoun I Storage o f N i t rate Amate u r S t i l l -Camera
Fi l m Nega t ives (1953)

42 V i l i a L. Heed I H ow to \!\fork Flestoration Magic on Wrinkled

N egat ives ( 1 980) 375

43 Douglas Munso n I The P e l l i c u l a r B u rlesq u e ( 1 997)

44 Peter Z. Ade lste i n I F ro m Metal to Polyester: H istory o f Pic ture­

Ta king S u pports ( 1 987)

45 David Horvath I The Acetate Negative S u rvey: F i n a l Heport ( 1 988) 397

46 Mon ique C . Fischer and Andrew Robb I G u i d e l i n es for Care &

I dent ification of Fi l m - Base Photographic Materials ( 1 993) 401

47 Jean-Louis Bigo u rdan I Stabil ity of Acetate F i l m Base:

Acce lerated-Agi ng Data Hevisi ted ( 2006)

Part VI The Preservation of Color Photography 421

H EA DING 48 David C . Hubbe l l , Hobert G . Mc Kin ney, and Lloyd E. West I

IV l e t hods for Tes t i ng I mage Stabil ity of Color P hotographic
Products ( 1 967) 4 22

49 Peter Z. Ade l stein, C . Lore n Graham, and Lloyd E . West I

Preservation of Mot i o n - P i c t u re Color F i l m s H aving Permanent
Va l u e ( 1 970) 435

50 Henry W i l h e l m I Co lor Print I nsta b i l i ty: A Prob lem for

Col l ectors and P hotogra phers ( 1 978) 457

Robert]. Tuite I I mage Stabi l i ty in Color Photography ( 1 979) 471

52 Charleton C . Bard, George W. Larson, Howe l l Hammond,

and C l a rence Packard I Pred ict i ng Long-Term Dark S torage
Dye Sta b i l ity C h a racterist ics of Color P hotographic Products
from Short-Term Tests ( 1 980) 490

pjjj
 53 Peter Krause I Preservation of Au tochrom e Plates i n t h e
C o l l ection of the National Geogra p h ic Society ( 1 985)

54 Bertrand Laved rine and Jean-Pau l Gandolfo I The Addition

of Color. Au tochromes: Analysis and Conservation o f a Color
Photography Process ( 1 998) 512

Part VI I Developing Criteria in the Conservation

of Photographs: Collection Management
and Treatment 525

READING )) Lou is-A l phonse Davanne and Aime G i rard I Applied

C h e m i stry-Note o n the Ca uses o f Deterioration of Posi tive
Photogra p h ic Pri n ts and on a M ea n s of Restoring Them ( 1 85 5 ) 526

56 Al ice Swan I Conservation Treatments for Photogra p h s : A R eview

o f Some of the Pro b l e m s , Litera t u re and Practices ( 1 978) 530

57 Alice Swan I Proble ms in t h e Consen·ation of S i lver Gelatin

Pri nts ( 1 98 1 ) 533

58 Klaus B. Hendriks, Ben L. Tom, Christop her Sergeant, C h ris

Evans, Jac k M e l n ick, Pierre Poitras, and Doug Nish i m u ra I
Expe riments on t he Restora t i o n of D i sco lou red Black-and-Whi te
Photographs in C h e m ical Solu tions ( 1 984 ) 555

59 Charles T. Isaacs I Statement fro m the C o m m i t tee on

I nt e n s i fication ( 1 985)

60 James M . Rei l ly I Preserving Photograph Col lections i n

R esearch Libraries: A Perspective ( 1 99 1 )

61 D ebra H ess Norris I Preservation Plan n i ng fo r D iverse

Photograph ic H ol d i ngs ( 1 99 1 ) 5 77

62 Jose Orraca I Deve l o p i ng Treatment Cri te ria in the Conservat ion

o f Photographs ( 1 991) 586

63 M a r k I-I. McCormick-Goodhart I The Al lowable Temperature

and Relative Hu m id ity Range for the Safe Use and S torage of
Photogra p h ic M ateria l s ( 1 996) 591

64 Debra H ess Norris I S u rface C l ean i ng of Da maged P hotographic

M ateria l s : C u rrent Practice and Concerns ( 1999) 610

65 !<Jaus B. H en dr i ks I The Eva l uation of Conservation Treatments

( 1 995) 623

ix
 Part VI I I Exhibition Practice 633

R EA DING 66 Photograph i c Society of London I Preparing P hotographs for

Exhi bi t i o n ( 1 892) 634

67 H e n ry Wilhe l m I !V l o n i toring the Fading a n d S t a i n i ng of Color

Photographic P r i n ts (1981) 636

68 Douglas G. Severson I The E ffects of Exh i b ition on

Photograp h s ( 1 986) 654

69 Grant B. Romer I Can We Afford to Exh i b i t Ou r Val u ed

P hotographs? ( 1 986) 658

70 Nancy Reinhold I The E xh i b i tion of an Early Photoge n i c

Drawing by W il l ia m H e n ry F o x Tal bot ( 1 993) 660.)

71 John M c El hone I Determ i n i n g Respo nsi b l e D isplay Con d i t ions

for P hotographs ( 1 993) 669

72 Sarah S. Wagner, Constance McCabe, and Barbara Lemmen I

G u idel ines for Exh ibition Light Levels for Photographs (2010) 684

Appendices 691

APPENDIX A Robert A. Weinstei n and Larry Booth I Early Photographic

Process I d e n ti fication G u ide ( 1 977) 692

B James M . Reilly I Major 1 9t h-Cent u ry Photographic a n d

Photomechanical Processes: F lowch a rt (1986, adapted 2009) 694

c Monique C . F ischer and Andrew Robb I Identi fication of

F i l m - Base P h o tograph i c M aterials: I nstructions a n d Chart
( i993 ) 696

F u rther Readi ng
Abo u t the E d itors 712
Advisory Com m ittee
I ndex

x
 Foreword

One of the p r imary goa l s of The Getty Conservation Insti t u te i s to serve

the conservat i o n co m m u n i ty t h rough the d issem i n at i o n of i n formation
that advances t he field of heri tage conservati o n . To that end, i t s Rea d ings
i n Conservation series was developed i n the late 1990s to provide readers
with carefu l ly selected, orga n ized , and a nnotated semi na l texts that p res­
ent a c lear u nderstan d i ng of the h is tory, p h i l osoph ies, and methodologies of
conservati o n .
The fi rs t book i n the series, Historical and Philosophical Issues in the
Conservation of Cult u ral 1-/eritage, was i n i ti a l ly p u b l i s hed in 1 996. I t is n ow
i n its fourth p r i n t i ng and has become a val u ab l e resource for conservation
s tu dents, educators, a n d professionals. Issues in the Conservation of Paint­
ings, p u b li shed in 2004, i s a compilation of texts, ranging from the fifteenth
to the twen tieth cen t u ries, w h i c h reAect the c hanging p hi losoph i es a n d
approaches to t he conservation of p a i n t ings.
The t h i rd vol u me, Issues in the Conservation of Photographs, is the
res u l t of a s uccessfu l m u l t iyear c o ll aboration between vol u me editors Debra
Hess Norris, vice provost for grad uate and p rofessional education, and c h a i r
of t he A r t Conservation Department a t the U niversity o f Delaware, a n d Jen­
n i fer Jae G u t ierrez, assistant professor in the Art Conservation Department
of the U n i vers i ty of Delaware. They have involved a very dedicated advisory
c o m m ittee, a l l of whom have been at the forefron t i n the p ractice a n d teach­
i n g of the conservation of p hotogra p h i c m a ter i a l s . Together, they have cre­
ated a u ni q u e vol u m e that add resses the many topics-from i mage structure
a n d sta b i l i ty to treatment methods and exh ib i ti o n p ractice-comprising t h i s
q uickly evolvi ng and growi ng field.
\Ve t h a n k Debbie and Jae for their comm i tment to t h i s i mporta n t and
t houghtfu l vol u me. Debbie has been a longtime friend a n d p a rtner of the
GCI and was a mem ber of the origi n a l editoria l board that helped conceive
a n d devel op the Readi ngs in Conservation series. Her contr ib u tions to the
series, to t h i s vol u me, and to the field of conservation are beyon d measure.

xi
 ll E ,\ I) I N G '> I N C 0 N S E B I',\ T I 0 ,'I

As both a major publishing com mi t ment and an education initiat ive

of the CC I , t hese collected readi ngs are i n tended to represent the shared
knowledge that cu rrently defines and gu ides conservation pract ice in the
various specialt ies within the field. \Ne hope this vo l u me will be of benefit to
both students and professionals of photograph conservation.

Timothy P. Whalen
Director
The Getty Conservaliori lnstil11te

xii
 Preface

Issues in the Conservation of Photographs c h ro n i c l es the profo u nd chal le nges

in the Fie l d of p hotograph conservat ion and h ighl ights fu ndamental research
by i nternationally recognized professionals from the n i neteenth c e n t u ry to
the present day. Th i s i s the t hird vol u me to be p u b l i s hed as part o f the G etty
Conservation lnst i t ute"s Readings in Conservation series. L i ke the previous
vol u mes, t h i s p u b l ication compi les h istorical and modern writings that have
proven to be i nfluential in the deve lopment o f t h i nking about the conserva­
t i on of ( i n t h i s case) photographic materia ls.
Many o f the topics add ressed-sa fe environme ntal parameters, s i lver
image perma nence, and proper treatment methods-have been d i scu ssed
and deba ted s i nce the i n t rodu ction o f photography. Each part in this vo l ­
u m e is orga n ized to convey a n u ndersta nding o f the issues, c h a l lenges, a n d
principles t h a t l e d to the esta b l i s h m e n t o f the p hotograph conserva t ion pro­
fession and the p reservat ion of o u r global photographic heri tage. This p u b­
l ication ref lects important individuals, moments, a n d themes in the h istory
of the fie l d . However, u n l ike prior vo l u mes in the series, the t i m e period for
t h i s discourse is relatively short, as photography's l i fe span -annou nced to
t h e world in Jan uary 1 839-is short in comparison to that of wa l l pa i n t i ngs
or archeo logical materials.
Eight vol u me parts-some more phi losophical and others more
sc ientific-were defi ned Fol lowing years of review by the advisory commil lee
and other dedicated con servation profess iona l s and research scientists, who
a rc fu l l y acknowledged el sewhere in t h i s vol u me . The process began with
solic i ta t ions for truly Fu ndamental and tra ns formative p u b l ications from
more than F i fty i nternational photograph preservation profess ionals. J\ l ore
than t h ree h u n dred selections were n o m i nated . S u b m issions were carefu l l y
stud ied a n d eva l u a ted b y o u r advisory com mittee u s i n g m a n y criteria i nc l u d­
i ng: immediate a n d/or s u stained impact, ra rity, clari ty of writ i ng, length
( t ru ncations were to be avo ided where possible), hi storical con text, and

xiii
 HE,\D I NGS IN CONS E HVi\ T I O N

global perspective. As fundamental texts emerged , so d i d a series o f u niversal

t he mes that fu rther gui d e d the often a rd u o u s selection process.
Each part docu ments the critica l wri t i ngs o f key figu res in our fie l d .
S o m e o f t hese materi a l s - i n t h e form o f lectu res, memos, or letters-have
never been p u b l ished. Others are readi ly ava i la b l e b u t esse n t i a l to t h e dis­
cou rse each part conveys. Complete and fu l l y i l l ustrated texts a n d d iagra m s
have been incl uded when i mperative f o r the u nderstan d i ng o f t h e read i ng's
content. Regrettably, i n m any cases figu res, charts, and tables have been
excluded cl u e to space constra i n ts; in t hese cases, we encou rage readers to
seek out origi nal texts. B rief i nt roductory com men tary a n d a u thor b iogra­
ph ies provide context for each read i ng. The biogra ph ical con t e n t focuses o n
the a u t h or's co ntributions to the part t o p i c and is b y no means comprehen­
sive. Sad ly, m a ny s u perb writi ngs have not been i ncluded in this p u b l icat i o n ,
a n d the editors ask t h e i r readers to acknowledge that n o s ingle vol u me cou l d
b e a comprehens ive com p i l a tion o f t h e critical rea d i ngs for a n e n t i re profes­
sion. M any o f the exc l u ded wri t i ngs ca n be fo u n d in the F u rther Rea d i ng
sect ion at t h e encl of t h e vol u me .
Our photograp h ic h e r itage i s degrading at a n a larmi n g rate and there
re mains a pressing need for we l l -t ra ined conservators capable of preservi ng
and co nservi ng photographic materials. This co mpe n d i u m o f carefu l l y cho­
sen and sometimes c l i fficul t-to-F1 11cl wri t i ngs s h o u l d further the education of
rising conservation professionals a n d t h e aware n ess of those responsible for
t h e preservation of p hotographs. Most i m porta n t ly, i t is o u r s i ncere hope
that Issues in the Consen1ation of Photographs w i l l provide i t s readers w i t h an
engagi ng h is torica l record of the evo l u tion of t h e research a n d practice that
have defi ned t h e f i e l d o f photograph conservation. This book does not serve
as the conclusion of t h a t story but s i mply as a n i n troduct i o n , w h i l e the fie l d
o f photograph co nservat i o n con t i n ues to evolve to meet c u rrent preservation
cha l le nges. Vl/e hope i t w i l l i ns p i re needed scholars h i p a n d serve as a fou n ­
dation for fu t u re col laborative d ia logues a n d p u b l ications i n o u r fie l d .

Debra H ess N orris

\/.i.ce Provost for Graduate and Professional Education and Chair
of the Art Conservati.on De11art-rn.en.t at the University of Delaware

Jenn i fe r J ae G u ti errez
Assistant Professor i.n the Art Conservati.on Departrn.ent
at the University of Delaware

xiv
 Acknowledgments

We are e normously gra tefu l for t h e generous advice and ex'Pertise of many
c o lleagu e s . i\1l ore than flfty photogra p h i c p reservation p rofess ionals i n ter­
nationa l l y contribu ted suggested c i tations for considera t i o n , and we t h a n k
t h e m for t h e i r t i m e . S pec ial t h a n ks t o J o h n M c E l hone, Douglas N is h i m u ra,
a n d Gaiwan Weaver for their assistance w i t h rea d i n g selections and their
t hough tfu l commentary, and to o u r exceptional advisory c o m m ittee, i n c lud­
i ng M arc H a rn ly, Nora Ke n n edy, Bertrand Lavedr i n e , P a u l M essier, K l a u s
P o l l meier, J a mes R e i l ly, a n d Gra nt Romer, w h o advised o n t h e selection of
t hese read i ngs .
We also want to t h a n k o u r c o l l eagues at t h e Getty Conservation I nsti­
t u te : Timothy Whalen and Kri ste n Kel ly guided the development of t he i n i ­
t i a l p l a n s for t h i s book; Cyn t h ia God l ewski, w h o was n o t o n l y h e roic i n her
ex'Pert abi l ity to coord i nate t h e project's many logistical deta i l s b u t remained
constantly o p t i mistic; a n d J udy Sa ntos, who handled permissions for text
and i m ages . We also t h a n k the Getty Publications tea m : Tob i Kapl a n for
her gu idance d u ri n g the fln a l stages, Beatrice H ohe negger for her amazing
attention to deta i l and thoro ugh review of the content, Anita Keys for h e r
prod u c t i o n expertise, and J i m D robka f o r h is c reative i n put.
I n addition to t h e J. Pau l Getty Trust, we wou l d l i ke to acknowledge our
col l eagu es at the Un iversity o f Delaware for their e n t h u siastic support of t h i s
projec t . U . of Delaware students Bess \!V i l l i amson, J e n Moses, a n d J e n n i fe r
S c h n i t ker a b l y assisted w i t h formatting a n d w i t h the l ist of fu rth e r readi ngs .
Issues in the Co11ser11ation of Photographs is i l l u st rated w i t h magni fi­
cent i mages from t h e ]. Pa u l Getty Department of P hotographs. \Ve t h a n k
M a rc H a rn ly and Cyn t h ia Godlewski for t h e i r assistance i n selecting these
i m ages; t h a n ks a lso to the many staff a t t h e Getty who made t h e i r i nc lusion
possibl e . In t h e encl, i t is t h e long-term preservation of photograph collec­
tions worldwide that has i ns p i red t h i s p u b l icat i o n .
Debra H ess N orris
J e n n i fer Jae G u tierrez

:xv
. I
Note to the Reader

The readi ngs in t h i s vol u me come from a wide range of h is to rica l and con­
temporary sources and comprise a va riety of genres. In prepari ng t hese texts
for p u b l ication, a n u m ber of conventions have been observe d .
Every attempt has b e e n made to respect the text ual i n t egrity of the orig­
i na l materi a l . As is customary, only m i nor cha nges have been made, such as
correc t i ng grammatical errors, m isspe l l i ngs, or obvious n u mbering inconsis­
tencies, add i ng missing words or p u nctuation, a n d m i nor forma t t i ng changes
for the sake of c la ri ty. I n kee p i ng w i t h American p ractice, s i ngle quotation
marks have been cha nged to double, a n d commas and periods moved i nside
q uotati o n marks. Capital ization has been standard i zed i n tit l es and subtitles.
Footn o tes i n the origi n a l p u b lications appear here as endnotes-these have
not been e d i te d in conte n t or completed with addi tional i n formation, b u t i n
some cases m i n or corrections i n spel l i ng, pu nctuation, o r capital ization have
been made.
S u bstantive editorial add i t i o n s , restorations, and corrections to t h e
origi n a l text appear w i t h i n brackets. W h e n the origi n a l texts have b e e n edi­
tori a l ly abridged for p u b l ication here, de leted passages within t h e body o f
t h e excerpted text a re i n dicated b y e l l i pses i n brac kets; cross-references t o
e l i d ed m a t e r i a l have been d e l e t e d . E l isions o f one pa ragra ph or more are
i n dicated by the sym bol �'� , placed on a separate l i ne. Abstracts from t h e
original p u b l i cations a re not reprod uced here. E l l i pses and F rench points
cle suspension appearing in the origi nal text a re i n d icated by e l l i pses without
b rackets. lf the origi n a l text i n c l uded n u m be red notes, and some of them
have been e l ided, t h e rem a i n i ng notes have been re n u mbered consecut ively.
Type garbled in the origi n a l has been corrected in brackets. To avoid red u n ­
dancy, i n formation t h a t was ed itori a l ly extracted from t h e origi n a l text a n d
u sed i n t h e chap ter t i t l e ( a u thor n a m e , book or chapter t itle, and so o n ) has
been s i le n t l y deleted from the text itself.
P u b l ication dates appear as part of the t i t l e of each rea d i ng. I n cases o f
previously p u b l ished t ra nslations, the p u b l ication or compos ition elate o f t h e
text i n i t s origin a l language, i f k n o w n , i s give n . F o r a l l read i ngs, t h e elate of
p u bl ication and the origi n a l t i t l e o f the work as we l l as t h e edition and page
n u m bers from which o u r selection has been take n , a ppear in the source note
at the bottom of the f i rst page .
For texts origi n a l ly written i n a l anguage other t h a n E nglish and t rans­
l ated for t h i s vol u m e , every effort has been made to p roduce a t ranslation
that i s both acc u rate and styl istica l l y fa i t h fu l to t h e origi n a l . Part i c u lar
attention has been paid to the spec i fic m ea n i ngs o f conservation term i no l ­
ogy. Care has b e e n t a ke n to provide t ranslations o f such t e r m s that a r e c o n ­
temporaneo u s with the text and reAect t h e mea n i ngs of the h istorical period
in which i t was wri t te n .
 P A R T I

History of
Photograph Conservation

The pressing need for well-trai ned professionals capable of preserving a n d

conserving photographic materials emerged i n t h e late 1 960s, w h e n sensi­
tivities to the h istorical val u e of p hotographic m aterial s began to i ncrease
and both h istorical and contemporary p hotographs became more collectible.
Curators and photographers who were a larmed by the rapid deterioration of
historical p hotographs were the first to advocate for photograph conserva­
tion. Since then, the field has evolved thanks to research and methodologies
concerned with the permanence a n d preservati o n of p hotographic materials.
The rea d ings in Part I, p ublished over a 1 50-year period, introduce some of
the primary issues, challenges, and pri nciples that led to the establishment
of the photograph conservation profession; the readings also address curren t
concerns a n d challenges .

Hill & Acbmson (Scottish, active 1843-1848). Lad)' Mai)' Hamilton (Campbell) Rutliven (detail),
negative ca. 1847; printed ca. 1890. Photogravure print, 20 X 14.9 cm (]7/s X 57/s in.). Los Angeles,
] . Paul Getty Museum 84.xM.445 . 1 1
 R e a d i n g 1

THOMAS FRE D E R I C K HARDW I C H , E S Q .

On the Action of Damp Air

upon Positive Prints ( 1 8 56)

Using fu nds provided by Prince Albert, the 1 855 Fading Com:mittee (see Read­
i ng 15) cormnissioned chemist Thomas Fredericlz Hardwich ( 1 829-1890) to
conduct a series of controlled experi ments on ·positive prints. These were ai med
at elucidating which processes, substances, and conditions were responsible for
the patterns of print fading that had eroded contemporary confidence in sil­
ver hali.de 11hotography. The results of t;hese experiments were publ-ished in a
series offive i ns11ired 11a1nrs. The final paver 1nesented here outlines an accel­
erated aging r nethodology and enumerates the major causes of print; fading.
Hardwich 's M a n u a l of Photographic Chemistry was first 11ublished in 1 855. I n
1 856 h e was nanied Lectu rer on Photography at King's College, London. Hard­
wich researched and v ubli.shed extensively on photogra11hy until 1861 ·when he
becc11ne a niinister i n the Church of E ngland, Hardwich 's publications 11lace
him at the forefront of the aJ1plicati.on. of scientifi.c theory a nd methodology to
early photographic vractice. The present i.nfluential worh frames o u r ·profes­
sion and defines important preventive conservation 1neasures st-ill p racticed by
conservators today.

An exa m i nation of the properties of paper photographs wou l d be i ncom­

p lete without a deter m i nation o f their behavi o u r when exposed to a i r and
moistu re . Th is cannot be done correc t ly by the s i m p le process of suspe n d i ng
the pictu res, with water d ropping u pon them, on acco u n t of the accidental
i m p u ri ties a lways present i n t he a t mosphere. I t herefore enclosed each i n a
separate stoppered glass bottle, with a l i ttle d is t i l led water p l aced a t the bot­
tom, in order to keep the contai ned a i r saturated with aqueous va pour.

THOMAS F R E D E R I C !( l-IAHDWI C H , ESQ. " O n the Act ion or Damp A i r u pon Positive Prints,"
Journal of I.he Photographic Society 3, no. 42 ( M ay 1 856): 39-4 1 .

2
 Reading l 1 1 1\ B D W I C H

M ore than six dozen h a l f-pri nts, on every variety o f paper, were
mou n ted in this way in the early part of J a n u a ry in the present year, a n d
removed at the ex'P i ration of t h ree m o n t h s . Some were exposed to bright
daylight d u ri ng the greater part of the t i me , whilst others were kept in total
darkness. They were printed by various methods, toned i n d i ffere n t ways,
and mou nted with or without such su bstances as appeared l i kely to exercise
a deleterious actio n .
T h e n u m ber of p r i n t s operated o n , a n d the care expe nded i n t h e i r
preparation, 1 w i l l I tru s t give a va l u e to t h is series of ex'Periments, and estab­
l i s h the co n fi d e nce of the Society i n the res u l ts which have been obta i ned.
The list of ex'Peri ments i s as fol l ows:

No. 1. 7 prints devel oped o n iodide, o n bro m ide, a n d o n chloride o f s i lver,

on p l a i n paper; s i m ply Fixed i n hypos u l p h i te ; was hed in boi l i ng
water. Unchanged.
No. 2 . 4 d itto, d itto, the development stopped at the red stage .
Unchanged.
No. 3 . 2 d i t to, prepared b y M r. Sutton o f J e rsey; negative process; toned by
sel d 'or. Faded in t he light est shades.
No. + 2 d itto, Mr. S u t to n 's negat ive process; washed with boi l i ng water.
Unchanged.
No. 5. 2 di tto, printed by S i r W. Newton ; h i s negative process with bromide
of s ilver; sligh t ly toned without gold. A little faded in the half-t:ones.
No. 6. 2 d itto, d i tto; h i s negative process with iod ide and b ro m ide of s i l ver;
washed i n boi l i ng water, not toned. Unchanged.
No. 7. 6 prints, on p l a i n paper; s i mply fixed; washed in hot water.
Unchanged.
No. 8. 8 a l b u m i nized pri n ts , s o m e s i mp l y fixed, others t o n e d with gol d ;
washed i n hot water. So·m. e a re unchanged, others have lost t he
gloss of t he albumen and a litt le half-t:o ne in isolated patches.
No. 9. 3 a l b u m in ized prints toned with gol d , washed only in col d water.
The image al-most obliterated by m.oulcl-iness; the gloss of the albu­
men has disappea reel.
No. 10. 5 prints on paper prepared with casei ne; s i mp l y fixed. Faded in t he
half- tones.
No. 11. 8 d i tto, o n p l a i n , and on a l b u m i n ized papers; toned in old hypo­
s u l p h ite. All badly faded.
N o . 1 2 . 12 d itto, on p l a i n papers; toned in a single bath o f hyposu l p h i t e a n d
gold. A .few unchanged; so·me have lost a liule half-tone, ot hers have
faded badly.
N o . 1 3 . 2 d i tto, printed by M r. De la M otte on Towgood's paper -i1n m.ersed
i n very d i l u te salting bat h , a n d sensitized w i t h a m monio-ni trate;

3
P art I ll l S T O H Y O F P l- I O T O G B A l' l l C O N S E H VAT I O N

toned in a single bath of hypos u l p h ite o f soda and gol d; washed i n

boi l i ng water. ( N . B . The hot water makes t h e prints, prepared by
t h i s mode, very red, but t h e dark tones a re rega i ned by pressing t h e
d a m p print with a hot i ro n . ) Unchanged.
N o . 1 4 . 6 d itto, by iV l r. Shadbolt; toned by sel d'or; fixed in a m monia;
washed i n cold water. Uninj u red i.n t he half-tones; a lit tle c hange
of colo u r i.n t he E nglish 71apers.
No. 1 5. 2 d itto, toned by c h loride of gold; on foreign papers; s ize extracted
(one being a spec i m e n of t h i s mode o f toning sent to the Pri nting
Com m i t tee by Mr. Waterhouse of H a l i fax) . Unchanged.
No. 1 6 . 3 d i tto, s l igh tly toned in old hyposu l p h i te; waxed w i t h white wax
d issolved in ether. Faded badly.
No. 1 7. 3 prints, waxed; toned in a bat h of hyposu l p h i te and gol d (one,
a spec i men o f the waxing process received by the E d i tor o f the
J o u rn a l ) . All faclecl in half-tones .
No. 1 8. 2 d itto, varnished w i t h spi rit varn i s h ; one toned in old hypos u l p h i te,
the other in a bath o f hypos u l p h ite and gol d . The former faclecl
badly, t he latter unchanged.
No. 1 9 . 2 d i tto, toned in a gold bath; coated with gu tta-percha d i ssolved i n
c h loroform. Badly faded.
No. 20. 6 d i tto, u ntoned; s meared on the surface, some with paste, some
with starch, and others with resi n soap preci p i tated by a l u m . All
faded badly.
No. 2 1 . 4 d i tto, u n toned; a m i n u te q u a n t i ty of acetic acid, or a l i ttle a l u m ,
added t o t h e water in t h e bot t l e . All badly faded.
No. 22. 1 photogra p h , previously converted into s u p h u ret o f s i lver by
c h lorine and s u l p h u retted hydroge n . Unchanged.

l n reviewi ng the above experiments, it may be remarked 1 11 the first

p lace, that t h e test to which these prints were s u bjected was a severe one.
When we consider the i mportant i n fl uence which moisture exercises i n
favou r i ng oxidation, i t may, I t h i n k, be conc l uded, that a n exposure o f t hree
months in an a t mosphere satura ted with aqueous vapo u r wou l d be equ iva­
lent to ·many years i n air o f the ord i na ry degree o f h u m i d ity, and that t here­
fore prints which have s u rvived such a n ordea l a re safe as far as oxidation by
p u re air i s concerned.
N ow the experiments showed that plain paper pos i tives which had
been sin,,,ply fixed i n hypos u l p h i te, rem a i ned u n i nj u red. Whether developed
by gal l i c acid or prin ted by d i rect expos u re to l ight, the res u l t was the same;
a n d hence we may i nfer that the darke ned material which forms the i mage
of p hotographic pri n ts does not read i ly oxi d ize in a damp atmosphere.

4
 Reading l I I /\ n D \·\I I C I I

B u t i f by a process o f ton i ng the colour and chemical compos i t i on o f

the image be a ltered, or w h e n i n a d d i t i o n to atmospheric a i r and wa ter, cer­
t a i n deleterious su bstances a re p resent, the elq.>er i m e n ts prove that the res u l t
is d i fferen t , a n d t h a t t h e p r i n t t h e n becomes s u sceptible of oxidation. L e t u s
d iscuss these two condition s separately.
F i rst, fading may be i:nf/.uenced by the mode of toning th.e pri n t . ­
S u L P H U RATION a l ways has a bad effect. Ou t of several p r i n t s prepared i n a n
old hypos u l p h i te b a t h , not one reta i n ed its hal f- t i n ts after t h ree months'
expos u re to clamp.
Ton i ng by a single bath of gol d a n d hyposu l p h i t e of soda may also l eave
t h e image in a less stable cond it ion than before; for it was fou n d in some o f
the p r i n t s p repared i n t h i s way that t h e fi r s t s hades of darke n i ng b y l ight
had faded. It i s i mportant to notice that this happened particu larly when the
gol d bath, havi ng been long used, was not in an active state. T n one experi­
ment, o u t o f tvvo p r i n ts produced by t h e same process, viz. with c h loride
a n d Iceland moss, one prepared i n a q u i ckly acting bath proved to be highly
permanent, w h il s t t h e other, rese m b l i n g the l ast in colour b u t toned i n a fee­
b l e bat h , faded when exposed to moisture . This p roves that the view I have
before advocated as to the change of p roperties which the fixing and toni ng
bath u n dergoes by constant use, is correct, and that the solution at length
tones by sulphur if the supply o f go l d be not wel l kept u p . I fo u nd that the
pri n ts which faded in t h e moist air were far more read ily inj u red by bo i l i ng
water t h a n t hose which d i d not fade, a n d t h i s is one of t h e characteri stics of
ton i ng by s u l p hur-that t h e tint q u ickly degen e rates i nto a d u l l brown when
t reated with hot water.
Ton i n g by means o f c h loride of gol d appeared to be h ighly satisfactory.
I t \·Vou l d have been better, however, if a l a rger n u m ber o f prints had been
operated on. The s e l d'or process also seemed to l eave the print u n i nj u red;
no commencing yel l owness or bleac h i ng or h a l f-tones being visible after
ex'Pos u re to the moist air.
The presen t series o f experi ments has confirmed the observation made
i n a former paper, t h a t some t i nts obtained in posi tive p ri n t i ng are more
perma n e n t t h a n others. The violet tones produced by s u l p h u r soon pass i nto
brown by t h e action o f moisture, a n d even when gold i s used, t hese p u rple
colours are apt to become more or l ess reddened by the cla m p a i r. Th i s i s
especia l l y the case when English papers a r e used, or c a s e i n e i s added t o
t h e salting bath. C hocol ate-brown t i nts which withstand boi l i n g water (espe­
c i a l ly those upon a m m o n i a- n i t rate paper) are l east affected by cla m p a i r; a n d
i n d eed i t i s evident that the long-continued action o f m o i s t a i r has an effect
s i m i l ar to that o f boil ing water in te nding to redden the p r i n t , s i nce l not ice
i nvariably that the t i n ts which stand the hot water are u na ffected by the
Part I 1-l l S T O H Y O F P H O T O G H f\ P l l C O N S C H V A T I 0 .'\1

m o isture , a lt hough the fo rmer test is the most severe, as far as m ere cha nge
of colour is concerned .
Secondly. Deleterious mat ters left i n t he papa may promote fading by
moist air.-Th i s was evidently seen in two experiments in w h i c h pos i tives
toned in an old go ld ba t h and washed in cold water were d ivided i n to halves,
one of which was treated with a m m o n i a so as to extra c t the s ize. The res u l t
showed t h a t the halves i n w h i c h t h e size was a l l owed to re m a i n faded, w h i lst
the others were scarcely i nj u red.
The removal of the size also prevents the formation o f m o u l dy spots,
which w i l l be seen more or l ess u pon all the prints, exce p t i ng those which
had been washed in hot water, or t reated with a n a l ka l i .
The a l b u m e n proofs, washed o n ly i n cold water, were rendered per­
fectly u se l ess by t h i s acc u m u lation o f m o u l d . \Vhe n boi l i n g water was used,
no mou l d occu rred ; b u t even i n t h i s case t here seemed to have bee n , on
some o f the p r ints, a l i t t l e pu.t refact i.ve decom11osit ion o f t h e a l b u me n , which
destroyed the gloss i n isolated patches, but affected the i mage l ess than
m ight have been a n t ic ipated . 'vVhen casei ne was u sed in p lace o f a l b u men,
the res u l t was a l so less satisfactory than with plain papers prepared without
casei ne; a n d i t seems evident that t hese animal s u bstances, a l though stable
under ord i nary con d i tions, wi l l , even when coagulated by n i trate of si lver,
undergo decomposition i f kept long in a moist state.
The u s e of i m p roper s u bstances for m o u n t i ng i s also proved to be a
cause of fadi ng by oxidat ion; and the observations i n the first report of t h e
Pri n ting Com m i ttee a re confirmed. Ac ids of a l l kinds, a n d acid salts, wi l l
s lowly b u t s u re ly destroy t h e image. H e nce alum used i n sizing should not
be perm i tted to rem a i n i n the paper; and paste and starch, both Ferme n t i ng
su bstances a n d susceptible of conversion i n to acetic and l actic acids, a re
contraindicated . If we a l low t hat the h a l f-tones of the picture contain a s u b­
oxide of s i lver, the fol l y of l eaving anyt h i ng in t h e paper which may ge nerate
a n acid becomes m a n i fest; t h e acid, when formed, u n i tes with the oxide and
the p i c t u re i s destroyed.
Effect of coating t he p rint with wax, etc . - F rom the experience ga ined
in t hese experiments, I i n fer that when a pri n t i s prepared i n s u c h a way as
to fade o n exposure to clamp, it cannot be protected by the application of a
solution of wax to the su rface. I fou n d that the p r i n ts which had been waxed
appeared to fade q u i te as much as, and in some cases more than, othe rs
which were left u n touched. 'vVaxi ng wi l l not therefore be a remedy for the
adoption of a bad mode of printi ng; and l t h i n k we m ust be careful l est, in
attempting to p rotect the p hotogra ph from t h e air, we i n t roduce s u bstances
which a re h u rt fu l . \Vh ite wax is an article much a d u l terated, and t u rpen t i ne,
com monly u sed as the solvent, i s l i able to con t a i n a p r i n c i p le possessi ng oxi­
dizing properties, as may be s hown by agitating comm e rcial o i l of t u rpen t i ne

6
 Reading 1 I I A H D \\1 1 C II

w i t h d i l u te solution o f s u l p hate o f indigo, t h e b l u e col o u r o f w h i c h i t often

q u ickly b l eaches. I f a coating is req u i red to pro tect p r i n ts from the a i r, i t
may be applied i n the form of a d i l u te spirit varn i s h , the p i c t u re havi ng been
previously re-sized with p u re ge latine; this plan appeared to m e to afford
some p rotection.
The s u pposed acce lerating i n fl u e nce of l ight u po n the fad i ng o f posi­
tive prints is negatived by these experi ments, as far as they extend. M a ny of
the bottles conta i n i n g the photographs were placed outside t h e window of
a house with a sou thern aspect d u ring the whole of the t i m e , excepting two
or t h ree weeks , but no d i fference whatever cou l d be detected between these
prints and others kep t in darkness. I t wi l l be satisfactory, however, that t h i s
part o f t h e investiga t ion s h o u l d b e repeated , al lowing a longer t i m e .
Expos u re t o d a m p a i r w i l l a fford a ready means b y w h i c h t h e photog­
rapher may estimate the permane nce of h i s proofs. They s h o u l d be enclosed
in a clean glass bottle w i t h pure water at the bottom; if at the end o f t h ree
months the colour is u n changed , the l ightest s hades perfect, and t he paper
free from m o u l d i ness, t h e mode of p ri n t i ng adopted i s sati sfactory.
Reca p i t u lating the preca u t ions suggested by these experim e n ts, they
may be conde nsed as fo l l ows: -Avo i d s u l p h u retting the positives i n the pro­
cess of toni ng, and cleanse the proof from eve ry t h i ng but the vegetable fibre.
The print w i l l then i n all proba b i l ity be perma nent, as far as i n trinsic causes
of fad i ng are concerned.
In conclusion I may remark, that the i nvestigation which I u ndertook
at you r req u est and wh ich it is my i n tention to c l ose with t h i s paper, has con­
vi nced m e t ha t the fad i ng of photograp h i c pri nts does not depend upon any
i n here n t i nstabi l ity o f the image, but that it i s d u e to i nj u rious conditions,
which l trust have now been ascertained, and i f so, may eas i l y be removed.
M H . S l-IADBOLT. - 1 cannot a l low the occasion to pass without offer­
i ng my testi mony to the great d i l igence and s ki l l which M r. H a rdwich has
brought to bear on these experi ments, t h e res u lts o f which he has laid before
u s . I regret very much I was not present at the last meeting, because he t h e n
gave the res u lts of h is i nvestigation i n to the nature of the deposit u p o n the
pri n t . I can only say, that u pon read i ng h is paper I experi enced the greatest
poss i b l e a m o u n t of satisfaction. I consider it one o f the poi nts we shall have
to be most proud of, when we come to s u m up o u r doi ngs for the Sessi o n .

Notes

1 The glass hollies were new <111d had never before been used; t hey were well
ri nsed with d i s t i l led water, which was afte rwards tested and Fo u nd lo conta i n
nothi ng. I t is therefore certa i n t hat t h e pos it ives have been fa i rl y tested, and
that no accide ntal impurities were prese n t .

7
 R e a d i n g 2

E UGENE O STROFF

Preservation of Photographs ( 1 967)

Eugene Ostroff ( 1 928-1 999) was cu rator of photography for t:he S niit:hsonian
Institution from 1 960 to 1 994. Trained as a photographer, Ostroff published on
the history and technology of p hotography and the care of photographic nwte­
rials. /-le curated a variet.y of exhibitions by leading photographers-including
Richard Aveclon ( his fi rst ever solo exhi.bition), f r n.ogen Cu n ni ngham, Elliott
Erwit:t, and Robert Ca71a-and established a 6, 500-square-foot /- /all of Pho­
tography at the S mit hsonian in 1 972. As t h. is reading wit h extensive footnotes
demonst rates, Ostroff examined photograp hic ·materials, detenni. ned causes of
deterioration, and suggest:ed p reservation techn iques as early as t he 1960s. /-le
also published a series offour technical a rticles t itled "Conserving and Restor­
ing Phot:ographic Collect ions" in several 1974 issues of i\11 use u m News, which
alerted a wider readersh ip to the fundamental challenges associated wit h the
p reservation of photographic materials.

Last year a t the S m i t hson i a n , we i n it iated a study of long-term storage sta­

b i li ty (arc hival q u a l i ty) of p hotographs. This work i n c l u des a n i nvestigat i o n
o f m e t h o d s to restore photographs prod u ced by h i storica l l y e a r l y processes.
In a rel atively s hort t i me t h is study has obta i ned a n swers to a n u m ber of
problems, but i t also has i ntrod uced a large array of new questions about
preservat i o n which, as yet, rem a i n u mmswerecl .
Pictu res a re in consta n t clange r of attack by various conta m i n a n t s .
Al though s o m e photogra p h i c processes demo nstrate excep t i o n a l stab i l i ty,
none i s com pletely res istant to a l l e n v i ro n m e n t s . The col lector s h o u l d be
aware of the pote n t ial sources of degradation in order to avoid i ncorporat-

EUGENE OSTHOFF, "Preservation of Photographs,'' Plwt.ograpliic jo11rnal 107 (October

1 967): 309- 1 4 . Heprinted by permission of the Hoyal Photographic Society of' G reat B r i ta i n .

8
 Reading 2 O S T H O F F

i n g them i nto his col lection . Let u s consider various photographic processes
which m ight be contained in a photographi c archive and note some of the
major preservation problems and procedures.

Processes

Early paper photographs (ca . 1 8 3 5-1 85 5 ) . These inc lude "salted paper" pho­
tographs or photogen i c drawings and calotypes (tal botypes, both negatives
and prints). The earlier photographs frequently fade because they were
imperfectly fixed and washed. As photograp hers became i ncreasingly aware
of the need to improve fixing and washing practices the later paper photo­
graphs, i . e . , those produced after the mid - 1 84 o' s, show i mproved preserva­
tion characteristics.
To detect potential sources of trou ble, test the photographs for
res idual hypo or silver. 1 If chemical tests are posi tive, then degradation
m ight be arrested by refixing and u s i ng a wash accelerator, fol l owed by a
thorough water was h . 2 U nder certai n c i rcumsta nces i mages can be i n tensi­
fied chemical ly.'
Special care should be exercised in treati ng these early prints. They
usually possess a very low wet strength and are l i kely to tear if manipu lated
with the fi ngers. To m i n i m ize damage when hand l i ng wet pri n ts, support
them with a fibreglass screen "sandwich" arrangement, taki ng care not to
handle more than one or two prin ts at the same time.
I f a test pri n t shows evidence of emulsion soften i n g while wet (emul­
sion separa t i ng from the paper base, possibly along the edges or by forma­
tion of bl isters) use a harde n i ng solution. 4

Daguerreot;ypes (roughly 1 8 39-1 85 5 ) . These i mages, cons1st111g of an amal­

gam of merc u ry and si lver on a si lver-plated copper sheet, are extre mely
fragi le, and can be eradicated with an accidental wipe of a finger or cloth.
The picture is subject to d iscoloration by i m perfections i n here nt in the plate
itself, or by atmospheric contami nation, e.g., su lphur compounds in the
storage environ ment. Residual hypo does not appear to be a problem with
daguerreotypes because the meta l l ic plate washes readily. A relat ively si mple
clea n i ng formula is avai lable, but before u si ng it fi rst ru n tests with expend­
able pictures.5

Early plate negat ives. These consist of albumen ( c a . 1 848- 1 8 55) and col lodion
( 1 8 5 1- 1 880) e m u lsions coated on glass. The col loclion emu lsion tends to dis­
colour and flake off from the glass base. N itroce l l u lose (cel l u lose n i trate),
which is used i n the preparation of col lodion, freq uently decomposes with
age, l i berating nitric oxide, nitrogen d ioxide, and other gases. These gases,

9
Part I II I S T 0 H Y 0 F P II 0 T 0 G H 1\ I' I I C 0 N � E B \' A T I 0 N

u n less permi tted Lo escape, accelerate additional decomposi t io n w i t h i n L he

material i tsel f.
Collodion e m u ls i o n tends Lo last longer t ha n t h e more recen t n i t rate
f i l m base. The e m u l s i o n coati ng, phys i c a l l y much t h i n ner t ha n a film base,
permits the gases of decom pos i t i o n lo escape read i ly, t hereby m i n i m izing the
effect of the gases o n t he e m u ls i o n itself. The i m permeable glass base protects
t he reverse side of the e m u l s i o n From at mospheric attack, t h u s con t r i b u t i n g Lo
its preserva t i o n . For s torage, p l ales s h o u ld be placed in paper e nve lopes w h i c h
a re fa irly poro u s . E nvelopes prolecl t h e e m u l s i o n from acc i d e n t a l abras i o n ,
d i rt a n d finge r- p r i n t ma rks. Plates s h o u ld b e stored o n edge, s l ightly separated
From each other to perm i t air c i rc u l a t i o n and d issipation of harmfu l gases.
The plate cabi net or container also s h o u l d be vented for air c irc u lat ion .

Gela t in ·plates. Commerc i a l l y i n trodu ced i n 1 878, t hese e m u ls io n s u s u a l l y are

more stable t h a n t hose p roduced by h i storica l l y earl ier processes. Genera l ly,
the same storage a n d preservation proced u res s h o u l d be fol l owed with t hese
as with the a l b u men and c o l lodion plates.

Flexible film-cellit lose n i t rate ( n i t rocel l u lose, 1 888- 1 95 1 ) . The hazards

of t h i s p roduct were d ra m a t i c a l l y b rought lo t he attention of the gen e ra l
p u b l i c as a res u l t of severa l serious fi l m fires, e . g . , Ferguson B u i ld i ng F i l m
Exchange ( m o t i o n p i c t u re f i l m ) , P i u s b u rgh. 1 909, a n d the C leve l a n d C l i n i c
fire (X-ray fi l m ) , 1 929. I n t h e early 1 92o's, t h e n o n - i nAammable advantages
o f safety fi l m (cel l u lose acetate} s p u rred its i n t ro d u c t i o n for 1 6 m m motion
p i c t u re f i l m a n d in the early 1 93o's, for X-ray, 3 5 m m s t i l l p i c t u res, a n d some
sheet-fi l m appl icatio n s . It was not u n t i l 1 9 5 1 , however, that p roduction of a l l
n i t rate fi l m was stopped, 3 5 m m motion p i c t u re materi a l being t he last from
w h i c h it was abandoned .
From t he standpoi n t of preservat i o n , the dege nerati o n of n i t rocel l u lose
f i l m probably has attracted t he greatest attention of the col lector beca use
deteriora t i o n o f this material invo lves gross p hysical changes a n d a lso pres­
e n ts a fire hazard .
A c e l l u l ose- n i t rate base, as ment ioned previous ly, is c h e m i c a l l y u nsta­
ble, a n d t he very t h ickness o f t he s heet itself m a kes i t i m poss i b le to e l i m i ­
nate i m mediately the gases of deco m pos i t io n . Trapped w i t h i n the s heet,
t hese gases acce lerate fu rther decompos i t i o n . The degenerative p rocess is
fu rther aggravated when the negatives a re stored i n i n ti mate con tact with
other n i t ra te fi l m . The material first d iscolo u rs (ye l l owi s h ) , t he n becomes
sticky, fuses together, a n d f i n a l l y is red uced to a powder. Fresh air c i rc u la­
t io n aro u n d the film s u rfaces helps Lo m i n i m ize t h i s deteriora t i o n process.
Part ia l l y decomposed n i t rate f i l m m ight ign i te spontaneo u s l y at temper­
a l u res as low as 1 20° F . S heet and rol l n i t ra te f i l m s s h o u l d be stored u n ro l led

10
 Reading 2 O S T H O F F

i n strips and filed i n paper envelopes (porous). Th is decreases intimate con­

tact between film surfaces and lessens the possibility of combustio n . The
eventual loss of nitrate film is inevitable, and the only solution to this prob­
lem is to photo-copy the origi nals. I dentification tests and a more detailed
description of n itrate film characteristics are available in the l iterature.6

Contemporary negatives. Hesearch on the preservation of other types of black

and white photograph i c materials, from the arc h ival viewpoint, has been rel­
atively neglected. The one exception , micro fi l m , has been the subject of very
i n tens ive investigations because of recently d iscovered deterioration, and a
Fu l l description of this work can be found in the literature.7

Residual Chemicals

Gelatin emu lsions wash with relative ease. Chemical conta mination, there­
fore, is more likely to be prese nt with paper prints than with i mpermeable
glass plates or flexible film base. The fibres of paper base tend to retain
c hemicals and are d ifficult to wash thoroughly. These contaminants with
t i me attack the i mage. With poorly fixed and washed pri nts, the i mages even­
tually turn a brownish-yellow and fade. The white image a reas might acq uire
a light sepia colour and the paper becomes brittle. H e re aga i n , refixing,
using a wash accelerator, and a thorough wash in water, should arrest the
decomposition.8·9 Film base, relatively impermeable to processing sol utions,
presents less of a was h i ng problem than paper prints.
I f improved i mage stability is desired with any of these materials, a gold
toner should be used . 1 0 Treatment i n such a solution chemically forms a pro­
tective gold coating around image si lver particles. Gold, being more stable
than si lver, offers greater resistance to attack by contam ina nts. Tests should
be made to note the reaction of a photograph to gold toning. With prints, the
change in i mage colour by the toner m ight be aesthetically u ndesirable.

Storage

Photogra phs are suscepti ble to attack not only from res idual processing
chem icals withi n the picture itself, but also from other contaminating mate­
rials in the same storage area. The effect is strongest where the conta m inat­
ing source is i n c losest proxi m ity to the picture and where it is present in
the h ighest concentration. The attack on a photograph m ight occur not only
th rough direct contact with conta m i nated material, but also as a res ult of
volatilization of the offending ingredients which, in turn, contam inate the
storage atmosphere. H ydrogen su lphide, suphur d ioxide, ozone, a nd perox­
ide all can attack the photographic image. 1 1

I I
Part I 11 I S T 0 B Y 0 F P 1-1 0 T 0 G B 1\ P II C 0 N S E B V A T I 0 N

Materials u sed i n the construction of envelopes, wrappi ngs, con tain­

ers, cabinets, and even the fin i shes on storage area wal l s, either i n d ividually
or i n concert, could be pote ntial sources of trouble. To complicate the situ­
ation even fu rther, the effects of any of these are accelerated by e levated
relative h u midity and temperature. 1 2

Coa t i ngs

Lacquers, varn ishes, acrylic resins, and any other su per-coatings on the
i mage su rface m ight conta i n solve nts, residual catalysts or i mpurities wh ich,
eventual ly, cou l d attack the i mage. Ma ny of these coatings d iscolour and
occasionally become tacky, not only with age but also u nder adverse storage
conditions such as excessive temperature or h u m idity, or in the presence of
conta m i nating fumes.

Adhesives

Degradation of photographs also can be i ntroduced by ad hesives used for

mou nting prints, i ncorporated into the construction of paper, or, those coated
on the paper a nd c loth u sed for "hingi ng" prints. \i\/ith commercially avai lable
prod ucts it is q u i te possi b l e to obtain a partic u lar batch of adhesive which,
according to analysis, contains no trou blesome i ngred ients. A su bsequent
batch from the same source cou ld prove to be u n u sable because of conta mi ­
n an t s. The sam e manufactu rer coul d have obtai ned one i ngredient fro m a
new sou rce where it was produced i n a sl ightly d i fferent manner and, per­
haps, now contai ns a t race of some additive or i mpurity, such as i ron , copper
or sulphur, which is harmfu l to photographic images. Some adhesives tend to
be hygroscopic, thereby i ncreasing the possi b i l i ty of local chemical activity.
The best material for mou n t i ng pri n ts appears to be d ry-mount tissue
which is relatively i nert and forms a bond broken only by heat.
Add i tives u sed for negative envelope seam closures always a re a poten­
tial sou rce of tro u ble. Where a seam re mains in contact with an emu lsion
for an extended period, there is apt to be i mage bleac hing and occasional
d iscolorat ion. The extra envelope th ickness of the fold can cause pressure
marks. For photographic storage it is desirable to use envelopes with edge
seams which are not coincidental with the negative image.
M ou nting or matt board is produced by glueing or laminat i ng a n u m­
ber of thin sheets together to form a si ngle sheet of appropriate th ickness.
For this pu rpose, some m a n u facturers use a starch-base adhesive conta i n i ng
various additives. Others u se synthetics. Matt board which is 1 00 per cent
rag and "acid free" can, with time, shift i n pH. A periodic check should be
made on these materials until more i n formation becomes ava i lable on man­
u facturing quality con trol and long-term stabil ity characteristics.

12
 Reading 2 O S T R O F F

Sheet plastics

Transparent s heet p lastics freq uently are u sed as protective covers or as

envelopes for prints a n d negatives. All of t hese produ cts should be tested for
long-range stab i l i ty and i nertness. The p hotographic image can be adversely
affected by plexi glass-type plastics containing residual catalysts. Here aga i n ,
a s with adhesives, w h i le one batch m ight b e i n ert, a subsequent batch might,
upon testi ng, prove to be completely u n u sable. Another precau tion to note
abou t these plastics is that even though they appear to be made of dense
material, they do not necessarily provide a barrier layer, and harmful gases
might readily diffuse through the sheet.
Plastic print and negative envelopes also could serve as moisture traps.
Rapid, large changes in atmospheric conditions might condense moisture on
the i nside of the envelope, t hereby establishi n g conditions ideal for bacteria l
incubation which wi l l even tually attack the emulsion. Also, excess moisture
i ncreases the possi b i lity of local chemical activi ty. 1 3

Papers

Paper products are probably u sed more frequently than any other mate­
rial in the storage of photographs. Paper e nvelopes, i n terleavers, stiffen ­
ers, mount a n d matt board, containers a n d wrappers are usually i n d i rect or
indirect, fu l l-time contact with stored p hotographs. These materials, with
the occasional exception of some specially selected mount board, are a lm ost
always of poor quality. This i n c l u des t h e brown kraft and glassine enve­
l opes trad itionally u sed by the p hotographer and col lector as containers for
negatives. The brown kraft papers contain l igni n and additives such as alu­
minium su lphate1 4 which, over a long period of time, could affect the photo­
graph ic i mage.
Another short-lived paper, frequently u sed for photographic enve lopes,
is glassine paper, which d u r i ng m a n u facture is more "hydrated" than other
papers. This results i n a so mewhat degraded fib re. Various add itives, such
as plasticizers for Flexi b i l i ty, are u sed to i mp art certai n optical (tra nspar­
ency) , mechanical an d chemical c haracteristics. 1 5 These, with time, vola­
t i l ize or leach out and can have a detrimental effect on i mage stabil i ty o n
adjacent p hotographs.
N u merous studies have show n that papet' acid ity is one major consid­
eration i n paper preservation. Atmospheric conta mi nation by sulphur dioxide
can lead to the formation of s u l ph uric acid in the paper, which then attacks
the paper itself. I mp u rities such as i ro n and copper serve as catalysts and
i ncrease the paper's affi n i ty for sulphur d ioxide. Also the presence of free
acid in the paper serves to absorb atmospheric ammonia, a silver solvent. 1 6

13
Part I ll l S T O H Y O F P l l O T O G H :\ P l l C O N S E B V AT I O N

The purer the cel l u l ose of the paper, the higher its "alpha cell ulose"
fibre content (the percentage of ash-free material resisting the action of
sod i u m hydroxide of mercurizing strengt h ) , and the more permanent is the
paper. 1 ' Photographic paper base, now made of highly purified wood fibre,
is high in alpha cel l u lose content. M u seums sometimes use a p H n eutral,
1 00 per cent rag stock which is very h igh i n alpha ce l l u lose as a photograph i c

mou nt board beca use it demonstrates long-term stability. N o t o n l y is such

rag stock very expensive to prod uce but manufactu rers fi nd it extremely d i f­
fic u l t to purchase rags which do not contain traces of synthetic fibres and
various add i t ives i ntended to i mpart certain physical attri b utes, such as
added wh i teness. Chem ical processing, u n i njurious to the rag fibres, cannot
successfully remove all such foreign matter. In the fi n i shed paperboard their
long-range storage effects on photographs are u n known.
I t probably is Fai rly safe to ass ume that all of the paper products asso­
c iated with the storage of photographs shou Id be a t least as good as the h igh
al pha-cel l u l ose paper used for modern photographic paper base. Using this as
a m i n i m u m qual ity standard we are trying to i nterest various manufacturers,
m i l l s and converters i n su pplying photographic-quality paper i n the appro­
priate weights and fi n ishes for envelopes, i n terleavers, and mount board. To
e l i m i nate the problem of envelope seams, we are exploring the practicabil i ty
of using " fold-over" or cri mped seam closures to e l i m in ate u s i ng adhesives.
I f adhesives prove unavoidable, perhaps a photograph ic quality gelatin or
polyvinyl acetate res i n ( heat-sea lable) m ight be a safe solution to the prob­
lem. These adhesives also m ight prove applicable to the manufacturing of
matt and mou nt board stock.

Storage A t 1 nosphere

P hotographic images are sensitive to traces of peroxides which are generated

by most fresh paints, res inous uncoated woods, and bleached woods. Many
of us are aware, however, of circumstances where pictures have been safely
stored close to these materials for many years and, apparently, i m ages are
not always adversely affected u nder these conditions. It is qu ite l ikely that
with t i me t hese paints and woods lose their harmfu l volatile constituents.
Atmospheric po l l utants 1 8 such as sulphur d ioxide, hydrogen sulphide and
nitrates also can attack photographs.
I mage fad i ng can occ u r in areas where paint has been freshly app lied.
Generally the damage takes place within the first three to fou r weeks after
painting and apparently has the greatest effect on fresh ly processed photo­
graphs. Those older than six months appear to be resistant, possibly because a
su fficient amount of i mage su lphiding or other reaction with residual chemi­
cals already has taken place to protect the individual i mage silver grains from

14
 Reading 2 0 S T H 0 I-' F

being attacked by t h e pa i n t Fu mes. Formation of the h a rm fu l gas depends on Lhe

type of pa i n t , e .g. , t h e d ry i n g age n ts i n corporated d u ri ng pa i n l m a n u fact u re .
G ood relative h u m i d i ty ( r . h . ) a n d tempera t u re controls p l ay a vital ro le
i n the l i fe of a photogra p h . Low r. h . a n d temperatu res retard c h e m ical act iv­
i ty, t h e reby decrea s i ng t he rate o f attack by con t a m i n a n ts.
I dea l ly, nea r-freezi ng tempera t u res a n d a very low r . h . , i . e . , 20-30 per
cent, wou l d e n s u re t h e longest l i fe for photogra p h s . Pract ical considerations,
however, normally I i mil storage c l i mate contro l because t h e cost o f p u rchas­
i n g a n d m a i n t a i n i n g storage fac i l i t ies of t h i s type wou l d be pro h i b itive. /\lso,
removi ng pict u res from such a n atmosphere to the one in w h i c h we work
wou l d req u i re a very s l ow adj u s t m e n t period to the new set of atmospheric
conditions in order to avoid formation o f condensati o n . Practically speaki ng,
by way o f compromise, the storage atmosphere shou l d approach 40-45 per
cent r. h . and 60-65° F .

Summa ry

Photographs are s uscept i b l e lo degradation from many sources. Attack o n

the i m age or base can occ u r from resi d u a l processi n g chem icals, ind ustrial
at mosp h eric pol l u ta n ts, conta m i na n t s from storage a rea construction mate­
rials or From t he materia l s u sed for m o u n t i n g a n d conta i n i ng the pict u res.
Degradation from poor proces s i ng can be detected with s i m ple c h e m i ­
cal tests. U n t i l more becomes k n o w n a b o u t t h e m a n y prod ucts norma l l y asso­
c i a ted w i t h the preservation o f photographs, one s h o u l d avoid u s i ng i n t h e
storage area fresh pa i n t , r a w woods a n d vol a t i le s ubstances, a n d n e a r or o n t he
photographs avoid adhes ives, plastics a n d poor q u a l i t y papers. Regar d less of
t he preservation tec h n i q u e used i t i s hel pfu l to rem em ber t hal t he storage l i fe
of photogra phs can be extended by s l owing clown chemical activity. This can
be achieved by carefu l con t ro l o f storage tempera t u re and relative h u m i dity.

Acknowledgements

I wish to acknowledge s u pport From the C h a rl es D. and M a ry Va u x Wa l ­

c o t t Research F u n d a n d the F l u id Research F u n d which have m a d e t h i s
work poss ible.

References

Test solutions:
(a) Hcsidual hypo, l i l m a n d paper
A Foird11pois J\llelric
water 24 oz. 750 cc.
28% acet ic acid 4 oz. 125 cc.
Part I H I S T 0 R Y 0 F P H 0 T 0 G H A P II C 0 N S E 11 V A T I 0 N

silver n itrate 7 · 5 gm.

water Lo make 32 oz. 1 .0 litre
(Solution should be stored in a scaled brown bottle away f'ro111 strong
l ight. Avoid contact with skin and clot h i ng, otherwise stains w i l l resu l t . )
(b) Hesidual silver, fi l 111 and paper (to lest proper fixation)
A11oircl11pois Metric
water 4 oz. 100 cc.
sodi u m sulph ide 36 grains 2 gm.
For both tests, place one drop on edge oF clear margin area. Let stand
for two m i nutes, blot excess. Anyt h i ng 111orc than a very l ight stain indicates
eventual discolora t i o n .

2 (a) Thoroughly w e t photograph in water.

(b) U se two-bath fixer systc111; 3-5 111 i n u tcs i n each bath (do not exceed
maxim u 1n).
(1) Start with 2 one-ga l lon baths.
(2) Discard No. 1 after 200 8 X 1 0 prints or equ ivalent.
(3) No. 2 moved to No. 1 pos i t ion.
(4) Fresh ga llon for bath No. 2, repeat steps 2 and 3.
(5) Discard both sol utions after fifth cycle ( 1 ,000 S X 1 0 prints).
(6) 1 -2 minute rinse in pla i n water.
Bathe prints in a working sol ution of Kodak Hypo Clearin g Age n t
( K H CA) for two 111 i n u tes for si ngle-weight papers and three m i n utes for
double-weight papers, then wash in r u n n i ng water for at least ten m i n u tes and
twenty m i n u tes, respectively. For detai ls, sec KHCA carto n .

3 I F the p icture is properly r1xed and free of non-i111age s ilver i t m ight b e

i ntensified w i t h e i t her Kodak S i lver I ntens i fier l n-5 or Bleach-Hcdevelopmenl
I ntensifier ( Kodak T-7a ) .

4 Kodak Special H a rdener S H - 1 .

Daguerreotype clea n i n g procedu re:

(1) \>\/ash daguerreotype i n dist i l led water to remove surface dirt.
(2) Drain and immerse until discoloration i s removed i n a sol ution of:
Disti l led water 500 cc.
Thiourea 70 gm.
Phosphoric acid (85%) So cc.
N o n - I o n i c wetting agent ( Photono) 2 cc.
D i s t i l led water to 111akc 1 l i t re
(3) Hemove From bath and i111 mediately hold u nder ru n n i ng water.
(4 ) Place in a m i ld soap sol u t ion ( Face soap) and agitate briefly.
( 5 ) R inse thoroughly in ru n n i ng water, then wash i n a second bath of
disti l led water.
(6) I mmersc in 95% grain alcohol. Dra i n .
( 7 ) Hold h i g h over a small name u n t i l dry.
Advantages of t he method:
S ta i n is completely removed without the plate bei ng etched.
Details oF the picture arc brought out clearly, and the m irror- l i ke q u a l i ty
oF t he s ilver plate is retai ned.
Daguerreotypes can be left in the chemical sol u t ion i ndefinitely without

16
 Reading 2 O S T H O F F

rellloving the i lllage. In one experilllent the p l ate was left i n the solution
for one hour and twenty Ill i n u tes without vi si ble change. Consequently,
daguerreotypes forlllerly considered beyond restoration because of their
extensive discoloration can now be restored.
Plates can be cleaned over again as often as necessary without harlll.
It should be noted that daguerreotypes w hic h have previ o u sly been
restored with cyanide lose their original l ustre. Thu s , plates that have not been
cleaned before with cyanide will show far superior resu l t s .
-The M issouri Historical Society's Method for t h e Restoration o f
Daguerreotypes, devised b y Mrs. Ruth K. F i e l d , Assistant C u rator.

6 Brown, l-1. G . , " Problellls of Storing Fillll for Archive P urpose s . " B ritish
Kineniatography, 20, 1 50- 1 6 2 ( May 1952 ) .
Calhou n , ] . M . , "S torage of N i trate Alllateur Still-Calllera Film
Negative s ." ]BPA, 21, 1 - 1 3 (August 1 953).
Cullllllings, J. vV . , H u tton, A . C . , and Silfin, H., "Spontaneous Ignition of
Decolllposing Cellulose Nitrate Fil Ill . " ]SMPTE, 54, 268-274 ( M a rch 1 950).
H utchison, G . L., Ellis, L., and Ashlllore, S . A . , 17ie Surveillance of
Cine1natograph Record Film During Storage. M inistry of S u pply, Explosives
Research and Developlllent Establish lll ent and the Departlllenl of the
Governlllent C hemist, Report No. 2/R/48, February 1948.
Nuckolls, A . H . , a n d Matson, A. F . , "Sollle Hazardous Properties o f
M o tio n Pict ure Fillll ." ]SM PE, 27, 657-661 ( Decelllber 1936).
Ryan, J. V., C u mmings, J. W., and H u tton, A . C., Fire Effects and Fire
Control in Nitrocellulose Photographic Film Storage. B u i l d i ng Materials and
Structures Report 1 45, U.S. Government Printing Office, 2 April, 1956.
Scribner, B . W ., Sumn'[{lry Repoi·t of R esearch at the Nation.al B ureau of
Standards on. the Stahility and Preservation of Records on Photographic Film..
NBS P u b l i c . M 1 62 , 6 May, 1939 ·
Standards for Storage and Handling of Cellulose Nitrate Motion Picture
Film. National Fire Protection Association, May 1962.
Storage and Preservation of Motion Picture Film. Eastlllan Kodak
Colllpany, Rochester, New York.
Sulzer, A. F . , "The Epoch of Progress in Film Fire Prevention." ]SNIPE,
34, 398-408 (April 1940).
Weber, C . G., and Hill, ] . R., "Care of S l ide Films and M ot i on Picture
Films in Libraries." ]SIVIPE, 2 7 , 69 1-702 (December 1 93 6 ) .
Weber, C . G . , a n d H ill, J . R. , "Evaluation of Motion P i c t u re F i l m for
Perlllanent Records." NBS Miscellaneous Publication M 1 58 Q u ly 1 937).

7 Henn, R . vV., Wiest, D . G., and Mack, B. D., " IVl icrofilm, M icroscopic Spots
i n Processed: The E ffects of Iodi de. " Pliot. Sci. & Eng., 9 , 167 ( 1 965).
H e n n , R . \,Y., and Wiest, D. G . , "M icroscopic Spots i n Processed
M icrofilm, Their Nature and Prevention." Phot. Sci. & Eng . , 7, 253-261
(October 1 963).
M c C amy, C . S . , Inspection of Pmcessed Photographic Record Films fo•­
Aging Ble1nishes. N B S Handbook 96, 24 Janu ary, 1964.
McCallly, C . S., and Pope, C . I . , Summary of Current R esearch on
Archival Microfil1n. NBS Tech n ical Note 261 , April 1965.

8 Refer to l and 2.

17
Part I 11 I S "J' 0 I� Y 0 F P 11 0 ·1· 0 G I� t\ 1> 11 C 0 N S E H V t\ ·1· I 0 N

9 Ostroff, E . , " Photofixi ng: Science and Practice." PM/, 1, 28-31 ( September
1 958).

10 Henn, H . \�r .. and Wiest, D. C., " Properties of' Cold-Treated M icrofil m
I mages . .. P/101. Sci. & Eng., 1 0, 1 5-22 (January/February 1 966) .
H e n n , H. W., and Mack, 13. D . , "A Cold Protective Treatment for
M ic rofilm." Pliot. Sci. & Eng., 9, 378-385 (November/December 1966).
Kodak Cold Toner T-2 1 , Processi11g Clie111icals and Fo1·nwlas for Blach and
\,V/1ite Pl10t. ograpl1y (data book). Eastman Kodak Company, J u ne 1966, pp. 6 1 -62.

II Carrol l , J . F . , and Calhou n , J . M . , ''Effect or N i t rogen Oxide Cases on

Processed Acetate F i l m . " .JSMPTE, 64, 50 1-507 (September 1955).
H e n n , H . \,Y . , and \•\ licst, D. C . , ''M icroscopic Spots in Processed
iV l icro r i l m , Their Nature and Preservation." P/wi. Sci. & Eug. , 7, 253-261
(October 1963).
H e n n , H. \M., v\liest, D. C., and Mack. B . D., "M icrofi l m , M icroscopic
..
Spots i n Processed: The Effects of· Iodide . P/101. Sci. & Eng. , 9, 167 ( 1 965).
i\ l cCamy, C. S., lnspeclioa of Processed P/101.ugrapliic Hecord Fi/JJ1sfo1·
Agiug BleJJ1ishes. N B S H andbook 96, 24 January, 1 964.
M cCamy, C. S., and Pope, C. I . , S11JJ111"1C1J')' of C11rre11t Hesea1-cl1 on
Archival J\ll icroft/JJ1. NBS Tech nical Note 26 1 , April 1 965.

12 Henn, H . v\I., and O livares, I. A. , "Tropical S torage oF Processed Negatives."

Pliot. Sci. & E ng., 4 . 229-233 (J u ly/August 1 960).

13 I bi d .
Lan ner, M . F . , a n d Wilson, W. K., ''The Photochemistry of' C e l l u l ose
.
Effects of' Water Vapor a n d Oxygen in the Far a n d Near U l t raviolet Hegions . .
j. of the ACS, 7 1 , 958-962 ( 1 949).
H i c h ter, G . A., and \!\fel ls, F. L., '' I n f luence of Moi sture in Accelerated
Ageing oF Cellu lose." TAPP/ , 39, 603-608 (August 1 956).

14 Barrow, \!\!. J., " M igration oF I mpu rities in Paper." Arcliiv11rn., I l l , 105-107
( i 953).
Buyn, K. E. C . , " La Durabilite d u Papier." Congrcs Annual, 6-8 Octobre
1948, Paris, Association Technique de l ' l ndustrie Papeticre, 5c An nce, Bullet.in
No. s . pp. 23 1-238 (J u i llct 195 1 ) .
Card, A . J . , "Some Practical Aspects o f Chelation i n Papcrmaking."
TA PP/, 4 7, 198A-20 1A (January 1 964).
H a l l , Costa, " Permanence of Paper." Paper Trade .Jo11rnal, Techn ical
Sect ion, pp. 52-58 (8 April, 1926).
Langwell, v\I. H., "The Permanence oF Papers." British Paper and Board
Makers Association. Technical B 11lletin, 29, 2 1-28 ( Part I ) , 52-57 ( Part 1 1 ) ,
170-1 75 ( Part I l l ) ( 1 952).
Langwell, v\I. H., "The Perma nence oF Paper Hecorcls." Th.e Libra1T
Association Hecord, 55, 2 1 2-2 1 5 ( 1 953).
Lrn1gwel l , \,Y. H., "The Permanence of Paper." British Paper a n d Floarcl
Makers Association. Technical B11/let in, 36, 1 99-207 ( 1 955).
S t rochen, J . , "Chemical Hcsidues i n Paper." The Paper Maher and British
Paper Trade journal, supplement, pp. 65-66 ( 1 M ay, 1 935).
 Reading 2 O ST H O F F

15 Borden, J . C . , J r. , and v\lolpcr, P. K., ''The What and How or G lassinc."

Tech n ical E11gineeri11g, Met lwds, Testing , pp. 1 1 1- 1 1 7, 1 69 (August 1950).
Briggs, J . , and Hall, F., " Some Problems i n G lassi n c M a n u facture. "
Australian Pulp and Paper f 11.dust 1)' Tech n ical Association, 13, X V I 1-X X I
Uanuary 1960).
Conner, C . H . , "The i\ l a n u faclure of G lassine and G reaseproor Papers. ''
Paper Trade)o11mal, I ndustrial Development Sect ion, pp. 34-35 (7 J u ly,
1 949). "Glassine and G rcascproor," Paclwgi11g Parade, pp. 89-93 ( Fcbruarv
1 956) .

16 Collection of Material 0 1 1 t he Preservat. io11. of Library Resou rces, Nos. 2 and 3 ,

N S F , translated f'rom Russian, 2 5 8 p p . ( 1 964).
Kantrowitz, M. S . , Spencer, E . \•\/., and Si mmons, R. \V., Per111anence
and IJ1 1 rability of Paper, c111 A 11 1 1ot.ated Bibliograp'1y of the Tech n ical Litera t u re
fro 111 1 885 A . /J. to 1 939 A . /J. U .S . Government Printing Office, Division or
Tests and Tech nical Cont ro l , Tec hnical B u l leti n No. 22, 1 940.
Kimberly, A. E., and E mley, A. L., A S tudy of t '1e /Jet.erioratio11 uf Booh
Papers i n Libraries. National B u reau of Standards, M iscel laneous Publ ication
No. 1 40, April 1 933.
Kimberly, A. E., and I l icks, J. F . , A S 1 1 111ey of Storage Condit irms
i 1 1 Libraries Relative to the Presenl(Jt ion of Records. N B S M iscellaneous
P u b l ication No. 128, October 1 93 1 .
Kimberly, A . E . , and Scribner, B . '"' . , S u 11w1ary Report of Natio1wl
B u reau of Sta nclarcls Research 011 Preservat.ion of Records. N BS M iscellaneous
Publ ication M 1 54, March 1 937.
Kimberly, A. E., and Scribner, B. W., S 1 1 111 111CJJ}' Report of / 3 u rer111 of
S t a 11dcmls Researc/1 on Preservation of Records. N B S M i scellaneous P u b l ication
No. 144, M ay 1 93+
New Methods for the Restoration and Preservat io11 of /Jocu 111e11ts 011d
Boohs. N S F , translated rrom Russian, 1 30 pp. ( 1 964); " latest advances or the
Laboratory or Conservation and Restoration or Books of the Academy oF
Sciences oF the U . S . S . H . "
Scribner, B . W., "The Preservation of' Records i n Libraries. " Tlie Lil11·c11)'
Q11arterly, IV, 37 1-383 U u ly 1 934).
Sec also ( 1 4 ) .

17 H anson, F . S . , " H esislance or Paper lo N at u ral Aging. " Paper World, p p . 1 1 57-
1 1 63 ( February 1939).
" Permanence oF East man Photographic Papers." St udio Ligl1 t , pp. 9-1 4
(October 1936).
"Production of Pulp with 1-1 igh Alpha-Cel l u l ose: Review or U.S. Patents. "
Paper Trade journal, TA P P I Sec t ion, p p . 48-49 ( 2 5 August, 1927).
Hossman, J., " M a n u facture of' H igh Alpha-Cellu lose." Paper Tracie
J o u rnal, TAP P I Section, pp. 206-2 1 0 ( 1 2 April, 1 928).

18 A i r Poll11tion. Meas11re111e11ts of t /1e National A i r Sa11171ling Net.worh, A11alyses of

1 957- 1 96 1 . U . S . Department of Health, Education, and
S uspended Part iculates,
Wel fare, Public Health Service, Wash i ngton, D . C . , 217 pp. ( 1 962).
Ibid., 1 963.

19
Part I H I S T O H Y O F P H O T O G H /\ P l l C O N S E R V A T I O N

Hochkeiser, S . , Met lrnds of Meas11 ri11g c111d Monitoring At mospheric S u lfu r

Dioxide. U . S .Department ol' Health, Education, and Welfare, P u b l i c Health
Service, C i ncinnati, Ohio, August 1 964, 48 pp.
Lyn n , D. A., and M c M u l l e n , T. B . , Air Pol/11tion in Six Major Cit ies
as Measured by t he Con.ti1111ous A i r Mon.itorin.g Progra 111 (CA M P ) . U.S.
Department o F H e a l t h , Education, a n d v\lel fare, Public Health Service, J u ne
1 965, 30 pp.
Selected Methods for t h e Meas11re111ent of A i r Pol/11tants. U . S . Department
ol' Health. Education, and \,\lelf'are, Public H ealth Service, C i nc i n na t i , Ohio,
M ay 1 965, 5-1 pp.
Tabor, E . C . , and Colden, C . C . , " Hesults oF Five Years' Operation oF
the 1\J ational Gas Sampling Network." ]O'tirnal of t.he Air PoUuhon Con t rol
Association, 1 5 , No. 1 Qanuary 1 965).
Personal correspondence from Dr. W. Clark, Kodak Hesearch
Laboratories, to E . Ostroff. 23 J u ne 1 965.

20
 R e a d i n g 3

G E O R G IA O ' KE E F F E

C onditions for the Alfred

S tieglitz Photographs
and Photogravures ( 1 972)

Upon the death of Alfred Stieglitz ( 1 864-1 946) his second wife, Georgia
O 'Keeffe ( 1 887-1986), becaine custodian of his 1Jhotographic estate that was
disseminated in sets to American museums between 1 949 and 1 950, including
the Art Institute of Chicago, Fish University, Library of Congress, T1ie Met­
rn1Jolitan Museum of Art, Museum of Modern Art, Philadelphia Museuni of
Art, and a hey set of approximately 1 , 600 images to the National Gallery of A rt.
O 'Keeffe was a tireless "voice " for the care of her husband's art (see Downey,
Laura, and Therese Mulligan, "A Voice for the Prints, " in The P hotography of
Alfred Stiegl i tz: Georgia O' Keefe's E n d u ring Legacy (Rochester, NY: George
Eastman House, 2000). \i\lith each distribution she established specific condi­
tions regarding the storage, handling, exhibition, and reproduction of Stieglitz
m.aterial. In 1 9 5 1 Beaumont Newhall accepted a gift and purchase of 77 worhs
at the George Eastman House. Tn this 1 972 letter to Van Deren Cohe, director of
the George Eastman House, O 'Keeffe updates conditions for the care of the
Stieglitz Collection donated in 1 9 5 1 . She expresses her heen awareness of
the importance of proper handling and environmental standards necessary
for t he long-term preservation of photographic materials. T1'lis docwnent con­
tinues to resonate and inform (with modifications) present-day m.useum pres­
ervation practice.

G EORGIA O'KEEFFE, personal correspondence to Van D er en Coke outli n i ng "Condi t i o n s

for t h e Alfred Stiegli tz Photographs and Photogravures," M ay 8, 1 972. © Georgia O'Keeffe
M useu m.

21
Part I H I S T 0 B Y 0 F P 1-1 0 T 0 G H 1\ P I I C 0 N S E H V A T I 0 i\1

Ab iquiu
New M exico 875 1 0
May 8 , 1 972
M r. Va n Deren Coke, Direclor
George Eastman House
900 East Aven u e
Rochester, New York

Dear M r. Coke:
I have been going over the Conditions of Gi ft for the Stiegli tz Collec­
tion, and wou l d l i ke to make severa l cha nges i n t hese. As the years pass, one
sees things d ifferently, and problems arise which d i d not exist originally.
In order to keep t hese changes as clear as possible, I enclose new cop­
ies of the Conditions i ncorporating the changes [ am requesting of George
Eastman House for the Stieglitz Col lect ion of h i s own photographs. These
present con d i tions wou Id supersede all previous correspon dence with the
George Eastman House about such matters.
I wou l d appreciate hearing from you whether t hese changes are
agreeable to George Eastman House. If you have any suggestions for
changes you can write me, or discuss them with Doris Bry if you are in New
York, as she would know my wishes. S he can be reached at 1 1 East 73rd
Street (TR-9-7270).

S i ncerely,
G EO R G IA O'KEEFFE

cc: Doris Bry

G EORGE EASTMAN H O U S E M ay, 1 972

Conditions for the Alfred S tieglitz Photographs and Photogravures

1. The photographs and photogravures by Alfred Stieglitz received by

George Eastma n House from mysel f and the Al fred St iegl itz Estate are to be
known and designated as the Alfred S tiegl itz Collection.

2. S ince t hese photographs are selected fro m prints which Stiegli tz made
from his own negatives, and kept and mounted for h imself, i t is requested

22
 Read i ng 3 0 ' K E E F 1: E

that t hey be kept as a u n i t in their own boxes, and not mixed with Stieg­
l i tz prints given to you by anyone but Stiegli tz and myself. Should you be
given origina l Stiegl itz prints fro m other sou rces, the donor should be c learly
indicated.

3. All of the photographic pri nts were mou n ted and matted by S tieglitz.
They are to be left mou nted and mat ted as received, except for the removal
of glass and frames, which is optiona l . They are to be placed as received i n
the rag board ha ndl i n g mats si m i lar to t hose u sed by a museum print depart­
ment to protect its fi ne etchi ngs and engravings.
A sample handl ing mat was sent with the prints. The board of the
handling mat u nder the Stieglitz mount should be one-q uarter to one-half
inch wider than the St ieglitz mount, and the Stiegli tz mount centered i n t h i s
space. (The q uarter-inch margin looks better than th e half-inch margin , b u t
t h e half-inch margi n is more apt t o keep fi nger marks off the Stieglitz mats
and mounts.)
In a very few i nstances in which the Stieglitz print is dry-mounted so
that it is raised very high from the original mount, the four-ply handling
mat is not thick enough to protect the surface of the pri n t . ln such cases,
the handling mat must be made thicker. This can be clone by cutting out a
double set of mats for the handl i ng mat, which raises the total height of the
hand l i ng mat above the print su rface.
S hould you consider it necessary to remount or remat the photographs
for the sake of their preservation, this may o n ly be clone after consultation
with Doris B ry or myself, or, after our l i fet i mes, with a curator or conserva­
tor from within or outside of George Eastman I-louse who has the most expe­
rience with the handling and preservation of rare photographs.
Should such remounting or re- matti ng be necessary, it is requested
that it be clone as nearly as possible to resemble the original presentation,
with a rag mat of the same overa ll size as the origi nal S tiegl itz mat. The
new mat should match as nearly as possible the color and texture of the
Stieglitz mat. The ope n i ng i n the new mat is to be exactly the same size and
in the same position on the print su rface as the opening on the St iegli tz
mat. I ts exact p lacement could be made certai n by making a pin prick at the
corners of the pri n t i n the origi nal mat openi ng, before the Stieglitz print
and mat are moved.
Under no cond itions may t he d i mensions of the mount or mat be
cha nged .
The Stieglitz photogravures may be mounted and matted with rag
board handli ng mats-di mensions left to you r discretion .
Prints may be fra med for ha nging, if this is done without changing the
size of the Stiegl itz mount or mat in any way. They may be h u ng for a period
Part I 1-l l S T O H Y O F P H O T O G H J\ P l l C O N S E H V /\ T I O N

of two months every two years i f des ired, b u t I believe that they are best
seen without glass on a table, and that they are best preserved with m i n i 111al
exposure to l ight. Frames should be as si mple and narrow as possible, to
resemble the original Stiegli tz fra111es.

4. I t is u nderstood that the Stiegl itz pri nts are to be stored properly i n an
air-conditioned space to rn i n i 111ize the c hances of their deterioration. and
tJiey wiJJ be SlOted, J1alldJed, cliid sJioHli ill tJie Sallie liicliiliel dS tJie
tJ1at
George Eastn1di1 Ilouse's f111e etcliillg and ellgtavillgs [strikethrough as i n
original] .
They are to be kept i n boxes of not more than two and one-half inches
depth, inside measurement.

5. It is u n derstood that a respo nsible member of your c uratorial staff will

watch at al l ti mes anyone not on you r i mmediate staff looking at the prints,
to i nsure the enforcement of the Conditions.

6. No pen or ink or ball-point pens or indel ible penci l s or comparable

i m plements may be u sed on the table while the prints are on i t .

7. H ands should b e washed before handling prints. N o o n e is t o touch

t h e surface of the print i tself, n or the paper or board on wh i ch i t is mounted,
nor the original Stieglitz mat. Th is means that pri nts may o n ly be handled
and exa m ined by picking up the hand l i ng mats.
Stiegli tz's i ntention was that the print be seen as he mounted it. The han­
d l i ng 111at i s s i 111 ply a device for the preservation and protection of what he did.
I f the handling mats are made fol lowing the sample sent to you 1 11
1 949, the original Stieglitz presentation may be seen by those who wish to
look at it by s i mply l ifti ng the front of the han d l i ng mat.
Pri nts should always re111ain face up and should lie Aat. They should
be picked up with two hands, re111oved from the storage box to its lid one at a
t i 111e, and retu rned to the box in the same manner.
The original mat should never be l i fted fro m the print, nor should the
photograph be l i fted to view the verso.
Glassine or kodapak protective sheets may be removed by the viewer
and are to be replaced. No 111arks 111ay be added or erased on the p hotograph,
its mount or its 111at.
No books, papers, or other objects may be laid on the photographs.

8. Prints may not be loaned at any time for any reason to any person or
i nstitution, with the exception that should Doris Bry, for the p u rposes of her
 Reading 3

d e finitive Stieglitz photographic catalogue, or For work on her other St ieglitz­

O' Keeffe projects, need to borrow them, she may do so.

9. I n order to administer the Conditions relating to visitors' looki ng at

the prints more easily, it is suggested that the Conditions re levant to their
viewi ng be m i meographed on a separate page or card, and that each person
coming to l ook at the prints be given a copy of this page to read before being
shown the pri n ts.

1 o. No copy prints or reproductions are to be made from the Stieglitz

prints without permission from Doris Bry or myself.
After our l ifeti mes, George Eastman H ouse may make up to flve repro­
ductions For the pu rposes of institutional publicity in c u rrent magazines or
newspapers, or for small b u l letins or leaAets published as i nstitu tional pub­
l ic ity by itself. It may not authorize reproductions for books, port folios, or
other such major projects.
\!\!hen perm issions are given to reproduce the Stieglitz prints, i t is
understood that his photographs are to be reprodu ced u n c u t .
No copy prints may b e sold or given t o i nd iv iduals req uesting them For
their personal use since this wou ld be contrary to S ti egli tz's wish.

1 1. The Stieglitz prints may not be sold or exch anged for any reason at
any ti me.

12. The prin ts of mysel f are to be received on deposi t as a loan ret urnable
to me at my request. They are to be considered as part of the Alfred Stiegli tz
Col lection of P hotographs and hand led, mounted, and cared for from the
time of receipt under the same conditions as the other Stiegl itz photographs
fro m the Alfred Stiegl itz Estate.

1 3. S hould Doris B ry outl ive me, 1 wou l d l i ke to h ave the George Eastman
H ouse consider her my representative, d u ring her lifetime, to answer any
questions which may arise concerning the above, and to consider that she has
any powers of decision about these matters which I have reserved for mysel f,
si nce she has worked with me on these problems since 1 94 7, and would
know my wishes. S hould George Eastman H ouse wish to ask her to make
exceptions to these conditions, l wou l d l i ke her to have the same authority
to do so as George Eastman House considers me to have. I wou ld also l i ke to
have any necessary correspondence about these matters sent to M iss Doris
B ry [ . . . ]
 R e a d i n g 4

J o s E 0 R RACA

Philosophy of Conservation ( 1 974)

Trained at the Libra ry of Congress and supported by a grant from Georgia

O 'Keeffe to survey t:he Stiegl-itz collections at all recipient institutions (see
Reading 3), Jose Orraca ( 1 938-2009) (see also Reading 62) was hired as the first
photograph conservator at the fnternational Museum, of Photography in 1 971 ,
I-le established advanced training in photograph conservation at the Univer­
sity of Delaware where he worhed fron,,, 1977 to 1 98 1 , In 1976 he founded the
Photographic Materials G roup of the American Institute for Conservation of
Art and Historic Artifacts, fn the 1 970s, as the field of photograph conservation
was evolving, Orraca advocated very effectively for increased research, train­
ing, and collaboration with the phot:ographic industry This c itation articu lates
Orraca 's philosophical views and ethical principles, the problems inherent in
the preservation of photographic materials, and the growing need for enhanced
research and ex1nrimentation,

I have d ivided my a llotted t i me i n to two areas of concern: one being the

philosophy of conservation as i t applies to photographic collections, and the
other the deterioration of cell u lose d iacetate film materials.
Ever since the word "Conservation" and "Conservator" became part of
the museum vernacu lar, we have been barraged with every Tom , Di ck, and
H arry, and to be fair, every Mary, Sylvia, and Esther, who wishes to claim
the title of "Conservator." I n a ga me where there are no laws, everyth i ng is
fair. The m u seu m professional, however, should rea l ize that t here are con­
servators, and t here are Conservators. The proper choice could mean l i fe or
death to their collections,

JosE OnHACA, " Phi losophy o f Conservation," u n pu b l is hed remarks presented t o the Soci­
ety of American Archivists, Toronto, Canada, October 1, 1974, Repri nted by permission oF
J ose Orraca, Conservator of Photographs,
 Reading 4 O H B A C A

The t h i n king i n Conservation to which I ascri be has an u nwritten set

of pri nciples which most of us fol low and which, when properly understood
by the museum professional, should give them ample gu idelines by which to
make that c hoice. These are as fol lows:

1. In every museum and l i bra ry the o bject, the artifact should be of

su preme i mporta nce.
2. The conservation of a col lection, that is the arresting of cond it ions
which cause deterioration, is far more i mportant than the restoration
of any one object .
3. The Conservator must respect t h e artistic a n d h istorical i n tegrity o f
a n y object o r art i fact.
4. The Conservator must adhere strictly to the law of irreversi bi l i ty­
never do anything that cannot later be u ndone.
5. Cosmetics is not the encl of con servation, i t i s only a by-product.

In terms of photographic col lections t hese principles t ranslate them­

selves in this manner:

1 . The object is of supreme i m portance. The function of a muse um

or l i brary is to gather and preserve those i t em s that fal l within Lheir i nter­
est or purs u i t . I t borders on the i m moral for an institution to acquire much
more than i t can adequately preserve. Often an object runs a h igher risk of
destruction in the hands of an i nstitution than i n the concerned hands of a
col lector, however ignorant. \!\fhen making c hoices as to whether a photo­
graph should be exhibited or not because of the possible effecls of ligh t i ng
or olher environmental conditions on its sta b i l i ty, the choice should always
be on the wel l-being of the photogra p h . The l ight levels in a pholoclupl ica­
L ion mac h i ne m ight be harmfu l to some photographic i m ages, and human
po llut ion, perspi ration i n part icu lar, is a powerfu l sou rce of deterioration
to the sta b i l i ty of photographic i mages. I t is true that a l l i nstitutions have
a certain degree of responsibil ity to their public and to scholars, but the
supre me choice is clear when an object is at stake. On another level, it is
t he original object that is of i m porta nce. Copyi ng can only be viewed as
a precautionary measu re to preserve the i nformation, not to replace the
object. I still s hudder at the advice given concerni ng an h istoric site by a n
i ndividual from industry, w i t h whom I am acquainted, a s a means of pre­
serving a rather i mporta nt col lection. H is advice was: "Copy and t h row
away the originals." One would never think of solving a problem of dete­
rioration in a l ithograph or a pa i nting by copying; in spite of the fact that
there are enough tricks i n the trade to make a copy "look" l i ke an origi­
nal, complete with textu re and foxi ng, why then delegate photography to the
secondary?
Part I ll l S T O H Y O F P l-I O T O C H A P l-1 C O N S E H V A T I O N

2 . The conservation of a collection, that is the arresting of t hose condi­

tions which cause its deterioration, is far more i m portant than the restora­
tion of any one object. An i nstitution m ay somet i mes spend t housands of
dollars having one painting restored while their other collections, usually
photographs, are allowed to sit in wet basements and i n acid fol ders. I call
these basements "curators' graveyards," for it is often c u rators who make
these "decisions" as to what is worth preserving in a collection. One can
always make a case to the board for funds with which to restore a pai n t ing,
but a photograph? " . . . couldn't we j ust recopy?" is usua l ly the answer. I
have better words for t h i s sort of mentality, but they a re best left for the pri­
vate hours. Th is is not to belittle the conservation of paintings, but si mply to
st im u late a more equ i table system of priorit ies.

3. The Conservator must respect the artistic and h istorical i ntegrity of

any object or artifact. This is a poi n t upon which I wou l d l ike to dwe l l at some
lengt h. A photograph, j ust l i ke any other object, has a h i story. It begi ns with
the i ntent of the maker and goes on further to the i ndividual who col lects.

A. The tonalities of a part i cula r p hotograph are part of the i ntent of

the photographer. If the photographer chose as its med i u m a pho­
togra phic paper that rende red images i n black and white, with rich
blacks, l i ke Karsh's Ve lour, it wou ld be i mmoral to change these
tones to browns or any other color, no matter how good the i n ten­
tion. Gold toning has been widely advertised by i ndustry as a way
of i nc reasi ng the stabi l i ty of p hotographic i mages. The belief has
been, and this is open to much skepticism, that by replacing the
si lver with gol d , which is a more stable metal, the l i fe expectancy
of a photograph is i ncreased. I n the process the tona l i ty of a black
and white photograph is changed to shades of brown. We might
i ncrease the l i fe expectancy of a photograph, though the same can
be accomplished t h rough archival was h i ng and good storage con­
d itions, but it is no longer the same photograph , and in my view,
not of much val u e as a h i storical doc u ment.

B . Toward the t u rn of the century, ten or fifteen years i n either d irec­

tion, much to-do was made over the presentation of a photograph.
Kodak mounted its pri n ts on clay coated mounts; em bossed moun ts
with e laborate writ i ng were supposed to give photographs respect­
abi l i ty; photographers often chose double and triple mounts with
alternate colors i n order to " enhance" the beau ty of their p hoto­
graphs. These mou nts a re in fact part of the "tota l " photograph.
 Reading 4 0 B n /\ C A

To remove a photograph From such a mount, even u nder the pre­

tense of preserving the i mage, ren ders that photograph a cripple
to our own i nsensitivity. There are better ways of preserving such
a photograph, t i me and money con s u m ing, tha t's for sure, but our
choices a re l i mited. I n each of these cases the photograph should
fi rst be u n mou n ted, being carefu l not to damage the mou nt . The
mou ntant or adhesive should be scraped off the photograph. The
mount board should then be cleaned and deacidified to a pH of
approxi mately 7. The photograph should then be re mounted on
the origi nal board with a good polyvinyl res in or a nother stable
adhesive.

C. A photographic album is not a grou p of u nrelated i mages; a l l t he

p hotographs together, i n precisely that sequence and i n that posi­
tion, a.re t h e albu . m . The parts can never be as strong as the whole.
Often a n album gives u s a fee l i ng of continu ity, as i n the case of
a travel album, a series of events, a central group of people; we
become i n t i mately related with these people through the pages of
the a lbu m . At other ti mes war is brought to our eyes, i mages Aash­
i ng i n rapid progression before us. Others are sets of la ndscapes or
architectu ra l studies, often taken by various photographer but col­
lected by one i ndividual . B u t always they belong in the album, not as
separate i mages. To brea k an album apart because it might be eas­
ier to preserve or to exh ibit, or because it m ight be more val uable,
speaking in dollars and cents, as separate i mages, denotes a n igno­
rance of the med i u m and a lack of respect for photographic images.
I recently visited a major federal institution and found to my
d ismay that a beautifu l album of Civil \i\lar photographs was being
taken apart, the photographs were u n mou nted and were being
matted separately. H aving ra ised the kind of hell to which my
friends are accustomed, the c u rator was cal led for d iscussion. H e
gave three reasons for h is decision that I would l i ke t o quest ion.
One was that the album did not have the continu ity of a
travel album and did not, therefore, merit being kept together, that,
in fact, they were stoc k photographs c hosen by another i ndividual,
a collector, and then placed i n the a l b u m . The fact that they were
c hosen by this collector and placed in exactly that sequence reveals
not o n ly the matter of "choice" as a force in photographic h i story,
but also the i ntent of the col lector, which is also i mportant, and
is, as such, part of the h istory of this albu m . Th is album is after all
one man's view of the war through a nother man's ca mera.
Part I 11 I S T 0 H Y () F P II 0 T 0 G H A P II C 0 N S E n V t\ T I 0 N

A seco nd reason given was that the p hotographs, once over­

matted, wo u l d be p laced in a box in t he seq u ence in w h i c h t hey were
origi n a l ly. You s h o u ld some t i m e compare t h e d i ffere nce i n mov i n g
m o u n t board over m o u n t board a n d pagi n g t h e leaves of a n a l b u m .
I t is a tota l l y d i ffere n t fee l i ng; each overmatted photograph acq u i res
now its own sphere of rea l i ty, q u ite apart from the rest of t he a l b u m .
T h e f i n a l reason given was t hat t he photogra phs wou l d be
more read i l y access i ble for exh i b ition pu rposes. \Ne l l , my a nswer
to t hat s h o u l d be read i ly u n derstood . \1\/h i c h is more i m porta n t ,
t h e a l b u m or one c u rator's h a l l u c i na t i o n ? I n my view, that a l b u m
is n o lo nger a m o n g the l ivi ng.

D . One fu rther poi n t conce rn i ng h i storical i n tegri ty, w h i c h w h i l e not

tota l ly f i t t i n g t h e c o n text of' t h i s paper, bears d i s c u s s i o n . D u r i n g a
rece n t trip to t h e F . D. R . home i n H yde Park, New York, I looked
at a gro u p of p hotographs dea l i ng w i t h l i fe in the 1 93o's by a New
York C i ty p hotographer. They were not origi n a l p hotographs, b u t
rather pri nted by a modern photogra p her. M o u nted o n maso n ite,
t he edges t r i m med w i t h black magic ma rker to ob l i te rate t h e rea l i ty
of t hat two-d i me n s i o n a l stru c t u re , a n d some i n s izes so vu lgar that
t hey lost a l l sense of coherence, t he exh i b i t io n was heavy in design,
b u t very s h a l l ow i n h istorical i n tegrity. I have n o way of know i n g
w h e t h e r any origin a l photogra p h s b y t h i s m a n are ava i lable, b u t a
bit of resea rc h , a l ook at t he p hotographs of, for exa m p l e, Lewis
H i ne, wou ld have given the designer a fa i rly acc u ra t e idea of what
style was preva l e n t among photogra phers in New York C i t y at t hat
t i m e . The right of every photographer is to deal w i t h his med i u m
as h e sees i t , i n w h i c h [ case h e develops h i s own art i s t i c i nt e n t ,
a n d i t i s i rrespo n s i b l e for somebody e l s e to prese n t a n ot her] m a n 's
work with whatever modern tec h n iq u es are ava i lable, i t is rat her to
preserve t hat orig i n a l i n i t s h istorical con text, no matter how m u c h
i t offends h i s artistic sen s i t ivities.

+ The Conservator s h o u l d never do anyt h i ng w h i c h cannot later be

u ndone. I n h i s c h o ice of materials with w h i c h he preserves a given object,
t he ad hes ive, the m o u n t board, the solve n t s , the setti n g age n t s , the stabi­
l ization processes ( i n c l u d i n g t o n i ng), he must m a ke s u re that the p hoto­
graph can be u n mo u n ted, to use a common conce rn , or that the toner can
be removed. This bri ngs to l ight my other object i o n to go ld ton i ng; there is
j u st no way to reverse t h at process; t h e very sta b i l ity of the t h i n gold coa t i n g
makes it i m possible to b e reversed. Any restora t i o n or conserva t i o n process
 R eading 4 O H l1 A C A

must be totally removable without causi ng damage to the object or without

leaving any residues.

5. Cosmetics is not the encl pursu i t of a conservator, preservation is.

Among that legion of would-be conservators there a re many who are thor­
oughly trained in the arts of cosmetics. They can make an object look as
beautifu l as when i t was new, o r, at least, as bea u t i fu l as t hey thinlz i t was
when i t was new, but i n the process they have destroyed its h istory, the evi­
dence whi c h time leaves on everyth i ng in the process of growing old. F u r­
t her, the process by which something is made to l ook beautifu l i s sometimes
its death. An object will look exceed ingly beau ti fu l now, a plasticized object
i n a plastic world, but how long will i t last)
\Vi t h these principles i n m i nd the choice of an honest conservator
should not be t hat hard .

H aving said enough about that matter, a llow me to move from the phil­
osophical to the practical. It has been commo n knowledge that early negative
and movie fi l m s on a cellulose n itrate base deteriorate to the exte n t that the
i m age i s not usable. This deterioration proceeds, though at a m u ch slower
pace, even when storage conditions are adequate. J. VII. C u m m i ngs, i n an
article on the "Spontaneous Ignition of Decomposi n g Cel l u lose Nitrate F i l m "
f o r the Journal of t he Society of Motio n Picture and Television Engineers,
Mar c h 1 9 50 , described five stages in the deterioration of cel l u l ose n i trate.

F i rs t stage : Amber d iscoloration with fad ing of the pi ctu re i m age.

Second stage: The e m u lsion becomes adhesive and the fil m tends to
stick togethe r.
Thi rd stage: The fi lm contains gas b ubbles and emits a noxious
odor.
Fourth stage : The fil m is soft, welded to adjacent fi l m a n d frequently
covered with viscous fro t h .
F ifth stage: The fi l m mass degenerates partially or enti rely i n to a
brownish acrid power.

M ost m u seums and l ibraries have clone someth i ng regarding [the iden­
t i fication and proper storage of their c e l l u lose n i trate negatives to m i t igate ]
deterioration, but also because they fear explosions and the possi ble dete­
rioration of paper fibers through the n itrogen oxide gases that evolve from
deteriorating cellu lose n i trate. These i nst it u t ions have thought themse lves
"safe" as long as they took care of their c e l l ulose n i t rate.
Last year I began to receive samples of deteriorated negatives from
various i nstitutions, among them the Bishop M useum in Hawa i i , The U n i-
P art I H I S T O R Y O F P l· I O T O G R A P H C O N S E H V A T I O N

versity of Chicago, The B rooklyn M useu m , and the G ibbs Gallery i n North
Carolina. Their samples were all the same, cockling around the edges,
t i ny bu bbles a l l over, wri n kl i ng of the emu lsion and supping layers, and in
extreme cases, total separation of the layers with deposits of a salt crystal . My
fi rst i m pressi o n was that they were good examples of the t h i rd stage of cel­
l ulose n itrate deterioration. H owever, other samples started arriving, i n the
same condi t io n as the ones previously received, but edge- marked "Safety"
and u nder a variety of trademarks, among them Kodak, Defender, Dupont,
and others. A 1 6 m m rol l edge-marked D u pont Pathe, and i n the same condi­
tion, made me q uestion my earlier judgement, because, as I was able to fi n d
o u t , 1 6 m m fi l m was never made w i t h cellu lose n itrate. F u rther research has
t u r ned u p the fol lowing i n formation which I thin k should make you rush
home and take a c loser look at you r collection :

1 . From 1 937 on cel lu lose d iacetate and later cell u lose t riacetate slowly
replaced c el l ulose n itrate as a fi l m base. By their very nature, cellulose d iac­
etate and, to a lesser degree, cell ulose t riacetate, begi n to shrink from the
very moment they are manufactured as the plasticizers used i n their manu­
facture, which are volatile, begin to evolve from the fil m layer. In time this
shrinkage becomes more d istinct, in some cases being as much as 1 cm in
either d i rection. Since the e mu l si o n and supping layers do not allow for even
release of t hese plasticizers, t he fi l m begins to cockle arou nd t he edges. Th is
can be viewed as the first visible stage of deterioration in cel l ulose d i acetate.

2 . From the t i me that i ndustry sta rted shi fting from cellulose n i trate to
cell u lose cl iacetate, which was accomp l ished slowly, the final change clone
i n 1 950, c e l l ulose n itrate was used as a n ad hesive between the e mulsion and
s upping layers and the cellulose d iacetate base. The tiny bu bbles that are
seen in the second state of deteriorating cel l u l ose d i acetate are, in fact, the
same b u bbles docum en ted by C u m m i ns i n the t h i rd stage of deteriorating
cellu lose n itrate as bei ng n itric oxide gases given off by decomposi ng n it rate.
The fact that some fil m s tend to deteriora te at an earlier t i me than others
i s probably d u e to the fact that the adhesive layer i n them is thicker than i n
others, a s was t h e case with Defe nder. H owever, i t i s safe t o assume that i t
i s al l a matter of time.

3. Shrinkage of the base combined with the deterioration of the cel­

l ulose nitrate adhesive cau ses wri nkles on both sides of the fil m , and, as a
fi n al res u l t, total separation of the layers occ u rs . I n extreme examples, such
as those from the B ishop M useu m , i t was fou n d by them i ndependently that
Triphenol P hosphate, which was used as a plasticizer and fire retardant by
film manufacturers, had crystallized between the emulsion a n d supping lay­
ers and the fi l m base.

32
 R eading 4 O H H A C A

All of the samples l have received so far are from study collections of
arc haeological objects, fu rniture, paintings and the l i ke. As study collections
they are inva l uable to scholars. My recommendation has been that i n order
Lo preserve the information, which I t h i n k is of primary i mportance i n t h i s
case, the negatives b e isolated and t ransferred to Kodak- Fi l m S0-05, D i rect
Duplicating Film. This fi l m al lows one to copy a negative without first goi ng
t h rough the positive step. I t , therefore, gives better q ua li ty at a cheaper
price. Ma ke certain that the new films are washed to a rch ival standards,
the recommendations for which you will fi nd in H en ry Wi l helm's pa mphle t
on Arch iva l Processing. H owever, a n d t h i s is i mporta nt, keep the originals!!
Research will continue into methods of restoration. These are doc u ments in
and of themselves and t hey deserve to be preserved for posterity.

33
 R e a d n g 5

WALT E R C LA R K

Conservation Center and

Laboratory : What Are the
Objectives? ( 1 974)

\;\!alter Clarh ( 1 899-199 1 ) was a consultant t o the Center for the Conserva­
tion of Photographic Materials of the International Musemn of Photography,
George Eastman F-louse. He was renowned for his defi.nitive research. on th.e
photographic recording of infrared radiation. Th.is July 14, 1 974 memo est;ab­
lishecl the principal objectives for the fi.rst national conservation laboratory ded­
icated to th.e conservation of photographic materials. The goals outlined were
realized. Today, the conservation department at t;he George Eastman House is
a n international leader responsible for the preservation. of the Eastnwn. House
collections; the identification of photograph technology and degradation pro­
cesses; th.e development of innovative conservation t reatment techniq ues and
materials for preservation; recom.1nendations for long-term care; an.cl the edu­
cation and training of conservation professionals. In 1 999, th.e George East1nan
House-in collaborati.on with the I mage Permanence Institute at; t he Roch­
ester fnstitute of Technology-established the Advanced Residency Program
(ARP) in Photograph Conservation, a ten-year progra n'i generously funded by
the An.drew W. Mellon Foundation . This program h.as provided exceptional
t raining for a new generation of photograph conservators wh.o are fully able
to serve the complex and growing elem.and for individuals capable of superior
treat;ment, research, consultation., plan.n i.ng, education, and leadersh ip in the
field of photograph conservation.

The National E ndowment for the Arts awarded in 1 974 a grant for "support
of you r regional ce nter for the conservation of ph otograph i c materials." I n

vV/\LTER C LARI<, .. Conservation Center and Laboratory: \,\/hat f\re the Objectives?" I n ter­
national M u seum of Photography Records, i n ternal memo, J u l y 14, 1 974. © 2009 George
Eastman H ouse, I nternational M u seum or Photography and F i l m .

34
 Reading 5 C L A H I\.

accordance with our application for the gran t , we are a regional center giv­
i ng advice without charge on matters of conservation of their photographic
holdings to h istorical societies, museums and archives. O u r present fac i l ities
consist of a modest laboratory. Space has been selected for renovation and
conversion to a complete l aboratory with darkroom, and related equ ipment.
Dr. \!\falter C lark is consul tant on conservati o n ; Jose Orraca, as conservator,
has established a pi lot conservation program .

The objectives should conform basically to the conditions for the grant.

The objectives are:

1. M aintenance and Contro l of the Eastman House col l ections and

acqu isitions:
P hotographs ( i ncluding motion pictures ) ; apparatus; books and
other docu ments.
Exa mi nation of all existing material :
Condition of material (a) on display
(b) i n s torage
and (c) new acqu i s i t ions on receipt
Review of environment, storage conditions, di splay conditions, con­
ditions of use.
Recommendations for appropriate keeping of the collections, halt­
ing deterioration, "rescue," restoration.

2. Review of the essential nature of all the p rocesses, incl. graphic a rts.

3. E stablish methods for identification of all processes and m ateria ls.

4. Identification of the nature of defects-stains, spots, markings, fu ngus,

d i rt, detritus, b iological action, physical, i nsects, h u mans, m icroscopic
studies.

5. Review known and reported tec h n iques for p reservation-enclosures,

mounts, storage means, environmental conditions, etc.

6. Recom mendations for proper storage, use and d isplay.

7. Analys i s of enclosures etc. , to study their effectiveness. L ittle i s know

basically in this area. \i\fhat is recommended for paper in l i braries does
not necessarily apply.

8. Chemical and b iological tests on items in the collections in relation to

long-term keepi ng potential.

35
Part I H I S T O RY O F P H O T O G H A P l- I C O N S E R VAT I O N

9. Compi lation of a manual of test methods, and a kit for possi b le sale.

10. Develop new techniques and materials for preservation .

11. Study restoration methods.

1 2 . Restoration of all i mportant items already u ndergoing deterioration,

or on the brink. This wou l d i n c lude dupl icating a l l the n itrate fil ms
and destroying the originals, and copying, retou ching and treating, and
clea n i ng others, and chemically restoring. Very careful examination of
the h istorically most i mportant.

13. M ake recommendations for the preparation of new photographs having

opt i m u m potential for permanence.

14. Study the effect of the i l l u m i nation qua l i ty and level on the
deterioration potential of prints and transparenc ies on display. This
is extremely i mporta nt, and has on ly been dealt with in a fragmentary
manner.

1 5. Acc u m u l ate all avai lable knowledge on the stabi l i ty of color prints,
negatives and transparencies. Suggest techniques for optim u m keep­
ing . . . preserve originals with u tmost care, make working duplicates
from color i nter-negatives, or black-and-wh i te separation n egatives.
Be particularly cautious about the pH of the mounts and enclos u res.
Fadi ng tests on color photographs.

16 . Fu ngicidal treatments.

17. Apply all knowledge to apparatus i n the collection.

1 8 . Recommendations for fi l i ng, i ndexing, classifying, retrieval .

19. Generate knowledge to be available to a l l . Trai n conservators.

20. Publish. I nformation Service. Bi b l iography.

Walter Clark
[signature]
J u ly 14, 1 974
 R e a d n g 6

R O B E RT A . WE I N ST E I N
A N D L A R RY B O OT H

C ollection, Use and C are of

Historical Photographs ( 1 978)

Robert \Veinstein is a photographic historian who published several boob

about photographers of the American West. Larry Booth ( 1 920-2003 ) was cura­
tor of photographs at the San Diego Historical Society for almost fifty years. He
and his wife Jane ( 1 922-2008 ), a photogra1?hic archivist at the same institution,
were lifelong advocates for the preservation of photographic materials. In May
2001 , their pivotal worh was recognized by the San Diego Save Our Organiza­
tion through the honor of a Lifetime Achievement Award. Today, the Booth
Historical Photograph Archives of the San Diego Historical Society contain
more than two million images. The influential booh Collection, Use and Care
of H istorical Photographs (from which the present reading was excerpted)-a
compilation of thirty years of preservation lmowledge-infonned and inspired
dedicated collection caretahers and private collectors eager for expert advice
on the preservation of historically significant photographs. Here, the authors
sumniarize the state of photograph preservation in 1 977 and the urgent need
for shared research and trained p rofessionals equipped to properly care for
photographic materials. The closing sentences encapsulate their hopes for the
future of the then fledgling field: "We trust this book will be used, amended,
questioned, and in ti·m e, replaced; we welcome such a course. Nothing can
replace the endless research and serious study required to care for and preserve
our photographic legacy. " As desired, this booh remains a treasured historical
resource and foundation for countless publications that have followed it.

HoBEHT A. \NEINSTEIN and LAHHY BOOTH, " I n t rod uction" in Collection, Use and Care of
1-/istorical Pliotogra1'hs. Eds., Hobert A. \Ne i n stein and Larry Booth. (Nashvi l le : American
Association for State a n d Local H istory, 1 978), xi i-xvi . Heprin ted by permission of Ameri­
can Association for State and Local H is tory, Nashvi l l e , TN, www.aaslh.org.

37
Part I H I S T O H Y o r: P JI O T O C B A P ll C O N S E B V AT I O N

Introduction

The d iscovery of means to make i m ages formed by the camera obscura more
or less permanent is only one h undred and thirty-seven years old. The l i ttle
we have l earned in that time abou t how to col lect, restore and preserve pho­
tographic i m ages has proved i nadequate. As there have been few col lections
and fewer collectors until recently, the lack of such knowledge hasn't mat­
tered very m u ch ; these p roblems became the near-excl u s ive concern of a t i ny
gro u p of i ndividual and i nstitutional col lectors. Virtually alone, t hey were
u nable to mount a major effort to learn how to care for old p hotogra ph s.
If the n ineteenth-century photographs n ow b e i n g collected a re t o s u r­
vive, their care and p reservation is our major problem. I m mense in their
n u m bers, bewi ldering in their tec h n ical com plexity, fiscally demand i ng i n
their endless archival and research requ i rements, the d i lemmas posed grow
more p ressing. Enthusiasm for h i storic p hotogra ph s i s high now; al most
overn ight, in the worl d's marketpl aces, i t has transformed photographic a rti­
facts i nto objects of va l ue, awake n i ng new interest i n their care and use.
Hequ ired techn iques and p rocedu res for their care are being developed, i n
fragmented fashion; many needed solutions to the problems o f p h otographic
conservation still lacking a coord i nated effort. U n tested advice in place of
solid knowledge, misinformation and ignorance-al l are freely available,
even wi thout aski ng for them.
The serious collecting of h is torical photographs was for a long period
very casual, u n t i l some accu mulations fou nd their way i n to the l i braries of
the nation. Librarians, u ntrained then i n cari ng for photographs, did the
best they could. They i ncorporated these i mages for the fi rst t i me i nto nor­
mal l ibrary cataloging and retrieval p roced ures. They sorted, organized and
housed the p hotographs so they could be used . They s u rrou nded the pho­
tographs with large collections of reprod uctions c l i pped from books, maga­
zines and newspapers, form ing picture col lections of m ajor i mportance; the
col lection at the New York Public Libra ry u nder the direction of Homana
J avitz is a notable exa m ple. Their contri butions at that time were life-saving
for photograph collections and we are a l l i ndebted to them. Their loving care
in most situations bought va luable time, but u nfam i l iar with p roper archi­
val procedu res requi red to preserve old photographs, their attentions proved
i ns u fficient. P hotographs in their custody faded, were often abraded, bent,
torn ; sometimes priceless original prints were lent to the u ncaring public as
casually as if they were cu rrent magazi nes.
Evident gaps i n reliable preservation procedures encouraged the
gradual entry of professional archivists and s pec ial collections l i brarians.
 Reading 6 \V E J N S T E I N A N D B O O T H

I t was wel l , for the help of many d i fferen t spec ialists was needed. O n ly
conservator-technicians cou Id provide the trained expertise necessary for
a rchival preservation of photographic i mages; art h istorians, the aesthetic
leadership, needed to i nterpret and evaluate; and the professional c u ra ­
t o r to eJqJlain and develop mounti ng, storage and viewing requ irements.
Experts in each of these fields were fo und and sometimes put to work; their
research provided some answers but Fel l short, still , of affordi ng a coher­
e n t view of the whole problem. To many sympathetic observers, the par­
able of the b l i nd Indian fakirs-each fee l i ng the newly d iscovered elephant
for themselves-seems t ragical ly applicable. I ncomplete answers to complex
problems, a degree of harmfu l advice, and an eagerness for q u i c k sol ut ions
to vexing problems sti l l subst i t u te for pat ient research. Consequently we
continue to pu blic ize certain hasty efforts and p ractice u nsatisfactory a n d
dangerou s tech n iques. The single special ist's work is b y i t se l f contin u i ng to
prove i nadequate, u nderl i n ing the need for larger horizons of u nderstan d i ng.
This book is i n tended to help establish new horizons.
Serious i n q u iry i s growing and conservators have begun to report their
research findings, s t i m u lating further work from other special ists. Sometime
in the foreseeable fu t u re conservation techniques will be developed, evalu­
a ted and disseminated by the George Eastman House, the Library of Con­
gress and other national and regional conservation centers.
S t i l l locked i n the experience of scattered individuals a re many use­
fu l bits of information, too l ittle of it recorded or d isseminated widely. We
have offered here some of those experiences an d our own work in this field.
More w ill be d iscovered and published, for more is still needed. We trust
this book will be used, amended, q uestioned, an d in t i me, repl aced ; we wel­
come such a cou rse. Nothing can replace the e ndless research and serious
study req u i red to care for and preserve our photographic legacy.

39
 R e a d i n g 7

J A M E S M . R E I L LY

S tability Problems of 1 9th

and 20th C entury Photographic
M aterials ( 1 9 80)

As photographs became increasingly collectible, those engaged with 11hoto­

graph-ic collections recognized a need to formulate techniques and methods
for identifying, describing, and distinguishing the numerous photographic pro­
cesses. Some of the ea rly suggestions for doing so aJ?pear in Appendix B of this
publication. James Reilly (see also Readings 19, 36, and 60) has served as direc­
tor of the Image Permanence Insti,tute in Rochester, New Yorh, since it was
founded in 1 985. The following excerpt by Reilly outlines the coniplex, layered
structure of many photographic processes and defines the terms used by conser­
vators to describe those layers. The defining of vocabulary used to describe the
different elements of photographs was critical to mahe it possible for conserva­
tors to communicate anwng theniselves and with others about the identifica ­
tion, interpretation, and condition of photographic materials.

I ntroduction

The complexity, variety, and extreme fragi li ty of early p hotographic m a te­

rials are often u nderestimated by archivists and collectors. Their stabi li ty
problems have both tech nical and h u man d i mensions; to preserve them i t i s
essential t o know the objects and their problems, a n d to continually monitor
how they are being h and led and stored.

From jAMES M. R E ILLY, S t abi l i ty Problems o F 19th and 20th Century Photographic M a t e ­
''

,
rials," American I nstitute For Conservation, Annual Meeti ng San Fra n cisc o Post-Prints
1 980. © James M . R e i l ly. R e p ri n ted by permission of J ames iVl . Reilly, Rochester I nstitute
of Tec h nology.
 Reading 7 R E I L L Y

To assess stability problems, it is useful to consider each p hotographic

material in the light of a structural analysis in which the fol l owing "ge neric"
components appear:
A. I m age-formi n g S u bstance
B. Binder
C. S upport
D. Case/Packaging/Secondary S upport
E. I nteractions of the Above

The p u rpose of this "generic" structural analysis is to make it easier to iden­

tify possible stabil ity p roblems for a given photographic object, not on ly
with its constituent materials, but also with i n teraction s or incompatibili­
ties between i ts components. The exercise of fu lly c haracterizing a p hoto­
graphic object in l ight of this a nalysis method is s urprisingly i n formative,
and it leads to a more well-developed sense of stability problems than sim­
ply listing the known problems with each p hotographic process (though that
too i s usefu l ) .
A definition of the terms u sed i n t h e a n a lysis follows:

A. Image-forming S ubstance

In every photographic material something creates an image by absorbing or

scattering light. The su bstance which actu a l ly comprises the image i n the
finis hed, processed photograph is known as the image-forming substanc e .
The most commonly encountered image-forming s u bstance is metallic silver,
b u t there are other possibilities. For example, in a modern color transpar­
ency there are three image-forming s u bstances, al l organic dyes; in a plati­
num print the image-forming s ubstance is metallic platinu m . If nothing else
were known about a photographic material but its image-forming s ubstance,
a general assessment of its relative permanence and many of its specific sta­
b i l i ty problems could be predicated.
For example, knowing that an image consisted wholly or partially of
metallic platin u m wou l d s uggest that such a p hotograph wou l d be q uite
resistant to fading, because platin u m is a very stable chem ical s ubstance
which does not oxidize or tarnish easily. On the other hand, knowin g that
organic dyes are the image-forming s u bstances i n a color transparency might
cause concern because of the tendency of p hotographically generated dyes
to fade in light or in the dark u nder moist, warm conditions. Further, eac h
of the three dyes might fade at a differen t rate-it is i mportant to be specific
when considering an i m age-formi n g s u bstance.
Part I 1-l l S T O H Y O F P H O T O C H A P H C O N S E R VA T I O N

Metallic Silver as an Image-forniing Substance

J n discussing silver as an image-forming su bstance, the form of the meta l l ic

si lver and the re l ative size of the i ndividual i mage particles should be consid­
ered. Examination of p hotograph i c materials in the e lectron m icroscope
shows that silver is deposited in two general forms: as twisted, i ntertwined
strands known as filamentary silver, and as spherical or rounded l u mps
known as phys i c a l ly developed s i lver. Whether the i mage deposit is made
u p of filamentary si lver or physically developed silver depends on what kin d
o f developer solution was u sed i n the origi nal processing. Nearly a l l black and
white prints and films made after 1880 have fi l a mentary s ilver as the i mage­
forming substance. Examples of h istorical processes with physically devel­
oped s ilver i mage deposits are calotype negatives, ambrotypes, and tintypes.
Another i mportant aspect of si lver as an i m age-forming su bstance is
the relative size of the individual i mage particles. Larger particles of silver
tend to lead to more i mage stability and i mpart a blacker i mage color. I n
general, fi lamentary s ilver i mage particles are larger, appear blacker, and
have more i mage stability than p hysically developed i mage particles. The
smaller the i ndividual particles, the less stable the i mage wil l be and the less
neutral black the i mage wi l l appear.
A spec ial case of physically developed silver is fou n d in nearl y a l l
1 9th-century prints. M ost pri nts o f that t i me were not developed at a l l , b u t
"pri n ted-out," meaning that t h e i mage was produced b y prolonged exposu re
to daylight. I n this event physically developed partic les of extremely small size
comprise the i mage. I n accord with the general principle stated above, such
i mages are very u nstable and have a warm , reddish image color ( u n less modi­
fied by ton i ng) . Examples of this type of print are sal ted paper prints, albu­
men prints, gelatin printing-ou t papers and collodion printing-out papers.

B. The Image B inder

It is useful in most cases for the image-forming substance to be dispersed i n

a transparent layer whi c h w i l l keep it suspended t o maxi mize its l ight absorp­
tion, and protected from p hys ical and chemical attack at the same ti me. The
material which su spends and protects the i mage-forming substance is known
as the b inder, and the m ost commonly encountered b i nder is gelatin. Two
other binder materials which have been used extensively in historical materi­
als are a l b u men and collodion. J ust as a knowledge of the general attri butes
of the various i mage-forming substances is helpfu l in assessing stabi l i ty
problems, an awareness of the properties of the common b inder m aterials is
also helpfu l .

42
 Reading 7 H E I L L Y

Gelatin

Gelatin is a protein material m ade from the bones and h ides of cattle. I t is a
chemically stable substance; most of the stabi l i ty probl e ms associated with
gelatin res u l t from i ts physical properties (see I n teractions below). Gelatin
becomes brittle and contracts in dry conditions, and softens, becomes more
permeable and swel l s u n der h u m id con d i tions. Gelatin is easily abraded
u n l ess adequately hardened. H a rdening of gelatin (accomplished with vari­
ous substances or by adj usting p H ) affects its water solubility and perme­
ability to gases which would attack the i mage. Some kinds of deterioration
affect the hardness or solu b i l i ty of gelatin layers, sometimes making them
very sol uble i n localized areas and complicating conservation treatment.

Albumen

Alb u men is an i mage bi nder which was used extensively for prints during the
1 9th century. Albumen (chicken egg whi te) i s a protein substance which di f­
fers significantly i n structure and properties from gelatin . Both the chemical
and p hysical properties of albumen lead to stab i l i ty problems. Because of its
chemical makeup, albumen tends to yellow u n less kept cool and dry. As a
consequence, most a l b u me n prints have yel l owed h ighlights. The p hysical
properties of albumen resemble gelatin somewhat in that a l b u me n softens
and swel ls i n moist condi tions and becomes brittle and contracts under dry
conditions. H owever, albumen tends to fracture i nto a network of cracks and
fissu res, which in album en prints often have a parallel orientation along the
m achi ne d i rection of the paper su pport. Albumen does not tend to become
soluble upon deterioration as gelati n does, and also i s less susceptible to
mechanical damage such as abrasion .

Collodion

Collodion is produced when guncotton (ce l l u l ose n i trate) is d issolved in a

mixture of alcohol and ether. Col lodion was used as an i mage binder for
the "wet collodion" fam il y of photographic processes (wet p late negatives,
ambrotypes and tin types) and for photographic papers i n the era 1885-1930.
Collodion as a binder material does not have the notoriou s instability of cel­
l u lose n itrate as a s upport material. U n l i ke gelatin which must be hardened,
collodion is naturally brittle and must be made pl iable and permeabl e with
plasticizi ng additives for use on prints. Collodion does not absorb water and
is very easily abraded. It is readi ly soluble in alcohol and a n u m ber of other
solvents. Although i t does not tend to fissure as extensively as albumen does,

43
Part I 1-1 I S T 0 11 Y 0 F P 1-1 0 T 0 G H A I' I I C 0 N S E R V /\ T I 0 N

collodion layers on prints often display nu merous hairline cracks. Al l collo­

dion pri n ts are of the p rinting-out variety and are on baryta coated stock.

C. S upports

The component of the photograph i c material upon which the b inder rests
is known as the support. B i nder layers are by n ecessity very thin and do not
have the mechanical strength or optical properties to be a complete photo­
graphic object. The most common support materials a re paper, glass, and
fi l m . In most cases the su pport m aterials do not contribute major stability
problems i n their own right. A notable exception i s cellulose n i t rate fil m
base, which destroys the photograph a s a resu l t o f its own i n herent chemical
i nstability. Su pports are i nvolved in stab i l ity problems mostly through i nter­
actions with other components, and m ostly because their physical properties
do not harmonize with those of other components bonded to them.

Paper Supports

The most frequently encou ntered support materia l is paper, which has been
u sed as a su pport for both negatives and prints over the course of photo­
graphic h istory. The most essential req u i rement i n paper s upports is their
purity, or chemical i nertness toward the photographic coatings. It was
learned very early that only the finest and purest papers were suitable for use
i n photography. I n the 1 9th and early 20th centuries, this meant that paper
had to be made from l i nen and cotton, which contained the least i m pu ri t ies
to start with and req u i red a m i n i m u m of chemical treatment during paper­
making. M odern paper su pports are m ade entirely from wood pulp.
Paper has fou n d i ts p ri ma ry application as a support for reAection
prints. To increase the whiteness and smoothness of the paper surface, after
1 885 the p ractice of baryta coating was adopted, i n which the surface was
given a smooth top l ayer consisting of barium sulfate (a white p igment) and
ge lati n . The photograph i c emu lsion was t hen appl i ed to the baryta coated
stock. The p hysical properties of paper are largely determined by the fact
that it i s composed of cellulose fibers al igned mostly i n one direction by the
papermaking machinery. This means that when the paper absorbs moisture
it expands more i n one d i rection (across the long axis of the fibers) than the
other. There is no such orientation on the expansion of gelat i n or albumen .
Paper also contracts and becomes embrittled at low h u m i di t ies, and may
tear or break easily under those conditions. Paper supports for photographs
req u i re much more carefu l handling than the casu a l handling given paper
objects in everyday l i fe, and the p hotographic layers coated o n them are even

44
 R eading 7 R E I L L Y

more delicate. Secondary supports should be provided for u n m o un ted pho­

tographic prints.
Another stab i l i ty problem wit h paper supports, especially thick ones, is
the tendency of paper to retai n thiosulfate from fixing solu tions. The resid­
u a l " hypo" may be adsorbed to the paper sizing or baryta layer, or trapped i n
s m a l l capi llaries between a n d among t h e paper fi bers. This residual thiosul­
fate is difficu l t or i mpossible to remove, even by prolonged wash ing. Film or
glass supports do not share this u n desirable c haracteristic. Thi n paper sup­
ports with n o baryta layer (such as are fou n d i n al b ume n prints) are washed
free of thiosulfate relatively easily. P hotographic paper supports are also
deteriorated by the same forces that affect other paper objects, namely UV
and visible radiation , h igh h u mi dity, acidity an d oxidants. Th e h igh p u rity of
p hotographic paper supports makes t h e m more resistant to these forces than
most other types of paper, however.

G lass Siipports

G lass supports are chemically inert u nless kept in very moist conditions, and
their main features of i nterest lie i n their physical properties. The attraction
of glass as a su pport originally came from i ts p lanarity and transparency, and
i t was i n use extensively for negatives and transparencies from the late 1 84o's
to the 1 92o's. G lass is extremely dimensional ly stable and does not shri n k or
swell with changes in ambient h u mi d i ty. I ts stability problems origi nate from
its weight, fragi l i ty and smoothness. G lass has considerable weight which
generates n umerous storage problems and creates breakage. The fragil ity of
glass is obvious from everyday experience an d the sharp edges of hand c ut or
broken glass also are a problem in the storage of glass photographic objects.
The smooth surface of g lass causes many problems of separation of b i n der
materials carrying the photographic i mage.

Film S upports

Film supports are a complex field of study in their own right. The term film
is used to designate a wide variety of Aexible, transparen t m aterials used
as p hotographi c supports. Early fi l m s upports present a n um ber of stabil i ty
problems, b u t modern fi l m bases are remarkably stable. The earliest flex­
ible film s were made of cellulose n itrate, either cut from a solid b lock or
cast from a solvent solution poured onto a s mooth table or dru m . Cell u lose
n itrate films slowly decompose and release oxidants and acidic gases whi c h
destroy the i m age. M aterials w i t h cel l ulose n itrate supports should n ever be
stored together with other types of photographs. Cellulose nitrate shri n ks as

45
Part I H I S T O H Y O F P H O T O G H f\ P l-1 C O N S E H V f\ T I O N

i t decomposes, and this is often the first serious manifestation of its instabil­
ity. The overriding concern with cellulose n itrate fi l m is a lways the serious
fire hazard which i t poses.
Thin fi l m supports of a l l types can have severe curling p roblems at
low h u midities, b u t the modern fil m bases cel l ulose triacetate and polyes­
ter (polyethylene terephtha late) presen t few chemical or physical problems.
The dimensional stabil ity and overall retention of p hysical properties i n
accelerated aging tests of p olyester fil m s exceed that of cell ulose triacetate
m a terials.

D. Case/Packaging/Secondary S upports

Many photographs are part of an i ntegral package which is designed to

support or p rotect the p hotograph. Exam ples of this are the cases used to
e nclose daguerreotypes and the mounts of cartes de visit: e. S uc h accessory
materials may be designated as i ntegral secondary supports . S ince they are
regarded as part of the p hotograph, i n tegral secondary supports contribute a
wide variety of potential stabi l i ty problems.
Original mou n ts for p ri n ts are the most common form of i n tegral sec­
ondary su pport. A mount for a pri n t involves both an adhesive and the mount
i tself. Starch and gelatin were widely used as adhesives and u s u a l ly did not
cause serious damage. S u lfur-contai n i n g adhesives such as rubber cement
are very harmful to si lver i mages. Use of poor quality moun t board is the
most frequent source of stability problems from i ntegral secondary supports.
Many 1 9th-centu ry moun ts were composed of a l a mi nate of good quality top
and bottom sheets with a center which contai ned gro undwood or h ighly l ig­
nified fi bers. D iscoloratio n and fad i ng of photograph s can res u l t from the
use of such mounts. The extent to which such defective mounts deteriorate
and affect p hotographs is controlled in large measure by the ambient rel ative
h u midity.
M any albumen prints, for example, are mounted on very poor quality
mount board which should be isolated from other photographs by i n terleav­
i ng. Deterioration causes embrittlement of such moun ts and they should
also be provided with additional secondary supports to prevent breaki ng of
the mou nt (and the photograph) duri n g handli ng. The variety of i n tegral sec­
ondary su pports is enormous, si nce to a degree such constructions reAect
i ndivi d u al taste and expression . Elaborate or si mple, both their p hysical a n d
their chemical properties should be considered i n light o f t h e s usceptibi l ities
of the photographic object i tself.
 Reading 7 R E I L LY

E. I nteractions

The component materi als of a photographic object may be en tirely stable i n

a n d o f themselves, b u t t h e photograph whi c h they constitute may not. l t i s
i mportant t o consider n o t only t h e i n d ividual constituents o f a p hotograph,
but also how the various components i n teract. The largest class of harmfu l
i nteractions arises from t h e l aminate structure of p hotographic m aterials,
where the p hysical properties of the support do not h armonize with those
of the binder layer. An example is the separation and teari ng of the gela­
tin em ulsion layer often seen at the edges of gelatin dry plates. The glass
s upport does not swell in moist conditions or contract in d ry conditions, as
the gelatin does. The stresses which can develop are more than enough to
tear or delaminate the emu lsion layer. U nequal stresses of this sort also fre­
quently cause cracking and tearing of binder layers on paper s upports . The
contraction of albumen layers at moderate and low h u mi d ities i s so strong
that unrestrained prints curl i n to tight, cigarette-like rolls. These rol l s are
very d iffic u lt to relax without harming the p ri n t, especia l ly when a n u m ber
of prints h ave been rolled up together for m any years.
I nteractions or i ncompatib i lities between otherwise stable components
of a photograph may be chemical as well as physical. An example of this is
the high catalytic activity of plati n u m or silver-gold-plat i n u m i mage deposits
i n p hotographic prints. The plat i n u m i m age often catalyzes the deterioration
of paper (particu larly lower quality paper) and causes a "transfer" positive
i mage to appear in any paper material i n contact with the print surface. This
can sometimes include creating a "transfer" i mage i n photographs on faci ng
album pages. The catalytic activity may extend through the primary support
of the pl at i n u m print (without affecting it) and cause i magewise d iscolor­
ation of a lower quality secondary support.

47
 R e a d n g 8

I A N L . M o o R AN D A N G E LA M o o R

The I mperfect Image ( 1 982)

Ian Moor was seni.or conservator i n the Oriental JVIanuscri.pts Department of

the Brit ish Li.brary fro m 1 976 to 1981. Angela Moor established a conservation
program for the British Petroleum Archive at the B ritish Petroleum Research
and Analytical Centre, London, in 1976. In 1 981 the Moors joined in partner­
ship and in 1982 they established the Centre for Photographic Conservation,
London., which continues to offer ex11ert 11rogra 1ns on photographic 11reserva­
tion, conservati.on, and disaster recovery internationally. In 1992 t he Moors
organized "The Im11e1fect Iniage: Photographs, Their Past, Present and Future, "
the first international conference on photograph conservation, which tooh its
name fro1n the 1 982 article reproduced here. T1ie conference publication is an
essential co mpendimn of international photographic preservation research and
practice in the early 1 990s. This reading su·1n1narizes the 11hilosophy of these
two early and highly influential photograph conservators and addresses the
need for greater hwwleclge and practi.cal solut ions to 11resen1ation 11roblenis.

Photography is the most expressive and i m mediate of med i u ms, it evokes a

response at al l levels and ages, and i t captures the very essence of rea l i ty,
h u man achievement and existence; it is a positive statement of being, a liv­
ing record and memory of t h i ngs past.
I f the developing market i n n ineteenth and twentieth century photo­
graphic i m ages has done anything for this most expressive and i mmediate of
medi u ms, it has at least elevated its i mportance i n a field dominated by other
more prestigious graphic mediums.
---

From IAN L. M oon a n d ANGELA M oo n , "The I mperfect I mage," The Photographic Co/.lec­
tor 3 , no. 2 (Autumn 1 982): 1 7 1-82 ( 1 7 1 , 1 73 excerpted here). Repr i n ted by p e r m i ssi o n of
Ian L. M oor and Angela Moor, the Centre for Photographic Con servation, London.
 Readi ng B M O O R A N D lVI O O H

I n a n attempt to raise the status of the lowly photograph, making it

both marketable and col lectable, more and more emphasis is being p laced
upon i mage quality; that much sought after, talked about, and yet elusive
q uality so often couched in terms of aesthetic appreciatio n . I mage quality
can relate to a particular p hotographer whose work typified that perfect mar­
riage between pure expression and the nature of the materials involved, so
m anipu lated as to fac i l i tate that expression. A lternatively, i mages on a more
simplistic level can portray events of sociological or h i storical i mportance. Of
course there is something to be said for simply liking an i mage; that i nstinc­
tive gut reacti on that needs neither justification nor rationalisation. Never­
theless, once an i m age has been selected as m arketable and col lectable, then
value enters the scene, and what i t is worth depends upon how wel l , and to
what extent, it meets the kind of criteria mentioned .
At the moment the market obsession is perfection; the sligh test flaw,
whether it is an i n trinsic feature of the techniques and processes i nvolved,
or, a p hysicall y or chemically produ ced blemish, w i l l make or break a poten­
tial sale. What constitutes a perfect i m age? I n real i ty there is no such thi ng.
The experience gained from seeing several copies of a particu lar pri n t will
only enable one to say which print i s i n by far the best condition; this hardly
m a kes it a perfect im age . Condition is an inseparable part of the i ntrinsic
m a keup of a p hotograph, as al l photographic images exist i n an a ltered,
imperfect state.
It is a depressingly sad fact that a vast amount of photographic m ate­
rial is being neglected or totally disregarded simply because collectors, custo­
dians, c urators and the market alike feel that this material has little intri nsic
value in that it is not representative of a known p hotographer, has no socio­
logical or h istoric merit, or, is not an outstanding piece of p hotograph ic art.
In this respect the photographic m arket is in great clanger of becoming yet
another elitist arty faction that treats objects, in this case photographs, as
t h ings that only have val u e if they express this so-called perfection.
There is one factor affecting i m age condition that as yet has not been
touched upon, but it is the most i mportant factor of a l l , and that is i mage
permanence. Of a l l artifacts the p hotograph is the most sensitive, on a l l lev­
els of its existence.
P hotographs exist o n four distinct levels and t hey are prone to degra­
dation on each, which makes them unique. The external factors affecting
degradation in p hotographic materials are: environ mental, physical and con­
taminants. I nternals factors affecting degradation are: residual chemicals,
m igratory contamina nts and physical i ncompati b i l i ties. Therefore, we m u s t
not consider t h e i nfl uences o f degradation a s a totality, w e muc h consider
the i n herent qualities of the materials being affected too.

49
Part I H I S T O H Y O F P H O T O G H A P H C O N S E H V AT I O N

1 . The base or support material . Thi s can be e i ther paper, glass, metal ,

leather, wood , fabric, bone or cera m ic , and these materials will react i n de­
pendently to the i mage-bearing e m u lsion inducing p hysical incompat i b ili­
ties. E m ulsions also vary.
2. The emu lsion if present can be albumen, collodion or gel atine and
a l l of these m aterials are degradable as a d i rect res u l t of their i n herent quali­
ties, for example albu men has a natural free s u lph ur element i n its compo­
sition; collodion-cell u lose trin itrate i s susceptible to h igh h u m id i ty, mould
attack a n d acid and alkal i n e conditions. Aga i n these materials will react
i n dependently to the i r support.
3. The p hotograph ic i m age for a l l i ntents and p u rposes is c lassified as

a work of art, but u n l i ke i ts counterpart , the pai nting or d rawi ng, it cannot
effectively be restored u s in g the same mediums that produced i t .
4 . F i na lly, it is i r o n i c t hat it i s t h e deliberate degradation of known
sensitive materials by l ight and chemical agents that give rise to the phe­
nomenon known as a p hotograph, and yet, it is these very same agents which
must be control led in order to p revent the p hotograph from being degraded
to the poin t of destruction.
This clearly demonstrates that a ll p hotographs exist i n a n i mperfect
state. It is a further sad fact that despite its relatively short h istory, some one
hu ndred and forty plus years, photograph s , because of their i n herent degrad­
able q u a l it ies and complex nature at all l evels, are deteriorating and being
lost at a n alarm ing rate . I n comparison, a fou rth century Ch i nese manu­
script will still exist long after too great a percentage of our fabulous p hoto­
graphic heritage has been lost.
The biggest and most viru lent enemy in the fight to preserve our pho­
tographic past i s not e nvironmental or residual complexes in photographic
materials-ph rases bandied aro u nd b u t l i ttle u n derstood in our so cal led
enl ightened age-i t is our very attitude to photographs. An attitude that
i nva riably keeps photographs i n the basement i n cardboard boxes, polythene
[polyethylene] bags or anyth ing that comes to hand. U nfort unately the art
market h as been flooded with supposedly archival ly sound products and
cou ntless other commercial products that are totally unsuitable for the stor­
age, mount i ng and treatment of photographic artifacts.
Photography, a reprod uctive medi u m in a th rowaway age, is so often
u sed in a supportive role, for example, the early carte-de-visite, aicl [e-J
memoire, book i l lu stration, fashion photography, advertising and journal i s m ,
that i s h a s been slow i n establishing i tself a s a n art mediu m i n i t s own right.
On the ladder of i mportance and respectab i l i ty p hotographs come way
clown at the bottom whilst the more fashionable materials, manuscripts,
prints and painting, enjoy the l ion's share of any financial and aesthetic com-
 Reading 8 /\ll O O R A N D M O O H

m i tment whether i t i s a national m u se u m , gallery, local record office or what­

ever. Thi s position must be reversed before it is too l ate. The situation is not
helped by the u njustifiable bad p ress the photographic art world has received
as a resu lt of recen t forgery cases, articles and television progra mmes, that
s ucceeded only i n asking all the wrong questions, to all the wrong people;
belittl ing what fragile respect the photograph has struggled to achieve.
Fortunately a disce rn i ng few recognise the u n i que qualities of p hoto­
graphic i mages and at least some of our vast p hotographic heritage is being
saved. Yet i f you compare the i nterest i n p reservin g and collecting photo­
graphs to values bestowed upon other reproductive mediu ms, for example
pri n ts, engravings, l ithographs and such l i ke, then it i s a joke, a case of pen­
n ies against tens of pou nds. This i s parti cularly so with n ineteent h century
material, which has yet to be surpassed i n terms of its visionary qual ities,
and the sheer tech nical brilliance needed to overcome the i mmense diffi­
c ulties a nd inadequacies of the processes i nvolved. H ow rel atively easy it i s
for u s today t o simply p ress t h e button a n d t h e manufacturers d o the rest,
supplementin g the market with a never-ending stream of twentieth century
i m ages, many lacking i n vision, direction and tech nique.
The photographic ma rket, in putting a rea lizable monetary value on
p hotographs, is promoting t h e preservation o f a body of material t ha t oth­
erwise wou l d disappear with successive generations. Th is, however, is only
an i mportan t tip to a very huge iceberg. Britai n ashamedly has hardly begu n
to i nvest money or time i n photographic research, public awareness, or, the
p reservation of its collections; h owever, i t i s not true to say that nothi n g is
being clone at all. Our coll eagues in America who are much more socially
and nationally aware of the supreme i mporta nce of p reserving photograph i c
materials, are spending m ore a n d more money an d resources on research
p rogra m mes, or, in the p u rchase on a l arge scale of photograph i c records
a n d artifacts, at a l l levels. But, on the conservation level, lacking a long tra­
dition of practical conservation, they conti n u e to seek both knowledge and
u nderstanding by peering at photographs through the eyepiece of a mi cro­
scope a n d experimenting on d issected portions of origi nal, yet presumed
worth less images, a p ractise that defies all basic ethics in conservation. Then
we are told that it wil l take at least ten years before practical solutions can
be fou nd. This is absolute nonsense. Photographs are physical objects with
physical properties. They cannot be described as, or viewed as chemical
equations that fit delineated, neat l ittle packages, that react to strict rules,
and only u n der laboratory conditions, n o doubt.
\Ne can ill afford to wait ten years, the problems are with us now; too
h igh a percentage of material is not goi ng to be with us in ten years, and
what is, wil l be even more degraded. We need practical solutions to practical
Part I 1-1 I S T 0 R Y 0 F P H 0 T 0 C H A P II C 0NS E R V ATI 0 N

problems, not scientific theories that leave i n d ividuals as confused and as

i ncapable of affecting beneficial meas ures as ever.
" I n order to evolve safe and sound restoration techniques it is of vital
i m portance to u nderstand fu lly the natu re of the materials used in the origi­
nal process. It is bad conservation practise to si mply experiment with origin a l
material, j u stifying i t s expendability b y its com monness and apparent lac k o f
va lue, monetary o r otherwise . " 1

References

1 Ian M oor, "The Ambrotype-Research i n to its Restoration and Conservation­

Part 1 , " n1.e Paper Conservcll. o r, Vol. 1, 1 976; Part 2, n1e Paper Conservator,
Vol. 2, 1 977.

52
 R e a d i n g 9

K LA U S B . H E N D R I K S
AND B RIAN LESSER

Disaster Preparedness
and Recovery: Photographic
M aterials ( 1 983)

Klaus Hendrihs ( 1 93 7-1 996) (see also Readings 24, 58, and 65) was a prolific
research scientist lznown for his studies in photographic permanence and
his remarlzable command and critical evaluation of relevant published scien­
tific research, 11ast and present. He joined the National Archives of Canada
(NA) as a photographic conservation chemist in 1 975. The NA was the first
national institution to employ a full-time chemist to study the preservation and
restoration of photographic images. In 1 977 he became director of the NA Pic­
ture Conservation Division, and in 1 990, director of the National Archives' then
recently founded Conservation Research Division, which was later transferred
to the Canadian Conservation Institute. 1-Iendrilzs's national and international
professional involvement was extensive. He exerted a profound influence on
the field of photograph conservation in teaching, developing treatment tech­
niques, and scientific research. Hendrihs and Lesser's Disaster Preparedness
and Hecovery: P hotographic M aterials was the first publication to address
emergency response niethodology for the salvage of water-damaged photo­
graphic materials, both 1nints and negatives, in blaclz-and-white and color.
This applied research (presented in summary form here) is stunning in scope
and impact; it remains a guidepost for understanding and implementing disas­
ter preparedness and response procedures related to the care and preservation of
photographic materials.

From KLAUS B. H ENDRIKS and BRIA'.'! LESSER, " Disaster Preparedness and Recovery:
Photographic M aterials," American Archivist. 46, no. 1 (\"linter 1983): 52-68 (64-68
excerpted here). Reprinted by permission of the Society of American Archivists, www
.arc h ivists.org.

53
Part I H I STORY O F P H O T O G B A P ll C O N S E RVATION

Results and Discussion

The S . P . S . E . H andbook of Photographic Science and Engineering1 flatly

states as an i m portant storage cond i ti o n for processed photograph i c materi­
als: " Protect photograph ic records from fire, water and physical damage."
No other forces are l i kely to be more destructive than fire and water. Water
damage [ . . . ] may be caused not only by a flood b u t may occur as a res u l t
o f efforts t o extinguish a fi re. The experiments reported here shed l ight o n
t h e reaction o f p hotograph i c materials toward p rolonged i mmersion i n water
and subsequent drying. Our observations show that the resi stance of pho­
tographic materials to wet i mmersion depends on the type of photograph,
whether or not i t was hardened d uring processi ng, the i mmersion time, and
the water temperature . 2 The contemporary black-an d-wh i te en larging speed
paper that had been fixed i n a non-harde n i ng fixer was completely destroyed
when the gelatin layer slid off the paper support after being i mmersed i n
water at room temperature for 7 2 hours. By comparison, t h e hardened sam­
p le of the same paper essentially kept its gelatin layer i n tact u nder the same
conditions. The contact speed paper, made by a different m a n u facturer than
the enlargi ng paper, regardl ess of whether i t had been fixed i n a hardeni ng or
non-harden i n g fixer, survived the same treatment virtually without damage.
While d imensional cha nges i n black-and-white fil m s could not be observed
with our equipment, i n paper pri nts a shrinkage was genera l ly determi ned
to be greater i n the length d i rection than in the width direction . Air-dryi ng
caused the l east dimensional changes in prints.
After short dra i nage t imes, no sticking of photographic records to p las­
tic s leeves (made of cellul ose triacetate) was observed. A loss of reflection
density, which was to a large extent caused by a loss i n s urface gloss, was
regu larly observed i n black-an d-whi te prints. A simi lar, b u t m uch smaller,
loss of transm ission density was observed for b l ack-an d-wh i te negatives. For
both prints and negatives it can be assumed that the fi lamentary structure
of the i mage silver u ndergoes changes d uring soaking, freezi ng, and drying
to form more roun ded-out silver particles which show less l ight absorption
and therefore cause a density loss. 3 ·4 The considerable decrease of reflection
dens ity in pri nts can be explained by the loss of surface gloss. 5 This was also
noticed by the mottled appearance of soaked and freeze-dried prints. The
effect is small after ai r-drying or after freezing-thawing and vac u um-drying
above freezi ng point. It was most pronounced after freeze-drying.
Because of the foregoing we feel that a i r-drying ( i .e ., wi thout prior
freezi ng) of water-soaked p hotographic materi als appears to be the prefer­
able treatment. Freezi ng may be necessary, however, in order to slow down
deterioration of soaked materials and to gai n time for gathering person-

54
 Reading 9 ll E N D H I K S A N D L E S S E H

nel and supplies. I n that case, freeze-thaw-vacuum-drying-as clone with

books-cannot be recommended cl ue to blockin g and sticking of gelat i n lay­
ers in stacked p hotograph i c pictures.
\!\!hen freeze-drying was applied, the res u l ts showed that it wou ld be
the preferred treat ment only for documentary photographs mounted in a n
a l b u m, particularly if they conta i n h istorical captions of some value. For a l l
other cases i t shou ld b e avoided ; t h e loss o f surface gloss ( a s i ndicated b y the
l oss of density) was stro n gest after freeze-d rying. This can be explai ned by
the observation that water in the freeze-drying process is not allowed to ru n
off as is possi ble after freezing, thawing, and vacuum-d rying. As subli mation
from solid ice to water vapor occ urs , al l i mpurities i n the frozen water will be
deposited on the su rface of the pri n ts or negative, having no p lace to escape
e lsewhere. If photographic materials that have been soaked i n water cannot
be air dried (because of lack of personnel, faci l i ties, and t i me), they should
be frozen , thawed, and ai r-dried . Freeze-drying would be the next preferable
alternative, while freezing, thawing, a nd vac u u m-drying above freezing point
must be avoided .
Although less ex1Jerimental data on color photographic materials were
gathered, our observations i n d icated that color photographs made by the
c h romogenic development p rocess showed res istance to i mmersion i n water
and su bsequent drying which was comparable to that of black-and-white
materials. H owever, chromogenic color pri n t materials made by one manu­
facturer showed not o n ly loss in su rface gloss but also changes i n color cast
and color saturation after freeze-drying. These changes were not observed
when the pri n ts were frozen , thawed, and air-dried. The two samples made by
dye i m bibition processes were particularly susceptible to soaking. D i ffusion
of dyes i nto the water bath was observed with i n a short t i me after i m mersion.
Whi le albumen prints and collodio-chloride prints survived the soak­
i n g and drying cycles remarkably wel l , the behavior of the binding agent i n
s ilver gelatin materials i s most in teresting. As can b e seen from the tables
showing experimental data [not reproduced here ] , neither scratch resistance
data nor melting poin ts are sign i ficantly affected by soaking and dry i ng of
materials when compared to contro l prints. 'v\/hile these treatments caused
some observable changes-loss of surface gloss, loss of adhesion, stai n ing,
and mottling-such properties as resol u tion, melting poi nts, mushiness, and
scratch res istance did not change appreciably. Gelatin , within a certa i n range
of circ u mstances, appears to undergo changes reversi bly, such as swe l l ing/
deswe l l i ng or softeni ng/hardeni ng, u nless it reaches a breaking point, or point
of destructio n . There seems to be no gradual deteriora tion; i nstead, an abrupt
deterioration takes place when conditions are d riven past a certain l imit.
The most significant res u l t of t h is study is, in our view, the i nability
of glass plate n egat ives made by the wet collocl i o n process to survive i mm er-

55
Part I l-I I S T O H Y O F P l- I O T O G H A P l- I C O N S E H V AT I O N

Table 1
Hecommendations For treatment oF water-soaked photographs.

Keep imn1ersion t i n1 e to a m i n i m u m .
Keep water temperature low.
Freezing of photographs retards Further deterioration.
• As fil ms appear to be more stable, salvage prints first.
If personnel and time are available, proceed in t h i s order:
a. air dry (without Freezing)
b. Freeze-thaw-air dry
c. Freeze-dry i n vacu u m c h amber
Freeze-thaw-vacuum-drying, as done with books, not recommended due to
blocking or sticking of gelatin layers.
Protect wet collodion glass plate negatives completely from being i m mersed in
'''ater.
\Net collodion glass plate negatives m u s t never be freeze-dried; none w i l l survive.

sion 111 water and subsequent drying. O f several p lates tested, one half did
not survive a 24-hour soaking period. The i mage layer of t hose that barely
s u rvived the i m mersi o n in water shattered i n to many pieces d u ri n g freeze­
d ryi ng. Recal l i ng the s i mple fashi o n i n which they were made, i t seems rea­
sonable to assu me that the lack of a special substratum , which usua l ly serves
to i mprove the adhesion between i mage layer a n d support, is one factor con­
tributing to the i nstab i lity of wet collodion plates. One has to conclude from
t hese observations that negative glass p lates made by the wet collodion pro­
cess-and the col lodion positives known as ambrotypes and tin types, which
were made by a s i m ilar process-should be kept in any collection i n a way
that w i l l preven t them from ever bei ng fl ooded or soaked i n water. Without
having done any ex'Periments in this d irection, we have d iscussed the ques­
tion i nformally with cu rators i n the National Photography Collectio n. The
u se of water-tight a m m u n ition boxes, or rigid polyethylene boxes with snap­
o n covers (sim ilar to Tupperware products), or covering cardboard boxes
with flexible polyethylene bags, are a ll u nder consideration. The problem i s
urgen t a n d requ i res a practical solu ti o n .
A s u mmary o f our conclusions and recommendations i s presented i n
Table r .

S ummary

A fairly large n u mber ( more than 630) of stil l photographic negatives and
prin ts in b l ack-and-whi te and color were i m mersed i n Ottawa C i ty tap water
(approximate p H 8) for varying periods of t i me a n d dried i n four differen t
ways: a ir-drying (wi thout freezi ng); freezing-thawing-air-drying; freezi ng­
thawin g-vacuu m-dryin g; and freeze-drying. I n addition to evaluating the
 Reading 9 H E N D H I KS A N D L E S S E R

res u l ts by c lose visual i nspection, attempts were made to quantitatively mea­

sure changes i n test sa mples after soaking them i n water and subsequent
drying. These i ncl uded d imensional c hanges, densi ty, resolution, and hard­
ness of the gelatin.
O u r results show that the materials most s usceptible to water damage
are glass p late negatives made by the wet collodion process. They should
n ever be freeze dried once they have been i mmersed i n water. \Vh i l e salt
p r in ts, albu men prints, and collodio-chloride prin ts survived surprisingly
wel l , black-and-white silver gelatin materials showed specific deterioration
ranging from total destruction-clue to solution of the gelatin layer i n non­
hardened prin ts-to severe mottl i n g of the gelatin in freeze-dried materi­
als and to a barely perceptible loss i n surface gloss i n ai r-dried prints. The
formation of i ce crystals when freezi ng water-soaked silver gelatin materials
was not observed . F u rt hermore, there was no evidence of damage clue to
freezing of water-soaked fi l m . These observations have been confirmed by
experi ments conducted at the Eastman Kodak Company on a variety of their
own photograph i c materials. \Vh ile b lack-and-white materials commonly
appeared to be more resistant than color photographs, the former were also
more stable when they had been processed u s i ng a harden i n g fixing bath.
After p hotographic materials are soaked in water, air-cltyi ng or freezing­
thawing a n d a ir-drying are to be preferred over freezing-t hawing-vacuum­
drying and freeze-drying.
No prediction can be made from our observations with respect to the
long-term effect of soakin g-freezi ng-drying cycles o n the described photo­
graphic materials. Photographic records which have u n dergone such cycles
should be l abeled accordingly, specifying as many detail s as possible. Valu­
able observations may then be made i n the future on the possible effects of
soaking and drying on the long-term stabi l ity of p hotographic materials.

N otes

1Woodl ief \"1. Thomas, SPSE /-/andbooh of Pliotograpltic Science and

Engineering, \"1i ley Series on Photographic Science and Technology and t he
Graph i c Arts ( N ew York: W iley & Sons, 1 973).
2 Soaki n g experiments, carried out at two d i fferen t tempera t u res, showed t ha t
samples soaked at h i gher temperatures d i s integrated before others soaked at a
lower temperature.
3 R . K. B lake and B. Meerkemper, "Developed I mage Structure," Journal of
Photographic Science 9 ( 1 9 6 1 ) : 1 4-25.
4 H. Zwicky, " U eber den Unterschied der Schwaerzu ngswerte p hotographischer
Schichten in trockenem und nassem Zustand," Zeitscltrift. fuer wissenscftaftliche
Photographie, Pliotophysih, und Photoche,,,1.ie 50 ( 1 955): 4 1 5-424.
H o l l i s N. Todd and R ichard D. Zakia, Photographic Sensi.tometry: The St. udy of
T'one Reproduction ( Hasti ngs-on- Hudson, N .Y.: Morgan & M orga n , 1 969).

57
 R e a d n g 10

AN NE CARTI E R - B RE S S O N

A N ew Discipline :
Preservation and Conservation
of Photographs ( 1 987)

Anne Cartier-Bresson is a photograph conservator and educator who has spent

her career worbng in Paris wi.t h frnportant collections, including those at
the Vi.Ile de Paris and the Nlusee Carnavalet. Paris has been a focal point for
photograph conservation and education in Europe, in part because of Cartier­
B resson 's 1vorh and her conimitment to the field. As director of l 'A telier de
Restaurat:ion et de Conservation des Photographies de la Vi.Ile de Paris (A R CP)
and formerly of the conservation t raining 1nogram of the lnstitut National du
Patrimoine ( IN P ), she has mentored niany students in the photograph conser­
vation 11rogra m. This reading outlines hey trends in the developnient of photo­
graph conservati.on in France, including the increased cultural and historical
value of 71hotograph ic collections, the im11ortcmce of niininial intervention,
and strengthened collaborations anwng conservators, scientists, and scholars.

The history of preservation and conservat ion is l i n ked to the history of

how the works are viewed and to the desire to prolong their q ualities over
time. The con cepts and practice of photographic conservation have cha nged
in the course of photograph ic h istory. Conservation is not only a technical
operation; it i n fluences the way i mages are perceived, conferring a certai n
status and i mparting a concrete va l u e to them.

ANNE C1\l1TI EB-l3BESSON, " U ne nouvelle disc i p l i ne: l a conservation-restauration des pho­
tographies, " La Recherche Photograph ique, no. 3 ( December 1 987): 69-73. Repri nted by
permission of· Anne Cartier- 1 3 resson. Atelier de Restauration et de Conservation des Pho­
tograph ies, M ai rie de Paris.

58
 Reading 10 C A H T I E H - ll H E S S O N

The Arch ives of M emory

Beyond the polemics that riddle the advent of p hotography, we are generally
i n agreement i n what we ask of p hotography: that it prolong the appearance
of thi ngs while at the same time preserving itself; that is dissemi nate knowl­
edge; and that is preserve me mory.
The exceptional i n formative and didactic capa bilities of photography
opened up new documentary and iconographic perspectives, and the first
photographers who traveled the world-often with the aid of government
s u pport-made the most of them. ' Photography, which rapidly conquered
space a nd recorded the trace of h istory both private a n d pub l ic, has not
a lways been capable of sec u rely preserving such traces and, t hus, of dealing
with the problem of d u ration . Yet i ts "practical u t i l i ty" has val u e only t hrough
its existence i n space and time. While the metal pl ate made the daguerre­
otype a fragi le but rel atively d u rable i m age, i ts nonreproducibility l i m ited
i ts dissemi nation. Conversely, as of the late 1 840s, the negative-positive
system a llowed images to be d u p licated on paper. But the chemical i nsta­
b i l i ty that threatens them with disappearance makes them i ncapable of pre­
serving the moment. 2
Aware of the d iscredit affecting photography,' the i nventors-who
were often e>-']Jerimental chemists-sought to improve the stability of i mages
and give them an "i ntrinsic value ."4 I n the n i neteenth cen tury, research was
conducted s im u lta neously i n two d i rections: u nderstanding how and why sil­
ver pri n ts deteriorate i n order to i mprove their manufacture, and searc h i ng
for new "nondeteriora t ing" processes that wou l d n ot use s i lver salts. As of
the m id- 1 85os, the Societe franc;; aise de photographie and the Royal P hoto­
graphic Society of London encouraged such work. I n the ten years that fol­
lowed, the major factors i n volved i n the deterioration of s ilver images were
correctly identified a n d isolated. 5
I n such context of tec hn ical trial and error, i n which the permanence
of prod ucts was a condition for the development of the p rofession, p hotog­
rap hers themselves performed chemical proced u res on their i m ages. Tal bot
rei nforced his faded calotypes, whi l e H u mbert de Mola rd, Le Gray, and
Davan ne pu bl is hed "remedies" and methods of "revivifying " deteriorated
pri n ts.6 All of these treatments sought to mask or mitigate the i mperfections
of their own production.
\,Yh ile s ilver salts arou sed doubts and mistrust, as of i 855, carbon-"the
most fixed and most nondegradable of materials"-was presented as the
sol u tion to the prob lem of "indefinite" preservation of prin ts.7 This battle
aga inst transience resu l ted in the devis i ng of other so-called "permanent"
processes-plati num and l ater palladiu m8-and the i mplementation of pho-

59
Part I H I S T 0 RY 0 F P 1-1 0 T 0 G H A P I I C 0 N S E RV AT I 0 N

tomechanical techn i ques-photogravure, col lotype printing, etc.-whi c h

produced prints wit h printer's i n k from a photograph i c plate. Easily repro­
duci ble, "in destructible," and cheap, these i n k p ri nts attracted the atte ntion
of the j u ry at the 1 855 U n iversal £:,.,'Position, and of Ernest Lacan and Charles
Negre h imself, to such an extent that they came to consider photography per
se as merely a "transitory process."
The tech n ical i mperfections of photography therefore forced i ts prac­
titioners to confront the problem of preserving their i mages, which resulted
i n a considerable physical i mprovement of the prints. Th is movement was
contemporary with a prod uction of very h igh aesthetic quality.

Curbs to the Idea of Conservatio n

As of the 1 880s, the rapi d technical development of the process e ncou raged
the development of the p hotographic i ndustry, marking the e n d of the pio­
neering era and open i n g the way for a new generation of practitioners, which
was also larger in n u m bers. Being easier to u se, the practice of p hotogra­
phy spread . And among the genres, " u t i l itari a n " photography experienced
an u n precedented s uccess i n the areas of advertisi ng, fash i on, fa m i ly photo­
graphs, etc.
The ease of use and the i mage d u p l ication capaci ty contributed to the
trivial ization of photography, earni n g it a certa i n i ndifference or, at best,
an i n terest l i mi ted to i ts didactic and i nformative aspects. For a long time,
photographs were considered simple doc u ments or i l l ustration supplements.
This lack of i nterest-qu ite marked i n French p u bl ic collections-broke with
the prior period and contrasted with a few private i n it iatives, as for example
that of G abriel Cromer, whose collection now constitutes the wealth of the
George Eastman M useum i n Rochester.9 Whi l e presen t in n u merous institu­
tions starti n g in the l a te n i neteenth centu ry, it took p hotography a long t i me
to be recognized and attract the atte ntion of c u rators.

E m p i rical Conservation

U n t i l recently, the emphasis placed on the usage val u e of p hotographic

i mages promoted the development of a n empirical practice of conservation
as well as the publ ication of numerous u nverified " m i racle" recipes. Certain
otherwise very serious works on the history of photography do not hesitate to
provide con servation formulas that are now banned for their long-term harm­
fu lness . 1 0 Photographers and collectors widely used such formu las-many
oxid ized daguerreotypes were recklessly treated in chemical solutions i n this
way. These procedu res, appl ied to achieve i m mediate aesthetic results or

60
 R eading 10 C A ll T I E H - ll ll E S S O N

s imply to recapture some lost i n formation, have created spec i fi c new deterio­
ration problems. \Vhi l e as of the 1 920s , p hotographic i ndustry research labo­
ratories provided a great deal of help i n u nderstanding complex deterioration
phenomena, 1 1 their primary goal was to resolve problems related to the prod­
u cts made by the compan ies with which they were affiliated. 1 2 Designed for
modern materials, their treatments i l l -advised ly u sed on h i storical originals
someti mes produced catastroph ic res u l ts . 1 3 U nrestrained experiments were
performed on original p hotographs, since they were abundant and had l ittle
market val u e .
I t is t h e same u nawareness of the h istorical and physical nature of an
original that leads some, sti l l today, to confuse betwee n reproduction and
conservation of originals! 1 4

P l a c i ng Photography Back in its H istorical Context

In the 1 960s and 1 970s, first in the U . S . and then i n France, the poi n t of
view on the c u ltural and h istorical rol e of photography began to change.
But many i mages had already been lost due to negligence and spontaneous
deterioration. This renewed i nterest i n old photograph ic prints, along with
the awareness of their progressive d isappearance, contrib u ted to i ncreasing
their symbolic and commercial value. The movement, which wou ld spread to
modern a nd contemporary photography, gave birth to a specialized marke t 1 5
and contributed t o defin i ng t h e d i fferent types o f prints (original print, vin­
tage print, reprint, duplicate, etc. ) as wel l as their respective quali ties (for­
mal and tec h n ical aspects, state of preservation, etc . ) .
A s t h i s market grew, i nstitutions were rediscovering t h e n i neteenth­
century masters of photography; special ized collections were being put
together, 1 6 while other collections, whose richness was sometimes i mpressive,
were being reorgan ized, often thanks to the i m petus of public expectations.
Studies and research on photography were also increasing. The si mple
h istory of techniques was enr i ched by i ncorporat i ng the aesthetic, cu ltural,
and d idactic d i mensions of the i mage. 1 i
Consideration was given to the connections between h istorical mate­
rials and formal content o f the works, to the metamorphoses of "form as
it passes from one materia l to another," 1 8 and to the relationship between
tech nical c hoices and the particular aesthetic of the i mage. 1 9 Taking into
account the actual material of the i mage, and not just its descriptive quali­
ties, req uires a c onstant going back to the original print.
From this perspect ive, the deterioration of prints becomes a critical
issue for researchers and amateurs who are confronted with an object that
is more and more rarely visible i n its original state, to the point of prevent-
P art I 1-l l S T O l1 Y O F P l l O T O G l1 A P l l C O N S E H V 1\ T I O N

i ng its prope r evaluation. The very basis for this way of t h i n ki ng about the
history of photography is weakened by the t ran sformation of i mages-whether
gradual or brutal ly sudden-that took place i n the past century. The wel l­
known example of the yel l owing of albu men prints shows just how false an
idea we can get of their original appearance after less than a century. 20
Yet, the evaluation of deterioration is often subjective. \Vhile some
alterations seem to affect the ''essence" of the i mage, others a re conside red
acceptable and even contributing to the bea uty of the i mage . It is the form
and nature of the i mprint of time that determines whether the critical j udg­
ment goes toward "travesty"2 1 or "patina of age . "22
U n fortu nately, the deterioration of i mages can lead to a complete l oss
of their bea uty and even to a complete loss of the i n formation they conta i n .
It is t h rough t h e awareness of these problems a n d t h e attention devoted
to the p reservation of public collections that a new concept of conservation
of photographs has ari sen , which req u i res spec ialization and fa l l s within the
general context of preservation of a rtworks.

A N ew Concept of Conservation

Conservation pract ices, therefore, evolved with the advent of a market for
photography as wel l as a reAection and resea rch on i mages and their h is­
tory, b u t also with the changes that affected the very concepts of conserva­
tion. After \i\lorlcl \!\far I I , a critical trend arose in the field of con servation,
which paid a new kind of attention to the history of art and to aesthetics. 2 3
From this perspective, the goal of conservation was no longer to repai r or
renovate objects in order to adapt them to the style of the clay or give them
a u sage va lue. On the contrary, if the material is i nd issoc iable from the
meaning of the work, its i ntegrity must be respected . Critical conservation
no longer obeyed only techn ical criteria, but took the global nat u re of the
object i nto accou n t : its history, 24 its c u l t ural context, its aesthetics, and its
evolution over t i me. 2 5
For the last twenty years, other considerations-essentially coming
from Anglo-Saxon countries-have made preservation a priority as one of
the main elements in the conserva t ion of artworks.26 Taking i nto accou n t
cha nges in critical judgment a nd avoiding abus ive or overly subjective
practices led to li m i ti ng conservation to safeguard i ng the actual physical
ent ity of the artwork and preserving it over the long term . 2 7 These minimal
in terventions-''less is more" could be the new conservation motto-must
be reversible and scientifically control lecl. 28 This presupposes a m u l ti d is­
cipli nary approach to problems, an appropriately poi nted use of scientific
in struments, and special ized tra i n i ng in each of the Fields i nvolved.
 Reading 10 C /\ H T I E R - B H E S S O N

From Product Stab i li ty to the Conservation of Artworks

These n ew conservation concepts were progressively extended to the field

of photography. 2 9 The recognition of the material and h istorical specific­
ity of photographic images is a recen t phenomenon, dating back some ten
years, and is the result of a movement that arose within specialized public
i n stitutions in North America before arriving in E u rope .30 This movement,
spearheaded by conservation professionals with train i n g related to photo­
graphic material s , rel ied o n a close cooperation among i nd ustry profession­
als, sc ientists, conservators, and c u rators , who met regul arly at national and
i n ternational conferences or in research groups.31 Such exch anges of infor­
mation and experiences are all the more n ecessary i n that the divers ity of
photographic materials- i n and of i tself a source of artistic wealth-makes
conservation extremely complex. I n addition to knowledge of the reactions
i nherent in each type of m aterial, conservation requ i res a familiarity with
p hotographic c u lture, which is n ecessary to identify and understand the i mag­
es.3 2 \,Yh ile photographs can genera l ly undergo conservation wit h the ordi­
n a ry resou rces of a processing center, sometimes they also req u i re the more
i n -depth analytical methods of a research laboratory. 33
G u ided by a scientific and critical approach, the goal of conserva­
tion i nterve ntions 34 is to reestablish the p hysical and chemical in tegrity
of the i mage through various treatments for the mechan ical consolidation
or elim ination of chemical stains.35 Whi l e m i n i m al i n te rventions are pref­
erable, other, more in -depth interventions are used with caution and o n ly
after eva l uating their long-term effects on the i m age and i ts support. 36 I n
the case of a collection, rather than aggressive treatments, i t i s preferable
to i mplement a general conservation policy that e l i m i nates the causes of
deterioration by acting directly on the i mage and its environment. 37 Thus,
a n i ndividual treatment of plates or prints i n a collection w i l l occu r onl y
i n t h e context of gen eral conservation measu res t h a t are determined based
on the past, present, an d future use of the artworks. S ince handling is one
of the pri mary deterioration factors, periodic treatments and i nspections of
assets should be supplemented by preven tive measures, e.g., dupl ication of
n egatives and reproductions of artworks so that duplicates may be used for
ord i nary viewi ng.38
Despite its difficu l ties and delays, the con servation of photographs has
made marked progress since it was recognized as a specialty field. Adm i t­
tedly, certain empirical practices are still used on originals, but these are
i ncreasingly marginal an d a remi nder of the al l too often secondary place
of p hotography within the h ierarchy of cultural val ues. The s t i l l precarious
position of this new discipline in E u rope and its nonexistence in n u m er-
P art I 1-1 I S T 0 H Y 0 F P II 0 T 0 G R A P II C 0 N S E B VAT I 0 N

ous coun tries bear witness to the obstacles that a fu l l official recogn ition of
photography sti l l faces. Yet, today, the enth usiasm for photography and its
i ncreasingly i ntensive use threaten it as much as the indifference it experi­
e nced yesterday-this is part ic u larly true for p ri n ts from the last century.
Sati sfying the new pass ion for photography and protecting the artworks from
its destructive effects are the raison d'etre of conservation.

Notes

1 Just a few months after publication of the daguerreotype, the French

government financed a "daguerreian" can1paign to African coasts. See
E. Ostroff, " Herschel and Talbot: Photographic Research," The Jmirnal
of Pliotograpliic Science, Vol . 27, 1 979.
2 "One of the most interesting appl ications of photography is the Faithfu l and
unquestionable reproduction of monuments and of historical or art istic
docu ments that time and revolutions always end up destroying [ . . . I so that
photography may ful fi l l the great hopes that it has aroused i n this regard we
must, above a l l , be certai n that prints will be preserved indefinitely. " " Rapport
relatif a u prix fonde par J\11 . le due de Luynes" [ Report on the prize established
by t he D u ke de Luynes ] , B u lletin de la Societe .fran9aise de p hot.ograp'1-ie, Paris,
1 856, 2 1 4- 2 1 8 .
3 ''One of t h e most common criticisms o f photography is the i nstability o f i ts
products. Too often [ . . . ] these beautiful plates I . . . ] are gradually degraded
by light and end up disappearing. This u n toward outcome is a discredit to
p hotography and makes the p u b l i c d i sgusted with i t ." J ury report, U n iversal
Exposition of 1855.
4 G ustave Le G ray, Pliotographie, t.raite 1101111eat1 t. heorique et pratiqHe
[ Photography, new theoretical and practical treatise], Paris, 1 852. Le G ray
asserts that if "a print is beau t i fu l and complete and d u rable, it acq u i res
i ntrinsic val u e . "
" F i rst report of the Committee appointed to take into consideration the
question of the fad i ng of positive photographic pictures upon paper, "
The Joun1al o.f Tiw Photographic Society, Vol. 36, London, November 2 1 , 1 856;
A. Davanne and J. G i rard, " Note sur les causes qui amenent ! 'a l teration des
i mages photogra p hiques posi tives ct sur u n moycn de les revivifier" [ Note on
the causes of deterioration of posit ive photographic images and on a method
for reviving them ] , Comptes rendus hebdornadaires de l'Acade111ie des sciences,
Paris, Octobe1· 22, 1 855.
6 See A. Davannc and J. Girard, op. cil . ; Gustave Le C ray, " Procedes nouveaux
pou r obtenir des cpreuves pos itives S U I' papier d'unc coloration t l'CS variee
et d'une fixi te p l u s complete q u c par les anciens proccdes" [ New processes
for obtai n i ng positive prints on paper wit h very varied coloration and more
complete stabil i ty than with former processes] , La Lmn.iere, No. 8, Paris,
February 14, 1 852.
7 " Report on the prize established by the Duke de Luynes," op. cit .
8 J . i\tl . Eder, 1-/istory of Phot.ogrnpliy, Dover, New York, 1978, reprint.
 Reading 10 C A R T I E ll - B ll E S S O N

9 C . Homer, "Some notes on the past, present and Future of photographic

conservation," 1nrnge, Vol . 27, No. 4 , Hochester, December 1 984.
10 H. Taft, Photography and t he American Scene, Mac m i l la n , New York, 19 3 8;
C . B . Newh a l l , Tl·1 e Dag11erreotype in. Ainerica, 1 96 1 , Dover, New York, 1 976,
rep1·int.
11 The earliest, that or Eastman Kodak, was charged with "studyi ng the scientific
principles of p hotography, t he development of new photographic materials,
and the d iscovery of new appl ications for photography." K. M ees, "The
Kodak Hesearch Laboratories,'' The Photographic Society of America joHrnal,
Vol . i 5, '949·
12 J. I. Crabtree, " Les taches des c l ichcs et des eprcuves photographiques,
leurs causes, comment Jes eviler, comment Jes faire d isparaltre" [ S tains on
photograph i c plates and prints, their causes, how to avoid them, and how to
make t hem disappear), La Revue fran.i;aise de photograph.ie, Paris, May 1 , 192 1 .
1 3 A . Swan, "Conservation o F Photographic Prin t Collections,'' Libra1y Trends,
Vol. 3 0, No. 2, 1 98 1 .
14 I n t h e press, w e s t i l l find ads For "restored" photographs t hat arc actually
reproductions made using optical methods, which restore i n formation t ha t was
masked on the degraded original.
1 5 C . Barriere, " Les photographies, q u e val e nt-elles?" [ P hotographs, what are
t hey worth ? ) , Co1rnaisscm.ce des arts, No. 29 3 , 1 976.
16 J .-C. Lemagny, " Des an nces soixa nte aux a nnees soixantc-dix: !'expa nsion de
la c u l ture photographique" [ From the sixties to the seventies: the expansion of
the c u l tu re of photographyl , /-listoi.-e de la photogra71hie, Bordas, Paris, 1 986.
17 J.-F. Chevrier, " La Photographic clans les musees'' [ Photography in museums],
Art. Press, Paris, November 1 986.
18 1-1. Foci lion, " Les Formes clans la matiere" [ Forms w i t h i n matte r ] , \lie cles
.fon11es, P . U . F . , Paris, 198 1 , 7th ed.
19 A. J ames and E . Parry J a n is, The Ari of French Calotype, Pri nceton U niversity
Press, 1 986. Some books have recently been emphasizing t h i s aspect oF t he
h istory of photography. Suggesting t he superior status that the early i mages o n
paper acqui red i n France, A. James and E . Parry J a n i s note: " O u r i nterest i n
t hese p hotographs derives from a n allraction to their beauty, den ned i n part
by t he manner in which the world leaves its trace o n their chemistries and
malcrials."
20 J . H c i l ly, N . Kennedy, D. B lack, and J . Van Dam, " I mage structure and
deterioration in albumen prints," Photographic Science and Engineering,
Vol. 28, No. 4 , 1984.
21 1-1 . Foci l lon, op. cit .
22 J. C u i llerme, L"Atelier cl.u te111ps: essai s11r l'alteralio11 des peintw·es ! The
workshop of time: essay on the a lteration of p a i n t i ngsJ, Herman, Paris,
1 984.
23 C. Brandi, Teoria de/ restauro [Theory of conservation I , E i naudi, Turi n
1 977, reprin t ; C. Carbonara, " P h i l osophie de la reslauration" [ Ph i losophy of
conservation ] , JV/011.1111ie11ts h.isloriq11es, No. 1 49, January-February 1 987.
24 H. 1-1 . i\t l arijn i ssen, Degradat ion, conservation. el; restauration. de l'oe11vre d'art
l Degradation, preservation and conservation of artworks ] , Arcade, Brussels,
1 967.

65
Part I H I S T O R Y O F P H O T O G R A P H C O N S E R V AT I O N

25 P. P h i l ippot, "H istoric Preservation: P h ilosophy, Criteria, Guidelines,"

Preservation and Conservation: P.-i.nciples and Pract ices, North American
I nternational Regional Conference, \�l i l l iamsburg, September 1 972.
26 S . \i\lalden, T1ie Havished Tniage or /-low to Ruin Mast.erpieces by Hest.ora t ion,
\i\lei denfeld and N icolson, London, 1 985.
27 "Conservation can not be allowed to become s u bject to fash i o n . Any move away
from the values of p reserving the evidence of the original nature of historic
objects m u s t i nvolve destroying that evidence.'' J. Ashley- S m i t h , 'The Ethics
of Conservation , " Tiie Conservator, No. 6, London, 1 982.
28 "The process and products used m u s t be chosen based on their o p t i mal
compa t i b i li ty with the object and their stabi l i ty over t i me. Due to the evolution
of conservation and the techn ical progress to come, the treatments initiated
respect the principle of reversibility to the extent possible. Their action should
allow for future treatments and access to i n formation by way of scientific
exa m ination." "Charle frarn;aise de la restauration" [ French Conservation
Charter) p u b li s hed by the French Section of the I nternational I nstitute for
Conservation, I IC.
29 I. M oor, 'The Conservation and Restoration of Photographic I m ages,"
lnst.itu.te for the Conservation of C u lt. u m / M aterial Bu./. let;in,
Vol. 10, No. 1, 1 984.
30 K . Hendriks, D. Hess Norris, and J. Reilly, "Photograph Conservation: The
State of the Art," A . I .C. Preprints, C h i cago, M ay 2 1-25, 1 986.
31 Society of P hotographic Scientists and Engineers ( S P S E ) International
Sympos i u m : "The Stability and Preservation of Photographic I mages," Ottawa,
1 982, 1 985; " P ioneers of Photographic Science and Technology," Rochester,
1986.
32 ]. Reilly, Care and Identification of 1 9 t. h-Century Photographic P1·int.s, Eastman
Kodak Company, 1 986.
33 A. Cartier-Bresson, "Techn iq u es d'analyse appliques aux p h o tographies
d'Eugene Atget conservees clans Jes col lections de la Ville de Paris'' [Analytical
tech niq ues applied to the photographs of E ugene Atget preserved in the
collections of the C i ty of Paris], Trien n ial meeting of the ICOM Committee
for Conservation, Sydney , 1 987.
34 A. Cartier-Bresson, "Les D i vers N iveaux d ' i ntervention en restauration des
p hotograph ies" [The various levels of i n terven tion i n the conservation of
p hotograph s ) , Conservation et resta uration du pat.rhnoine p hotogra·p hiqiie,
B u reau of C u l tu ra l Affairs of the City of Paris, Paris Aucliovisuel, Paris, 1 985.
35 S. Rempel, "The Care of B l ack-and-White Photographic Col lections: Cleani n g
a n d Stabilization," Canadian Conservation Tnst.itu t.e Technical B u llet.in, No. 9 ,
1 980; I<. Hendriks , B . Tom, C. Sergeant, C . Evans, J . M e l ni c k, P. Poitras, a n d
D . N is h i m u ra, " Experiments on t h e Restoration of' Discoloured B lack-and­
White Photographs i n Chemical Sol utions," Triennial meeting of t he I C O M
Committee for Conservation, Copenhagen, 1 984.
36 A. Cartier-Bresson, " Les Papiers sales: alteration et restauration des premieres
photograph ies sur papier" [Salted paper: deterioration and conservation
of early photographs on paper] , Consei-vation et, restau ration cl-u pat.ri ·1noin.e
photographique, B u reau of Cu ltural Affairs of the City of Paris, Paris
Audiovisuel, Paris, 1 984.
37 i\11 . G i llet, C. Garnier, and F . F l ieder, " I n fl uence de l'environnement sur
la conservation des documents photographiques modernes" [ Influence of

66
 Reading 10 C A R T I E R - ll ll E S S O N

the environment on the preservation of modern p hotographic doc u ments ] ,

Trienn ial meeti n g o f t h e I C O M Committee for Conservation, Ottawa,
1 98 1 ; A. Cartier-B resson, " La Protection des p hotographies clans le cadre
d'une exposi t i o n ou d ' u n archivage de longue clu rc�e" [The protection of
p hotographs in the context of an exh ibition or of long-term arc h ival storage ] ,
L a Mission pliotographique d e l a DATAR, Paysages-photog.-a·p hies, Hazan,
Paris, 1 985. Regular p u b l ication updates of national norms (AF N O R ,
A N S I , D I N, e t c . ) a n d i n ternational I SO standards make i t possible t o stay
i n formed on recommendations on archivation issues as wel l as processi ng
and manufacturing p hotographic pictures. See Association fran\:aise de
normalisation (AFNOR), Recueil de norm.es franqaises: opU .que, pliotographie,
cinematographie, A F N O H , Paris, 1 980.
38 M. L. R itzenthaler, " M a naging a Photographic Copy Service," Acln·1 inistration
of Phol.ographic Collections, Society of American Archivists, C h i cago, 1 98+
 R e a d n g 11

C O N STAN C E M c CAB E A N D
L I S HA D E M I N G G L I N S MAN

Understanding Alfred S tieglitz'

Platinum and Palladium Prints :
Examination by X-ray Fluorescence
Spectrometry ( 1 995)

As the field of photograph conservation began to nwture i n the 1980s, so did

the sci.entifi.c examination of photographic materials. X-ray fluorescence spec­
troscopy (XRF) is a technique used for elemental analysis of art objects. This
form of analysis does not require that a sample be re·moved from the object
being examined and is therefore described as nondestructive. One of the earli­
est publications on the use of XRF to exaniine photographs, "Non-destructive
Elemental Analysis of Photographic Paper and Emulsions by X-Ray Fluores­
cence Spectroscopy, " was published by James Enyeart et al. i.n 1 983. It sunima­
rizecl the qualitative analysis of blach-ancl-white and color 11hotogmphs frnm
the Center for Creative Photogmphy Collection at; the University of Arizona.
In the introduction to that reference, the authors note that "an elemental pro­
file may be used to characterize these special e1nulsions, to identify falws and
to elate prints. " Although the focus of the reading reproduced here was not
authentication but rather proper identification, both goals contin·ue to moti­
vate twenty-first-century i.nvestigations such as the research conducted at the
Getty Conservation Institute and by Paul Messier to characterize certain fea­
tures of twentieth-century photographic paper (see Reading 13). The worh pub­
lished here is one of several collaborative projects in which Constance McCabe,
senior photogra11h conservator, and Lisha Deming G linsman, conservation sci-

CONSTANCE M cCABE and L 1 s 1- 1A D E M I N G C LI N SMAN, " U ndersta n d i n g A l Fred Stieglitz'

P l a t i n u m and Palladium Prints: Exam i nation by X-ray Fluorescence Spectrometry,"
Research Tecliniq11es in Phot.ographic Co11servat.ion. ( M ay 1 995): 3 1 -40. Origi n a l l y p u b l i shed
in u nabridged form in Conservat.ion Research, S111dies i11 the HislOIJ' of Ari, Monograph
Series 11 (Wash i ngton, DC, 1 995) 5 1 : 70-85. Royal Danish Academy of F i ne Arts School
o f C o n servat i o n I © 1995 Trustees of the National Callery of Art, Washi ngton. Text and
i mages rep ri nted b y permission .

68
 Reading 11 fVI C C A l3 E A N D G L I N S M A N

entist at the National Gallery of Art, Washington, D . C . , used X R F to exaniine

photographic materials. It was chosen because it sought to define an analytical
protocol for using X R F specifically on photographic materials.

I ntroduction and Background

Alfred Stieglitz ( 1 864- 1946) was one of the leadin g ex'Perimenters and i nno­
vators in p hotography, known for h i s aesthetic vision and h ighly respected as
a p hotographic chemist. At the turn of the century, he pub l ished extensively
o n the platin u m printing process and i ts many variants. He used this process
a lmost exclusively u n t i l the increase in the price of p latin u m during \Norld
War I made plati n u m papers nearly u nobtainable. The u navailabil i ty of plati­
num gave rise to an a lternative process, which substituted salts of pal ladium
for salts of platin u m , to produce the l ight-sensitive photograph i c paper.
Stieglitz' tech nical publ ications describe many of his early approaches
to the platinum process, inc l uding generic recipes for sensitizers, developers,
and toners and other variations in h i s darkroom tec h niques. 1 U n fortu nately,
he published nothing regarding his use of the pallad i u m process, and men­
tions of it in h is personal writings are ambiguous. 2 Despite his tra i ning as
a scientist, i t appears that Stiegli tz did not systematically record his p hoto­
graphic experiments or the spec ific methods by which his i ndividual prints
were made. Stieglitz' p u b l ished l i terature is a val uable aid for u nderstan d i ng
the ge neric approaches h e used to produce his platin u m photographs. H ow­
ever, that no other records exist regardi ng his extant platin u m or palladi u m
prints i s u n fortu nate from t h e perspective o f a p hotograph conservator who
m u s t deal with a photograph as a p hysical object made of a complex com­
ponent structure . U n li ke some other p rocesses, platinum prints, pallad i u m
prints, a n d variants o f these processes are freq uent ly i n distinguishable by
their appearance alone; the chemical nature of Stieglitz' prints simply can­
not be accurately or completely described by visual examination.
The National Gallery of Art, \i\fashington , is fortu n ate to house the
largest existing collection of photographs by Alfred Stieglitz, selected from
his estate by Georgia O'Keeffe as the "key set" of his finest fi n ished work.
Responsible approaches m u st be taken to preserve these artisticall y a nd
h istorically i mportan t p hotographs b y maxim izing t h e ir longevity and con­
tinued availability for viewing without sign ificantly altering their physical
c haracteristics. To accomplish this goal a conservator must be fam i liar with
the artist's aesthetic i ntent. Equally i mportan t , however, is a n u nderstand­
ing of the p hysical and chemical nature of the p hotograph to be treated or
displayed. A reasonable u nderstan di n g of the chemical and physical n ature
of a ny work of art or h istorical artifact is essential for making decisions
P art I ll l S T O H Y O F P l-I O T O G R A P l l C O N S E H V 1\ T I O N

regarding i ts preservation and exh ibition needs and for approaching conser­
vation treatment. Disastrous fadi ng or darkening could result, for example,
from the exh i bition of a l ight-se nsitive p hotograph that is misidentified as
one that i s stable to l ight.3
Secondary em ission energy-d ispers ive x-ray fl uorescence spectrometry
(XRF) has been used with some success in the past to gai n a better u nder­
standing of the chemical nature of the F111 a l i mage in photographs. 4 The fol­
lowing are results of n ew research fu rther deve loping an a nalytical protocol
designed specifical ly for the u se of XRF i n studying p hotographic i m age
materials. This n ew protoco l has been successfully used to determ ine what
metal l ic elements make u p the fi nal i mage in some of t he photographs in the
collection of the National Gal lery of Art. The res u l ting data h ave served to
extrapolate methods of produ ction that Stiegli tz m ight have used to fabricate
his plat i n u m and pal ladiu m p hotographs.

T h e Platinum a n d Palladium P r i n t i ng Processes

The plati n u m printing process was favored by many turn-of-the-century

photographers, i nc l u d i ng S tieglitz. Wi l l i a m Crawford's excellent description
of the process i n The Keepers of Light is i n dispensable in assi st i ng modern
practitioners to recreate early photographic processes. 5 The first step i n pro­
ducing a photographic paper is to coat it with a sensitizer. Platin u m pri nting
paper is sensitized with a n aqueous solution of one of the platinous com­
pounds, genera l ly sod i u m tetrachloroplati n i te tetrahydrate, N a2 PtCl 4 ·4I-1 2 0,
or potass i u m tetrac h loroplatinite, K2 PtCl 4 (someti mes referred to in the l i t­
erature as sod i u m or potassiu m ch loroplati n i te , or as sod i u m or potassi u m
tetrachloroplatinate), a n d ferric oxalate, Fe 2 ( C 2 0J3· 5 H 20, which i s allowed
to dry. This l ight-sensitive paper is then placed in contact with a negative
and exposed to l ight. The action of l ight converts the ferric salts to ferrous
salts that gradu ally become vi sible as a weak printed-out i mage . The print is
then placed i n a potassi u m oxalate developer t h a t serves t o dissolve t h e new
ferrous salts, FeC 2 04 ·2I-1 2 0, thereby reducing the potassiu m tetrachloro­
platinite to metallic platin u m . The action of development completes the
i mage-forming process. Any u n exposed and soluble ferric salts i n the print
are t h en el im in ated b y convertin g them to ferric ch loride by clearing (or fix­
ing) the print i n a d i l u te hydrochloric acid solution. These soluble iron salts
are removed i n the final water wash. I n other words, this process uses the
l ight-sen s i t ive properties of an i ron ( l l l ) compound, which, on ex'Posure to
l ight, is red uced to an i ro n ( I I ) compound, which in turn has the abil ity to
reduce a compound of plat i n u m to its metallic state. When this procedu re is
properly carried o u t , the fi n a l i mage of a platinotype consists of chemically
stable, fi nely d ivided meta l l ic plati n u m .
 Reading 11 M C C A B E A N D G L I N S M A N

The primary difference between palladium prints and platin u m prints

1s that palladium salts replace the salts of plati n u m in the sensitizer. The
p a l lad i u m compounds generally used to sensitize the paper are in the form
of potassi u m tetrachloropal ladite, K2 PdCl4 , or sod i u m tetrachloropal ladite
trihydrate, N a2PdCl4 · 3 H 2 0. The che mical processing of pallad iu m prints is
similar to that of the plati n u m process, but the resu lt i ng final image consists
of metallic pal lad i u m . 6
Because o f the sim ilarity o f t h e chemical processes used t o produce
p l a t i num and pa lladium prints, the variants of both processes are also vir­
tually i n terchangeable. These variants can i nclu de n u merous chemical
formu lations of sensitizers, developers and toners; variations of the length
of a print's exposure; or va riations of the developing sol u tion tempera tu re.
The variants of both processes were used to manipulate the image h u e
a n d tonal properties. S tieglitz conti nually experimented with these chemi­
cal variants to achieve very specific aesthetic results. V\!h ile h e mastered
both processes, he considered the plati notype to be "that pri nce of all pro­
cesses,"7 and it took years for h i m to accept the palladium process as a viable
s ubstitute for plati n u m .
Platin u m prints tend t o have a neutral gray-black i mage hue, whi l e
palladi u m pri nts are generally slightly warmer i n hue. H owever, depen d­
ing on variations i n processi ng, such as temperature of the devel oper, the
i mage h u es of either process can be manipu l ated to range from cool, slightly
purple-black to a very warm brown. Modifying standard processing pro­
cedures, such as a l tering the form u lation of the sensitizer or developer or
employing chem ical toning or i n tensi fication , can resu l t in a wide variety
of hues. One possible modification of either process is toning the fi n ished
print with gold. Gold toni ng can change a warm i mage to black or purple­
b lack. I ntensifiers, such as a combination of gal l ic acid and silver n itrate,
h ave been u sed to change the image color, i ncrease the i mage contrast, a nd
highl ight the detail o f a fi nished p r in t . I n add ition, any of these modi fica­
tions can h ave a n i mpact o n the chemical stability of photographs and resu l t
i n cha nges i n t h e appearance o f prints over time. F o r example, toni ng with
compounds such as u ra n i u m can change the color of the image to reel, green ,
o r blue o r can even resu l t in split tones i n a pri nt. H owever, ura niu m t oning
is known to result i n gradual changes in the appearance of a fi n ished print.
B y 1 9 1 1 it was known that the use of u ran iu m as a toner "does not give very
perman e nt res u l ts."8
To S tieglitz, a n i mportant feature of the basic, u n modified platin u m
process was i ts permanence when com pared, for example, to t h e silver pro­
cesses, such as salted paper prin ts, a l b u men prints, or gelatin prints. I n a
1 902 article he said, "\,Ye hear m u ch of the permanence of the plati n u m
print, a n d while it is u n dou btedly true that a careful a nd conscientious

71
Part I 1-1 I S T 0 R Y 0 F P 1-1 0 T 0 G R A P II C 0 N S E R \! A T I 0 N

tec hnical handling of the process wi l l in sure a pri nt practically as permanent

as i ts paper support, yet with modern sloppi ness this is no longer true."9
H e acknowledged, however, the val u e of other, less permanent processes:
"I willingly gran t that 99 per cent. of the negatives produced by the ' camera
artists' ought to be printed o n a m ost nonpermanent process, for the sake of
coming generations." 1 0

I de ntification of Photographic Processes

It is frequently possible to distinguish the process by which a p hotograph was

made just by looking at it. In general, a n ex']Jerienced observer can recognize
the difference between an a l b u men pri nt and a gelatin prin t and can further
differen ti ate between the prin ted-out versus a developed-ou t gelatin prin t . 1 1
Some p hotographs, however, are difficult or i mpossible to identify visually
in terms of process. S in gle-layer p hotographs i n which the fi nal image exists
in t he u pper surface of the paper su pport, such as platinum and palladi u m
prints, can be particularly difficu l t to identify.
As disc ussed, varyi ng the chem ical form u lations used to produce plati­
num and palladium prin ts resu lts in a variety of i mage appearances; therefore,
visual identification is complicated. For example, plati n u m prints (consid­
ered cool or neutral in hue) can be made warm by the addition of a mercu ry
compound to the developer. Conversely, a warm hue is usually associated
with palladi u m prints. Cooler h ues, however, can be attained by developing
or toning the print in various chemical solutions or at different temperatures,
as described above. Because of these variations, platin u m prints sometimes
masquerade as palladiu m prin ts, and vice versa. Tn some cases, a salted paper
print might be confu sed with a platinum or pa lladi u m pri n t . F u rther com p l i ­
cating t h e issue, m a n y silver gel at in prints were manu factured t o m i m ic the
appearance of p l at i n u m papers and other historic process types. In addition,
visual exami nation alone can not determ ine what chemical toner might have
been u sed to alter the origin al appearance of a pri nt .
P hotographs t h at have an a m biguous appeara nce require more than
visual examination to determine the components that make up the final
image . The in A u ence of so many factors produces a n almost i n fi nite vari­
ety of n u a nces and su btleties in the appearance of different types of photo­
graphs. It is this enormous variety of processes and final appearances that
has led even experienced observers to t urn to chemical a nalysis, such as
examination by XRF, for objective i n format ion . This i n formation is especially
u seful for prin ts made by a n u nknown photographer or by a n experimenter
who kept no records, such as Alfred Stieglitz.
XR F is a wel l-established analytical tech n ique that provides rapid,
simu l taneous m u ltielement analyses in many applications. Because of its

72
 Reading 11 M C C A B E A N D G L I N S M A N

nondestructive capabi lities, it has proven val u ab l e in the study of art objects.
To use XRF for the study of p hotographs of u n known composition, it is
i mportant fi rst to determ i n e if the very small traces of elements that m ake up
the photographic image can, in fact, be detected by the i nstrument.

Fabrication of P hotographic Facsimi les for Use as XRF Standards

I n using XRF to analyze photographs, it is essential to maxim ize the sensitiv­

i ty of the i nstrument to any rel evant element that m ight occur i n the fin a l
i mage material . For t h i s reason, facsimile photographs o f known composition
were produced and analyzed by XRF, and the detection of the known i mage
materials was optimized. It was determi ned that the elements that m ade u p
t h e i mage in the known samples could, in deed, b e detected b y XRF. A s a
result, a protocol was developed that u sed the facsimi les produced by known
chemical processes as a na lytical standards. These standards were compared
with several Stieglitz p hotographs i n the National Gallery of Art.
To assist in producing analytical standards with which to compare
Stieglitz' prints, photographic working methods of Stiegl i tz and h is contem­
poraries were studied. Stiegl itz general ly used a potassi u m oxalate solu tion
as a developer for his p l at inotypes, to which h e sometimes added glycerine to
delay the action of the developer and a mercu ry compo u n d applied loca l ly
to modify the image hue. 1 2 He was also known to use u ra n i u m compounds
to tone his platinum prints . 1 3 Salts of gold and even iridi u m and osm i u m
were also mentioned i n contemporary handbooks for use a s toners for plat­
i n u m prints. 1 4 Therefore, the presence of any of these elements could be
attribu ted to the developer or to a postprocessing to ni ng treatment.
Early i n his career, S tiegl i tz experimen ted with sensitizi ng his own plat­
i n u m paper. For most of his platin u m work, however, he used commercially
prod uced, p resensitized photograph i c papers. He carried out h is chemical
processing experiments u s i ng commercial papers, i nc l u d i ng those made by
E astman Company (American Plati n u m Paper), 1 5 the Platinotype Company,
a nd Willis and Clements. 1 r' While Stieglitz described the inclusion of "lead
chloride or a m ercury salt to the sensitizer" in a patent b y W. Wi llis as an
i mprovement of the process, 1 7 very l ittle is known about what papers were
u sed to produce specific pri n ts. B ecause commercially manufactured papers
were made with a variety of chemical sensi tizer formulations, it is possi b le
that along with metallic platinum or pallad i u m , lead or mercury m ight be
present as part of the fi n al i mage.
H ydrochloric acid was generally u sed for the cleari ng or "fixi ng" baths,
followed by a ru n n i ng water wash . I f fresh baths of hydrochloric acid were
used u n til the pri nt was thoroughly c leared, followed by a water wash that
thoroughly removed residual processi ng chemicals, the i mage in the fi n a l

73
Part I 1-l l S T O R Y O F P H O T O G R A P l-1 C O N S E H V /\ T I O N

pri n t should consist of metallic plat i n u m and/or pallad i u m possibly i n combi­

nation with traces of mercu ry, u ra n i u m , or other elements that were depos­
ited on the pri mary i mage clue to chem ical reactions of the sensitizer, along
with the developer and possible toners.
There are many ways to produce plati n u m and palladium prints and
their variants. However, the bas ic rec ipes used for sensitizers, developers,
and toners are s i m i lar in many h a ndbooks a nd journals of Stieglitz' time.
For this reason, facsi mi les of processes that may have been used by Stieg­
l itz were prod u ced by the author ( McCabe) accord i ng to rec ipes given by
Crawford in The Keepers of Light . 1 8 These rec ipes were selected beca use
t hey are chemically sim i lar to those given in early descriptions by Stieglitz. 1 9
Although Stiegli tz d i d n o t incl ude sod i u m sulfite i n h is 1 893 rec ipe for ura­
n i u m toner, 2° Crawford's reci pe is virtually identical to one descri bed in 1 902
by James M cCorkle in Caniera Notes, 2 1 both of which refer to the crystal of
sod i u m sulfite to be u sed as the s ize of a "pea." The photographic facsimi les
were emp loyed as XRF standards for com parison with the Gal lery's Stieglitz
Collection photograph s . They are :

• platin u m pri n t
• palladi u m prin t
• combination plati n u m/palladium pri nt ( 50:50 ratio)
• palladi u m print, mercury developed
• combi nation plati n u m/palladium pri nt, merc u ry developed
• palladiu m pri nt, gold toned
• palladiu m prin t , si lver intensified
• pallad i u m pri nt, u ra n i u m toned

X-ray Fluorescence Spec trometry and Photographs

The i n terpretation of the XRF spectru m of a p hotograph can be better u n der­

stood with some basic i nformation on how X R F works. XRF used x-rays for
sample excitation. X-ray p hotons that are directed at a sample, such as a
photograph, i nteract with atoms i n the sample. As an x-ray travels through
a sample, it may be absorbed, giving up its energy to a sample e lectro n that
escapes from its orbital, leavi ng a vacancy. The atom is then in an unstable
(excited) state. To regain stability, a n electron from an outer shell drops i n to
the i nner shell vacancy, em itting x-rays as it does so. The atom is said to be i n
the stable (grou nd) state. Each x-ray e m itted h as a spec i fic energy described
by t he energy difference between the exci ted and ground states of an a to m
or i o n . These are referred t o a s transitions. Each element h a s m a n y possible
series of transitions occ u rring simu ltaneou sly. These result in the generation
of the K, L, M (among o thers) transition lines that are observed as peaks on

74
 Reading 11 l\'I C C A B E 1\ N O G L J N S M A N

Range : .. OkeV
Vert= 2 000

Cu

Sn

Sn

Figure 1
Detail of X R F spectrum of a
Pb bronze standard. Note the clear
peaks indicating the presence of
Pb copper, lead, and tin, and the low
Sn

amount of backgrou n d "noise."

�argctA
NI Sn BaCl 2 Also note the very small inelastic

\
BaC12
n Pb scatter peaks related to the

ltlJ
Rh

�
Sb rhodium and t h e barium c h loride
/\J � A A
( Ba Cl,) secondary target
OkeV 40kcV
(vertical scale=2,ooo).

the x-ray spectra. The energies of the electron tra nsitions are c haracteris­
tic of the elemen ts present i n a sample and are detected and recorded as a
series of peaks i n a spectru m by the XRF instru ment. 22
XRF analyses of p hotographs are difficult to i n terpret, due primarily
to the low signal-to-noise ratio, which is due to the extre mely low p hysical
density of the paper support of the photograph as well as the small amount
of metal actually present i n a pri nt. 2 3 When the spectru m for a p hotograph
is compared, for example, to a bronze sculpture, which has a h igh density,
i nterpretation of the distinct peaks foun d i n the spectral data of the high­
density bro nze is relatively straightforward ( Figure 1 ) . H owever, the low
den sity of p hotograph s resu l ts i n a large amount of inelastic scatter in the
spectrum when compared to the small amou n t of metal actually being ana­
lyzed. Th is scatter is seen as a h igh level of background "noise" that dis­
guises the actual spectral peaks. Because these peaks can not be positively
distinguished from the noise, an XRF protocol was developed to m i n i mize
this noise and enhance the spectral l ines of specific elements relevant to the
photographic materials in qu estion.
The detection of either the two major K transition li nes (alpha and beta),
or the t hree major L transi tion li nes (alpha, beta, and gamma) vvas requ i red
in order to confirm the presence of the specific fi nal i mage constituents. The
metals palladium (Pd) and s i lver (Ag), and i mpurities such as calcium (Ca),
i ron (Fe), copper ( C u ) and zinc (Zn) , are deter m ined by the presence of their
series of K transition lines. Plat i n u m ( Pt) and traces of elements that might

75
 Part I II I S T 0 n Y 0 F P H 0 T 0 G H A P II C 0 N S E H V A T I 0 N

Rangc:ZU.:: eV Rangc:'IOkcV
Vcrt=2000

Scaner BaClz
�
Rh
target

.4tll u:V

Figure 2a
Deta il of X B F spectrum of Alfred Stieglitz' Se/f-Porl mil,
Cortiiw, a 1890 pla t i n u m print, probably processed wiLh a
mercury developer, seen with a molybde num ( M o )
secondary targcl. N o t e the s m a l l b u t wcll·dcflncd peaks f'or
platinum ( Pt ) and mercury ( H g) (vertical sca le= 1 1000).
Figure 2b
Detail of XH.F spectrum or same. SCl'll with a barium chloride
secondary ( BaCl2.) target. Note t he indistinct peaks for pbtinum
and the absem.:c of' pa lladium peaks (vertical scale= 2,ooo).

have been u sed in the toner or developer formu lation are identified by the
presence of their series of L transition l i nes. These e lements coul d include
mercury ( H g) , gold (Au ) , or u ran i u m ( U ) ( Figu res 2a and b ).

Developi ng a n X R F Protocol for Analyzing t h e Elemental Content

of P hotographic I mages

To interpret the XRF spectrum of a photograph and determi ne the i mage

material, the elements presen t i n the paper su pport as wel l as those i n the
mounting board must be e l i mi nated from the spectrum so that analysis can
be based on the contribution from the image components alone. A protocol
was developed that acquired a spectrum from a dark region ( maxim u m i mage
density) of the photograph and one from a l ight region ( m i n i m u m i mage den­
sity) . \t\lhen possible, a spectrum from the mou nting board was also obta i ned.
Once the elemental contributions of the photograph's l ight region and its
mount are subtracted from the spectru m of its dark region, the resulting spec­
tru m wi ll characterize those elements used in the final i mage material of the
pri n ting process. The spectra obta ined by analyzi ng the National Gallery of
 Reading 11 M C C A B E A N D G L I N S M A N

Art Stiegl itz photographs were compared to the spectra of the facsimile p ho­
tographs (standards) prod uced accord ing to methodology l i kely to have been
employed by Stieglitz. N ote that in some of Stieglitz' prints there is no i mage
area that has a very low-density i mage ( that is, very light). I n these cases, the
data from the l ightest area were acq u i red, but generally these spectra were
not subtracted from the spectra of the maxim u m density area.
The XRF ana lyses were performed u s i ng a Kevex 0750A spectrom­
eter, which is a freestan d i ng i n strument with the x-ray tube and detector
moun ted on a steel col u m n that allows for vertical and horizonta l movement
of the spectrometer. The photograph is p laced on an easel in front of the
XRF where a laser and i ncandescent lamp are used to focu s o n the desired
sample area. An acryl ic block was placed behi n d the photograph to preven t
t h e x-rays from passing through t h e p hotograph t o the back o f the easel.
S ince the Kevex 0750A is an air path i nstrument, it was not equipped with
a l ight-element detector. Therefore, elements l ighter than s ulfur were not
detected with this setup and are not inc l uded i n these a nalyses. 24
The XRF was equipped with 6 m m col l i mators and either a bariu m
chloride ( BaCl 2 ) or molybden u m ( Mo) secondary target. 2 5 Secondary targets
provide nearly monoch romatic x-rays to exci te the sample and enhance the
spectral l i n es of the el ements analyzed. When the element's spectral l ines
are close to the absorption edge of the secondary target, the e nhancement of
those l ines improves sign i ficantly. After considerable experime ntation with a
variety of X R F conditions and secondary targets, two sets of conditions were
fou nd to be the most u sefu l for detecting the metallic elements relevan t to
plati n u m and palladium photographs. A bari u m c hloride target was i nitially
u sed i n order to differentiate the primary metallic elements of the final i mag­
i n g material, that is, platinum or palladiu m . A m olybde num target, which
i mproves the detection of platin u m an d other relevant metal l ic elements, was
then used to detect the presence of any e lements that m ight be attrib u table
to the use of special developers or toners. The palladium K tra n s ition l i n es
are h igher i n e nergy than the molybde n u m l i n es of the secondary target and
w i l l not be exc i ted and, therefore, cannot be seen with the m olybdenu m tar­
get . H owever, the L transition l i n es of mercury, gol d , and u ra n i u m become
enhanced and are readi ly detected when using the m olybdenu m target.

Results of X R F Analysis of Photographic Facsimiles

The results of XRF analyses clearly show that p latin u m and palladiu m p hoto­
graphs can be easi ly disti ngu ished from one a nother. F igure 3 is a n XRF spec­
trum of a platin u m photographic facsimile using a molybden u m secondary
target. H ere the plat i n u m peaks are readily evident. F igure 4 is a n XRF spec­
trum of a palladium photographic facsimile using a bari u m c hloride second-

77
 Range:ZOkcV Range:40keV
Vert=l ODO Vert=2000

Pt

Pt
Scntter

Pd
Bac12
tnrget

(\
OkeV
- ·"1/1..i. Ju) Lif""" + Scatter

�
2DkeV 40keV

Figure 3
Detail of X H F spectrum of a dark area of a standard pla t i n u m
photogra p h ic focsi111ilc1 w i t h t he background subtracted,
using a molybdenum secondary target. Note the presence
of' t he t h ree major L transition l i nes (alpha, bct�1, and
gam ma) f'or platinum (vertical scnlc= 1 1000).
Figure 4
Detail of' X H F spectrum ur a dark area of a standard pa l ladium
photographic facsimile. with the background subtracted, using a
barium chloride secondary target. Note t he presence of t he two major
K ( a l pha and beta) transition l i nes for palladium ( Pd ) , as well as
the lower energy L transition lines (vertical scale= 2,ooo).

Annge:40keV Rnnge:40keV
Vert= 2000 Vert=l 000

�
Scntter
Pt

BaClz
target Hg Pt twto tnrgct
t Scatter

�OkeV ZOkeV

Figure Sa
Detail of X H F spectrum of a dark area of a slandarcl mercury­
clevdopcd combination plati num and palladium pholographic
Facsimile, with background subtracted, using a bari u m chloride
secondary target. While t he peaks For palladium { Pd ) are well
defined, the peaks for mercury ( Hg) and platinum ( P t ) arc not
distinct. A molybdenum ( M o ) t a rget must be used to e n hance
the detection of d1cse clements (vertical scale=2,ooo).
Figure Sb
Detail of X H F spectrum of' a dark area of' a standard mercury­
developed combinat ion plat in um and pal l a d i u m photographic
facsi m i le, with background subtracted, using a molybdenum
( N l o ) secondary targcl. The platinum (Pt) and mercury
( H g) peaks arc clearly defined (vertical scal e = 1 1000).
 Reading 11 1\tl C C A B E A N D G L I N S M A N

Rangc:ZOlccV
Vcrt•l ODO Range:401ceV
Vcrt•2000
Mo target

Scatter r-

� Pd Bac12
target

Pd Ag

� �fp�0g
eac12
Au
target flh

�
OlceV
.. -·· J,,, ; Au
·' ,L
Mo ta1gct
• Scatter �
20kcV
\/ '<J
OkcV
Fe Cu

A.ViA J l
40kcV

Figure 6
Detail o[ X R F spectrum of a dark area of a standard gold-toned
palladium photographic focsimile, with the background
subtracted, using a molybdenum secondary target. The
presence of gold (Au) is detected (vertical scale= 1,000).
Figure 7
Detail of XRF spectrum of a dark area of a standard silver-intensified
palladium photographic.: Facsimile, with the background
subtracted, using a bari u m chloride secondary target. The
presence of si lver (Ag) is detected (vertical scale=2,ooo).

ary target for the analysis. This spectru m reveals not only the h igher-energy
K l ines for palladiu m , b u t also the lower energy L l ines of pallad i u m .
The usefu l ness o f varying t h e secondary target i n order t o optimize
the elemental i n formation can be demonstrated with the XRF analysis of a
mercury-developed combination plati n u m and palladium print. I n the XRF
spectrum with a bariu m chloride secondary target ( Figure 5a) platinum and
palladium peaks are easily observed; however, the traces of mercury are barely
visible. By using a molybden u m secondary target ( F igure 5b) the mercury l ines
become e n ha nced and ful ly resolved from the plati n u m lines. The pallad i u m K
l ines are higher i n e nergy than the molybdenum l i nes of the secondary target
and cannot be excited and, t herefore, are not detected on this spectrum.
E n h ancement of the spectral l i n es by changing the secondary target
is aga i n i l l ustrated by analyzing the stan dard gold-toned palladiu m photo­
graphic facsimile. The pall adi u m K and L l ines are discernible when the
bar i u m c hloride target i s used. H owever, only the L alpha l in e for gold is
detected above background. Repeat i ng the a nalysis with the molybden u m
secondary target i ncreases the excitation o f t h e small amou n t o f gold pres­
e n t, causing all three L l ines to be c learly visible ( Figure 6). X R F analysis can
also be used to detect si lver in a s i lver-intensified palladiu m pri nt (Figu re 7).

79
 Part I H I S T O H Y O F P l- I O T O G H A P l- I C O N S E H V A 'f l O N

Range:,.DkcV
Ver1= 2000

Figure 8
BaCl 2
Detail of X H F spectrum of a target
Pt
dark area of a standard uranium­ BnCl 2
target
toned platinum p h otographic
facsimile, with the background Rh
subtracted, using a barium c h loride
secondary target. The presence
of uranium ( U ) is detected
�OkeV
{vertical scale=2,ooo).

I n the event that ura n i u m ton i ng was used, u ra n i u m can be detected ( Fig­
u re 8) . It was determi ned that to detect a l l the elements that might make
up the fi nal image, a nd thus to characterize fu l ly each u n known col lection
p hotograph , both excitation conditions (us ing the bari u m c hloride and the
molybdenu m secondary targets) m u st be used.

Results of X R F Analysis of Stiegl i tz Photographs

Several p hotographs in the National Gallery of Art's collection of Alfred

Stieglitz photographs were selected for examination by XRF. Some of t hese
were c hosen because of their u n usual appearance and others because of
skepticism expressed regardi ng earl ier records of process identi fication from
u n known sources. The accurate identifi cation of the p rocesses was a critical
element in the i ntellectual content of the fal l 1 99 2 exhibition at the National
Gallery, "Stieglitz i n the Darkroom." Therefore, selec ted p hotographs were
an alyzed to establish or verify the identification of t he processes by which
they were made.
Two portraits of Katharine N . Rhoades, pri nted from the same nega­
tive displayed in "S tieglitz in the Da rkroom," had been previously identified
by u n known sources as platinum prints. One has the archetypal appearance
of a plati n u m print, with a very neutral image hue accompan ied by off-wh i te
highlights. The other has a very different appearance; both its image h u e a nd

So
 Reading 11 M C C A B E A N D G L I N S M A N

Range:40keV langc:40keV
Vert= 2000 Vert=ZOOO

40keV 40keV

Figure 9
Detail of X H F spectrum of' a dark area of the neutral-hued
l<atJwri11e N. R hoades at '291,' with the backgrou nd subtracted, using
a bariu m chloride secondary Larget. The presence of plati n u m ( Pt )
is readily detecled. Despite t h e neutral h u e of t h i s print, a trace o f
palladi u m { Pd ) appears to be present {vertical scale=2,ooo).
Figure 10
Detail of XHF spectrum of a dark area of the warm-hued
Katharine N . Rhoades at. '29 1 , ' wit h the background subtracted,
using a bariu m chloride secondary target. The presence of plati n u m
( Pt ) i s a l s o detected. W h i l e analysis by X H F detected platinum
a s the primary i mage component, a t race of pallad i u m
(Pd) was al so discernible (vertical scal e = 1 ,ooo).

h ighligh ts are quite warm. After completion of a na lysis of these p hotographs

using the X R F protocol described above, platin u m was foun d to be present
in both the neutral-hued and the warm-hued portraits. H owever, a trace of
pallad i u m was also detected in both portrai ts ( F igures 9 and ro); the two
spectra are nearly identical. I t is possi b le that the presence of palladiu m con­
tri b u tes sign i ficantly to the difference in appearance. H owever, variations i n
the temperature o f the developer may have caused the differences i n i mage
h u e . Despite the newly revealed i n formation regarding the fina l i m age mate­
rials of t hese prin ts, what plays the pri mary role i n the appearance of these
two p hotographs remains u nclear.
A c irca 1 906 portrait of Stieglitz' daughter, Kitty, had been identified
by an u n known sou rce as a pallad i u m print. For various reasons, i n c l u d i ng
the date of the print and its u n usually neutral i m age, this process attrib ution
was q uestioned. Indeed, analysis by XRF revealed that the i mage consisted of
plati n u m and merc u ry; n o pallad i u m was detected in this i mage ( Figures r 1 a
a n d b ) . I t i s l i kely that this platin u m print was processed with a mercury
developer, which Stieglitz commonly u sed.

81
 P a rt I II I s T 0 n y 0 r. p 1-1 0 T 0 G n ,, p I I c 0 N s E n \I A T I 0 N

Range:40kcV Rangc:2 0kcV

Vcrt= 2000 Vcrt=1 000

Scancr
BoClz
� target Pt
Rh

40tccV

Figure lla Figure llb

Detail of XHF spectrum of a dark area of' Ki11y with t he background
sublraclcd, using barium chloride secondary target. The presence
of pallad ium is not detected in t h is print. Positive identification of
mercury cannot be made with this target (vertical scalc = 2 1ooc).
Dclail of XH.F spectrum of a dark area of Kiuy, with the background
subtracted, using molybde num secondary targeL. The platinum ( Pt )
a n d mercury ( H g) peaks are evidence of their presence. Compare
this spectrum with t hnt of t he combination platinum/pa llad i u m/
mcrcury�dcvcloped facsimile ( Figure 5b). The trace amounts of'
mercury present in t h is print are at t h e edge of the detection l i m i t s of'
t h is instrumental protocol. but t he Fully resolved mercury peaks
allow its positive identification (vertical sca l e = 1 ,000).

Another photograph, a portrait of Georgia O'Keeffe, had been identi­

fied by an u n known sou rce as "black pallad i u m or platin u m . " Analysis by
XRF detected no pa l lad i u m, but confirmed the presence of only platin u m .
The photograph can now, therefore, b e identified a s a platin u m print, thus
clarifying the d u bious process attri bution.
Analysis using X R F of i mages with very s i m ilar warm hues, Reflec­
t ions and Self- Port;rait, Corti na demonstrated a differe nt point. The pri mary
i mage material i n both pri nts was fou n d to consist of plati n u m . H owever,
mercury was detected in Self-Portra i t , Cort ina but not i n Reflect ions (com­
pare Figu res 2a and b to 1 2a and b ). vVh i le it is evident that R eflections is a
si mple plat i n u m pri nt, it is probable that Self- Portra i t , Cortina i s a mercury­
developed plat i n u m prin t . Perhaps the d i fference i n appearance is related
to the temperature of the deve loper. H owever, it i s i mpossi ble to d raw
categorical conclusions regarding the exact procedu res used to produce these
very si m i lar-h ued pri n ts. The two merc u ry-developed p latin u m pri nts, Self­
Port rait, Cort ina and J<itty, are stri ki ngly d issi m i lar i n appearance, another
 Reading 11 M C C A B E A N D G L I N S M A N

Rangc:40keV Ronge:20keV
Vert=ZOOO Vert=l 000

Scatter

� BaCl2
target

Pl
Fe

A.jA �-,.,�
Mo target

40keV
f\
OkcV
.� ··· • Scatter
�
20kcV

Figure 12a Figure 12b

Detail of' XHF spectrum of a dark area or ReflccU011s, with
the background subtracted, using barium ch loride secondary
target. The presence oF platinum ( Pt ) is detected in
this print (vertical scalc =2.ooo).
Detail of-' XHF spectrum of' a dark area of Hefle cJio11s, with t he
background subtracted, using molybde n u m secondary target. It is
interesting that, despite t he s i m i larity in image hue of t h is image and
t h e mercury-developed Self-Port mil, Cortina. n o mercury or other
toners were detected in Reflections (vertical scalc = 1 .ooo).

i n dication that a pos i t ive identi fication of process can not be made by visual
exa m i nation alone.
Another example of the usefu l ness of a na lysis of a photograph by
X R F to establish its process attribution is fou n d in Georgia O 'Keeffe: A
Portrait-Feet . The XRF spectrum shows the presence of pal ladiu m and
mercury ( Figu res 1 3a and b ) . The presence of m ercury i n dicates that this
pallad i u m pri n t was probably processed in a mercury developer. Th is spe­
c i fic analysis is interesti ng in that, while it is often possible through visual
exa m i nation to segregate St iegl itz' plat i n u m prints from his pal lad i u m prints,
it is i mpossible to ascerta in whether mercury is present without the aid of
chem ical analysis.

Su 111 m a ry

As this study i l l ustrates, the exact nature of photographs m ade by the plati­
n u m and pa l la dium processes is d i ffic u l t to determine by visual observation
alone. Photograph conservators, hi storians , cu rators, and practitioners of
 P art I II I S T 0 n Y 0 F P 1-1 0 T 0 G H 1"\ P II C 0 i\ S E H V A T I 0 N

Rangc:t10kcV Rangc:20kcV
Vcrt•ZOOO Vcrt=l 000

Mo targct ---1--+I

Scatter ,---- I

Scatter

� Pd
Bac1 2
target

<40kcV

Figure 13a Figure 13b

Detail or X H F spectrum of a dark area or Cenr� i" O'Keeffe: "
Portrait-Feel , w it h t h e backgro u nd subtracted, using barium
chlorid e se co n dary t a rget. V\/hilc palladium ( Pd) is dct.cc.:tcd
us i n g this targe t . m e rc u ry (Hg) is not detected. Sec Figu re r3b Fo r
confirmation or t he presence or m e rc u ry (vertical sca lc=2,ooo).
Deta i l or XRF sptxtrum of' a dark area of Georgin O'l<eej]C:
a Portrait- Feel , with t he backgro u nd subtracted, using t he
m o l yb de n u m sccond:1ry tnrgct t hat c l e arly reveals t he p rcsc n t: c
oF mercury (I lg). Th e presence of' palladium, however, cannot
be confirmed wit h t h is t a rget {vertical sca l e = 1 ,000).

the early processes with a t ra i ned eye may be able to narrow the possibilities
concerning the process by which an i nd ivid ual pri n t was made. The virtu­
al ly u n l i m i ted va riations of processes ava i lable to and used by photographers
over the past 1 50 years, however, arc manifested by a practica l ly i nfinite
assortment of photographic i mage appearances. The variety of su btleties and
nuances displayed by plati n u m and pa ll adium prints can be exp lai ned not
only by their original exposure and processi ng but often by chemical and
physical changes (such as fading, sta i n i ng, and mod i fication of su rface char­
acteristics) that have occurred over t i me.
Exam i nation of the physical chara cteristics of photographic pri nts is
essential to [a ] collection's care. X R F an alyses can acid i mporta nt informa­
tion rega rdi ng the chemical nat u re of photographs. The presen t study dem­
onstrates that the materials that const itute the final i mage in a single-layered
photograph can be confi rmed using X R F . Th is analytical protocol req u i res
that photographic standards are fabricated usi ng known processes and are
analyzed by XHF. Then XRF spectra of collection photographs made by
u n known processes are compared to t he standards' spectra. XRF is useful
 Reading 11 J\'l C C A B E A N D G L I N S M A N

i n reassess ing previous assumptions about a specific photograph ; a na lysis by

XRF may u ncover i n formation that exposes commonly held assu mptions as
mislead ing or i nacc u rate.
The primary concern of this study was to eval u ate the c haracteristics
exhibited in plati n u m and pallad i u m prints by Stiegli tz. Therefore, facsimi­
les of other photograph i c processes were not fabricated for i n c lusion i n this
study. Further i nvestigation by the authors i n to the use of X R F on other
photographic processes will include the production of addi tional facsimi­
les. These facsim iles w i l l i nclude sample pri n ts with a n umber of different
ratios of platin u m to palladiu m and the addition o f compounds of lead and
other elements to the facsimile p hotographs. In addition, the study will be
expanded to include a variety of si lver i maging systems with one or more
component layers. A l l t hese variants of photograph i c processes i n fl ue nce the
appeara nce and the preservation of photographic m a terials.

Conclusion

It is clear fro m this study that visual observation combined with XRF a naly­
sis will not necessarily reveal why a pri n t has certain visual characteristics.
Other in formation may be req u ired ( fo r example, known chemical method
of prod uction, previous conservation treatment, storage and exhi b i tions h is­
tory) for a complete u nderstanding of a print's appearance. Whi l e XRF is, in
fact, usefu l in determi ni ng what meta l l ic components are present in a pho­
tograph, it does not reveal the prec ise chemical structu re of the final i mage
materials or the m a nner by which a photograph was created. Other analy­
ses, i ncluding trans mission sca n n i ng electron m i c roscopy, may reveal usefu l
i n formation such a s metallic particle size. This i n formation m ay help explain
what makes a particular p hotograph appear the way i t does.

Acknowledgments

The a uthors wish to express their thanks to J ul i a Thompson, exhi bitions

assistant and Sarah Greenough, curator, department of p hotographs;
E . Rene de la Rie, head of the scientifi c research department; Shel ley
F letcher, head of paper conservation ; and Jan ice Gruver, editor for the con­
servat ion division, National Gallery of Art; Sarah Wagner, senior p hotograph
conservator, National Archives and Records Adm i nistration; and M oge ns
Koch, professor, Kon servatorskolen, Royal Danish Academy of Fine Art .

N otes

1 A l Fred Stiegli tz, 'The Plati notypc and the New York Amateu r," The Ainerican
Amateur Photogrnpher 4 ( 1 892), 1 53-1 55, "The P l a t i n otype U p to Date," The

85
Part I II I s T 0 R y 0 F p 1-1 0 T 0 G n A p II c 0 N s E n \! A T I 0 N

Canadian Photographic ] 0 1 1 nui l , 1 no. 1 1 ( December 1 892), 26 1 -263, continued

i n vol . 1, no. 1 2 , (J a n u a ry 1 893), 286-287, " U ra n i u m To ning of Plali notypes,"
T"he American Amat.cur Photogrnpher 5 ( 1 893), 2 10, "S loppiness i n the
Plat i n u m Process and i t s Effect, " T h e f\ 111. e rican A n m1al of Phot.ography a n d
Photographic Times Al111a1wc jor 1 902 ( 1 902), 28-30; Al fred S t ieglitz a n d
J oseph T. Keiley, " P l a t i n otype i n Colours: Controlled Development by
G lycer i n e Process, " The Amateur Phot.ographer 1 2 (4 M ay 1 900), 3 5 1 -355.
2 Sarah G reenough and J u an 1- \ a m i l to n , A lfred St.ieglit.=: Phot.ographs and
\!\!rit.ings (Wash i ngton, 1 983) , 230.
3 Douglas G . Severso n , "The Effects or Exhi b i t ion of Photogra phs, "
Pict u reScope 32, n o . 4 (Winter 1 987), 1 33- 135; N a ncy Heinho ld, 'The
Exh i b i t i o n of an Early Photoge n i c Drawing by H e n ry Fox Ta l bot," To·p ics in
Photographic Preservat io n . 5, American I n s t i t u te For Conservation Photographic
Materials Group (v\lashi ngton, 1 993), 89-9+
4 J a m es L. E n yeart, Adelaide B. Anderson , Steven J . Perron, D. K. H o l l i n s , and
Q u i ntus Fernando, "'Non-Destructive Elemental Ana lysis or Photographic
Paper and E m u lsions by X-ray F l u orescence Spectroscopy, " /- l istory of
Pl101ography 7 (April-J u n e 1 983), 99-1 1 3 ; Siegfried Hempel, "Quali tative E nergy
X- Hay F l uorescence Examination of H istoric Photographic A rt i facts," paper
given a l the P hotographic Materials G roup W i n ter M eeting of t he American
I nstitute for Conservation, C h a rleston, South Caro l i na (22 M a rch 1 986);
Valerie Baas, J u dith J. B i schoFf, and Leon Stod u \ ski, "Ongoing I nvestigatio ns
i n to C hemical E n hancement of Faded Vin tage Photographic Prints," i n
Topics in Photographic P.-eserval ion 5 , American I nstit ute For Conservation
Photographic M a teria l s Group (Wash i ngton, 1 993).
v\li\\iam Crawford, The Keepers of Lig h t : A /-listo11' and Worhin.g C 1 1 ide to Early
P/101.ographic Processes ( Dobbs Ferry, New York, 1 979) . Sec espec i a l l y part 2,
" Ferric Processes: Plat i n u m and Palladium. " This chapter describes, i n deta i l ,
t he procedures used t o produce t h e Facsi m i les used i n t h i s study .
6 M u ch has b e e n p u b l i shed regard i n g the chemistry of plat i n u m a nd pallad i u m
processes, y e t t h e precise chem ical nature of the reactions i nvolved is n o t fu l l y
u nderstood. S e e A d a m S . G o t t l i e b , Chem istry a n d Conservat.ion. of Plat i n.·1. 1 m
a n d Pa/.ladiuin Photograpl1s ( B .A. thesis, Princeton U n iversity, Dept. of
C h e m istry. 1 993). A mechanism For these c h e m ic a l processes is proposed b y
IV l ichael 'Nare, " A n I nvestigation o f " Plat i n u m and Palladium Printi ng," Journal
of Phot.ographic Scien.ce 34 ( 1986), 1 3-25, w h i c h should he consu lted.
7 Al fred Stieglitz, "The Platinotypc and the New York Amate u r, " The A merican
Alllale11r Pliotographer 4 ( 1 892), 1 54.
8 Bernard Edward J ones, Cassell's Cyclopaedia of Photography ( London, 1 9 1 1 ),
42 1 .
9 A l fred Stiegl itz, " S loppi ness i n the P l a t i n u m Process and i ts Effect,"' The
A lllerican A n . n u al of Phot.ography and Phot.ogmphic Thnes A/.m.anac Jar 1 902
( 1 902), 30.
1 0 St ieg l i tz 1 892, 1 54 , S t iegl i tz' italics [sic] .
1 1 For a d i scussion of prin ted-out and developed-out gel a t i n prints, sec J ames \1i 1 .
Heil ly, Care and Identification of 1 9 t h -Cen l. 1 1 1y Photographic Prints ( Hochester,
1 986), 2-3.
12 Stiegl i tz, December 1 892. 26 1-263; J a n uary 1 893, 286-287.
13 Stiegl itz 1 893, 2 1 0.

86
 Reading 11 i\I C C A B E AN D G L I N S i\ l AN

14 W. De W. Abney a n d Lionel C lark, Platinotype: Its Preparation and

Manip u la t ion ( N ew York, 1 898).
1 5 S t iegl itz to Paul H aviland, 22 April 1 9 1 3; letters Fro111 Stiegli tz to George
East111an, 1 1 J u ne a n d I December 1 9 14; S t iegl i tz to n . C h i l d Bayley, 9 October
1 9 1 9 ; Stieglitz to Pau l Strand, 6 October 1 9 1 9 , a l l in Al fred Stieg l i tz Archive,
Col lection of American Li terat u re, Bci necke Hare Book and M a n uscript
Library, Yal e U n i versity, New H ave n , Con necticut, u n catalogued .
16 Stiegl i tz a n d Kei ley 1 900, 35 1-355.
17 Stieg l i tz, Dece111ber 1 892, 286-287.
18 C rawford 1 979, see n. 5.
19 St iegl i tz, Dece111ber 1 892, 26 1-263.
20 Stiegl i tz 1 893, 2 10.
21 Ja111es iVl cCorkle, "On the U ra n i u 111 Ton i n g of P l a t i n u 111 Paper," Ca'/llera Not.es
6, no. 2 ( 1902), 90.
22 Eugene P . Bert i n , Principles a1•1. cl Pract.ice of X-ray Spectro11·1.e t :ric Analysis,
2d ed. ( Ne w York, 1 984) 2 1-49.
23 The lower l i m i t of detect ion ( L LD) has not yet been esta b l i s hed For the
111eta l l i c elements t hat may be contained in the f i n a l i 111age material ol '
photogra p h . To deter111 ine the L L D , considerable extra work wou l d have been
req u i red, and the res u lts wou ld have been a p p l i cable only to t he X H F analyses
perf'or111ed w i t h the set-up and exc i tation condition s of the i nstrument al the
National G a l lery of Art. However, work i s i n progress to establ is h L L D i n so111c
practical for111 t h a t would relate X H F detect ion l i 111i ts to optical dens ity i n
various t}1Jes o f photographs.
24 The elements that are of i n terest i n t h is s t u dy can be detected using the free­
stand i ng i nstru 111en t with t he a na lytical protocol described i n this paper.
25 The conditions u n d e r which the a nalysis was conducte d were: The a node
voltage and c u rre n t were 6okeV and o.4111A, respectively, for the bariu111
c h l oride target a n d 4okeV a n d o . 2 111A, respect ively, for t h e 111olybde n u 111
target. Live acc u m u lation t i me was 300 seconds. A Compaq PC 386 co111 p u le r
equi pped w i t h Kevex X H F Toolbox software provides the proces s i ng a n d
storage o f the data.
 R e a d n g 12

N O RA K E N N E DY

The C oming of Age of Photograph

Conservation ( 1 996)

Nora Kennedy (see also Reading 36) is the Sherman Fairchild Conservator of
Photographs at the Metropolitan Museum of Art, where she has worlwd since
1990. She is also adjunct professor for New Yorh University's Conservation Cen­
ter of the Institute of Fine Arts and co-owner of T11e Better Image, a private
conservation firm in Milford, New Jersey. T11irty years ago, the accepted course
of study for individuals wanting to conserve photographic ·m aterials in.eluded
an1renticeship or graduate school training in paper conservation supplemented
by the study of photographic science, photographic history, and the practice
of photography. Today, several well-established graduate and undergradu­
ate progra1ns offer photograph conservation as an in.dependent area of study
internationally. Tn January 1996, Kennedy surveyed fifty photograph conserva­
tion professionals worhing around the world to determine what constitutes the
ideal training for a photograph conservator. A summary of this fundamental
research-some of which may be surprising-and a history of photograph con­
servation. training are provided in the following reading. T11is worh addresses
the need to systematically reevaluate, redefine, and further promote photograph
conservation education.

NonA KENN EDY, ''The Com i ng of Age of' Photograph Conservation," 1 1 th Trien n ial. Meet.­
in.g, Edinburgh, Scotland, 1-6 Sept.en1ber, 1 996: Prep1·in.ts ( ICOM Committee For Conser­
vat ion), Janet Bridgland, ed. ( 1 996): 591-96. Reprinted by perm iss ion of Nora W. Kennedy
and The Metropolitan M useum of' Art.

88
 Reading 12 K E N N E DY

The H istory of Training in the Conservation of Photographs

The history of photography began as recently as 1 839, with the offici a l

a n nou ncement o f its invention. The creation of i mages th rough l ight­
sensit ive systems has b lossomed and grown, entering our lives in its many
forms. Al though photographers and collectors have been experi menting with
some form of restoration and even preservation of their works si nce photog­
raphy's inception, the discipline of conserving p hotographs, in the present
sense of that term, is the j u nior member of the fam i ly of conservation spe­
cializations. Phi losophies about the need for, the ski l ls necessary, and the
tra i n ing of professionals to preserve and conserve p hotographs have u nder­
gone considerable evol ution during this brief 30-40-year history.
I n 1 976 specialized tra i n i ng for photograph con servators was formally
established at the U n i versity of Delaware/W'intert h ur M useum Art Conser­
vation Progra m . Prior to this, the accepted course of study for a photograph
conservator incl uded tra i n i ng in paper conservation supplemen ted by the
st udy of photographic science, the history of photography, and the practice
of photography. Often these supplemental studies were carried out in a com­
pletely self-directed manner, as precious few m e ntors were avai lable from
whom to learn. I f one was fortu nate, one could also learn as an apprentice
at the side of a practicing conservator of photographs. These opportun ities
were rare in the early years due in part to the dearth of photograph conserva­
tion specialists, and in part to the fact that t hese i ndivid uals te nded to be i n
private practice, making the acceptance of apprentices a d i ffic u l t and finan­
cially prohibitive endeavor.
This situation has improved considerably i n the last ten years as more
graduate and u ndergraduate tra i ning programs are offering photograph con­
servation as a n option . Formal apprenticeship programs continue to contrib­
ute a small percentage of professionals, though the contribution seems to
shrink as the graduate programs grow i n their willingness and competence to
focus on photography. I n addition to formal tra i n i ng programs in the U SA,
n u merous other countries have joined the effort, i nc l u d i ng France, Den­
mark, Switzerland, and Mexico. In addition, s hort courses in the identifica­
tion and preservation of photographs are growing in n u mber. These sem inars
are genera lly directed at arc hivists, l ibrarians, cu rators, and keepers of col­
lections, but are also pop u lar with conservators from other areas who coun t
a mong their responsibilit ies the care o f p hotographic collections.
Th is growi ng i nterest i n trai n in g photograph conservators and preserva­
tion perso n nel has been sparked in part by the c ha nging role of photography
in our soc iety. Certa i n ly a l l major historical and art collections have a lways
maintained large holdings of photographs, but it is o n ly in rece n t decades
that the i n herent artistic, historic, and monetary val ue of these collections is
Part I 1- l l S T O H Y O F P H O T O G H J\ P l l C O l\ S E H V A T I O N

being appreciated. The current upsurge of digital i maging tec h nologies may
be threatening to make extinct si lver based photographic systems, but in so
doing it may cause the val u e of existing collections to apprec iate and freeze
forever that 1 60-year block of time when trad itional p hotography was actively
created. The more collections are val ued, the greater becomes the u rgency
to care for them. This is reflected in the upsurge of i nstitutional positions
for photograph conservators in North America which has more than doubled
over the last ten years. A s i m ilar increase is seen in the n u mber of photo­
graph conservators in private practice.
I n spite of these positive signs of growth i n the field, it is c lear that
there is ample room for more. Perhaps i t is also t i me for a re-eval uation of
our attitudes about the profession as well as existi ng education and tra i n i ng
pract ices. There are benefits consequent from submitting to a natura l evolu­
tion, but some deliberate pru n i n g of ou tdated i deas and refinement of exist­
ing paths of study is critical to prosperous growth i nto a healthy future.

The Conservation of Photographs as a Separate and Disti nct Field

Historical ly, photograph conservation has been regarded as a sub-spec ialty

of that of paper conservation. This is evidently a prej udice we conti nue to
battle today. 1 Although p hotograph conservation owes a good deal to paper
conservation for its support in the i nitial development of the field, this rela­
tionship's fu nction as the primary n u rturi ng source shri n ks as we rea lize its
i nherent l i m itations and continue to grow in our self-awareness. I n photog­
raphy we now rely much more on resou rces in tec h nical photography and
photographic h istory, i n addition to objects, pai n t ing, and paper conserva­
tion. The union of paper and photograph conservation is ul t imately a d isser­
vice to both disciplines i n that it d i m i n ishes the considerable expertise and
d iversity pecu l iar to eac h . For those who came to conservation from pho­
tography, this d i stinction between the two areas has always been eminently
cl ear. But for others who see photograph conservation only in the broader
context of general con servation, some clarification may be necessary.
The usual reason given for gro u p i ng the two fields is that photographs
are on paper and so should fa l l i n the rea l m of all paper objects. This is an
oversimplification, never more clear to a photograph conservator than when
confronted with a master drawing, a pastel, or a watercolor and the rea l iza­
tion that one is in no way equi pped to address the a nalysis or treatment of
such an object in any profound or responsible m a nner. Basic phi losoph i es
common to all con servati o n professionals will provide general guidelines, of
course. But in terms of the visual ization of the speci fics of h istory, manu­
facture, creation, and deteriorat ion of the object, and projecti ng how t hese
aspects m ight be affected by an i n terve ntion of whatever kind, the photo-
 Reading 12 l< E N N E D Y

graph conservator simply does not have the necessary tools at hand. J ust as
a paper conservation specialist cannot be asked to competently t reat a book,
nor a pain t i ngs conservator a textile, photographs are u n ique objects with
u n i que needs.
The view of photograph conservation as a specialty i n its own right is
not a new one for those of u s who have been dedicated to the field for many
years. This differentiation may not be as obvious to colleagues i n other a reas.
Fundamental ly, photographs are created chemically rather than by si mple
physical means, maki ng a thorough study and u nderstanding of photographic
chemistry essential to the photograph conservator. Paper chemistry m u st be
studied by both special ists, but to u nderstand the creation and deterioration
mechanisms of the photographic i mage, all types of photographic i mages,
additional requ i rements must be made.
The second fu ndamental d i fference is the l ami nar structure of a pho­
tograph, more related to the structure of a painting than a work on paper.
Photographs generally consist of a support on whic h rests a b i nder layer,
which in t u rn holds and suspends the final i mage material. The 19th century
albumen print, for example, consists of a paper support coated with a layer
of egg white or albumen as the bi nder. The final image material is made up
of finely divided si lver particles suspended within this binder. Later i n the
1 9th century a layer of white pigments and gelatin was coated between the
paper support and the b inder layer, fu l fi l l i ng a fu nction si mi l a r to the ground
i n the s tructure of a painti ng. This layered characteristic is res ponsible for
such d iverse problems as the notorious photographic c u rl , and for cracki ng
and Raking of photograph i c binder layers.
Fewer varieties of paper are used i n p hotography than in trad itional
paper-based art. In general, photograph i c papers tend to be of fa irly good
quality to m i n i m ize i nteractions between the photosensit ive layer before or
d u ring exposu re, and d u ri ng subsequent processi ng steps. In addition, the
paper must hold up we l l to repeated i mmersions in aqueous solutions as it
is processed. The exceptions to this are the infinite varieties of su pports pos­
s ib le in the ha nd-coated processes u sed early in the h istory of photography
and favored d u ri ng the Pictorial ist period.
The fact that m any photographs are not on paper at a l l a l l ies these
materials more closely to those traditionally cared for by objects conser­
vators. A photographic i mage can be created on any su rface onto which a
l ight-sensitive layer can be coated. The most pop u la r non-paper su pports
t h roughout the history have included glass, s i lver-coated copper, japan ned
i ron, and nu merous types of plastic. H owever, photographs also exist on tex­
ti les, leat her, wood, porce lain , stone, and even leaves. 2
I f one goes on to consider not just the support but also the binder layer
and the fi nal image material, the l ist of variables grows. The basic processes

91
Part I II I S T 0 R Y 0 F P H 0 T 0 G ll A P I I C 0 N S E ll V A T I 0 N

of the daguerreotype, salted paper pri nt , albu men print, and s ilver ge latin
developed-out print can be re latively straightforward to ide nti fy. However,
i n n u merable other processes exist and the matter is further compl icated by
the myriad variations in processi ng, manipulating and fi n ish i ng the i mage.
The ski l l of identification alone is one that takes considerable study and
years of exa m i n i ng i mages. I t is a skill which one is forever honi ng.
As is evident from the discussion a bove, photography alone comprises
many possible areas of speci a lizatio n : cased objects, photographs on glass,
negatives, X-radiographs, s i lver i mages, non-si lver i m ages, color materials,
and recently, o u tp u t from d igital i magery. The field is al most i ndefin i tely
su b-divisible, as are other specialties in conservat ion. To try to s u bsume a l l
this i nto a sta ndard train i ng course would hardly seem achievable, and t o add
the ski l ls of paper conservatio n to this l i st of goals wou ld be u n reasonable. I t
i s n o t b y a n y means the i n tention o f this paper t o downplay t h e i mportance
of i n ter-specialty comm u nication and i n terchange. I ndeed, we a l l are depen­
dent upon the open sharing of i n formation, and photographic conservators
in particular m ust rel y heavily on col leagues because photographic materials
are so diverse. Of critical i mporta nce is having the confidence a nd abil i ty to
recognize our own s hortcom i ngs, and the h u m i l ity to refer to our col leagues'
expertise in areas where we fal l short.

The Need for Photograph Conservation Professionals

The misconceived group i n g of paper a nd photographs is reA ected not only i n

conservation, b u t also i n the related cura torial a n d administrative domains.
I t is presen t s t i l l i n too many institutions with c u ra torial departments which
combine " Prints and Photographs" as one entity. It was as late as 1 992 when
the Department of Photographs won its i n dependence from the Department
of Prints and Photographs i n the Metropo litan M u seum of Art i n New York
City. M any inst i tu t ions with m i l l ions of photographs in their holdings and
su bstantial su pport from i n -house book con servators and paper conserva­
tors do not inc lude even one conse rvator of photographs on their staff. I n
other institutions, the photograph conservator may not have a n i n dependent
space, b u t works with colleagues, who may also include col l eagues i n book
con servation, u nder the auspices of a paper conservation department
The problem remains that photograph conservators, though growing
i n n u m ber i nternationally year by year, are as yet a rare breed. Paper con­
servators i n i nstitutional jobs in particular arc freq uently put i n the position
where they m u st deal wit h issues of the storage, exh i bi t ion, and even treat­
ment of photographic materials without t he option of referring to a spec ial­
ist. This is done willin gly by some and with a great deal of res istance by
others. Telephone cons u l tations with col leagues i n photograph conservation

92
 R e a d i n g 12 K E N N E D Y

can be made, but are of l i m ited assista nce. I n some cases, budgetary con­
siderations rule out the possibil ity of bringing in an on-site consultant or a n
outside contractor, l e t al one t h e establishment of a position for a conserva­
tor of photography. Frequen tly t i m e is also an element: the show m u st go
up in a week and the photographs need to be repaired , h i nged, or somehow
mounted before then.
The issue of how much i n formation should be shared between areas
of spec ial ization has been raised in the past. Concerns were i n it iated by a
proposed week-long course designed specifically for paper conservators who
had to work with photographs in the con text of their institution and fe lt ill­
preparecl to do so. Questions were ra ised about what should be covered i n
s o short a t i me period a n d whether it was responsi ble t o arm the conserva­
tors with a little bit of add itional knowledge which, without the fu ndamental
backgro u nd i n this special ized area, m ight lead to the maki ng of u n i n formed
and t herefore potentially damaging decisions. In this case, u l ti mately, the
course was designed around relat ively non-in trusive treatments with a heavy
dose of practical identification and preservation skills.3
This example is a man i festation of an issue of i nterest t h roughout the
broader field of conservat ion, namely that of the specialist versus the gener­
al ist. H ow much i nformation should be shared between specialt ies and how
much should a non-specialist be trusted with? The answers, of course, may
be dependent on more press i ng regional issues from coun try to country such
as economics and general conservation awareness. Not every country can
c hoose to have special ists in every area. In the U SA the tra i n i ng programs
often provide one to two years of tra i n i ng in all areas, after which spec ial iza­
tion is encouraged or even requ i red. Open com m u nication between areas
of spec ial ization is the norm, and it is assumed that profess ionals will not
undertake a treatment that fal l s beyond their area of expertise. Ul t i mately,
of course, this comes clown to the individual's professional commitment to
eth ics and sta ndards for practice. The American I nstitute for Conservation
(A I C ) Code of Ethics states: "The conservation professional shall practice
within the li mits of personal competence and education as we l l as with i n the
l i m its of the ava ilable fac i l ities." 4 All AJC conservators are expected to abide
by these gu idelines, though there are few ram ifications i f t hey do not.

Toward the I deal E ducation and Trai n i ng for

a Conservator of Photographs

I n January 1 996 a survey was di stri buted by this au thor among 50 photograph
con servators and related professionals in the U SA and abroad to poll opin­
ions about what might com prise the ideal tra i n i n g in the field.' The motiva­
tions for this su rvey i n c luded establish i ng what changes a nd i m provements

93
Part I H I S T O H Y O F P H O T O G H A P ll C O N S E H V A T I O N

could be made to exi st i ng apprenticeship and graduate tra i n i ng programs,

as well as laying the grou n dwork for fu ture discussions on cert i fication . The
survey asked that 1 3 areas be rated for their i mportance i n tra i n i ng. These
i n cl uded: photographic chemistry; the re-creation of historic and contempo­
rary processes; photographic h istory; connoisse urship; exposure to the sci­
entific princip les involved in research and test ing; photograph conservation
treatment; col lection-wide preventive care; thorough u ndersta n d i ng of the
code of ethics and gu idel in es for practice; an aware ness of conservation h is­
tory; fam i liarity with the l iterature in all appl icable fields; exposu re to other
conservation disciplines; sensitometry; and dupl ication techniques. G iven
that the three to four years normally allotted to formal appren ticeships or
graduate tra i n i ng program s is a relatively short time period, colleagues were
as ked whether they felt any speci fic area was best covered before, d urin g, or
could be left for after tra i n i ng.
Significan tly, the survey results i ndicate that opin ions about what con­
stitutes the ideal education i n photograph conservation are widely divergent
and at ti mes con trad ictory. Ma ny colleagues commented t h a t they h a d dif­
ficulty with the ratings because a l l the areas l isted were important. The aver­
aged rati n gs scored conservation treatment as a first priority, fol lowed by
photographic h istory and preventive conservation. Other critical areas l i ke
photographic chem istry and con noisseurship, which clearly set photograph
conservators apart from other conservation professionals, appear to be more
controversial as their standing was set back by a small n u mber of very low
scores. The study of sensitometry, fam i l iarity with duplication tech n iques,
and an awareness of conservation history came i n lowest in the rati ngs.
Wh ile the choice of subject matter is re lat ively easily made, the more
difficult question is that of determi n i ng the emphasis to be laid on eac h .
I n practical terms, h o w much t i m e shou ld be spent i n each area? Photo­
graphic chem istry and photograph ic h istory lend themselves well to formal
academic courses, where a m i n i m u m req u i rement can be made. In contrast,
the time comm itment toward subjects such as conservation treatment and
con noisseurship is indefinite, as one never ceases to add to one's experi­
ence in these areas. Therefore, the tra i n i ng period can o n ly be expected to
provide the fu ndamental tools for these, al lowing the learning experience to
con t in u e throughout one's career. Preventive conservation is achieving more
and more emphasis in tra i n i ng programs i n ternationally and received a h igh
average rating on the survey questionnaire. The theoretical knowledge can
be conveyed within the tra i n i ng period, al though the work in actual collec­
tions of surveyi ng large holdi ngs, eval uating existing conditions, ma king and
imp lementing pract ical recommendations for i mprovements, is u l ti mately
the best teacher. These han ds-on lessons may be attai ned through summer

94
 Reading 12 K E N N E D Y

work projects or internship e)qJeriences as ava ilable, but may also of n eces­
sity have to be postponed u n t i l after gradu ati o n.
The re-c reation of h istoric an d contemporary p hotograph i c processes
may not be considered by some to be an essential tool i n forming a conser­
vator, b u t this, l i ke ex'Posure to other conservati o n disciplines, deepens a n
i n dividual's u n derstand i ng a n d appreciation o f t h e m aterials, their h istory,
manipulation, and deterioration. These may not m a ke the conservator, but
they make more profo u nd h i s or her sense of awaren ess of the object. The
discipl i ne of sensitometry m ight a lso fall i n to this category, though obviously
o n ly a n i ntroduction to this area could be reasonably expected from most
tra i ning programs. The re-creation of p hotograph i c tec h n i ques can be i nte­
grated i n to the cou rse of study in the form of short workshops taught by
practitioners of the i ndividual processes. I n general, m ost graduate programs
require that students spend some part of their t i m e working in other conser­
vation discipl i nes.
Top ics such as a n awareness of conservation hi story, the study of the
code of ethics, and fam i l iarity with the l iterature in conservation and related
fields are largely a matter of a relatively brief exposure period followed by
conti n u i ng awareness, attention, and review on the part of the conservation
professional.
Ex'Posure to scientific prin c i ples i nvolved in research a nd testi ng
i s essential to the degree that a conservator m u st be capable of a critical
u n derstan d i ng of published studies. In addition, a conservator should feel
comfortable formulat i ng q uestions an d discussing i ss ues with colleagues in
con servation science. Conservators are not scientists, and tho ugh there is
the temptation to compensate for the rel atively s ma l l n u m ber of conserva­
tion scientists by conducting quasi-scientific research , these projects are not
to be considered on the same l evel as professional scientific studies. S i m i­
larly, the area of dupl i cation and copyin g i s a field u n to itself. The conserva­
tor should be aware of parameters i n volved i n these tech niques, and of the
options c u rre ntly considered to be accepted practice. Otherwise, it suffices
to be aware of col leagues i n the field to whose expertise one can turn for
consultation and advice, and to whom one can refer work of this kind.

Possible Modifications t o Existing Courses of Study

I t should be stated at the outset that existing conservation train i ng programs

are produ c i ng a very h igh level of conservation professional i nternationally.
The dedication and commitment of i n d ividuals i n volved in the educational
process is admirable. Most i nstitutions seem to be i nvolved i n a consta nt
process of re-eval uation and amelioration o f t h ei r programs to cont i nue to

95
P art I II I S T 0 H Y 0 F P H 0 T 0 G R f\ P II C 0 N S E H V 11 T I 0 N

provide the h ighest standard of education possible. The comments presented

here are to be seen as a part of this ongo i ng process.
The need for add itional qual i fied conservators of photography is evi­
dent. Existing programs h ave recognized this internationa l ly by adding pho­
tography to the areas available for spec ialization. As this com mitment grows,
c u rren t offerings are contin ua l ly re-eval uated to determine how best to serve
students in this speci a lized area. One of the llrst i mpositions this places
on the i nstitution is that of flexibility to al low the student to replace exist­
ing course offerings with offerings more specific to their needs. At times it
becomes necessary to go o utside a conservation tra i n i ng curri c u l u m to have
access to more specialized course work. Depending on the establ ished pro­
gram of study and the type of i n stitution, this type of mod i fication may be
more or less feasi ble.
One possibility for e)qJa nding the resources of i ndividual programs
would be to share resou rces with other conservation programs regionally
with short, i n tensive semi n ars and workshops. The idea would be to organ ize
a series of i nter-program activities, which in the case of p hotograph conser­
vation education, where resou rces are l i m ited, would provide t he necessary
courses with a m i n i m u m of disru ption to existing curricula. C learly some
topics lend themselves to this format more easily than others, as disc u ssed
above. As an exa mple, seminars i n connoisse urship, emphasizing the tech n i ­
c a l a n d hi storical details critical t o conservation a s wel l a s the aesthetic con­
cerns, are non-existent at the present ti me. A series of i ntensive week-long
courses held i n an i nstitution with a major collection of photographs, and
attended by al l students majoring i n the conservation of photographs i n a
region, m ight be a feasible way of presenting this i n formation . This approach
wou ld i nvolve viewing training more by discipline than by alma mater, a phi­
losophy most conservators seem to take to readily. The commitment is more
to the qual ity of the profession as a whole rather than to an i ndividual edu­
cational institution.
There has been some discussion i n the past of making more demands
on a student i nterested in p hotograph conservation prior to enteri ng, or a fter
graduating from a conservation program . So many requi re ments are a l ready
made that it seems hardly fair to i mpose more, but this is an option t hat
warrants fu rther study. It may be that equitable solutions exist, such as the
s u bstitution of photographically oriented courses for some of t he existing
prerequ i si tes. If fi nancial support were avai lable, the student m ight also be
i n formed from the o u tset that an addi t ional fou rt h or fifth year of fu nded
study wou l d be necessary, not for graduation, but to attain a certa in level of
profess ionalism. In t hese difficult ti mes of c utbacks in all sectors, this latter
solution of extended study may be di fficult to contemp late practical ly, but
still should be proffered as a possibil ity.
 Reading 12 K E N N E D Y

The Issue of Certification

Conservation comm u nities around the world have grappled for many years
with the notion of cert ificatio n , its advan tages to the profession, a nd the
myriad practical obstacles to actua l ly estab l i s h i ng a workable and equitable
system. The critical q uestions remai n s : what is the m i n i m u m level of knowl­
edge, skil ls, and education that can and should be requ i red of a con serva­
tor entering the field? I n order to determ i n e these criteria, the field i tself
req uires fu rther defin ition. \Ve u ndoubtedly h ave years ahead of us of nego­
tiation a nd planning before our diverse field can come to an agreement on
the defin ition of the essence o f our profession. It is hoped t h a t some of t h e
ideas and concepts presen ted above w i l l provide a concrete contribution t o
t h e discussion of certification and ai d i n t h e formulation process.

Conc l u s ion

The conservation of p hotographs is a u n ique and distinct field, one of the

many spec ia lizations in conservation . In the past it has been strongly associ ­
ated w i t h paper conservation, but is gradual l y gai ni ng i ndepe ndence, relyi n g
on i n p u t from t h e related disciplines of p hotographic history and tec h n i ­
cal p hotography, objects a n d p a i n ti ngs conservation, a s wel l a s paper con­
servation. As the need for speci a li sts grows, the education and trai ni ng of
photograph conservators m ust be re-eval uated and exi sting courses of study
conti nually modi fied to accommodate this need . Establishing the essential
skil ls necessary for the conservator of p hotographs wi l l aid in determi n i n g
standards on w h i c h a future system o f certification may b e based.

References

1 "Course Heview: Advanced Photographic Conservation at the S m i thso n i a n

I nstitution," by C heryl Jackson, AICCJ\11 Nati.on.al Newslel:ler, J u ne 1 994.
2 Accra Shepp, a New York artist, created p hotographic i n1ages o n leaves in t h e
e a r l y 1 99o's.
3 Course ent itled " M i d Career Tra i n i n g for Paper Conservators i n the Field
of Photographic Conservation" at the Conservation Analytical Laboratory,
Sm i t hsonian I n stitute, February 1-4, 1 99+
4 "Code oF Ethics a n d G u id e l i nes for Practice," D i rectory of American I ns t i t u te
for Conservat ion, Washi ngton, DC ( 1 996) 24-29.
The res u l ts of this su rvey were presented i n a paper entit led "Towards the
I deal Tra i n ing for a Conservator of P hotographs: S u rvey Hes u l ts" at the
American I nstitute for Conservation Meeti ng, Norfolk, Virgi nia, J u ne 1 996.

97
 R e a d n g 1 3

PAUL MESSIER

Notes on Dating Photographic

Paper (2006)

Paul .Messier (see also Reading 37) i s a photograph conservator i n p rivate

practice in Boston, Massachusetts. Since the late 1990s, Messier h.as collected
more th.an 4,000 historical photographic papers used by photograph-ic scien­
tists, conservators, and dealers to strengthen an understanding of these unique
substrates. l\!Iessier's "Notes on Dating Photographic Paper" su1n:1narizes his
own 1vorh focused on identifying techniques for dating fiber-base gelatin silver
11rints. It also represents a current trend in th.e field to characteri.ze certain
traits of p hotographic 11apers for the purpose of better treatment-making deci­
sions, authenticity, and historical chronology.

1 .0 I ntroduction

Knowing when a p hotographic print was prod uced has value. For the conser­
vator, print elate may carry i mp l ications for treatment, display and storage.
l n the marketplace, pri n t date is probably the largest single variable affect­
ing the price for a photograph . For the collector and curator, establishing a
chro nology of prints is a key toward u nderstanding the course of a photo­
grapher's aesthetic development and the h istory of the med i u m . \,Yhe n prov­
enance is lacki ng, incomplete or disputed, spec ial ists from many spheres are
often able to m ake j u dgmen ts based on criteria such as state of preservation,
marki ngs and paper type. Dating pri n ts in this manner can often be quite
accurate t hough i t is highly dependent on the expert interpretation of often

PAUL M ESSIEH, " Notes o n Dat i ng Photogra p h i c Paper," Topics in Photographic p,.eserva­
Lion 1 1 (v\lashingto n , D C : American I n s t i t u te for Conservat i o n , P h otograp h i c Material s
G roup, 2006)1 1 23-30. Repri nted b y permission o F Paul Messier, Conservator oF Photo­
graphs, Bosto n , MA, USA.
 Reading 13 M E S S I E H

subjective criteria. I n cases where sufficient expertise is lacking, op1n1ons

conflict or when a u thenticity is qu estioned such a nalysis may not be suffi­
cient. U n t i l recently, however, there were no widely accepted tech niques for
objectively determ i n i ng the manufacture elate of 20th century photographic
papers. Begi n n i ng in the late 1 99o's photograph conservators and conserva­
tion sc ientists gai ned significant ground with the promise of more develop­
ments i n the near future ( Messier 2000 and 200 1 ). Th is paper exa mi nes some
of the more usefu l tec h niques for dating photograph i c papers, their strengths
and weaknesses, and describes some promising n ew direct ions.

2.0 Existing M ethods

2. 1 Optical Brightening Agents

Optical brighte n i ng agents are a special c lass of dyes used to make materi­
als, especially paper and textiles, appear whiter and brighter. The dyes emit
a cool blue white l ight when exposed to certai n wavelengths of ultraviolet
rad iation. There is strong evidence, including m an ufacturer records ( Paper
Service Division 1 9 5 1 ) and i n dependent surveys of refere nce collections, indi­
cating the u se of brighteners i n photographic p aper began i n the early to mi d
1 95o's. A s u rvey conducted at t h e au thor's studio comprisi ng 2,076 black a nd
white, fiber-based papers of known origi n fou n d the earliest brightened pho­
tograph i c paper occu rred i n the period 1950-1 954 ( M essier, Baas, Tafilowski
and Varga 2005). Th is same survey fou n d peak use of brighteners in the peri­
ods 1 960-1 964 and post-1980. In the former time fra me 55% of papers con­
tained brighteners . In the l atter period 78% of papers showed brighteners.
The s u rvey also concluded that brighteners were found predominantly i n the
emulsion side of papers produced between 1 950 and 1 960. After t h is decade
brighteners were fou n d o n the e m u lsion side and paper base.
Identification of brightened paper is relatively simple: The pri nt is
exa mined in a darke n ed room while exposed to near u ltraviolet ( U .V. ) radia­
tion. If brighteners are presen t the pri n t will emit a distinct b l ue/white glow.
I nexpensive i n candescent or flu orescen t "black l ights" are often suitable
for this p urpose though these can emit a great deal of blue l ight that more
expensive models m ight filter. U l traviolet fi l terin g eye protection should be
worn when perform i ng this test especially as darkened room conditions will
cause pupils to dilate al lowing maxi m u m passage of rad iation to the retina.
In practice, this tech n ique has some drawbacks. Ch i ef among these
is that i t requ ires a moderate level of experience and interpretation ( Baas
200 1 ) . I n some cases paper can appear "bright" u nder U .V. but Jack the dis­
tinct blue-white blow of brightened paper. Blue l ight e mitted by the U .V.
source and reflected by the pri n t h i gh l ights of the paper base can some-

99
P art I H ! S T O H Y O F P l-I O T O G B A P l-I C O N S E H V t\ T I O N

t imes be con fu sed with the bl ue-whi te fluorescence characteristic of optical

brighteners, especially when brighteners are present in low concentrations.
Brighteners can also fade with ti 111e, especially upon exposure to l ight and
U .V. radiation.
From the evidence cited above and elsewhere, the presence of optical
brightening agents is a c lear i ndication of post 1 950-55 production. However,
a fi n d i ng that a pri n t lacks brighteners is of l ittle u se for the p u rposes of dat­
i ng. A substantial 111i n ority of papers produced after the mid 1 95o's did not
contain brighteners. J n addition to the che111ical breakdown of brighteners
by n ormal environmenta l factors ( l i ke the e>.-posure to l ight) b righteners can
be 111asked by the addition of other colora nts [or] coatings a nd be destroyed
by co111 mercially ava ilable chem ical compounds. Despite t hese l i m itations,
the fi n d i ng that q uestioned prints attributed to Man Ray ( 1 890-1 976) and
Lewis H in e ( 1 874- 1 940) contained brighteners was key in e>.-posing these
major au thenticity scandals (Robinson 1 997; Fessy 1 998; Vincent 1 998; Fal­
ken stein 2000; Woodward 2003) .

2.2 Paper Fiber lclentificati.on

The discovery that an a nalysis of the base paper for photographic pri nts
held potential for the datin g of 20th Centu ry p hotographic papers also owes
to work perfor111ecl on q uestioned Man Ray and Lewis H i ne p hotographs.
In the case of Man Ray, this work was performed by the Felix Schoeller
Company i n 1 997. Schoeller, an i mportan t supplier of baryta-coated base
paper, found Man Ray prin ts submitted for a nalysis not only contained opti­
cal brightening agents but m ixtures of hardwood and softwood consistent
with papers the company produced i n the 1 95o's to 1 97o's ( Fe l ix Schoeller, Jr.
Company, 1 997). For H i ne, samples from questioned pri nts were gathered
by this author and assessed u s i ng optical m icroscopy by \Valter Rantanen of
I ntegrated Paper Services i n Appleton, W I . Rantanen ident ified fiber source
( hardwood species vs. softwood species) and method of chemical processing
(sulfite vs. kraft). These res u l ts were compared to a reference collection con­
tain i n g h u n d reds of elated prints assembled by Rantanen ( Rantanen 2000;
200 1 ) . Thi s work revealed some broad trends that are extremely usefu l i n elat­
i ng p hotograph ic papers. To s u m 111arize the findi ngs: Papers i n the early part
of the century u sed fibers 111ostly de rived from textiles, either cotton or fl ax.
A transition toward the use of solely softwood bleached s u lfi te took place
in the 1 92o's. By the 1 93o's papers contained al most exc lusively softwood
b leached sul fite. By the l ate 1 95o's m ixtures of softwood bleached s u l fite and
hardwoods became more commo n. I nitial uses of hardwood kraft fiber are
seen in the 1 97o's. Also in the 1 97o's alpha grade cel l u lose, usually m ixed

100
 Reading 13 �I E S S I E B

with softwood bleached su lfite, begi ns to appear. The finding that many of
the qu estioned H ine p ri n ts contai ned hardwood b leached kraft was a strong
i ndication that they could not have been prod uced duri ng H i ne's l i fetime.
A minor drawback of this tech n ique is that i t requi res the remova l of
a min ute sample of paper fibers (about half the head of a p i n ) taken from
the edges or reverse. For mounted pri nts, obtaining a sample can be qu ite
chal lengi ng, especia ll y as cross contam i nation from mounting papers can
muddle res u l ts and i nterpretations. The microscopic identification of fibers
and pulp processing tec h nique req u i res high levels of specialized tra i n i ng
and experience. I n practice, the greatest drawback i n the present tech n ique
is when res u l ts indicate i oo% softwood bleached su l fi te since this Fi ber m ix is
[consiste nt] with papers produ ced over a very broad ra nge of dates, from the
1 93o's to the present.

2.3 Bach Printing

I n some cases manufacturers appl ied i n ked logos and other i nformation on
the reverse of their papers. Though there are some exceptions, back print­
i ng is consistently used o n ly on Agfa papers and o n the l ongstanding Velox
brand produced by E astman Kodak.
While some superficial differences are evident in the typefaces, s ize
and positioning of the Kodak back pri nting it is u ncertai n how much value
these observations have when it comes to dating p hotographs. This a u thor
is just start i ng a methodical c hronology of Velox and other back printing on
Kodak papers and any u sefu l resu l ts from this exercise m ight be a year or two
away. A preli m inary find is that the si ngle word "Velox" with no other graphic
embellish ments was u sed to mark papers manufactured in the U n i ted S ta tes
dating fro m the late 1 92o's to the late 1 94o's. After 1 950 or so, back pri nting
on Velox stacked the words " Koclak/Velox/Paper." The three stacked words
were used at least u n t i l the m id 1 96o's. Another finding is that Kodak papers
manufactured i n E ngland, and probably elsewhere, had completely different
typefaces and back p rinting styles.
The Agfa company was much more consistent in its use of back pri nt­
i ng. \l\lh ile not every paper in the Agfa line carries back printing many do.
\!\!hen present, Afga's m arkings can sometimes be u sed to establish a rough
elate of production (Agfa-Gevaert 1 997; Auer 1 999). Prior to the late 1 95o's,
Agfa identified i ts papers u sing two words compri s i ng the ma n ufacturer
name and the brand name such as "Agfa Brovira," "Agfa Portriga," Agfa
Lu pex" etc. Following the late 1 95o's, use of the brand name was dropped,
leaving the one word "Agfa. " Aside from dropping the brand name in the late
1 95o's, Agfa changed typefaces, added and su btracted quality control markers

101
P art I 1-1 I sT0 n y 0 F p 1-1 0 T 0 G n A I' II c 0 N s E 11 v /\ T I 0 N

and other graphic elements over t i me. A chronological compilation of this

i nformation wou ld be tremendously u sefu l , though the a uthor lrnows of no
such resource.
On the whole, the use of back printing for elat ing papers is of l i m i ted
u se si nce comparatively few papers show any man u facturer appl ied mark­
ings. Though re latively rare given the ent ire population of photographic
papers it is a remarkabl e fact that many of the questioned photographs attrib­
u ted to Man Ray and Lewis H i ne, purportedly made i n the first part of the
20th century, were fou n d to contain the one word "Agfa" marking on the
reverse cl early i ndicating the papers were manufactured after the late 1 95o's.

2.4 General Lirn.i ta tions

The use of optical brightening agents, paper fiber identification and man­
u facturer back pri nting comprises the "state of the art" for dati ng photo­
graphic papers circa 1 999 and contin ues to be a n effective aid for sett l i ng
many cases when the origin of a pri nt is u nknown or in dispute.
\Vh ile t re mendously usefu l, these tec h n iques have certain Aaws and
gaps. An i mportant defect in the overal l methodology is that is provides the
date of paper man ufacture and not pri nt elate. This consideration may occa­
sionally cloud res u l ts for photographers that hoard expired papers i n their
freezer for decades but i t i s of greatest concern for the deli berate prod uction
of fakes using old paper stock. Not s i mply a hypothetical threat, Jens Gold,
i n his paper published e lsewhere i n this vol u me [ referring to Topics i: n . Pho­
togra1?h: ic Preservation.], i n d icates a patient and highly skilled worker can pro­
duce acceptable prints on very old paper stock. As stated, a nother defect i s
t h at resu lts often e ncompass extremely broad date ranges. While usefu l for
d iscrim i na ting between a 1 93o's and a 1 97o's pri nt, for exa mple, determ i n ing
a man ufacture elate within ten or twenty years i s often i mpossible.

3.0 N e w Di rections

3.1. Reference Collections of Photogra1?h:ic Paper

As the techniq ues l isted above were bei ng developed, it became increasi ngly
c lear that reference collections of photographic paper v;ou l cl be a t the foun­
dation of any future refinement of the existing methodology and h a d t h e
potential to open enti rely n ew d i rections for future researc h . Th e problem i n
t h e late 1 99o's was there seemed t o b e no such t h i ng a s a widely accessible,
adequately doc u mented, reference col lection of photographic papers. For
example, the col lection in the possession of Walter Rantanen, which proved

1 02
 Reading 13 M E S S I E H

critical for the i n itial stages of paper fiber analysis, contai ned elated samples
but lacked information on manufacturer, brand and fi nish.
To address this gap, this author began amassing a collection of u nex­
posed photographic paper i n origi n a l packaging and manufacturer sample
books. As of this writing the collection has grown to over 2,700 papers and is
cata logued by man u facturer, bran d , date, surface fi ni sh, weight, base t hick­
ness, color and presence of optical brighten i n g agent. As the collection con­
t i n ues to grow, plans are taking shape to make i t available to researchers as
broadly as possible. Owing to the source of papers, mostly internet auction
s ites l i ke e Bay, the collection i s heavil y weighted toward papers ava ilable
i n North America. There remains a need for the creation of s i m il ar coJlec­
tions, espec ially for E u ropean and Asian papers. Aside fro m the i n herent
value of doc u menting and preserving the methods and materials used by
p hotographers in the 20th Century, the p rom ise of this and other reference
collections is that future research w i l l be significantly more refined, mak­
i ng possible subtle distinction between m anu factu rer, brand and elate. The
research techn iques mentioned in this section are some of the i n itial and
most promising proposed projects developed u s i ng we l l-characterized refer­
ence col lections of p hotographic paper.

3.2 Quantitati.ve X-ray Fluorescence Spectroscopy of Baryta Coatings

This o ngoi ng study, conducted principally by D u san Stulik, Senior Scientist

at the Getty Conservation I nstitute, reli es on measuring the elements bariu m
and strontium found i n the baryta layers of p hotographic papers. Completed
i n 2004, the initial p hase of the project centered on the creation of thin
film standards conta i n i ng known concentrations of bari u m and stront i u m .
U s i ng t h e standards for i nstru m en t calibration, X-ray A uorescence spectro­
metry (XRF) is used to measure concentrations and derive ratios of bariu m
to stro n t i u m . I n itial stages of the project establ ished that concentrations of
bariu m and strontium are very u n i form across the plane of a single sheet of
photograp hic paper. Concentrations of these elements were also fo und to be
consistent across m u l tiple s heets of p hotographic paper ra ndomly selected
from the same commercial package (Stulik and M essier 2004) . While these
resu l ts show that bariu m and stro n t i u m l evels are the same for a given bran d
o f paper made during a certain time period, quantitative X R F data a lso show
some significant differen ces emerge across manufacturers, elate, brand and
surface finish. These data i ndicate that baryta coated photographic paper
p roduced over time differs e nough i n a!J determined analytical parameters
that quantitative X R F can provide i mportant clues needed for the develop­
ment of a future provenancing methodology (Stulik, Kaplan, Mil l er, M i!Jer

1 0'_)
Part I H I S T O R Y O F P H O T O G R A P H C O N S E R VA T I O N

and Messier 2005). As of this writ ing, this working hypothesis is being p u t to
the test. Stulik and h is team at the Getty have finished a systematic quan­
titative XRF assessment [of] approx i mately 1 , 000 samples of p hotograph i c
paper o f known origin . Once t h e a nal ysis o f these data i s complete, a base­
li n e of XRF data will exist against which papers of u n known or questioned
provenance can be compared.

3 .3 Paper Fiber Analysis: S1?ecies Identification and Ratios

Existing tec h ni ques used for dating p hotograph ic papers by fiber analysi s
have foc used on broad categories based on fi b e r source, s u c h a s rag, soft­
wood and hardwood and method for chemical pulp processing such as
sulfite and kraft. Based o n a reference collection conta i n i ng h undreds of
dated samples, the presen t stage of development rema i ns extremely useful
for datin g p hotographic papers. However, further refinements are possible
and needed, especially to address the apparen t monolithic use of softwood
b leached sulfite used from the 1 93o's to the r 96o's and i n d i m in is h i ng quanti­
ties up until the present.
A l ogical step is to catalog the use of different wood species over time.
A n expert such as Walter Rantanen can usually identif)' common wood spe­
cies used in the manufacture of p hotograph i c paper. Such species i n clude
softwoods li ke spruce/he mlock, white red and Scotch pine, and Douglas fir
as well as hardwood species such as m aple, a lder, basswood, birch, beech
and cherry. \!\The n fibers of different species and c he mical processing h istory
are present, the differen t fi bers c a n be counted to determine mi x percent­
ages. Thi s level of speci ficity applied to a h ighl y characterized reference col­
lection could identify i mportant tre nds showing how di fferent manufacturers
acquired p u l p from differen t sources over time. The conservation depart­
m e n t of the M useum of Modern Art, New York, is taking a n active i n terest
conducting a project along these l ines i n collaboration with Rantanen a nd
this author. Like t h e quantitative XRF research , the goal of this project i s t o
establish a chronological baseline comprising upwards of a 1 ,ooo papers of
known origin .

+o Concl usion

While the research outlined in this paper i s designed to be useful for dat­
i n g photograph ic papers of unknown origin , the impl ications are far greater.
These projects, and indeed any other project focused on characterizing
20th Century p hotograph ic papers, have tremen dous pote ntial to raise the
level of scholarsh ip across a n u mber of related disci p l i nes. 'With t ime, these
and other tech n iques can be harnessed to provide meani ngfu l insights i n to
 Reading 13 M E S S I E R

the selection and use of photographic papers by i ndividual p hotographers

and how these dec isions were rein terpreted over time. This type of techni­
cal analysis i n support of art h istorical research is common for other media
b u t is fairly rare for p hotography. The gen eral lack of catalog raison n e
studies is a case i n point ( In ternational Foundation for Art Research 2004) .
There i s more info rmation o n papers u sed b y Rembrandt and Goya, for
example, than for any of the 20th century m asters like Weston, Modotti,
Lange and Kertesz. With sustained effort this deficit can be addressed with
prin ts by these p hotographers an d others categorized into sets and su bsets
by date, paper man ufacturer, brand, and finish. This work will yield a tre­
mendous benefit by helping to u n derstand how the expressive i n tentions of
t hese artists were made m a n i fest t h rough their choices, use and manipula­
tion of materials.
Pursu i ng these goals as vigorou s ly as possible will, of course, yield some
i mportant side benefits especially when it comes to photographic prints of
q uestioned au thenticity. As stated earlier and d iscussed in depth elsewhere
in this volume [referring to Topics in Photographic Preservation ] , there is
a clear potential for u s i ng old paper to make new prints. Placed in a wider
context of art fraud, this type of menace is nothi ng new. Self-proclaimed
"master fake" Eric H ebborn used ch ronological ly appropriate papers , draw­
ing materials and tec h ni ques to produce fraudulent Old M aster drawings
( H ebborn 1 992). Such fakes are difficult to identify using the customary bat­
tery of analytical tech n iques as p hysical and chemical anachronisms simply
do not exist. Threats l i ke these m ake the need for materials-based catalog
raisonne studies all the more emphatic. The development of a tech nical
catalog of a p hotographer's work will allow m ea n ingfu l i nsight i n to which
papers were used with which negatives over time. Faced with this h igher
level of u n derstanding, or its potential, a determined fraud using old paper
would need exactly the right old paper in terms of manufactu rer, brand, fi n ­
ish, date and a host of other criteria. Combined with t h e l im itations o f m ak­
i ng a credible looking print o n rare, v i ntage, u n exposed paper, the potential
for success would be greatly d i m i nished.
The sign ificance of this work and i ts potential cross-d isciplinary appli­
cation h ighlight the need for building a credible, su bstantial and permanent
body of l iterature. Whenever possi ble, reports on the initiatives outlined i n
this paper will be submitted to the peer-review process and appear i n the
permanent conservation l iterature such as the Journal of the American Insti­
tute of Conservation. Ideally work on these and other future projects should
be collaborative and, to the extent possible, coord in ated; i nvolving data sets
a n d samples shared across m ultiple collecting i nstitutions. Just as building
a permanent l iterature and shared body of knowledge should be a priority,
t here remains a need for an effective forum where the issues of dating prov-

105
Part I ll l S T O H Y O F P H O T O G B A P ll C O N S E H V 1\ T I O N

enance a nd tec h nical studies can be d iscussed i n a broader context. The

Al PAD symposium, held at the Metropolitan M useum of Art in 200 1 , pro­
vided a useful model bringing together conservators, dealers, collectors and
curators. A sustained forum for the exchange i nformation among these a nd
related constituencies would be extremely benefici a l .

5.0 Refe re nces

Agf'a-Cevaerl. 1997. Deter111 i n i ng the age of Agfa paper stock. Letter lo Werner Bokelberg.
Apri l 1 8, 1 997.
Auer, J. 1 999. Person a l com m u n ication. National Tec h n ical 111anager, AgFa Consumer
I maging Products, H idgefield, NJ.
Baas, \/., 200 1 . Optical brighteners in photogra p h i c papers. Conference prese ntation,
Association of I n ternational Photography Art Dealers, New York, NY.
Felix Schoeller, Jr. Company, 1 997. Analysis o f Man Hay sa111 p les. Letter to \Me rner Bokel-
berg. M ay 26, 1997.
Falkenste i n , iVI . 2000. The H i n e quest i o n . AHTNews 99 (5): 2 1 0- 1 3 .
Fess, E . , 1 998. M agni fice n t M a n Hays l o o good to b e true. The A r t. Newspaper J u ne: p . 8 .
H e b b o rn , E . , 1 992. Master Falwr, t'1.efo1ging of an. artist. London : P a n Books.
I n ternational Fou ndation for Art Hesearch, 2004. Authentic i ty Issues in Photogrnphy.
l n.ternct/.ional Founclat:ion. for Art Hesearc h journal 7 ( 2 ) : 20-53.
Messier, P . , 2000. Toward a methodology for dat i ng pre & post 1 950 photograp h i c prints.
Conference prese n ta t i o n , Photogra p h i c M aterials C ro u p of' the American I nstitute
for Conservation meeti ng, P h i lade l p h ia, PA.
M essier P . , 200 1 . M e thodology of dating photographs relative to 1 950. C o n ference presen­
tati o n , Association of I nternational Photography Art Dealers, New York, NY.
Messier, P., \/. Baas, D . Tafi l owski and L. Varga. , 2005. Optical brighte n i ng agents in p ho­
tographic paper. Journal. of the f\ 111.erican ln.st.itu/.e fo1· Conservation., 44 ( 1 ): 1-12.
Paper Service Division. 1 9 5 1 . The use of l l uorescent dyes as brighteners for photographic
paper. East111an Kodak C o m pa ny, Hochester, NY.
Hantancn, \"1 . , 2000. The use oF paper a nalysis i n dating p h o tographic prints. Presentation,
Photogra p h i c M a terials Croup o F the A111erican I nstitute for Conservation 111eeting,
P h i ladel p h i a , PA.
Hantancn, 'v\/. , 200 1 . Using optical 111 icroscopy to date p h otograp h i c papers. Conference
prese ntation, Association of I n ternational Photography Art Dealer, New York, NY.
Hobi nson, \•\/ . , 1 997. Man Hay forgeries exposed. Arin.et Maga:ine: www.artnel .co 111/
M agazi n e/news/ro b i nson/robinso n 1 2-2-97.<isp (first p u b l i s hed December 2, 1 997,
accessed August 15, 2005).
S t u l i k, D and P. Messier, 2004. Quant itative X H F study of baryta coated photographic
paper. Photogra p h i c M aterials C ro u p of the American I n stitute For Con serva t i o n
meeti ng, Portland, O H .
Stul ik, D . , A. Kapl a n , D . M i l ler, G . M i l ler a n d P . Mess ier. 2005. Study of Baryta Coated
S i lver Gelat i n Photographic Papers: C h e mometrics Approac h . Photographic Mate­
rials G ro u p of the American I n s t i t u te for Conservation meeting, Va ncouver, British
Columbia.
V i n c e n t , S . , 1 998. D u ped. A rt & Auction, February: p. So.
V\/oodward, R . 13 . , 2003. Too much oF a good t h i ng: photography, forgery, and the Lewis
H i ne scan d a l . The Atlantic f\1/ onihly 29 1 (5 ) : 67-76.

1 06
 R e a d i n g 14

G RA N T B . R O M E R

What I s a Photograph? (20 1 0 )

G rant B. Romer (see also Readings 3 1 and 69) became photogra11h conservator
at the George Eastman House (GEH) in 1 979. I-le has been active in creating
a written and oral record of the history of photograph conservation through
several publications on the topic and the establishment of the Oral History
of Photograph Conservation project at GEI-I. Th.is reading addresses profound
challenges currently facing the field as the revolution in hnaging technology
continues and the definition of photograph conservation evolves. The author
published a sim ilar reading in Topics in Photographic Preservation 11 ( Wash­
ington, DC: American Institute for Conservation, Photographic M aterials
G roup, 2005); the version reproduced here has never been. published and was
submitted specifically for this publication.

In the early 19 70s the conservation of p hotographs began to define itself

within the conservation profession as a distin ctly separate specialty. The pio­
neers of the field argued then that the u n i fying and esse ntial nature of true
p hotographs was a common origin in chemical response to rad iant e nergy,
no matter how varied i n materials or structure, nor how much t hey m ight
resemble other forms of graphic i magery. F urther, they made the case that it
was the photograph as object, n o t just as i mage, that requi red a special con­
servation approach beyond what the p hotographic i ndu stry and paper con­
servation practice was offering. The new professional specialty establish ed
i tself by being able to clearly defin e the p hotograph . Today, as i f struck with
a confusion of tongues, the many conservation special ists who speak for the
p hotograph do not agree u pon a common answer to "\i\ihat is a photograph?"
For some, thi s is no problem at all . For others, it indicates a grave confu­
sion i n the craft, which t h reatens the very definition a nd effectiveness of the
specialty professio n . I ndeed, some begin to question, "What is photograph
Part I H I S T O R Y O F P l- I O T O G R 1\ P l-I C 0 1' S E R V 1\ T I O N

conservation?" V/ithout a clear defi n ition of "photograph," commonly held

by the profession, can it be possible to establ ish the doma in of the p hoto­
graph conservator?
The stretching and blu rring of the definition of "photograph " is a direct
resu l t of the evo lution of e lectronic i maging, which has profoundl y disrupted
the established p hotograp hic industry. Dai ly, the convergence of i n formation
and i m aging technology is establ ish i ng a new industry and c u lture , spawning
new words and altering old definitions.
The more than 1 50-year dominance of silver-halide technology is rap­
idly d i m i n is hing. An analogous, but essentially different, technology i ncreas­
i ngly serves i n the stead of trad itional chemical i maging systems: digital
cameras replace cameras that use fil m ; for some uses, scan ners rep lace
cameras; printers replace darkrooms; bathrooms that h ad been converted to
darkrooms are n ow being converted back i nto bathrooms. The truly marvel­
ous new tec hnologies are seen by most who embrace them as the natural
evo lutionary progress of photography. Some, however, see it as somet h i ng
entirely differen t . For those who express u nease or regret at change, advo­
cates of " Progress" poin t out that photographic technology h as always been
transformi ng since its commercial i ntroduction i n 1839. O ne process has
yielded to another, over and over aga in. What we are experiencing now, they
say, is just "the closing of another chapter in the history of photography."
B ut, i t is worth considering that it may be the l ast chapter i n the book.
" P hotography"-meaning "wri ting with ligh t"-was perhaps never a
sufficient neologism to describe the totality of the technol ogy. A cons u l ta­
tion of m ultiple dictionaries will reveal a disturbing variance of definitions
for such a profo undly present and i n Auential technology. In common u sage
"photography" and "photograph" are used as synonyms, quite i n correctly.
S i m ilarly, the profession devoted to preserving p hotographs is variously called
" Ph otography Conservation," "Photographic Conservation , " and "Photo­
graph Co nservation . " Recently, the sufficiently vague "Photo Conservation"
has been gai n i ng pop u larity, but i mp l ies, i f one reasons, "the conservation of
light." The most careful practitioners avoid the problem by referring to "Pho­
tograph i c M aterials" as their professional conservation purview.
Langu age has evolved in response to the disrup tive changes in tech­
nology. It is n ow most correct to use "Imaging" where once "Photography"
sufficed. People i ncreasingly say they take or make "pict u res" i n s tead of pho­
tographs. An i ndustry that based itself on si lver-halide chemistry now t h inks
i n i nk. I n the past, p hotomechanical reproductions were not considered true
photographs. Yet, today, i n k-on-paper images, never having been sensitive to
l ight during the course of the maki ng, are treated as photographs.
The lessons of photographic history teach that there is an astonish­
i ngly rapid loss of knowledge and skill attending the commerci a l ascendance

1 08
 Reading 14 H O M E H

of one system of p hotography over a nother. M uc h research effort i n photo­

graph conservation has been , is, and will con t i n u e to be devoted to rediscov­
ering and exploring past methods of mal<.ing p hotograph s . H istoric process
re-creation is a fu ndament of photograph con servation education. Today, it
is appropriate to view s ilver-hal ide-based p hotography as an h istoric process,
even though it is still with u s. The loss of knowledge of the craft of what is
now being called "Traditional Photography" is ongo ing. The experience of
developing the latent i m age in wet chemistry, which i n the twentieth cen­
tury was the alchemical essence of the photograph i c magic, will soon be
u n known to most who use a camera. The ambigui ty of the c urrent defi n i tion
of photography contrib u tes to the obliteration of the past.
Those who make a p rofession of co nserving p hotographs m u st now be
very clear to themselves and others about the definition of "photograph." It
is a profess ional requi si te. Outside the profession i t h as been recogn ized that
the word "photograph" cannot be i n fi ni tely stretched to describe the new
tec hnology. As the bounds of the tec h nology d issolve, so does the existing
profession of p hotograph conservation. " I n fo-Imaging" has been proposed as
the name appropriate for the n ew i n du stry now in formation. I s i t thus pos­
sible that someday t here wil l be I n fo-I maging Conservation? Whatever i ts
name will be, a new profession is evolvi ng because of revolutionary changes
in technology. But it cannot, anymore, continue to be properly cal led Photo­
graph Conservation.
The legacy of n ineteenth- and twentieth-century p hotography is vast,
va l uable, and vulnerabl e . There is a pressing n eed to u nderstand that the
photography of the present and fu ture i s and will be sign ificantly different
from, rather tha n substantially the sam e as, the p hotography of t h e past. It
will increasi ngly be the rol e o f the Photograph Co nservator to make t h a t dif­
ference c lear. For the Photograph Conservation fi el d to avoi d establishing a
common definition of what constitutes a photograph i s to contribute to the
forces that destroy p hotographs.
 P A R T I I

Silver Image
Structure and Stability

Fi n ely divided s ilver is the basic i mage-formi n g substance i n most b lack­

and-white p hotographic processes-negative or positive-from the calo­
type to the gelatin si lver developed-out print. These silver i m ages dominated
the n ineteenth and twentieth centuries until they were overtaken by color
photography in the 1 960s. Silver i s a react ive, often - impermanent imaging
material that is susceptible to oxidation, resulting in faded, mi rrored, and
discolored i mages. S i lver i mage stabil i ty is a compl ex subject, and, since the
d iscovery of the earl iest photographic processes, many have searched for a
more thorough u nderstanding of i mage degradation a nd vulnerabi l i ty. Part I I
highlights research b y recognized conservation a n d i magin g scientists, from
the n ineteenth century to the present day, who have i n formed our u nder­
standing of the structure and permanence of si lver i m aging materials.

M a n Hay (American, 1890-1976). Dead leaf (deta i l ) , 1942. Gelatin silver print, 2 + 1 X 19.8 c m
( 9 Y2 X i 3l1• i n . ) . Los Angeles, J . Pa u l Getty Museum 8+x•1 . 1 000.;5
© Mm1 Ray Trnst ARS-ADAGP
 R e a d i n g 15

P H I L I P H . D E LA M O TTE , H U G H w . D IAM O N D ,
T . F R E D E R I C K H A R D WI C H , T . A . M A LO N E , J O H N
P E R C Y , H E N RY P O L L O C K , A N D G E O . S HA D B O LT

First Report of the C ommittee

Appointed to Take into C onsideration
the Question of the Fading of Positive
Photographic Pictures upon Paper ( 1 8 55)

I n the 1 840s the rapid fading of salted paper and albumen prints threatened to
discredit photography on paper. In 1 855 the Photographic Society of London
(now the Royal Photographic Society) appointed a blue-ribbon committee of
cheniists and photographers, sponsored by Prince Albert and led by the accom­
plished chemist Thomas Frederich 1-Jardwich (see also R eading 1 ), to "consider
the question of the fading of positive photographic pictures on paper. " This
was the first extended scientifi.c inquiry into the permanence of silver images.
The committee's landmarh report published in November 1 855-only sixteen
years after the introduction of photography-identified tl1e adverse effects of
residual chemistry, atmospheric pollutants, and high relative humidity as the
primary causes of print fading. R ecommendations from the pioneering "Fad­
ing Committee" (as it was popularly hnown)-including the need for careful
washing, gold toning, dry storage conditions, and the use of protective coatings
and varnishes-are still highly relevant today. Unfortunately, later writers and
researchers in the nineteenth century addressed silver image stability princi­
pally in terms of residual sodium thiosulfate (hypo) and poor washing, ignoring
the other significant causes raised by this farsighted committee report such as
air pollutants (hydrogen sulfide) ancl high relative hum.iclity.

The Comm i ttee, in this Report, propose to confine themselves to a state­

ment of the evidence which they have col lected as to the permanence of

P H I LI P H . D ELAMOlTE, H UGH Vv. D IAMOND, T. F R E D E R I C K H ARDWI C l- I , T. A. MALON E, JOHN

PEHCY, H E N BY PO L L O CK, a n d GEO. S HADBOLT, "First Report o f t h e Commi ttee appointed
to take i n to consideration t h e Question oF t h e Fading of' Positive Photograph i c P i ct u res
u po n Paper," Journal of tlie Plwtograph.ic Society, no. 36 ( N ovember 1 855): 2 5 1 -52.

1 12
 Reading 15 D E L A M O T T E E T A L .

photographs up to the time of their appointment, adding some facts in con­

nexion with the causes of fading, which are of practical val ue, reserving for a
fu ture occasion the scientifi c part of the investigation.

Evidence of Permanence

The Comm ittee have u n q uestionable evidence of the existence of photo­

graphs which have remained unaltered for more than ten years, prepared by
salting plain paper with a c h loride, afterwards m aking it sensitive with either
n itrate or a mmonia-ni trate of si lver, fixi ng with a fresh ly-made solu tion of
hyposu lph ite of soda and washi ng in water;-also of positives produced by
Mr. Ta lbot's negative process.
They have not been able to obtain evidence of photographs having
been prepared at all upon al b u m in ized papers, or coloured with a salt of gold
or fixed with "old hypo," so long ago as ten years.
They have, however, ample evidence of the existence of u nal tered p ho­
tographs so prepared five, six, and seven years ago.
They have not fou n d that any method of printing which has been com­
monly followed, will necessarily prod uce fad i n g pictures, if certain precau­
tions be adopted, n or have they evidence that any method which has been
adopted, will n ot produce fad i ng p ictures u nless such precautions are taken.

Causes of Fading

The most common cause of fad ing has been the presence of hypos ulph ite of
soda, left i n the paper from imperfect washing after fixing.
The C o m m ittee t h i n k it right to state, that they have been u nable to
find any test to be relied upon, which can be used to detect a m i n ute portion
of hyposu lphite of soda, in the presence of the other substances which are
obtai ned by boiling photographs in distilled water and evapora t i ng to dry­
ness; yet they have no doubt of the tru th of the above statement, from the
history given of the mode of was h i ng adopted.
The continued action of sulphuretted hydrogen and water will rapidly
destroy every ki nd of p hotograph; and as there are traces of this gas a t a l l
time present i n t h e atmosphere, a n d occasionally i n a London at mosphere
very evident traces, it appears reasonable to s uppose that what is effected
rapidly in the laboratory with a strong solution of the gas, will take place also
slowly but surely i n the presence of moisture, by the action of the very m i n ­
u t e portion i n t h e atmosphere.
The Committee find that there is no known method of prod ucing pic­
tures which �vi i i remain u na ltered u nder the continued action of moisture
and the atmosphere i n London .
P a rt II S I L V E B I M A G E S T B U C T U B E A N D S T A IJ I L I T Y

They find t hat pictures may be exposed to dry sulphuretted hydrogen

gas for some t i 111e with co111p aratively l ittle alteration, and that pictures in the
coloration of which gol d has been used, are acted upon by the gas, whether
dry or in solution, less rapidly than any others.
They also find that so111e pictures which have re111 a i ned u nal­
tered for years, kept in dry places, have rapidly faded when exposed to a
111oist atmosphere.
He n ce it appears that the most ord i nary cause of fad i ng, m ay be traced
to the presence of sulphur, the sou rce of which 111ay be i n trinsic fro111 hypo­
su lphite left in the print, or extri nsic from the at111osphere, a nd i n either case
the action is much more rap id in the presence of 111oisture .

M ode of M ounting P hotographs

The Co111 111 ittee fin d that taki ng equal weights, dried at a temperature of
2 1 2 ° , of the three substances most frequently used, viz. gelatine, gu 111 and
paste, the latter attracts n early twice as much 111oisture as either of the for-
111er; and as i n practice a m uch smaller weight of gelatine is used than of
gu 111, gelati ne appears to be the best medium of these three; and the Com­
m ittee have evidence of fadi n g having in so111e cases been produced by the
use of paste.
ln i l l ustration of some of the circumstances a l l uded to above, the
Co111111i ttee th i n k it well to mention some i n stances of prints at present i n
their possession.
Out of several prepared together in 1 844, three only are u n al tered, a nd
these were varnis hed soon after their preparation with copal varni sh .
H a l f of another pri n t o f the sa111e date was varnished, and t he other
half left; the u nvarnished half has faded, the varn ished re111a ins u nal tered.
Th ree pictures were prepared in 1 846, all at the same time, with the same
treat111ent; when fin ished, one was kept u n mounted; the other two were
mou nted with Aour-paste at the sa111e time, one of these latter hav i ng been
first coated with Canada balsa111; at present the u n 111ou nted one and the one
protected with the balsam are u nchanged, whereas the other has faded .
A p icture prepared i n 1 846 was so exposed that the lower part of it
became wetted with rai n ; at present the part so wetted has faded, while the
rest of i t rem a i ns u n altered. Several pictures were prepared and mounted
about ten years ago, and kept in a dry room for about three years without
any change, after wh i c h they were placed in a very da111p situation, and then
faded decidedly i n a few months.
The Co111 m i ttee propose very shortly to actually test the durabi l ity of
the various modes of prin ti ng, by exposi n g pictures to differen t treatment,
 Reading 15 0 E L A i\ 1 0 T T E ET A L .

and they have been fortu nate enough to obtain a gran t of space for t h i s pur­
pose fro m the Crystal Palace Company.
The Committee make the fol lowing suggestions, arising out of the
above Report:-
1 . That the greatest care should be bestowed upon the washing of the

prints after the use of hyposulphite of soda, and for t h is p u rpose hot water is
very m u c h better than cold.
2 . The majority of the Comm i ttee think that gol d , i n some form, should
be used in the preparation of pictures, a lthough every variety of tint may be
obtained without it. 1
3. That photographs be kept d ry.

4 . That trials be made of su bsta nces l i kely to p rotect the prints fro m
a i r and moisture, such as caoutchouc, gutta percha, wax, and the different
varnishes.

Notes

1 Dr. Percy and M r. J\ l alone consider t hat t here is not sufficient evidence i n
favou r of gold, to warrant this recommendation of i ts general use.

115
 R e a d n g 16

TH O MAS H . }AME S

The S tability of Silver

Filaments ( 1 96 5 )

Thomas Howard James ( 1 9 1 2-2000) was a 1?hotographic research scientist who

worlzed for Eastman /(odah for 42 years starting in 1 936. His areas of research
included the develo1nnent of photographic film, latent image effects, and
chemical and spectral sensitization. Prior research, especially Crabtree et al.,
"The Elimination of J-lypo from Photographic Images" (Journal of the Society
of Motion 35, no. 5 [November 1 940]: 380), identified fixer as a substance that
caused degradation of the silver image at any concentration and that must be
re·moved completely. This 1965 article is the first published research to dem­
onstrate that small a·mounts of fi,wr left in a gelatin silver emulsion play a
1notective role by coating the silver particles and offering moderate resistance
to oxidation.

It is wel l known that direct development of si lver halides i n n ormal photo­

graphic e m u lsions produces filamentary silver. F i la ments that differ rem ark­
ably l i ttle i n size and form have been obtai ned in development of silver
chloride an d s ilver iodide grai n s as well as i n the development of the more
common chlorobromide, bro mide, and iodobro m ide grains. 1 Because of the
large surface-to-volume ratio and the corresponding high su rface energy,
however, these filaments should be t hermodyna mically u nstable, and i nsta­
bility has been demon strated in certain cases. Klein and Weyde, 2 for exam­
ple, have foun d that the filaments formed by development of a hardened

THOMAS H . ]AMES, "The Stab i l i ty of Silver F i l a ments," Photographic Science ancl Enginea­
ing 9, no. 2 ( Ma rch-April 1 965): 1 2 1 -32. Text a n d i m ages reprinted by permission of I S &T:
The Society for I maging Science a n d Tech n o l ogy, sole copyright owners of Phot:ographic
Science a n.d Engin,eeri.ng.
 Reading 16 J /\ M E S

si lver c hloride emulsion rec rystall ize to form rou n ded particles wi thin a few
m i n utes when the developed layer is dried at abo ut 1 20°C. The recrystal­
l ization, and the accompanying change in i mage density and tone on hot
drying (plu m m ing or bronzing), could be preven ted by adding 1 -phenyl-5-
mercaptotetrazole to the fixi ng bath. This agen t presu mably stabilizes the
filaments by formi ng a n adsorbed layer o n the silver. Genda and Sakagu chi 3
l i kewise have observed a recrysta l lization of filaments i n preparations made
for observation u nder the electron m ic roscope. A pronounced thickening of
the fi laments occurs when the gelat i n layer is d issolved in water at tempera­
tures above 6o°C.
According to Jaenicke, 4 the filaments formed d u ri ng development
are highly d isordered, and adsorbed i mpurities such as gelatin, sulfide, and
iodide are i mportant both in the growth and in the relative stabi lity of the
fi laments formed u nder normal conditions. Keith and M itchell,5 l ikewise,
have emphasized the i m p ortance of adsorbed impuri ties, parti c u larly s u l fide,
i n stabilizing the fi l a ments.
The work described in this paper shows that adsorbed thiosul fate from
the fixi ng bath, or possi b l y s ulfide formed by decomposition of the thiosulfate,
exerts a significant stab ilizing action o n the silver filaments formed in normal
processing of s ilver c hloride, chlorobrom ide, and bromide e mulsions. S ilver
fi laments formed by complete red u ction of the s ilver halide grains become
thicker and s horter when the u n fixed film is stored for a few days at 1 00%
R H at room temperature, and the filaments rec rystallize to rounded particles
within a few m i nu tes when the developed fi l m is i mmersed i n certain salt
sol u tions, particul arly t hiocyanate and c h loride solutions. These changes
occ u r m u c h more s lowly i n fil m s that have the n ormal fixing treatment in
a thiosu lfate ba th. I od ide, origi nating from a processi ng solu tion such a s
the developer, stop bath, or fixi ng b at h , or even from t h e silver halide itself,
exerts a significant stab i l izing action on the filaments. The protective action
of the iodide very probably depends o n its adsorption from the processing
solutions by the s ilver filaments. When the origi nal si lver hal ide contains
iodide, the iodide ions pass i nto solution d u ri ng development or fixation and
become ava i lable for adsorption by the si lver.
The conversion of filaments to rou nded particles duri ng storage at h igh
h umidity or by the action of the thiocyanate and c hloride solutions resu l ts
i n a loss in reflection density and a c hange i n the image tone to ref lected
l ight (bronzing), regardless of the size of the origi n al silver h a lide grains from
which the filaments came. Changes in transmission density, however, are
small or negligible for coarse-grain emu lsions, and i mage tone for trans­
mitted light is scarcely affected. Fi ne-grain e m u lsions may show an actual
i nc rease in transm ission density, and a sign ificant change i n i mage tone, for
transmitted l ight.

II 7
P a rt II S I L V E R I M A G E S T R U C T U R E A N D S TA B I L I TY

Experimental M aterials and Procedure

The experimental emul sions used in this investigation, which had been pre­
pared by various methods for other research projects, are l isted i n Table 1 . All
were prepared with i nactive gelatin. E m u lsions W and X were special coat­
i ngs of commercial emu lsions; E mu lsion ] was a chlorobromide counterpart
of W; and R was a p u re bromide counterpart of X. U nhardened, and also
u nsensit ized samples of several of the e mulsions were available, and tests

Table 1
E m u lsions u sed i n tests.

Approximate Ag
Designation H a l ide gra i n size ( p ) ( mg/sq ft)

A Br 0. 1 53a
B Br 0. 1 5i1
c Br 0.2 J OO
b

0' Br 0.4 89 "

E'1 Br 0.7 90 "
f' Br 0.7 77"
C '' Br 1 .2 99 "
1-l' Br 1 .9 54 °
I' Br 1 .4 54 °
Cl, Br Fine J OO

K Cl, Br Fine 54 °
L Br Medi u m 360
M Br Medium 435
N Br Fine 432
0 Br Coarse 381
p Br Coarse 54 °
Q Br Coarse 540
R Br Fine ,go
.)

s 1 0% 1 F i ne 360
T 5% I Fine 4 32
u 5% I Medi u m 46 1
\I 1 0% I Fine 395
w I , Br Fine 1 00
x I , Br Fine 380
y Cl Fine
z Cl M ed i u m

a coated a t 100 g gelatin/sq ft.

11Coated at 540 g gelatin/sq ft.
c c u bic grains.
11 Cubic and octahedral grains.
e Octahedral grains.

1 18
 Reading 16 J !\ M E S

on these showed that nei ther harde n i ng nor su lfur-sensitizing had any large
effect on the stability of the s ilver filaments obtain ed from these emulsions.
Emu lsions A and B , which were u sed for m u ch of the work, were coated at a
n ormal s ilver-to-gelatin ratio, but at a coating thickness of o n ly about 2 'fl.
I n general, the fi lm was exposed u niformly to a level corresponding to
the maxim u m deve lopable density a n d rate of development. The exposed fi l m
was developed for 2 m i n i n t h e dark i n a h igh-pH hydroxylami n e solution, i n
a Metol-ascorbi c acid ( M -AA) surface developer, o r i n Kodak Developer D- 1 9
at 20°C. Development was then continued for 1 0-30 m i n , depending o n the
developer, with the film rotating i n the prese nce of a 1 , 000-w t u ngsten lamp
at 50-cm d istance from the film. In all tests, substantially complete reduction
of the si lver hal ide was obtained in this way. The fil m was then washed for
30 m i n i n r un ni ng water at 20°C and d ried at room temperature. Other sam­
ples, developed in the same way, were rinsed in water, "fixed" for 4 min i n
Kodak F ixing Bath F-5, then washed 30 min , and dried.
Changes in the structure of the developed silver were detected by:
( 1) total transmission or reflection density measurements over the range
400-700 mri; (2) crystalli te-size determi n ation by x-ray d i ffraction/' u si ng the
( 1 1 1 ) reflection; and (3) electron m icroscopy.
Two types of equipment were u sed for the storage tests at h igh h u m id­
i ty. One was a simple desiccator containing about a n inch of water i n the
bottom . The second was a jacketed cylinder with a perforated tubu lar ring
at the botto m . The ring was covered by 3 i n . of water, and a slow stream of
water-vapor-saturated gas ( nitrogen , oxygen , or air) was passed through the
ri ng. The fi l m samples were suspended in the cyl inder so that the bottom
of the film was 3 in. above the water level. The temperature was controlled
by thermostated water ci rc ulated t hrough the jacket. Neither the hardened
nor the u n h ardened coatings reticulated u nder these conditions.

Experimental Results

Changes in Density on Storage at High Humidity

Figu re 1 s hows the spectrophotometric curves ( total transmission densities)

of samples of the fine-gra i n E m u l si o n A that had been developed a t 20°C i n
a solution of 4 . 1 g of hydroxylamine sulfate and 8.o g of sodiu m hydroxide/l,
washed, and dried before i n troduction i n to the desiccator. The n u merals on
the curves refer to hours in t h e desiccator at 2 1 °C. All samples were a l lowed
to stand i n an open room at 50% R H for at least 2 hr before densities were
read. Densities for a l l wavelengths i n c reased with i n creasi ng time of storage
at the r oo% R H , and a max i m u m appeared in the spectrophotometric curves

1 19
 Part II S I L V E H I M A G E S T H U C T U H E A N D S TA B I L I TY

3.0 �----�-----�--�

2.5

.£ 2.0
V>
c
(!)
"Cl
c
150

.2
V>
V> 3
E
V>
1.5
c
_g
15

Figure 1 � 1.0
Changes in transmission densities
of s i lver images developed by
hydroxylaminc in E m u lsion A.
The n u mbers on t he cu rves refer 0.5
to hours or storage over water
at 2 r °C in a desiccator. Solid
c u rves, u nf-ixed samples; dashed
cu rves, fixed samples. o �----�-----�--�
400 500 600 700
Wave length (mµl

of the u n fixed samples at about 620 myi. The change i n density of the fixed
samples was m u ch smal ler and no m ax i m u m appeared in the spectrophoto­
m etric curve.
S im ilar changes occurred in strips developed by the M -AA and D - 1 9
developers. O n l y m i nor differences were observed i n the behavior of the
u nsensitized, reduction-sensitized, a nd sulfu r-sensitized versions of this
emulsion, or between hardened and u nhardened coati ngs.
A decrease in reAection density accompa nied the i ncrease in transmis­
sion density in the sam ples stored at high h um i d i ty. Figures 2 and 3 i l lustrate
this for samples deve loped by the M -M developer of pH 9.7. The changes
i n density were less for the samples that had been treated in F-5 than for the
u nfi xed samples. A solution of 2 4 0 g of hypo and 1 5 g of sod i u m s u lfite/I at
pH 1 0 gave about the same degree of stab i lizati o n against the density changes
as that obtained with the F-5, indicating that pH was not a n i mportant factor
i n this action.
Oxidation of the s ilver by air did not appear to be involved to a ny large
exten t i n the den sity cha nges. Esse ntially the same changes in density were
obtained when the strips were stored i n a water-vapor-saturated atmosphere
of p ure oxygen or pure n itrogen as i n air. M oreover, after storage at the high
h u m idity, the i m age was altered to only a very sl ight extent by treatm e n t

1 20
 Reading 16 J i\ M E S

3.0 �-----�----� 3.a

2.5 2.5

\
\
\
\
\
\
\ \
\
2.0 2.a
\ \
\ \
\ \
\
\T \
\
\
T\
·� 1.5
>-
\ ]::-
·v; 1.5 \ \'
c
Ql '• Ql •

0 '• 0 ,
,,
::::::: :: ::::::
,

- - -- ------:::::::::- -
R
---- �- -----:::::::::::::
,,
__ _ _ _ _ _ _ _ _ _:::.

R R
1.0 1.0

0.5 a.5

o �-----"----"--' O �-----�----�
400 500 600 1ao 400 500 600 700

Wavelength (mµj Wave length (mµj

Figure 2 Figure 3
Ch<J ngcs in transmission, T, and reAection, R, densities Same condition as Figure 2, except fixed film was used.
on s torage of u nfixed fi lm for 1 32 hr over water at 2 1 ° C .
Dashed c u rves, original densities; solid c u rves, densit ies
<Jfter storage. E m ulsion B, development in M-AA.

i n the h igh-pH hydroxyla m i n e solution or in D - 1 9, which would reduce any

silver oxide or h alide, or by treatmen t in F-5, which would dissolve either of
these silver compou nds.
The rate of change of density i ncreased markedly with i ncrease i n the
te mperature of storage at the h igh humidity. Th is is i l l ustrated in Figure 4,
where the density measured at 650 myi was plotted against the duration of
storage for the three temperatures noted on the c u rves. The upper half of
the figure gives data for strips developed in the IVl-AA developer and washed
without fixing, and the lower half gives data for strips that had been soaked
for 4 m i n in F-5 before was h ing. The density of the u nfixed strip stored at
49°C passed through a maxi m u m . Thi s same phenomenon was observed at
lower temperatures on prolonged storage. In the short-wavelength region,
however, densi ty cont in u ed to i ncrease, and a maxim u m in the spectropho­
tometric curve appeared at a wavel ength sl ightly longer than 400 mp , sug­
gesting the appearance of a "colloid band." These changes are i l lustrated i n
Figu re 5 for strips developed i n D-19. Neither the short-wave maxi m u m nor

121
 Part II S I L V E H I M A G E S T H U C T U H E /\ N D S T A B I L I TY

No hypo treatment
18

;§
0
1.0
2'
·u;
113 1 8 Treated 4� minutes in F· 5
0

16 0.5
49.1°

,4 � : :
/ --. _
-__
38 5 '
_. ------
-·- 29.3
� '
2 3 �00
������00
5������6J
0_
0����-�
7 00
Duration of storage ( hours) Wave length (mµ)

Figure 4
Effect o f storage temperature on transmission densit y of unfixed (top
half) and Vixcd {bottom half) strips of Emulsion 13, developed i n M·AA.
n
Figure 5
C hange in transmission de sity of an unfixed image
developed by D-19 in E m ulsion B and stored over
water at 49°C for the duration stated on the curves.

the decrease 1 11 densities 111 the long-wave region were observed with the
fixed strips.
E lectron micrographs showed that a defi n i te change in the filament
structure occu rred d u ring the storage at h igh h u m id i ty. The original long,
thi n fi l a men ts of the u n fixed samples ( F igure 6) became t h icker and shorter,
and many of them appeared to break i n to segments ( F igure 7 ). Some nearly
spherical particles l i kewise formed. S i mi lar changes occu rred in the fi la­
ments of the fixed samples, but more slowly and to a smaller degree.
The crysta l l i te size of the developed si lver in the u n fixed samples
i ncreased considerably upon storage at the high h umidity, and the crystal l ite
size i n the fixed samples increased to a smaller extent. Some data are given
i n Tabl e 2 for fi lm stored at mo% RI-I and 2 1 °C .
Fi laments obta i ned b y development o f coarse-gra i n si lver bromide
e m ulsions appeared to be no more stable at h igh h u midity than those
obtained from the fin e-grai n emulsions, but the cha nge in form of the sil­
v er h ad l ittle effect o n the transmission dens i t ies. Table 3 gives density a nd
crystal l i te-size d at a for si lver deposits obtained from a wide range of sizes of

122
 R eading 16 J f\ � I E S

.... .

_.____._ _I_
Figure 6 Figure 7
Electron micrographs of fi l a mentary si lver formed by development Electron micrograp h of silver o f Figure 61 after 1 -wk storage
of E m u lsion B in D-19. The parallel bars indicate 1 11. over water al 2 1 °C . The para llel bars indicate 1 11.

Table 2
Change in density and crysta l l ite s ize, E m u lsion B, stored at 1 00% H H at 2 1 "C .

Density a t 6 5 0 111 µ Crysta l li te size in A

Developer Origin a l after 1 3 2 h r Ratio Original after 1 3 2 hr Ratio

M-AA-1 1.14 1 .49 1 .3 1 1 98 ± 5 247 ± 7 1 .25

1 . 14" 1 .23n 1 .08" 1 84 ± 4 1 94 ± 4 J .O)a
D-19 1 . 13 1 . 53 1 .35 1 94 ± 4 270 ± 9 1 .39
1 .08" 1 .24:1 I . 1 5:• 1 82" ± 4 2 1 4" ± 6 I . I i•

a v al u e refers to samples fixed in F-5; other values arc for unfixed samples.

s ilver bro m ide grains. The change in crystal l i te s ize on storage at the h igh
h umidity did not seem to depen d o n the size of the original s i lver bromide
gra i n . E lectron m icrographs confirmed the change i n fi lament structure to
s hort thick filaments and rou nded particles in al l of these e mulsions. On
the other hand, only the two finest-gra i n emulsions showed large increases

1 23
 Part II S I L V E H I M A G E S T H U C T U H E A N D S TA B I L I T Y

Table 3
Cha nge in density and crysta l l i te size on moist i n c u batio n .

C ry s t a l l i te size, A

Emu lsion AgBr crystal Origi n a l D, 6. D after 4 hr I \Vk % i ncrease

designation size, µ Fixation 7 00 m µ 4 hr 38.5°C Original 3 8 . 50C 2 1 °C I wk

A -0. 1 None 1 . 13 + 0 .54 191 248 3o5 60

c 0.2 None 1 . 64 + 0 .52 209 281

D OA None o .93 + 0.05 243 316 351 44

E 0.7 None 0 . 70 +0.01 1 80 237 288 60

F 0.7 None 1 88 23 1 337 79

c 1.2 None 0.46 0.00 23 1 297

H - 1 .9 None 0.9 4 - 0 .08 226 297 326 44

F-5 1 . 03 - 0 .08 226 26 1 253 12

-1.4 None 1 .05 - 0 .09 248 3o5 3 79 53

F- 5 1 .05 -0.05 248 267 273 10

in transmission density accompanying the change in filament struct u re .

Th e coarsest-grai n e m ulsions showed some density loss and, even wh e n the

fi laments had been converted largely to rou nclecl particles, the i mage tone
remained essen t ially neutral to tra nsmitted l ight.
Thiosulfate exerted a part ial stabi l izing action o n the filaments formed
by development of the l arger si lver brom ide gra i ns, just as it did on the fila­
ments formed by development of the fine grains. O n ly data for the two largest­
grain emu lsions are given i n Table 3 for the fixed samples, although a s i m i lar
stabil ization was observed for all e mu lsions of this pure bromide series.

Effe c t of Iodide

l ocl icle, l i ke thiosulfate, exerted some stab i l izing action on the silver fi la­
ments, as i l lustrated i n Figure 8 for E mu lsion A. The solid curves repre­
sent the u n fixed, u n treated control which had been washed for 25 m i n a t
20°C after development, and then dried. Th e lower soli d curve represents
the dry strip before storage, and the upper solid c u rve after 4.5 clays' storage
in the desiccator over water at 2 1 °C . The clashed curves are the correspond­
i ng curves for the sample that had been washed for 5 m i n after develop­
ment, i m mersed for 5 m i n in a 5% potassiu m iod ide sol ution at 20°C, and
then washed for an additional 15 min. Approxi mately the same densities were
obtained for a strip that had been rinsed for o n ly 30 sec fol lowing the iodide
treatment. Un Ii ke t hiosulfate, iocl icle prod ucecl some i ncrease i n the origi na I
density at the longer wavelengths. The addition of iodide to the th ios u l fate
fixing bath fu rther enhanced the stabilizing action of the thiosu l fate.
 Reading 16 J J\ M E S

3.0 .-------,--,---�

2.5

0 Figure 8
� 1.0 C u rves showing effect of storage
at 2 1 °C for +5 d ays over water on
transmission densities or u n t reated
{solid c u rves), Kl-treated {dashed

0.5 c u rves), and KCNS-trcatcd {clotted

c u rves) samples of E m u lsion 1 3 ,
developed in D-19. Lower c u rve of
each pair represents t h e sample
o �----�-----�--� before storage at high h u m idity.
400 500 600 700
Wave length (mµ)

Another i n d ication of the protective action of the iodide was its effect
on the catalyt ic activity of silver i n decomposing hydrogen perox i de. I n t h i s
test, square samples o f fi l m 1 5 m m o n edge were i m mersed, e mulsion side
up, i n a hydrogen peroxide sol ution prepared by d i l uting 20 ml of 2 5-30%
hyd rogen peroxide and 1 0 ml of reagent am m o n i u m hydroxide to 1 ,ooo ml
w i t h water. Fifty m l of solution at 22°C was u sed i n a 1 00-ml beaker for
each test. I n ti me, b ubbles of oxygen appeared o n the fi l m sample. These
genera l ly adhered to the fi l m and, when enough had become attached to
the f i l m , the sample rose rapidly to the su rface of the sol ution.7 The time of
first appearance of bu bbles on the f i l m and the time req u i red to "float" the
sample were noted.
B u bbles appeared on the developed, u n frxed samples of si lver bromide
or c h lorobrom ide e m u l s ions i n 3-4 sec, and the time req u i red to Float the
samples ra nged from 8 to 17 sec. \i\lhen, however, the developed samples,
after the i n i tial wash ing, were i mmersed for 5 m i n in 0.2% potass i u m iodide,
then washed a n additional 10 m i n and d ried, the time of appearance of b ub­
bles i n the peroxide test was 1 - 1 . 3 m i n , and the time requi red to Float the
samples ra nged from 3 to 9 m i n , depending o n the e mulsion wh ich sup­
plied the developed silve r. The post-development iodide treatment thus had
decreased the rate of peroxide attack by between one and two orders of mag-

1 25
Part II S I L V E H I M 1\ G E S T H U C T U H E A N D S T A B I L I TY

nitucle. Post-treatment i n the fixing bath also decreased the rate of peroxide
attack on the si lver.
I od ide derived from the development of si lver ioclobromicle e m u l­
sions also appeared to stabilize the si lver filaments to some extent. The time
req u i red to float the developed samples of the ioclobromicle e m u l s ions l i sted
i n Table 1 ranged from 30 to 265 sec, compared to the 8 to 17 sec req u ired to
float the samples of chlorobromicle and bromide emu lsions. Crysta l l i te-s ize
determ i nations on the developed si lver gave val ues in the same range for
both the pure bromide and the ioclobrom icle e mulsions, and the s i m ilarity
i n filament s ize was further su pported by electron m icrographs. H ence, the
d i fference i n reactivity towards the peroxide can not be attribu ted to a d i ffer­
ence in spec ific su rface of the filaments from the various e m u lsions. M ore­
over, the activity of si lver obtained by development of ch lorobromicle and
bromide e m u lsions i n D-19 to which 2 g of potassium iodide had been added
per l iter was s i mi lar to that obtained by development of the ioclobrom icle
emu lsions in D- 1 9 alone.

Effect of Thiocyanate and Chloride

Th iocyanate and ch loride had an entirely d i ffe re nt effect from that of iodide.
Thiocyanate and ch loride prod uced a larger i ncrease i n the density of the sil­
ver derived from the fine-grai n c hlorobromicle and bro m ide emu lsions, and
ca used a partial or complete destruction of the filamentary structure. The
effect of thiocyanate on density of developed E m u lsion B can be seen by
comparing the clotted c u rves of Figu re 8 with the sol id c u rves. The lower
so l i d c urve represents the developed and washed, but otherwise u ntreated
dry sample, and the lower clotted c u rve, developed fil m that had been washed
for 5 min after development, i m mersed in 5% potass i u m th iocyanate solu t ion
for 5 min, then washed for 15 min and dried . The u pper solid and clotted
c u rves represent the respective samples after storage in a desiccator over
water for 4 . 5 clays.
Potass i u m ch loride had much the same effect as potassium thiocyanate,
whereas the bromide had a much smaller effect. The action of the sod i u m
salts was nearly t h e same a s that of the potassium salts, i nd icat i ng that t h e
an ion is the i mportant agent. Potass i u m nitrate, potassi u m s u l fate, sod i u m
s u l fite, ammon i u m hydroxide, a n d u rea were substantially without effect.
The wet strips of film, fresh ly removed from the thiocyanate and c hlo­
ride sol utions, were yellow to orange when viewed by transmitted l ight, and
the tone changed markedly on d ryi ng. The change is i l lustrated by the spec­
trophotometric curves i n Figure 9. The d i fferences i n the forms of the cu rves
for the wet and the d ry samples that had been t reated in the t h i ocyanate
solution are i n con trast to the results obtai ned with the untreated control,
 Reading 16 J A M E S

...
�
• � .. .,.,,.

,,
...
�2.0
"'
c
Q)
u � ,,
c .,.,.
0 "
·� 1. 5
E
"'
2' "'\:
�
c

,
� 1.0

; l

0.5

� �
. . .,.
..

I L.� �
r

o �������
400 500 600 700

Wave length (m,u)

• •

Figure 9
Transmission density curves of unlreated (solid c u rves)
and KCN S-treated (dashed c u rves) samples ol' Emulsion B.
'
Cu rves 1. r ', wet samples: curves 2. 2 . dry samples.
Figure 10
Electron micrograph uf developed silver treated 5 min
in 5% KCNS. The parallel bars indicate 1 11 .

where dryi ng caused l i ttle more than a shift of the entire c u rve along the
density axis.
The thiocyanate and ch loride treatments caused a n i ncrease in crys­
tal l i te size similar to that obtained by storage of u ntreated fi l m at the 1 0o%
H.H . Electron micrographs showed that the fi laments had been completely
destroyed and had been replaced by spherical or somewhat elongated
rou nded particles ( Figure I O ) . Each filament appeared to have broken u p
i n to several s u c h particles. Neither t h e absorption spectru m n o r t h e appear­
ance of the particles in the electron microscope was altered s igni ficantly by
further treatment of the samples in D-19 or in F-5. Therefore, no substa ntial
amount of silve r salt which cou ld be reduced by D-19 or dissolved by F-5
had been formed by the t hiocyanate or c hloride treatment. Moreover, x-ray
a nalysis showed evidence of only s i lver.
Although an active developer such as D - 1 9 had no effect upon the
deposit remaining after treatment of the developed i mage in the thiocya­
n a te or chloride solutions, the presence of an active reducing agent, such as
Pa rt II S I L V E B I t\I A G E ST B C C T L H E 1\ N D S TA B I L I TY

Table 4
Treatments of' developed E m u lsion B at 22°C .

Test n o . Treutment
00 \"later o n ly
0 5% KC N S 5 m i n
J\ 1 -AA developer, p H 9 . 7, con tg. 5 % KC N S , 5 m i n
2 5 % KC N S satd. w i t h AgC N S , 5 m i n
3 5 % KC N S , 3 . 5% Koda l k, 5 m i n
-I 5 % KC N S , 25 m i n
J\11 -AA developer contg. 5% KC N S , 2 5 m i n
6 5 % KC NS satd. w i t h AgC N S , 2 5 m i n
7 5 % KC N S , 3 . 5% sod i u m s u l fltc, 2 5 m i n
8 5 % KC N S . 3 . 5% Koda l k, 1 % ascorbic acid. 25 m i n
9 5 % KC N S , 3 . 5% Kodalk, 0 . 5% hyd roxylamine s u l fate, 25 m i n
10 1 0% KCI. 3 m i n
II 1 0% l<C I , 3.5% Kodalk, 1 % ascorbic acid, 3 m i n
12 1 0% KCI, 3.5% sod i u m su l fite, 3 m i n
13 1 0% KC I , 2 5 m i n
1 -j 1 0% KC I , 3.5% Kodalk, 1 % ascorbic acid, 2 5 m i n
15 1 0% KC I , 3.5% sod i u m s u l fite, 2 5 m i n

Metol or ascorbic acid, in these solutions inAuencecl the rate and degree of
conversion of the fl laments to rou nded particles. The effect of several reduc­
ing agents is i l l ustrated by the series of tests described in Table 4. E mul ­
si o n B , developed i n D - 1 9 and washed and d ried without fou ng, was used i n
a l l tests. Th e solutions were contained in beakers i n air, and the test strips
were su pported so that only the lower half of each strip was i m mersed in
solution.
The t reated portions of strips o , 2 , 3, 4 , and 6, when wet, were orange
yel low to t ransmitted l ight from a tu ngsten lamp; strips 1 , 5, and 8 were
less affected by the treatment b u t had a yellowish appearance when wet.
Strips 10 and 13 were deep reel when wet ; 12 and 1 5 were similar to 10 and
1 3 in appeara nce but were of lower density. Spectrophotometric cu rves
(total t ransm ission density) of the d ry strips that had been treated in the
thiocya nate solutions (strips o through 9) arc shown i n Figures 1 1 and 1 2 . All
treatments ca used an i ncrease i n density and a change i n c urve shape. The
smallest changes were those ca used by sol ut ions 1 , 5, 8, 1 1 , and 1 4, which
contained one or more strong reducing agents (either ascorbic acid alone
or with J\ll etol) i n addition to the KC N S or KC I . S u l flte and hyclroxylami ne,
weaker reducing agents, al lowed a greater change (nos. 7, 9, 1 2 , 1 5) . The
greatest change occu rred in the strips immersed i n the KC NS-AgC N S solu­
tion ( 2 and 6).

128
 R ea d i n g 16 J i\ M E S

3.0 ----,--.---�
,-

2.5 2.5

2.0 2.0
:?:' :?:'
·v;
c ·v;
<l> c
" <l>
"
c
0 c
·v; 1.5 ·� J.5
.'!? "'

E
"'
c ·�c
_g �
0
1.0 0 1.0
;§ ;§

0.5 0.5

0 ------�----�
400 500 600 700 500 600 700
Wavelength (mp) Wavelength (mp)

Figure 11
Cu rves showing effect of KCNS solutions on transmission
density of a si lver image developed by D-19 i n E m u lsion B.
C u rve oo, water control; curve o, 5 % KC NS; curve 1 ,
5% KCNS in a M-AA developer; cu rve 2, 5 % KC NS
saturated with AgC N S ; curve 3, 5% KCNS, 3.5% Kodnlk.
All treatments are for 5 min at 22°C.
Figure 12
Curves showing effect of KCNS solutions on transmission
density of a s ilver image developed by D - 1 9 i n Emulsion B .
Curve oo, water control ; cu rve 4, 5% KC N S ; curve 51
[5%] KCNS in a J\11-AA developer; c u rve 6, 5% KCNS
saturated wit h AgC N S ; c u rve 71 ;% KC NS, 3.5% sod i u m
s u l fite; cu rve 8, 5 % KC NS, 3.5% Kodalk, 1 % ascorbic acid;
c u rve 9, 5% KCN S , 3.5% Kodalk, 0.5% hydroxyla mine
su lfate. All treatments arc For 25 min at 22°C.

Electron-microscope observations and crystallite-size determi nations

(Table 5) correl ated i n a general way with the observed changes i n dens ity
and shape of the spectrop hotometric cu rves. The filamentary s i lver formed
by development showed some cha nge towards shorter and thicker fi laments
i n the solutions con ta i n in g KC N S or KC I and ei ther ascorbic acid alone or
M etol and ascorbic acid, and some in c rease i n crysta ll i te size was observed.
G reater changes i n structure, as seen in the electron micrographs, appeared
in the samples treated i n KCN S or KC l solutions contai n i ng hydroxylamine
or sulfite as reducing agen ts, and a complete, or nearly complete, replace­
ment of filamen ts by rou n ded particles was observed when the KC NS or
KC I sol utions were u sed alone or satu rated with the s ilver salt. The changes
were irreversible, a n d no c hange i n appearance was observed when samples
that had been treated in the KCNS and KC I solutions were subsequently
i m m ersed i n the M -AA developer of pH 9.7 or in D - 1 9 .

129
Table 5
Crystall ite-size and electron-microscopic observa t ions on strips l i sted in Table 4 .

Observations from
R ed u c i ng Time C rys ta l l i te e lectron m icrographs
u gen t Test no. (min) size, A of silver

00 1 69 ± -l F i la mentary; a few rounded

part icles, usually attached to
Ii laments.

0 204 ± 6 Mostly rounded particles ol"

va rious sizes; a few Fi laments.

!YI-AN 195 ± 6 M ostly F i la me n ts, b u t shorter

than no. oo; some iso lated
ro u n ded particles.

2 215 ±: 6 i\ l ost of part icles rou nded;

rn rely f i l a me n ts .

3 1 99 ± 6 1\ l ostly rounded particles; a l"cw

I i laments.

-l 25 232 :!:: 8 Rounded particles on ly.

i\ 1 -AA 25 195 ± 6 i\ l ostly f i l a ments; some rounded

particles.

6 25 225 ±: 8 Rou nded particles on ly.

Sul lite 7 25 204 ± 6 S h ort Filaments and rounded

part icles.

AA 8 25 204 ± 6 F i la m ents and rounded

part icles.

N H ,0 1-1 9 25 1 99 ± 6 J\ l ostly rounded particles; some

short F i l a ments.

10 3 1 99 ± 6 Rou nded particles ; a few short

Ii laments.

AA I I 3 1 72 :::!: 4 F i l a m ents, t h i c ke r t h a n n o . oo;

some rounded particles.

S u l lite 12 3 199 ± 6 l�ou nded particles; a Few short

Ii laments.

13 25 209 ± 6 Rounded particles.

AA 1 -j 25 1 99 ± 6

S u l l i te 15 25 220 :::!:: 7 Rounded particles; a few short

f i l a ments.

·' � I = 1\ l e t o l : AA = ascorbic acid

 Reading 16 J t\ ,\ I E S

That air m ight play a role in the cha nge effected by the KC NS and
KC I solutions was i n dicated by the formation of a "col lar" on some of the
partia lly im mersed strips at the a i r-solution i n terface. The collar on no. 4
was deep red when wet; 5 showed a broad collar which was only sl ightly
darker than the immersed area ; 6 and 7 showed some collar effect; 8 had a
mu lticolor collar composed of p u rple, green, ye l l ow, and blue bands; 9 had
a b road collar; 1 0, u, 13, and 14 had no col lar, but 1 5 had a collar that was
darker than the fu l ly i mmersed area.
The effec t of air was i nvestigated fu rther by compari ng the change i n
density a n d si lver structure i n a 5 % KC N S so lution that had been deaerated
with nitrogen with the change in a solut ion that had not been deaerated.
'vVhen the strips were i ntroduced into the solutions d irectly from the wash
water, no diffe rence was observed in the rate of change of density i n the
deaera ted and nondeaerated sol utions. \!\!hen, however, a strip that had been
soaked in deaerated water for 1 hr was t ransferred in ni trogen to a deaerated
KC NS solution, l i ttle, if any, cha nge occu rred in the strip in 10 m i n . \!\!hen
the KC N S-soaked strip was brought o u t i nto the ai r, the customary c ha nge
in appeara nce took place within a few m i nutes. \!\!hen, however, a sol u tion
of KC N S that had been saturated with AgC N S was used i n the place of the
plain KC N S solution, the change i n the form of the si lver occurred even
u nder the anaerobic condition.
The preceding experiments suggest that s i lver ion pl ays a part i n the
recrystall ization of the filaments to rou nded particles. Some si lver ions would
be supplied u n der normal conditions by oxygen oxidation. The presence of
a strong reducing agent would tend to lower the si lver-ion concentration i n
the med i u m s u rrounding t h e si lver particles a n d wou ld tend to lessen the
ionic character of s ilver atoms on the si lver su rface. Whereas oxygen seems
to promote the recrystaJ l i zation, the red ucing agents retard it. Even in the
near-absence of oxygen , h owever, recrystall ization takes place readily when
si lver ions are supplied to the solution.
The rate of disappearance of the filamentary structure of the developed
i m age upon i m mersion i n the thiocyanate and c h loride sol u tions i nc reased
rapidly with increasing temperature of the solution. An i n crease of 1 0°C i n
temperature appeared t o i ncrease t h e rate several-fold, as i nd i cated b y the
c hanges in the spectrophotometric c u rves. An accurate measu rement of the
temperatu re-dependence of the rate cou lei not be made from the spectro­
photometric c u rves, however, because of the complex nature of the change
in curve shape ( Figure 1 3 ) . At constant temperatu re, the rate of c hange was
approxi mately proportional to the c h loride or thiocyanate concentration over
the range 1-5%, but the p roportionality d id not hold over a wide ra nge of
concentrations.
 Part II S I L V E R I �I A G E S T H U C T U R E /\ N D S T /\ B I L I T Y

3.0 --.------ - ,

II

�2.0
· v;
c:
<l.>
"
c:
0
·v;
(/) 1.5
·�
c:

_g
0
No treatment
� J.0
Figure 13
C u rves showing effect of a 5% KCI
solution on transmission density
oF a silver image developed by D·19 0.5
i n E m u lsion B . Dashed curve,
20.0°C; solid curvei 38.5°C. The
n u m bers on t h e curves are times
or treatment in m i nutes. o �----�-----�--�
400 500 600 700
Wavel ength (mf-L)

Postdevelopment treatment of the silver i mage i n a thiosu l fate fixing

bat h or i n an iodide bath stabilized the filaments against the changes cau sed
by the thiocyanate and c h loride. I mmersion of the developed fi l m for a few
m i n utes i n a thiosulfate fixing solution, i n a 2% potassiu m iodide solution,
or i n a thiosu lfate fixing solu tion containing 0.2-2% potassium iodide prior
to i m mersion i n the c h loride or thiocyanate sol ution largel y prevented the
change i n the structure of the si lver, and add i t ion of iodide or thiosulfate to
the ch loride and thiocya nate sol utions marked ly decreased the change.
Comparison of the effect of thiocya nate and c h loride solutions on
the reflection densities, c rysta l l ite size, and catalytic activity of si lver devel­
oped from c hloride, chlorobromide, bromide, and iodobromide emu lsions
suggested that even iodide derived from development of the iodobromide
e m u lsions had some stab i l izing action agai nst the "thiocya nate-ch loride
effect. " Table 6 shows the e ffect of a 5-m i n i mmersion in 5% KC I solution at
38-4°C on the reflection densities of several deve loped, u nfixed films. Table 7
shows t he change in crystall i te s ize caused by i m mersion of the developed,
u n fixed films i n 5% KCI solut ion and 5% KC N S solution for i5 m i n at 29-4°C.
The two c h loride e m u lsions had been developed i n a M etol-ascorbic acid
solu tion of pH 9 without b romide. Al l other e mu lsions h ad been deve loped
i n D- 1 9 .
 R e a d i n g 16 J A J\ I E S

Table 6
Effect of 5% KCI solution at 38 4°C on reflection density and catalyt ic
'
activity oF silver towards decomposi t ion oF hydrogen peroxide.

Densities at 700 m p
Coating
designation Type U n treated After KC I � D/Do
Cl, Br 1 . 59 0.98 0.38
K C l . Br 1 .00 0.75 0.25
L Rr 0.73 0.57 0.22
M Br 1.21 0.96 0.26
N Br 1 .37 1 .0 1 0.26
0 ll r a . So 0.63 0.21
p Br o.88 o.66 0.25
Q 13r o.99 �.72 0.27
H Br 1 .37 0.87 0.36
s 10% I 1.19 1 . 14 0.04
T 5% I 1 .83 1 .73 0.05
5% I 1.10 1 .05 0.05
v 1 0% I 1 .26 1 . 19 0.06
'v\f I , Rr 1.51
x I , Br 1 .46 1 -4 1 0.03

Table 7
Effect of KCI and KC N S t reatments of' crystal li te s ize.

Crysta l l ite size, A

Coa t i ng T)1>e U n treated 5 % KC I 5 % KC N S
y Cl 1 6-1 :':: 4 238 :':: 9
z Cl 1 79 :':: 4 269 :':: 1 2
C l , Br 1 64 :':: 4 252 :±: 10 238 :':: 9
L Br 278 :':: 1 2 299 :':: J 5 299 :':: 1 5
0 Rr 245 :':: 9 288 :':: 1 3 278 :':: 1 2
R Br 220 ± 7 269 :':: 1 2 278 :':: 1 2
p Br 252 :±: 10 288 :':: 1 3 288 :':: I _)
'

Q Br 245 :':: 9 288 :':: I .)

' 269 :':: 1 2
s I ( 1 0% ) Br 225 ± 8 225 ± 8 225 ± 8
T I (57r ) B r 1 99 :':: 6 20-1 :':: 6 20-j :':: 6
u I (5%) B r 252 :±: 1 0 252 ± 1 0 2-15 :':: 9
v I ( 1 0%) Br 232 ± 8 238 :':: l) 238 :±: 9
w + -
I , Br 1 76 :':: -I 191 - ) 199 :':: 6

x I . Br 1 83 :±: 5 199 :':: 6 195 :':: 6

133
Part II S I L V E R I 1\I 1\ G E S T R L. C T U B E r\ N D ST A B I L I TY

Discussion

F i laments formed by development of s i lver ch loride, c h lorobrom ide, and bro­

m ide gra i ns, when not fixed in a t h iosu l fate sol u t i o n , were h ighly un stable
a t 1 00% RH or when i mmersed i n t h i ocyanate or c h loride solutions. Even
at room t e m pe rature, the fi laments u nderwent recrystall ization to shorter,
t h icker Forms, and eve n t u a l l y to rou nded part icles. The change i n structure
of the deve loped si lver was accompanied by cha nges in optical density a n d
i mage tone i n the fi ne-grai n e m u lsions, where development produced o n l y
one or a few fi laments per deve loped gra i n . T h e s a m e cha nges i n struct u re
occu rred i n the si lver obtained by development of l a rge s i lver b ro m ide and
s ilver ch loride grains, b u t the optical propert ies with respect to t ransmi t ted
light were scarcely a ffected. M a ny filaments were formed per gra i n in the
development o f coarse-grai n e m u lsions, and the fi l aments formed i n c l us­
ters. The optical properties of the s i lver deposit were determi ned pri marily
by t he c l u ster, not by the i n d ividual f i l a ments, a n d the cha nges i n structure
of the i nd ividual fi laments i n fl u e nced the optical propert ies o n l y i nsofar as
t hey altered t h e ou tward form of t h e c l uster. The overa l l size o f the cl uster
remained nearly constant in these coarse-gra i n films d u ri ng the t ransit ion
from f i l a ments to rou nded part icles, and hence the density to t ra n s m i tted
light re mai ned nearly constant. The c ha nge d id a l ter the reflection densities
of the coarse-gra in f i l ms, however, j u st as in t h e fi ne-gra i n f i l m s .
T h e reason F o r t h e marked d i fference between t h e wet and t h e d ry den­
sities of the t h iocya nate- a n d chloride-treated fi ne-grai n e m u lsions ( Figu re 9 )
m ight l i e in a n o p t i c a l packing effect. T h e rou nded particles formed b y t h e
recrysta l l ization were i n t h e colloidal range o f s izes t h a t m ight b e expected
to p roduce a ye l low color. Klei n , M etz, and Weyde8 s howed that the color
of coatings with a small vol u m e concentration of c o l loidal s ilver formed by
physical development was in approxi mate agree m e n t with p redictions of t h e
M i e theory, but increased concen t ration was accompanied b y a s h i ft in t o n e
towards the neutra l . I n the w e t l ayer i n my experi ments, the particles de rived
from each f i l a ment might be s u fficiently separa ted from each other to show
the "co l loid color.'' O n d rying, the t h i c kness of the l ayer decreased several­
fold and t h e vol u me conce n t ration of the part icles i nc reased accord i ngly. l n
the coarser-grai n e m u l s i ons, the colloid color m ight be lacking i n the wet
layer as wel l as in the d ry beca use the vo l u m e concentrat ion of s i lver par­
ticles formed from the m u l ti p le filaments wit h i n the confines of each gra i n
w a s too large.
The high degree on i nstab i l i ty of the filaments in t h e t h iocya nate and
c h loride solutions was rem i n iscent of the instabi l i ty of black s i l ver formed
e lectrolytical ly. The latter was first observed by Kohl s c h l.itter and Toropoff,9
a n d was stud ied subseq u e n t ly by severa l workers, t h e m ost recent being ]aen-

' 3 -1
 Reading 16 J i\ � I E S

icke and S c h i l l i ng. 1 0 J ae n icke and S c h i l l ing obtained black si lver by cathodic
red uction of s i lver iod i d e , and meas u red s u bseq u e n t cha nges i n its struc­
t u re (smoothing) i n terms of changes i n the reflectance of t h e sample. The
black si lver was relatively stable in the d ry condition, but was s moothed on
contact with o"''Ygen -free s o l u t ions. The rate of smoothing was i nc reased by
the presence of ions that formed complexes w i t h silver ion, such as iodide,
cyanide, a n d thios u l fate. I n a 0.25 !VI potassi u m iod ide solution satu rated
with si lver iodide, the overa l l activa tion energy determi ned from rate mea­
s u rements i n the t e m pe ra t u re range 298-348°K was 7.2 ± o.6 kcal/mole. The
rate o f smooth i ng va ried as the % power of the total ion complex concentra­
tion i n s o l u t ion, calculated from pAg determinations and the known d isso­
ciation constants for the comp lexes. It was independent of the nature o f the
complex for the fou r complexing agents used (iodide, cyanide, s u l fi te , and
thios u l fate ) . I ndo l izine, p henyl mercaptotetrazol e , and n i t ro be nzi m idazole
decreased the rate of smoothing somewhat (to 0.62-0.84 of the origi nal for
1 . 1 X 1 0-> !VI i n h i b itor in the 0.25 !VI iod ide sol u ti o n ) , but gelatin decreased
the rate m u c h more (to 0.0 1 -0.02 ) .
J aen i c ke and Sc h i l l i n g exp l a i n t h e smoot h i ng of the si lver b y a d isso­
l u tion-reprec i pi tation process made possible by the partial ionic character of
the su rface atoms. The p rocess is s i m ilar to local cell act ion: s u rface ions in
the form of complexes m i grate along t h e su rface or t h ro ugh the l iq u i d phase
while electrons are displaced t h ro ugh the metal. The d riving force for this
process is the decrease i n the free su rface energy.
The mechanism suggested by Jaen icke a n d S c h i l l i ng may, in a broad
sense, be applicable to the res u lts obta i ned w i t h p hotographic e m u l sions,
although t h e parallel i n experimental res u lts is far from complete. The tem­
pera t u re-dependence of t h e recrysta l l ization is m uc h greater for the photo­
graphic e m u lsion. Whereas Jaenicke and S c h i l l i ng fou n d that the acce leration
of smoot h i ng by complex-form i ng ions was independent of the chemical
nature of the ion, the filament-destroying action in the photogra phic e m u l ­
s i o n depends q u i te markedly on the n a t u re o f t he i o n . I o d i d e and t h iosu lfate,
used by J aeni cke and Sch i l ling as comp lex-forming ions, restra i n rather than
promote the degradation of the filaments , whereas c h loride and t h i ocyanate
a re h ighly effective i n p romoting that degradation. The recrysta ll ization also
occ u rs i n t h e p hotograp h ic film stored a t high h u m id ity without a sol u t ion
being presen t . Mob i l i ty of hydrated s i lver ions on t h e s i lver su rface may s u p ­
p l y the necessary si lver-ion m igration for recryst a l lization at the h igh h u mid­
i ty. I t may be noted, however, that recrystall izati o n of dry, t h i n fi l m s of s i lver
has been observed at tempera t u res h u n d reds o f degrees below the melting
point of massive si lver. 1 1
The fac t t hat thiosu l fatc a n d iodide retard t h e recrysta l l ization both i n
t h e photograp h i c fi l m s stored a t h igh h u m idity a n d i n t h e films immersed i n

135
Pa rt II S I L V E H I l\ I A G E S T H L' C T C B E 1\ N D S T 1\ B I L I T Y

the c h l oride or t h i ocyanate solution, taken toget her with t h e observed s i m i ­

larities in appearance of t h e si lver partic les themse lves , suggests that t h e
m echanism of fi lament degradation is t h e s a m e for b o t h cases.
The action of the chloride and t h iocyanate may depend on the a b i l ­
i t y o f t hese i o n s t o form s i lver-ion complexes that a re m o b i l e on the s i lver
s u rface i n the prese nce of swo l l e n gel a t i n . The more strongly adsorbed ions,
s u c h as t h iosu l fate a n d iodide, may form complexes t hat are i m mo b i l e on
the gelati n-coated su rface, even though they may be mobi le in the absence
of gelatin. The experi ments of Jaenicke and Sch i l l l i n g 1 0 show that ge latin has
a marked retard i ng effect o n the recrysta l l ization of the black s i lver formed
in its absence. The gel a t i n decreases the rate of recrysta l l ization by two
orders o f magn itude. lt is c l ear, however, that the action of t h i ocyanate and
c h l oride in the present work i s not s i m ply a res u l t of soften i n g of the ge l a t i n .
Agents such as potass i u m n itrate and u rea at h igh concentrations a r e at least
as effect ive as th iocyanate and c h loride i n softe n i ng gela t i n , but are com­
pletely i n effective in promoting recrysta l l izat i o n .
The normal stabi l i ty of the s i lver f i l a m e n t s at roo m tempera t u re i n t h e
a bsence of t h iosu l fate or iodide i o n m a y depend on the p resence of some
pre-exist i ng stabi l iz i n g layer wh ich is destroyed by c hloride or t h i ocya nate
ion, or by h igh h u m id i ty. S u rface layers of oxide or other contam i nants from
the air are known to exert a l arge i n A ucnce on the mecha n ical propert ies of
s i lver and certa i n other metals. 1 2 · u Andrade and H e n derson, for example,
have shown that the rate of glide i n si lver crystals u nder stress is markedly
dec reased by such layers, and A n d rade and Randa ! J l 4 have fou n d that the
rate of Aow i n cad m i u m crys ta l s formed i n a i r is su bstan t i a l ly increased by
contact w i t h solutions w h i c h contained free cad m i u m ions. They attribute
this i ncrease to the a b i l ity of the cad m i u m ions to disrupt a stabil izing s u r­
face layer, probably of oxide. Cad m i u m c leaned by thermal evaporation does
not show Lhe effect. It seems u n l i ke ly, however, that an oxide layer is sta­
b i l izing the developed s i lver filaments. S ma l l amou nts of oxygen acce le rate
the action o f t h i ocya nate a n d ch loride, j u st as s i lver ions do, a n d deve l oper
solu tions, which should reduce a n oxide layer, retard the action of the t h io­
cyanate and c h l oride.
The p resence of a stabi l i z i ng layer of u n known compos ition can not
be ruled out by the presen t experi ments, however. If such an i n h i b i tor layer
were deslroyed without bei ng rep l aced by [an ] other i n h i b i tor, the fi l a m e n t
wou ld become su scept i bl e to recrysta l l ization j u st as though no i n h i b itor h a d
been on the su rface i n the fi r s t p l a c e . Thu s , c h e m i ca l or phys ical action
which su fficed to remove the i n h i b itor layer could i n duce i n sta b i l i ty in the
filament. It is u n n ecessary to provide for a mass ive chemical attack on the
s i lver to exp l a i n a conversion of fi l a ments to rou nded particles.
 Reading 16 J A iVI E S

The work on the c h loride-thiocya nate effect shows that a rapi d a n d

complete conversion of s ilver fi laments to rou nded particles can occ u r essen­
tially by a recrystall ization process. Th i s i s not to say, however, that the same
physical res u l t can not be a c h ieved by a n e n t irely d i ffere n t mechanism, s u c h
as o n e i nvolvi ng massive oxidation a n d red uction. I n t h e catalyt i c decomposi­
tion of hydrogen peroxi d e o n a si Iver catalyst , for example, s ilver is oxid i zed
and si lver ions are red uced. The re-formed s i lver atoms, in general, would
not be redepos ited i n t h e same spots at w h i c h they were oxidized origi n a l ly,
and a complete c h ange in the p hysical form of the s i lver can occ u r. I ndeed,
E . D . Salesi n 1 5 has shown tha t the filamentary structure in photogra p h i c
fi l m s disappears and rou nded particles appear i n i m ages attac ked b y hydro­
gen peroxide vapor. When agents are prese nt that can for m s ilver s u l fide, s t i l l
a nother mechanism m a y res u l t in destruction of fi laments. Th u s , the mere
physical form of the depos i t fou n d i n i mages t h a t h ave u ndergon e c hanges on
storage 1 6 does not clearly point to one or another mechanism of c hange. The
same p hysical result m ight be achieved by any one of several mechanisms.
The extent to w h i c h recrysta l li zation of fi laments may occ u r d u ri ng
development and prior to fixation can not be determined from t h e prese nt
results. It is clear that the p resence of h igh concen t rations of t h i ocyanate
or c hloride in "fine-gra i n " developers could promote such recryst a l lization
in iodide-free e m u l sions, and that t h e presence of rou nded, nonfilamenta ry
particles in t h e developed i mage is not conc l u s ive proof of sol ution physical
development. However, t h e experiments with t hiocyanate and c h loride solu­
tions conta i n i ng act ive developing agents s how t h a t the developing agents
i nterfere w i t h the rec rystallizat ion-promoting action of the t h iocyanate and
chloride, although t hey do not e n t i rely p reven t it.

Acknowledgment

I wish to ackn owledge my i ndebtedness to M r. C. F. Oster, J r . , and M iss

Rita M arti n for the elec tron m icrographs, and to Mr. S . J. Marino and M i ss
E ileen Keough for the c rystallite-s ize determ inations.

N otes

1 Cf. T. H. J a mes, Phot. Sci. Eng., 3: 225 ( 1 959).

2 E . Klein and E . Weyde, Mitt. Forsclwngslab. Agfa Leve..Jwsen.-Mii 11chen, 2: 1 1 7
( 1 958).
3 H. Genda and T. Sakaguchi, Res. Repl. Fae. Tech. no/.. Chi.ha Un.iv. , 15: 37
( March 1964 ).
4 W. Jaenicke, Phot .. Sci. E11.g ., 6: 1 85 ( 1 962).
H. D . Kei t h and J. W. M itchell , Phi/.. Mag. , (?) 44: 877 ( 1 953).

137
Part II S I L \I E R I �I A G E S T R U C T U 11 E 1\ N D S T t\ ll I L I T Y

6 C. R. Berry, Wiss. Pho t . , Ergebnisse Intern. Konf. Kain 1956, Othmar Helwich,
ed., Darmstadt, 1 958, 72.
7 C . W. Luckey, T. H. James, and VI/. Vanselow, Phot. Sci. Tech . , [ I I ] 2: 130
( i 955).
8 E . Klein and H . J . Metz, Phot. Sci. Eng., 5: 5 ( 1 96 1 ) ; E. Weyde, E . Klein, and
H . J . M etz, ). Phot. Sci . , 1 0 : 1 1 0 ( 1 96 2 ) .
9 V. Koh lschlitter and T. Toropoff, Z. Elektroche m . , 1 9 : 1 6 1 ( 1 9 1 3 ) .
.

1 0 W. Jaen icke a n d B . Schilling, Z . Elehtrnchern. . , 6 6 : 563 ( 1 962).

11 er. E . N . da c . Andrade, Trans. Faraday Soc . , 3 1 : 1 1 37 ( 1 935 ).
12 S . H a rper and A. H. Cottre l l , Proc. Phys. Soc . , 6 3 B : 3 3 1 ( 1 950) .
13 E. N . da C . Andrade and C . Henderson, Phil. Tran.s. Roy. Soc. London, 24 4A:
1 77 ( 1 95 1 ) ; Client. Abs. , 46: 1 404 ( 1 952) .
14 E. N . da C. Andrade and R. F. Y. Randal l , Proc. Phys. Soc. , 6 5 B : 445 ( 1 95 2).
15 E . D . Sales i n , private com m u nication.
16 Such as, for example, the spot formation described by R. VV. Henn and D. C.
Wiest, P/10t . Sci. Eng., 7: 253 ( 1 963).
 R e a d i n g 17

C A LV I N s . M C C A M Y A N D
C HE STER I. POPE

Redox B lemishes-Their C ause

and Prevention ( 1 970)

The first serious concern about image stability of microfilm occurred in the
early 1 960s when small, reddish circular spots-commonly lmown as redox
blemishes, red spots, or measles-were discovered on microfilm from several
collections, including the National Archives. These mysterious damages that
occurred primarily at the outer edges of microfilm housed in cardboard, rather
than metal containers, demanded immediate attention. Research efforts to
deterniine the cause and prevention of this formation were quicldy undertalzen
at the National Bureau of Standards and the Eastman Kodah Company. Cal­
vin McCamy joined the National Bureau of Standards (NB S ) in 1 952. He was
chief of the Photographic Research Section from 1 958 to 1966 and later led the
image Optics and Photography Section. Chester Pope joined the NBS in 1 93 6
t o conduct research o n the chemistry of paper and photographic processes. The
year before this publication Pope was awarded the Silver Medal of the U.S.
Department of Conimerce for "outstanding contributions to the chemistry and
preservation of archival records on photographic film. This reading from 1 970
11

summarizes the worh of McCamy and Pope on the identifi cation and charac­
terization of ble·mishes on microfilm. The authors expand upon information
provided in Henn and Wiest 's 1963 publication, "Microscopic Spots in Pro­
cessed Microfilm: Their Nature and Prevention, " and reinforce the essential
importance of proper processing, stable and low-humidity storage environ­
·m ents, and the use of archival-quality storage materials to ensure long-term
stability offilm-based imaging materials. Microfilm collections remain vulner­
able to image oxidation, and serious outbreaks of red spots have occurred even

CALVIN S. M C CAMY and CM ESTER I. PorE, " Redox Blemishes-Their Cause and Preven­
tion," Journal of Micrographics 3, no. 4 ( 1 970) : 1 6 5-70. Reprin ted by permi ssion of A l l M
I n ternationa l .

1 39
Part II S I L V E H I M A G E S T H U G T U H E A N D S TA B I L I T Y

i n recent years. Jn the 1 980s research at the Image Permanence Institute den't­
onstrated that, in addition to the preservation gu idelines cited by JVJcCamy and
Pope, sulfiding treatments offer the highest level of protection to microfilm.

I n 1 963, N B S received, from Kodak Research Laboratories, reports of spots

and other b l e m ishes of u n known cause o n m ic rofi l m s in private and p u b l ic
collections. I n the next few months, several thousand rol l s of m i c rofi l med
Governm e n t records were i nspected by N B S p e rson nel. B l emishes of six
general types were observed. Colored photomicrographs of these blem ishes
were p u bl i shed i n N B S H a n d book 96, which described procedu res for statis­
tical sam p l i n g of collections, microscopic exami nation of films, and report­
ing of observations . 1
The poss i b i l i ty o f biological cause o f b l e m i s hes was thoroughly
i n vestigated, not o n ly a t NBS b u t at t h e Armed Forces I nstitute of Pathol­
ogy a n d Kodak Research Labora tories. No evi dence of biological activ­
i ty was fou n d and all attempts to i n d u ce blemish formation by biological
i ncubation fa i led.
The National M icrofilm Assoc iation s hared o u r interest in this prob­
l e m and solicite d fu nds to support researc h . The N MA hired M r. Donald
Lehmbeck to work for one year at NBS as a research assoc iate.
About 1 00 inspectors were t rained to i nspect t h e microfi l m collections
i n the various gove rn m e n t agencies. They exa m ined 7,4 1 1 rolls of film and
a nswered about 50 q uestions on eac h . The B u reau of the Census encoded
the 370,000 observations o n p u nched cards. The corre lations were analyzed
and the statistics were t a b u lated in the N B S computation l a boratory, with
t h e ass istance of the S tatistical E ngineering S ec t i o n . M r. R. E. \Nil ey and
M i ss J . A . Speckman conducted the ana l ysis. 2

Mechan ism

M i c roscopy, electro n microscopy, e l ectron p ro be analysis, a n d severa l

chemical tests a l l i ndicated that t h e normal silver gra i n s were dissipated a n d
repl aced b y genera l deposits of col loidal s ilver, s ilver-gelatinate, a n d meta l l i c
s i lver. The si lver was appare n t ly oxidized to a n i o n i c form, which w a s free to
m igrate, and red uced aga i n to si lver. In 1 963, Henn and \Niest proposed t h is
oxidation-red uction mechanism and s uggested peroxide reactions, among
others, but had not identified the oxi d izing a n d red ucing age n t or its source.3
As a preventive meas u re, they proposed treati n g films i n a gold c hloride s o l u ­
tion to deposit a protective gold layer o n the si lver grains .3· 4
We s u bjected m i c ro fi l ms to a variety of l i kely d ry c h e mical contami­
n a n ts a n d to various sou rces of peroxides. Conside ration of many poss i b l e
 Reading 17 M C C A M Y A N D P O P E

sources of peroxides led to the hypothesis t h a t the principal source was t h e

cardboard boxes i n wh ich the fi l m s were stored. M a rracci n i a n d K l e inert
had fou n d that meas u ra b l e amou nts of peroxides form i n t h e n a t u ra l agin g
of commerc i a l p u l p papers. 5·6 They fou n d peroxide formation to i ncrease
with h u m id i ty and the rate of gen erat i o n of peroxides to i ncrease l in early
with agi ng. The fie l d s u rvey revea led that the i nc idence of blem ishes l i ke­
wise i n c reased with h u m i d i ty and with the time of storage. Sign i ficantly
greater n u mbers of blemishes were associated with the use of cardboard
or fiber reel s , rather than metal or p l astic ones. Except for fi l m s known to
have been poorly p rocessed, those stored i n metal cans were a l most e n t i re ly
free of blem ishes.
To test t h e hypothesis that peroxides from t h e paper a ttacked fi l m , fil m s
were stored at 50°C and 8 1 % rel a t ive h u midity with the emulsion in contact
with t h e card board car t o n . These fi l m s developed blemishes in 14 to 2 1 clays.
A lthough much research remai n ed to b e done, a t the request of the
N MA, an i n terim report, N B S Tec h n ical Note 26 1 , was issued i n Apri l 1 965
to make these res u l t s im mediately available to other government age n c i es
a n d the m i c rofi l m i n d ustry.7 Th i s p u b l i cation was soon followed by a more
detailed paper in the N B S Journal of Researc h . 8 The recommendations given
in those two p u b l i cations were conservative, b u t a re gen e ra l l y valid in view
of the fi n d i ngs s i nce that t i m e .

Test M ethod

One of the objectives of our work was the development of a p roced u re for
meas uring t h e tendency of fi l m s to form blemishes. S uc h a p rocedure wou l d
have d i rect p ractica l appl ications a n d wou l d be of great value i n research o n
b l e m i s h formation. Pope fou n d a convenient source of p e roxi d e for such test
p urposes. S m a l l p ieces of paper, such as is used for c hromatography, were
i m mersed a h a l f h o u r i n 5% hydrogen peroxi de, a n d dried. vVhe n films were
p laced in a jar maintai ned a t a re l ative h u m id ity of 86% at room tempera t u re,
a t a distance of about 8 c m from a 6 c m 2 p iece of s u c h paper, blemishes
formed. A l l of t he nat u ra l l y occu rring types of blemishes were produced by
t h i s method, t h e type depe nd i ng on t h e fi l m processing conditions and t h e
storage conditions p r i o r to testi ng. At fi rs t there w a s n o doubt t h a t t h i s pro­
cedure wou ld be a good practical test for the tendency of a fi l m to form
b l e m ishes, but soon a q uestion arose.
H e n n and \,Yiest fou n d that fi l m s fixed i n solutions that happened to
contain s m a l l concentrations of iodide ion resisted blemish formation in
actual storage.9 Such fi l ms, however, did form blemishes in t h e laboratory
e;qios u re to peroxide-treated paper. This suggested t h a t t here were other fac-

141
P a rt I I S I L V E H I J\I t\ G E S T R U C T U R E A N D S TA B I L I TY

tors i nvolved and led to t h e i nvestigation of other gases evolved by real paper
cartons. I t was fou n d t h a t rnost cornrnerc i a l l y ava i l a b l e cartons released
rneasurabl e q u a n tities o f forrnalde hyde and formic acid. These chemicals
were detected i n water stored for one day in a n open petri d i s h inside a
storage box. Further laboratory work confirmed the fi nding that f d rns fixed
i n a sod i u m t h i osu l fate sol u t io n contain ing a s rn a l l arnou n t of iodide ion
do resist attack when stored at h igh h u m id i ty in rnost, but not a l l, com­
m e rc i a l ly ava i la b l e paper containers. This work emphas ized the fact that the
s uscept i b i li ty of fi l rn s to blemish formation i n t h e presence of peroxides is
conditioned by many factors, i nc l ud i ng the presence o f other gases evolved
by carton stock, the concentration of c hl o ri n e in the wash water, and t h e
storage conditions before testi ng. T h e ava il a b il i ty of t h e peroxide-paper tech­
n iq u e has greatly accel e ra ted o u r research, by p rov i d i n g resu l t s q u i c kly u n der
controlled con d i tions . 1 0

S tability o f the S i lver I mage

The s ilver gra i n , as forrned in the gel a t i n matrix d u ring development, is i n her­
e n t l y u n stable. 1 1 The s i lver develops as very fine fi laments o n ly a few atorns
i n d iameter. In t he norrnal p hotographic process, these filaments becorne
coated w i t h s ul fu r atoms d u ri ng fixa t i o n . It is t h i s coating which stabi l izes the
gra i n structure. F i l rn s fixed a relatively Jong t i m e and fi l rn s reta i n i ng a s m a l l
a m o u n t of hypo after was h i ng acq u i re more s ul fu r a n d are q u ite res istant to
blemish formation when t hey are exposed to peroxi des at h igh h u m i d ity.
Pope had shown , some years ago, that a smal l amount o f iodide i n
t h e fixer p revents t h e s u l f1 d i ng o f t h e i mage. 1 2 Apparently a n iodide layer i s
formed i nstead of a s u l fide layer. Accordi n g to Jarnes, t h e iodide layer sta­
b i l ized s i lver gra ins. 1 1 This corresponded well with the field experience
with films p rocessed i n a fixer con t a in i n g iodide ions. We have deve loped
t h e tech ni q u e of cutting a thin transverse section of fi l rn having a t h ic kness
less than a wavelength of l ight. Electron m i c rographs of such t h i n sections
of b l em i shes, at a magn i fication of 750,000 diameters, reveal the d ivision of
the s ilver fi l a m e n ts i n to n u merous s m a l l e r particles o f the form observed i n
experimental e m u lsions by J ames.
When s i lver is oxidized and red uced in t h e p resence of c h loride ions,
the redu ced s i lver becomes incorporated with s ilver c h loride in a co11oi d a l
for m . P o p e demonstrated t h e formation of red d i s h colored col loidal s ilver
by the reaction of hydrogen peroxide wi t h p ur e rneta l l ic s i lver i n the pres­
ence of a s m a l l conce n t ration of c h loride ion. This colloid is yel l owish or
reddish i n color. We attri b u te the characteri s t i c color of t h e b lernishes to
the presence of this colloidal rnateria l . Spectrophotometry and rn icrospec­
trophotometry over the spectral range frorn 3 50 to 750 nano meters con-
 Reading 17 M C C A M Y A N D P O P E

firmed the c lose s i m i l arity of the spectral absorp t i o n of blemish e d areas a n d

experimental coatings bearing colloidal s ilver. T h e fact t h a t t h e formation
of t h is form of s i lver i s associated with c hl or in e suggested a n i nvest igat i o n
of w h a t effect t he concentration of c h l orine i n t h e w a s h w a t e r had o n t h e
stab i l i ty of t h e fi l m . F i l m s was hed i n d is t il l ed water were faded by peroxide
attack but typical b l e m ishes d i d not for m . A s m a l l concentration of c h lorine
appeared to be esse n t i a l to t h e formation of typi c a l ble m i shes, b u t a con­
centration considered h igh for tap water, over one p a rt p e r m i l l ion, h a d an
i n h ib i t i ng effect . The mec hanism of i n hibition was probably t h e same as that
i nvolving iodide.
The d istributions of si lver, s u l fu r , and c h l orin e i n typical blemishes
were measured by t h e tec h n i q u e of e l ectro n probe analys i s . The e m u l sion
was mou n ted on a t i ta n i u m d i s k, the blemish was scanned w i t h the e lec­
tron beam, and a characteristic x-ray e mission l i n e was m o n i tore d . We used
the La i l i n e o f silver, the Km l i n e of s u l fu r, a n d t h e Ka l i n e of c h lorine.
S ilver a n d c h lorine concentrations tended to correlate w i t h t h e morph o l ­
ogy of t h e b l e m ishes. S i lver was u s u a l ly somewhat depleted from the central
area and concentrated at t h e edges b u t often a s ilver speck appeared a t t h e
center. S u l fu r d istribution s d i d not fol low a fi x e d pattern, b u t sometimes
i nc reased i n the spots. White a n d Weston of E. I. du Pont d e N e m o u rs did
such a nalyses for s i lver a n d s u l fu r on about 50 of our samples a n d corrobo­
rated o u r fi n d i ngs . 1 3 A l l of the probe resu lts are consistent w i t h o u r theory of
blemish formation.

M orphology

The c i rc u l a r ring patterns in b l e m ishes are t yp ical of t h e patterns p ro duced

in chemical reactions i n a gel a t i n medium, patterns known as Liesegang
rings . 1 4 1 5 We repeated the c lassical Liesegang experi ment, p l ac i ng a drop
of s ilver n i trate sol u t i on o n a ge l layer con tain i n g potass i u m d i c h romate.
U n l ike Liesegang, we used a m icroscop ic d roplet and, as a consequence,
the ring pattern was not of t he usual large s i ze but t h e size of a Type 1 blem­
ish, about 0.1 mm in d i a meter. I n another ex']Jeriment, 8 concentric rings
formed i n 30 days u nder t h e action of a s ingle m in u te dropl e t of a metol­
hydroq u inone developer on a gel contain i n g s i l ve r s ulfide. Thus the Liese­
gang p h e nomenon is de monstrable o n the s m a l l scale encou ntere d in blem­
i sh es a n d i s adequate to exp lain t h e ring structu re . O n t h e other hand, t h i s
explanation m a y n o t be necessary, because i n s o m e experim e n t s , Pope has
contro ll e d t h e n umber of ri ngs by exposin g fil m s to a series of m i l d attacks of
peroxide.
Why some ble m i shes should conform to c h a racters a n d other i magery
as they do has not been i nvestigated i n deta i l , a l t h ough ex'Periments w i t h
Part II S I L V C H I l\l A G E S T H U C T U H E A N D S T 1\ B I L I T Y

h a rdeni n g and non-harden i ng fixers demonstrated a connection between

edge effects and ge latin hardness. lt i s we l l known t hat the hardness of the
gel a t i n l ayers is greatly a ffected by t h e density o f the si lver i m age, as are
the concentra t ions of res idual c h e micals. The gas permeabi l i ty o f the gel a t i n
may a l s o be m od i fied b y t h e i mage. These factors are adequate to ex1J l a i n t h e
i m age-dependence o f the b l e m i s h e s .
T h e very d i ffuse Type 6 b l e mishes usu a l ly had foreign m a t t e r at the
center. Some o f t hese central specks were s i lver. Others appeared to be
flecks of black fi l m backing w h i c h had been removed i n processing and had
become embeclclecl in o r adhered to t h e gelati n . Eve n i f small particles do
not penetrate t h e su rface of the ge l a t i n , they may act as s m a l l condensa­
tion cen ters where t h e effective h um i d i ty exceeds that i n t h e ambient a i r
and gaseo u s a bsorption i s accelerated. NI i n u te pores i n the gel a t i n m a y act
in the same way.

Dens it)'

Genera l ly speaki ng, in the field and i n the laboratory, the i n c idence of spots
tended to i ncrease w i t h the optical density of the i mage . I n one typical exper­
i m ent, a step tablet exposed to peroxide-treated paper developed blemishes
o n aJI steps havi ng densities o f 0 . 58 o r m ore, w h i l e none formed a t densities
o f 0-43 or less. The inc idence i ncreased for each step above 0.58. B l e m i shes
do not form on microfi l m s h avi ng dark c haracters on a l ight backgrou n d ,
even though the same fi l m s have b l e m i s hes in dense areas a ro u n d frames.
l m age s i lver catalyzes t h e reactions which we have described, so the rela­
tionship o f b l e m i s h fo rmation to density should be expected .

Observations S u pporting the Theory

Sometimes one observes a s i lver sheen on h igh density areas. This i s a

deposi t of red uced s i lver and s i lver sulfide. The observation of s u c h a sheen
was statistica l ly associated with a great i n crease i n blemish forma t io n . The
s uggested oxidation-red u c t i o n reaction accou nts for both effects.
S p ots were very freq uently fou n d o n the o u te r encl o f t h e roll a n d a t
the edges. \!\! h e n t here was no leader on the fi l m , t h e i ncidence o f blem­
i s h es on i n formation frames was 2 to 3 t i mes t h a t on rol l s w i t h leaders. The
i ncidence began to d ro p when the leader l ength exceeded 1 . 5 meters. These
effects s h o u l d be expected if peroxides generated i n the paper carton cause
b l e m ishes, beca use the a reas nearest the paper a re most affected. Peroxides
are notably s h o rt - lived species so t h ey are act ive o n ly a short distance from
a feeble sou rce. Fewer b l e m i s hes were fou n d i n wel l-venti lated storage areas
and there were fewer i n active files t h a n i n dead fi les. All t h i s evidence favors

1 44
 Reading 17 M C C A fVI Y A N D P O P E

t h e t heory that blemishes a re cause d by paper-ge nerated peroxides that con­

centrate i n t h e sti l l air in t h e storage c o n ta i ners.
Type 1 blemishes very commonly form i n a continuous l i ne along a
scratch i n the fi l m su rface. The break i n the gel a t i n ex'Poses t h e s i lver more
d i rectly to gaseous reactants.
I n all of the experiments, h u m i di ty has been a n important factor. Tem­
p e rature has been l ess i m portant b u t significant. In the s u rvey, we fou n d a
significantly lower i n c idence of b l em i s h es i n air-c o n d i tioned storage areas.
The blemish rate reported in the s u rvey was d i rectly related to reports
of d iscoloration, fad i ng, water spots, and other observed defects. When a n y
chemical resi d u e w a s fou n d , the b l e m is h r a t e tripled a n d the r a t e o n i n forma­
tion areas was high. The d i fferen ces in b l e m i s h i ng o n vari o u s brands of film
was n o t sign i ficant, b u t such was not t h e case with processing equipment.
Practically a l l fi l m p rocessed on one partic u la r kin d of machine eve n t u a l ly
developed blem ishes. I n fac t , the data from government agen cies which had
u sed that machine so ou t-weighed t h e other s tatistics that i t became n eces­
sary to ru n a second ana lysi s wi thout these d ata. I n one age n cy, this type of
processor had been rep laced by another type, years ago, a n d t h e fi l m pro­
cessed by the new mac h i n e has not become b l e m ished. The troublesome
m ach i n e h a d small tan ks, i nadequate squeegee action, a n d quick washing.
I t was customary to l oad d ry chem icals i n to t h e t a n ks without first d i ssolvin g
t h e m . As o n e m ight ex'Pect, chem icals were left on t h e fi l m . S u c h mac h i n es
are no l onge r on t h e market.

Aperture Cards

Reports o n films m o u n ted i n apert u re cards i n d i cate a rather low i n cidence

of b l e m ishes. However, one s h o u l d bear i n mind that such forms have not
been i n u s e as long as t h e rol l for m . I t i s reasonable to s uppose t h a t t h e bet­
ter ven t ilation and the fact that the film surfaces do not u s u a l ly touch one
another are benefi c i a l . Our fin d i ngs would s uggest caution i n t h e choice of
p a pers for use in apert u re cards.

"Redox"

The blemishes have gone by a variety of names, " m icrospots," m easles," etc.
One never knows what to c a l l a thing until h e knows what d i fferen tiates
it from other s i m i l a r t h i ngs. \!\le h ave called them "agin g b l e m ishes," but
now that we can p roduce them in the l aboratory in a few hours, that name
n o longer seems appropriate. The strengt h of t h e evidence for a n oxidation­
reduction mechanism i s s u fficient to warrant calling them "redox blemishes."
" Redox" i s a standard term i n chemistry for reactions of t h i s kind.

145
P a rt II S I L V E R I M A G E S T R U CTU H E A N D S T A B I L I T Y

Concl usions

One of t h e most importan t resu lts of t h e study is t h e clear demonstration of

t h e fact that j u dgments of t h e s u i ta b i l ity of materials for t h e preservation of
permane n t records cannot be made with respect to the materials considered
i n dependently. The archival process m u st be regarded and eval uated as a
complete system including materia l s , p roced u res, a n d s torage conditions.
In conc l ud i ng this study, we must recommend appropriate action to
archivists. All evidence adduced i n past research , recen t researc h , a n d i n prac­
tice indicates that i mages on silver-ge l a t i n materials which are properly pro­
cessed and stored, w il l l ast as long as records o n h igh-grade record paper. I n
addition to t h e obviously necessary safeguards again s t damage or destruction
of records by flood, fi re, riots, and other such i ncidents, we recommend that
arc h ivists take t h e fol lowing preca utions to guard against b l e mish formation
o n s ilver-ge l a t i n type fi l m s for the preservation of records of permanent val u e :

1. U s e safety base permanent record fi l m a s specifi e d i n t h e U n i ted S tates

of America Standard s I nstitute Specifications for Photographic F i l m s
for Perma n e n t Records.
2. Use n o h igher densities than a re required for t h e i n te n de d p urposes
and use dark c haracters on a l ight backgrou n d i f this is feasible.
3. The res i d u a l thiosu lfate concentration should not exceed 1 m icrogram
per s q uare centimeter, but one s h o u l d not attempt to reduce it to zero .
The optim u m concentration appears to be about 0 . 5 m i c rogram per
s q uare centimeter i n a clear area.
4. Keep processing machinery and fi l m clean.
5. Avoid scratching fi l m .
6. S tore fil m s i n containers made o f i nert materials, s u c h a s metals o r
p l astics o f proven q u a l i ty. With good ven ti l a ti o n a n d clean air, t h e
contain e rs n e e d not be sealed .
7. Do n o t permit storage tempera t u re to exceed 70°F nor the relative
h u m i dity to exceed 40%.
8. Avoid wide-range cyc l i ng of temperature and h u m i d i ty, since t hese
accelerate the i mbition of gaseous contaminants.
9. I n spect fi l ms o n a regu l a r sched u le, u s i ng p roper sampling a n d
m i c roscopic i n spection tec h n iques.
1 0 . M a i nt a i n records of p rocessing and storage conditions so t h a t the next
generation of arc hivists wi l l be able to u n derstand our s u ccesses or
fai l u res a n d act o n the basis of facts.

The a ut hors are gratefu l to the person n e l of the many gove rn m e n t

agencies t h a t cooperated with us a n d the National M i crofil m Assoc iation
for its s u pport.
 Reading 17 M C C A MY A N D P O P E

References

1 C. S. McCamy, "Inspection of Processed Photographic Reconl Fi/1ns for Aging

Blemishes," H a ndbook 96, National Bureau of Standards, V\lashington, D.C.
( 1 964) .
2 C. S. McCamy, S . R . \Niley, and ] . A. Speckman, " A Su. rvey of B /.en'1.islies o n
Processed Mic rofilm," ] . o f Research, N B S 73A, 7 9 ( 1 969).
3 R . W. Henn and D. G. Wiest, "Microscopic Spots i n Processed Microfilm: Their
Nature and Prevention," Phot. Sci. Eng. 7, 253 ( 1 963).
4 R . W. I-Jenn and Bernadette D. Mack, "A Gold Protective Treatn1ent for
Microfi l m , " Phot. Sci. Eng. 9, 378 ( 1965).
L. M. Marracci n i and T. N. Kleinert, Spectropliotumetric Estimation. of
Peroxide in. Cellulosic Materials,
Svensk Papperstidning 65, 78 (Jan-J u ne 1 962).
6 L. M. Marracc i n i and T. N. Kleinert, Aging and Col.our Reversion of B/.eaclied
Pulps,
ibid., 66, 1 89 (Jan-J une 1 963).
7 C. S. McCamy and C. I. Pope, "Sumnrnry of Current. Research on Archival
Microfilm, " N B S Tech . Note 261 ( 1 965).
8 C. S. McCamy and C. I . Pope, "Current Research on. Preservation of Archival.
Records on Silver-Gelatin Type Microfilm in Roll Form , " ] . of Research, N B S
69A, 3 8 5 ( 1 965).
9 R. W. I-Jen n , D. G. \�liest, and Bernadette D. Mack, Microscopic Spots i n
Processed Microfilm: T11e Effect of lodide, Phot. S c i . E n g . 9, 167 ( 1965).
10 C. I . Pope, "Blemish Fonn.ation in. Processed Mi.crofilnr," J . Res. NBS 72A, 2 5 1
( 1968).
1 1 T. H . James, "T1ie Stability of S i lver Filaments," Phot. Sci. E ng. 9, 1 2 1 ( 1965).
12 C. I . Pope, "Stability of Residi1al Thiosu.lfate in. Processed Microfi/1·1·1 , " J . Res.
N BS 67C, 1 5 ( 1 963) .
13 D . R . White and N . E . Weston, Electron Probe Exan'tination of Agi.ng
B lemishes in Microfil1n , Phot. Sci. E ng. 1 1 , 107 ( 1967).
14 R. E . Liesegang, Naturw. Wichschr. 1 1 , 353 ( 1 896).
15 R . E. Liesegang, Phot. Archiv. 2 1 , 221 ( 1 896) .

147
 R e a d n g 1 8

E D ITH WEYDE

A Simple Test to I dentify Gases

Which Destroy Silver I mages ( 1 972)

McCaniy, Pope, and others demonstrated the considerable importance of high­

quality en.closures in the permanent storage of silver i magi ng materials (see
Reading 17 ). R egrettably, the accurate assessment of sui tability of storage mate­
rials is complex. The first standard for this pu rpose ivas published in 1950; it
evolved over the following decades and was finally renamed t he Photographic
Activity Test ( PAT) in 1 978. In the meantime, Edith. Weyde ( 1 901-1989), an
accomplished chemist employed by Agfa-Gevaert i.n Germany, i ntroduced
a test 1n.eth.ocl using hi.ghly reactive colloidal silver for identifyi ng damag­
ing oxidizing atmospheres, such as a utomobile exhaust fu mes and specific
phenol-formaldehyde resins as docurn.en.tecl in this 1972 study. These proce­
du res requi red room-temperature conditions an.cl were extended over months
and even years; high-tem1?erature an.cl hu:1niclity-acceleratecl tests were not
described. Weyde 's groun.clbreabng test methods allowed photographic chem­
ists to more accurately identify unforeseen harmful effects of airborne pollut­
ants on photographic materials. Weycle 's research has influenced generations
of photographic scientists and conservators. Her scholarship h.as expanded our
hnowleclge of- photographic chemistry an.cl contributed preser11ation treatments,
including the use of an iodide alcohol solution to reduce silver ·m irroring froni
the su1face of gelatin silver p1·ints. In 1 965 \i\feycle was awarded Honorary Mem. ­
bership t o the Society of I maging Science and Technology, the highest award
bestowed by th.e Society.

E D ITH WEYDE, "A Simple Test to I dentify Gases \"1hich Destroy S i lver I mages," Photo­
graphic Science and Engineering 16, no. 4 (J u ly-August 1 972): 283-86. Text a n d images
reprinted by permission oF I S &T: The Society for I m aging Science and Technology, sole
copyright owners of P/101.ograpliic Science and Engineering.
 Reading 18 IV E Y D E

Figure 1 Figure 2
Silver pit:ture from the M u n i c h arch ives destroyed by blemishes. Enlargement of' a series of brown spots.

The destruction of s ilver i mages i n the archives in JVl u n i c h gave the reason
for the present work. The fi l ms a n d paper prin ts of t hese archives have shown
for some years brown spots where the i mage s ilver has been destroyed, s i m i ­
l a r t o t h e observations made b y M c C a my a n d Pope , 1 H e n n , Wiest, et a l . , 2
and Pope . 3 Figu re 1 s hows a badly destroyed fi l m from the M u nich archives,
and Figure 2 shows e n l a rgements of these b l e m ishes.
In t h e cou rse of t h e present i n vestigations two s i m p le test method s
were developed. W h e n s ilver coatings are exposed to oxidizing gases, sol u b le
s ilver salts form in t hese coati ngs. The p resence of even very s m a l l quantities
of these compounds can easily be established by pressing t h e test specim e n s
o n t o a p a p e r treated w i t h z i n c s ulfide w h i c h w a s moistened with water or
ammonia. The sol u b l e s i l ver salts transfer to t h e m o i stened paper a n d yield a

149
Part II S I L V E H I M A G E S T H U C T U H E 1\ N D S TA B I L I TY

recogn iza ble brown stain of s i lver s u l f i d e . This method proved to be very u se­
ful in the c l a r i fication o f the mechan i s m o f i mage destruction.
It was fou n d t h a t t h e s i lver salts fi rst originating are o n ly a m mo n i a sol­
uble and n o t water soluble. Since these s a l ts harden t h e gelatine, t hey p rob­
ably consist o f s i l ver gel a t i n ate. F u rther exposu re to oxidizing gases produces
s i lver salts which are a l so s o l u b l e in water. These salts are colorless and w i l l
rem a i n t h a t way for years i f they are protected from i n tense l ight expos u re
a n d kep t i n p u re air. The o n l y effect of the oxidizing gases is to reduce the
density o f t h e i m ages, which is eas i l y overlooked. H owever, the c o lorless s i l ­
ver salts are very eas ily co nverted to brown , water-so l u bl e compoun ds, i f t h e
a i r contains traces o f certa i n i m p u rit ies s u c h a s formaldehyde, acids, etc.
For exa m p l e , i t i s q ui te s u fficient to open a bottle o f formal dehyde in the
same roo m to stain t hese c o lorless s i lver salts brown. Light w i l l q u i c kly con­
vert these salts to si lver. All t hese c i rc u m s tances make the mechanism o f the
i mage destruction very vague. The fact that t h e speed of various react i o n s is
q u i te d i fferent depending on temperature and m o i s t u re fu rther compli cates
the i nvestigation. One fu rther p o i n t , w h i c h can not be d i s rega rded, is t h e
i n A u e nce o f t h e base-fi l m o r paper, w h i c h has a n aston i s h i n g storing effect
by adsorption o f oxi d izing gases.
Figu re 3 s hows smal l , separate, ye l low spots at the begi n n i ng of the
destruction process, o n ly recogni zable i n the m icroscope (same e n l a rgement
as F igu re 2 ) .
F i l m s from M un i c h w i t h many ye l low spots were pressed on a fil m
conta i n i n g a m o istened layer con tai n i ng zinc s u l fi d e a n d a m m onia. The pat­
terns o f yel low spots are there reproduced as l ight b rown dots. S o lu b le s i lver
s a l ts, contained i n the spots of the fi l m , m igrate i nto the z i nc s u l fide layer
where t h ey prec ip itate as brown s ilver s u l fides. S u c h a spot pattern tra n s fer
is shown in F igu re 4.
To detect very s m a l l amoun ts o f oxidizing gases, layers of yel low col­
l o i d a l si lver were u se d which had a gra i n size o f l ess than 30 n m . These
u n derwe n t a dark discoloration due to oxidizing gases and o n ly a t a very high
concen t ration o f the gases did they fade o r bleach. This discoloratio n is clue
to a change in gra i n , as s h own by e lectron m i c rographs. Very fine grains d is­
appear making the average grains coarser.
This test proced u re has been deve l oped d u ri ng the last t hree years a n d
u sed for the fol l owing p u rposes:
(a) Testing for da maging gases given off by a variety o f d i fferent mate­
ria l s : it has been fou n d that freshly produced plastic packagi ng o r storing
materials are da ngero u s . Such materials can sti l l be very active, releasing
monomer o r other compounds used i n m a nufa c t u re, such as po lymerization
cata lysts which a re very often peroxides. Of spec ial i n terest i s also the activity
of a u to m o b i l e exhaust fumes, which can d iffer great l y in t h e i r compos i t i o n ,
 Reading 18 \V E Y D E

Figure 3
In early stages oF image destruction,
spots appear only i n isolated areas.
Figure 4
Soluble silver transferred onlo a moistened layer containing
zinc sulfide produced prccipilatcs or brown si lver s u lfide i n a
paltern corresponding to the original spot distribution.
(a) representative original pattern: (U) represenlative transfer.

depend i n g on a variety of conditions. D u ri n g t h e oxidation of hydrocarbons,

a l kyl radicals are p roduced which, with m.'ygen , form peroxide radicals. Add i ­
tionally t hese engine exhaust fu mes often have a n acid reaction, as t h e y con­
tai n , among other s u bstances, ni tric oxides.
(h) Testing t h e atmospheres of various room s : S uc h colloidal l ayers of
si lver are i n te nsely d iscolored in l aboratories, garages, and bathrooms. The
res u l ts varied for rooms with oil and gas heating systems depending o n the
ven t i l a t i o n . Dr. M u el l e r of GAF also h u ng several test strips. One e:\'P osed
to the air i n s i d e a garage p roduced the strongest d iscolora t i o n . l n E u rope s i l ­
v e r i mages were frequently d i scolored i n p h otographic s hops, particularly i n
D e n m a r k a n d Sweden, where the d isplays were o p e n to the street o n ly . A n
 Part II S I L V E B I M A G E S T B U C T U B E t\ i\1 1) S T A B I L I TY

Figure 5 Figure 6
I mage generated on colloidal si lver by oxidizing a i r p o l l u l i o n . J\1\agniflcation I hrough brown spot, \·v h i c h
lies i n the protective overcoat oF film.

exa m i nation of these loca l it ies s howed that such s hops were u s u a l ly situated
i n very n arrow streets carrying a h i gh vol u m e of traffic, and were often located
at traffic l ights, or near parking lots, and gas stations. I n this case t h e layers of
colloidal s ilver e;.qJosed to t h e a i r were discolored, often i n a matter of weeks.
Tes t m a terials were prod u ced in l a rge q u a n t i ties by Agfa-Gevaert AG .
The colloidal s i lver layers were superi mposed with a lacquer pri n t resemb l i ng
an Agfa diamond, w h i c h p rotected the silver layers against oxidizing gases. I f
the air being exa m i ned contained oxi d izing gases, the area a ro u nd the dia­
mond darkened which l eft the symbol light u n der the lacquer cover. Figure 5
shows such an i mage gene rated by a i r pol l u tion.
The concentration of oxidizing gases in a i r i s u s ually q u i te s ma l l . The
d arkeni ng of the test layer takes considerable t i me . \Ne conc l ude that, where

152
 Reading 18 W E Y D E

Figure 7
Negative before (h), and after (a),
restoration with iodine solution.

darkening occ u rs after weeks or a few months, t he re will be danger for t h e

a rc h ival storage of valuable photograph i c docu ments. I f noticeable darken­
ing occu rs only after one or more years, there does not seem to b e serious
clanger for the s ilver i mages stored in vau lts or arc h i ves.
S u c h test strips were d istrib u te d m ore t h a n a year ago to 30 archives
mostly i n E u rope, where t hey were p laced in rooms and archive cabin e t s . I n
some cases t h e strips changed color after a few weeks, whereas n o change
could be determined i n other arch ives even after a year. Those archives show­
i ng the heaviest discoloration were near chemical factories, along very b u sy
t raffic routes a n d , i n one case, c lose to a furn i t u re factory w h i c h s tained and
varn ished i ts p roducts i n t h e open air.
M ore c a n be said about the archives i n M u n i c h : The tests revea led
t h a t i ndex cards made of phenylene-formalclehyd e mou lded materials were
responsible for the destru ction of s il ve r layers. S u c h cards had been u sed
i n the archives for 1 4 years and after 5 years fi rst signs of destruction were
Part II S I L V E H I �I A G E ST H U C T U H E A N 0 S TA B I L I TY

noted. These cards are now q u i t e d i fferent i n appearance and vary consid­
erably in their e ffect, so that o n ly systematic i nvestigations gave a pattern
o f activi ty. Recently m a n u factu red s heets were particularly active. Layers
of colloidal s ilver a n d d e l i berately scratched fi l m s of the u s u a l types were
p l aced on s u c h recently produced cards and on a l arge nu mber of cards from
the M u n ic h archives. Typical ly, a fresh card d iscolored the layer of col loidal
s i lver after a few months. Cards from t h e M u n i c h archives revealed discol­
oration i n periods of time varying between months and several years. The
fa m i l i a r yel low stai n s were only found i n isolate d cases on t h e fi l ms, w i t h t h e
exception of t h e recen t l y produced cards. I n t h i s case the fi rst stain appeared
a fter one year and today t here are a l ready about 30 stained spots.
From t hese resu lts i t was possible to draw the cautious conclusion that
color change of the layer of colloidal silver occurred about 10 t i mes earlier
than the first visible destruction of a photographic layer of si lver. Color c hange
of the layer of col loidal s ilver occu rring after a few weeks or months probably
i nd icates an atmosphere which can cause destruction of the s i lver layers.
I t shou lei be m e n tioned that it was possible to restore the negatives of
the iVl u n ich arc h ives s u ffi ciently for the object p h o tographed to be c l early
recogn izable agai n . Figu re 6 is a magnified section t h ro ugh a brown spot
showing that the spots l i e , for the most part, i n the t h i n p rotective overlayer
of the e m u ls i o n . The best method for restorat i o n was to bathe t h e affected
negative in a 0.5 to 1 % solution of iod i ne in alcohol. Penetrating s lowly i nto
t h e gel a t i n e l ayer this w il l change t h e yeJ Jow s ilver i n to s i lver iodide. The
fi l m is t reated for several m i n u tes. The process bei ng term i nated before t h e
i mage si lver itself i s attacked. Fol l owing the i o d i n e bath t h e negatives are
fixed and washed to archiva l s tandards. Figure 7 s hows a negative before a n d
after restoration b y t h i s method.
Presently the Agfa-Gevaert Company suppl i es test strips for arc h i ves,
which can be u sed to m o n i tor the air to recognize early whether catastroph i c
damage t o val uable p hotographic d oc u m en ts m i gh t occur.

Acknowledgments

\Vhen doing t h i s work I received assi stance from Dr. iVI . Scheibitz a n d
Dr. R . M eyer, of the Agfa-Gevaert la boratory i n Leverkusen, w h o I thank for
t h e val ua b l e contri butions.

Notes

1 C. S . iV l cCamy and C. I. Pope, ). Res NBS GSA ( Phys. and Che m . ) , 5: 385
( 1 965).
2 R. W. Henn and D . C . Wiest, Photogr. Sci. E ng., 9 : 378 ( 1 965).
3 C . I. Pope, }. Res NBS (Phys. and Chem. . ), 72A(3): 251 ( 1 968); 74A ( 1 ) ; 31 ( 1 969).
 R e a d i n g 19

D O U G LAS W . N I S H I M U RA, }AM E S M .

R E I L LY, A N D P ET E R A D E LSTE I N

Improvements to the Photographic

Activity Test in AN S I Standard
IT9.2 ( 1 99 1 )

This reading, coauthored by leading scientists at the Image Pennanen.ce

I nst itute ( I P/) in Rochester, New Yorlz, docu nients the developm.ent of t h e
i mpmved a nd highly sensitive Photographic Activity Test (PAT) at accelerated
ternperature a nd h u m idity conditions utilizing both colloidal silver on a poly­
ester filni base and a fixed-ou t fiber-base print as detectors for the eva luat ion of
si.lver i mage interactions and gelatin stai n format-ion. Founded i n 1 985, f Pl is a
un iversity-baseel (Rochester T nstitute of Tech nology), nonprofit research labora­
tory elevated to scientific research in t he p reservation of visual a nd other fonns
of recorded information. Douglas Nishhnura, a research scient ist at J P/, is a
me'l1'iher of t he joint I n ternational Organization for Standa rdizat-ion-A1nerican
Nat ional Standards lnst i. t u t;e com m iUee responsible for the physical proper­
ties and 7nrmanence of i maging materials. Before join i ng IPI, Nishi m u ra con­
ducted silver i mage stability research a t t he National A rchives of Canada. I-le
is tech nical supervisor for many major JP J research p rojects a nd is well lmown
as et t;eacher, lecturer, and consultant on i mage preservation. ( For ]a·mes Re-illy
see also Readi ngs 7, 3 6, and 60; for Peter Adelstei n see also Readings 44 a nd
49. ) I n t he 1 980s the PAT was rndes·i.gn.ed at J PJ, this time malting use of
Dr. Weyde 's colloidal silver detector as described i. n t he previous reading (we
stray froni the convention of 01·ganfring the readings chronologically here to
e ·mphasize the i nfluence of D r. Weyde 's research on current standards). This
made the test far more sensitive and has been successfully used to quan.t ita-

DOUGLAS \�I. N 1 s 1 11MU HA, ]AMES M . R E I LLY, and PETEH ADELSTE I N , " I mprovements to the
Photographic Activity Test i n A N S I Standard IT9.2, " journal of I maging Technolog)' 1 7,
no. 6 ( December 1 99 1 ) : 245-52. © 1 99 1 , I S&T: The Society for I maging Science a n d Tech­
.
nology Text and i mages reprinted by permission of I S&T: The Society for I maging Sci­
ence and Tec hnology, sole copyright owners oF Journal of l niagi·ng Teclinology.

1 55
Part II S I L V E H I 1\ I 1\ G E S T H C C T U H E t\ N D S T t\ 13 I L I T Y

tively evaluate ch.e·mical i nteractions between enclosure materials and silver

images ever since. For the fi rst time, t h.is sf; udy docu: 1nented that the presence
or absence of calcium carbonate buffering did not; affec t product 11e1formance,
discredi.ting the widespread fear that buffe red enclosu res could cause protein­
aceous binder layers (such as albumen and gelatin) to stai n. / P J 's research
clearly de monstraf;ed that there was much 11wre to good quality than just
aci.cl-free. Today f;he PAT is the worldwide sta ndard ( ISO Standard 1 8 9 1 6 ) for
archival qi1ality in 71hotographic enclos11res and t1sed regula rly to evaluate t he
components of enclos u res, such as adhesives, inhs, paints, labels, a ncl tapes.

Introduction

Processed photogra p h i c materials i n archiva l col lections req u i re a h igh

degree of i nd ividual packaging to protect them from at mospheric i n fl u ences,
dust, handl i ng da mage, a n d also to keep them from contaminating each
other. For t h i s p u rpose, a wide variety of paper and plastic materia l s are
commerc i a l l y avai lable, fabricated i nto boxes, s leeves, fol ders, mat boards,
and i n te rl eavi ng tissues. H owever, it i s absol utely essential that t h ese s torage
enclosures m u s t not themselves cause harm to the photographic i m age.
I n 1 978, the American National Sta ndards l n s t i t u te (AN S I ) p u b l is hed
a standard on fil ing enclosures for p hotographic materials. This s tandard set
specifications for the raw materials, design , and nomenclature of storage
enclosures. I t also provided test methods for cletermi ni ng t h e p resence of
known harmfu l su bstances, s u c h as red ucible s u l fu r. In addition, t h i s stan­
dard speci fied that a l l enclos ures must pass a ge nera l test for c h e m i cal i n te r­
actions known as t h e Photographic Act ivity Test ( PAT) . Th i s test method
i nvolved placing the processed p hotographic material of i nterest in contact
with the enclosure to be eval uated for 30 clays at 50°C , 86% R H . A m icro fiche
jacket, for exa m ple, wou l d have been i ncubated in co ntact w i t h a processed
m i c rofiche. Laboratory fi lter paper, i n c u bated at the same t ime, served as a
control for comparison p u rposes. Passing the test req u i red that c hanges i n
t h e photogra p h i c media produced b y con tact with t h e enclosure material not
exceed cha nges produced by contact with the f i l te r paper con t rol .
Th i s original test method was deve loped in the late 1 970s from i nc u ­
b a t i o n t e s t s on several photograp h ic materials i n contact w i t h s o m e known
bad materials, i nc l u d i n g ru bber bands, a poor q u a l i ty e nvelope, and ink from
fi ber-tipped pens. The 30 clays at 50°C , 86% R H i nc u bation s howed a l a rge
d i fference between a fi lter paper sample and the known bad test materia l s .
T h e i ncorporation of the PAT i nto the A N S I Standa rd on fi l i ng enclosures
was a significant step forwa rd . H owever, by 1 983, i t was recognized that t h i s
l ogica l , common -sense t e s t method had many s hortcomi ngs.
 Reading 19 N I S 1 1 I J\1 U H 1\ , H E I L L Y , A N D A D E L S ·1· E I 1'\/

Deficiencies of the Origi n a l Test M e thod

The m a i n defic iency of t h e origi nal test method was in t h e way it was deve l ­
oped. T h e test was c a l i brated u s i n g o n l y very b a d materials as sources o f
conta m i n a t i o n . As a res u l t , the t e s t d i d reasonably w e l l i n screen i ng out the
most h a r m fu l enclosures (with some except ions), but did not acc u rately d is­
cri minate between margi nal and very good materi a l s .
The b a s i s of the test method can be stated as, "test what y o u a r e i n ter­
ested in storing. " For exa m ple, if microfi l m boxes are being eva l u ated, then
p rocessed m icrofi l m was used as the "detector" o f harmfu l i nteractions.
Despite the logic to t h i s approac h , expe rimental work showed that s ign i fi­
cant i n teractions may be eas i ly overlooked. Th is i s t h e resu l t o f the photo­
graphic material of i n te rest fre q u e n t ly being a relatively poor detector in a
s hort t i m e test.
For exa m pl e , a 1 960s cardboard m i c rofi l m box, which had caused redox
bleniishes i n fi l m , was incu bated i n contact with processed Kodak A H U 1 460
l magecapture m icrofi l m . A second piece oF 1 460 m i c ro f i l m was i n c u bated in
contact with filter paper as a contro l . The d i fferences between the m icro­
f i l m s incu bated wi th the box and the fi l t e r paper con t rols were s l ight. Redox
b l e mishes were not observed . There was only a b l u e fi l ter d e n s i ty d i ffe re nce
o f 0.02 ( Fro m a starting density of 1 . 00) between the controls and the "bad"
box. Th i s i l l ustrated t h e need for greater sensitiv i ty in the PAT
Th is need was recognized by t h e A N S I c o m m i t tee, a n d i n 1 983, t h ey
requested research by the I mage Permanence I nstitu te. F u n ding was pro­
vided by the National iV I u seu m Act , the National E ndowment fo r the
H u ma n i t ies a n d t h e National H istoric Publ ications and Records C o m m i s­
s i o n . Th i s res u l ted i n a more sensi tive PAT that was p u b l ished i n a revised
A N S I standard ( IT9 . 2 ) in 1 988 and in a n I n ternational S tandards Orga n iza­
t io n doc u ment ( 1 50 1 02 1 4 ) in 1 99 1 . This paper provides the backgrou n d data
for the i m p roved test.

Detector Sel ection

There i s great vari a b i l ity i n the response of d ifferent photographic materi­

a l s to conta mi nants. C lea rly, i f the PAT is to have opt i m u m meaning as a
standard test, a standard ized and sensitive detector is req u i red. I n itial work
concentrated on Fi n d i ng s u c h a detector.
H a rm fu l i nteractions with b lack-and-white p h otographic i mages are of
two basic kinds: reaction with the s i lver i mage to cause fad i ng and other forms
o f i mage degradation , and sta i n i ng of the non i mage areas (pri marily a reaction
with gelat i n ) . Because t h e reactions that cause i m age fad i ng a n d D,,,;n sta i n i ng
a re very d i ffe ren t , i t was concluded that two detectors wo u l d be needed .

1 57
Pa rt I I S I L VE H I 1\ I i\ G E ST H U CT U H E A N D S T A 13 I L I T Y

Fade Detector

For accurate detection of potential i mage degradation, the most i mporta nt

attribute of a detector is the microstructure of its si lver i mage. The size,
shape, and spacing of the individual si lver part icles determine, to a great
extent, how su scepti ble the detector is to density change. Those si lver mate­
rials that show the greatest change i n response to the i ncu bation conditions
are likely to be the best detectors of i mage allack. Because there is a l i m ited
amount of si lver available in any photographic material, there is a realistic
l i m i t of density that can be lost to i nteract ions. If i ncubation alone causes
density losses that approach the origi nal i mage density, then the response
to various " bad " materials is l i m i ted. Table 1 presents the blue filter density
changes when samples of processed photographic materials were i ncu bated
for 30 clays at 50°C, 86% R I-I .
Except for the Agfa colloidal si lver coat i ng (that had a starting den­
sity of about 1 .70), all changes were from an in itial density of 1 .00. None of
the detector materials tested approached this maxi m u m possible density loss
d u ri ng straight i ncubation.
The most sensitive material to t h i s incubation was colloidal (Carey
Lea) silver in gelatin on a polyester F il m base. Coat ings of this type were
descri bed in 1 972 by Edith Weycle of Agfa-Gevaert . 1 Their i ntended applica-

Table 1

Density ol" processed photographic materials al"tcr 30 days

at 5o"C, 86% H f-I .

B l u e density
Detector change
Conventional Films and Papers
Kodak 4 1 68 Direct D u pe Film 0.13
Kodak Polyprint HC Paper
I odak \/crsalitc H C F Film o.oo
Kodak Azo Paper -0.01
Kodak El ite Paper -0.01
Kodak A H U 1 460 1\ l icrorll m -0.01
Kodak T-iVIAT G X-ray Film -a.o r
Kodak Linc F i l m 2555 -0.02
Colloidal Si lver t\ l atcrials
Kodak POP* "' I hcavv gold ton i ng -0.08
A l bumen paper I gold toned -0. 14
Kodak POP w I med gold ton i ng -0.26
Kodak POP w I l ight gold ton i ng -0.40
Agl':1 colloidal si lver on polyeste1· base -0.64

-¥-Studio Proof: POP. printing-out paper.

 Reading 19 N I S 11 I l\ I U H r\ , H E I LLY , A N D A I) E L S T E I N

tion was for use as an i nd icator of oxidizing atmosphe res. Coat ings s i m i lar to
these were a l so used by M ary Kay Porter to eva l uate adhes ives and papers. 2
A l t hough the p r i n t i ng-out papers were also sensitive to i nc u ba t i ons,
t h e Agfa c o l loidal s i lver coatings on a polyester film base had a n u mber of
advan tages. \Vhi l e esse ntially s i m i lar i n m i c rostructure to printi ng-ou t
papers, t h e C a rey Lea coati ngs gave m u c h l a rger density d i fferences when
i nc u bated i n contact with known harmfu l materi als a n d filter paper controls.
This i s apparently due to t h e Fact that t h e polyester base is i m permeable and
does not a l low reactants to be absorbed by t h e s upport . In addition to over­
a l l density c hanges, the Agfa coati ngs a lso became mottled in t h e presence
o f reactive su bstances to a much greater degree than d id the printi ng-o u t
paper. T h e mot t l i ng ( local ized Fad i n g a n d c o l o r c hange ) p roved to be another
use fu l ind icator of h a rm fu l enclos u res. Conseq u e n tly, Carey Lea s i lver was
chosen as the i mage fad i ng detector.

Stain Detector

Early experi m e n ts s howed a sign i ficant yel l ow stain i n the D"';" patch of
printi ng-out paper when i nc u bated with some enclos u re materials. The
res u l t suggested use of t h i s material as a stain d e tector by meas u ri ng the
i ncrease i n b l u e density. This st a i n i ng was not necessa rily accom pa n i ed by
i mage fad i ng i n the h igh-density patch, i ndicati ng the d i ffere nt nat u re of
the two c h e m ic a l reactions. S u bseq ue n t ly, a p re m i u m grade fiber-base pho­
tographic print material was used . The esse n t i a l features were a re lat ively
thick baryta layer a n d a thick e m u l s i o n layer. The paper was prepared for use
by fixing and t horough wash i ng (without expos u re or development), so that
i t contained n o s ilver and very l i t t l e residual hypo. The yel low sta i n i ng that
occu rred u pon i nc u bation with a c h e m i c a l ly reactive enclosure materia l was
cl u e to the i n teraction of t h i s material w i t h ge lat i n , not si lver.

O pt imum I ncubation Conditions

As indicated previously, t h e re was a l i m i ted amount of si lver i n the fade

detector. Consequently, the i nc u bation cond i t ions, by the mse lves, m u st not
prod uce a s u fficiently l a rge density loss, so that the sen s i t ivity of the Fad e
detector to p o o r enclosures i s compro m i sed . Therefore, i t w a s i m portant t o
i n i t i a l l y determi n e the sensitivity o f the colloidal s ilver fade detector to the
variables o f t i me , tempera t u re, and re lat ive h u m i di ty. This p re l i m i nary facto­
rial experiment i n vo lved t h ree leve ls of tempe rature, h u m i d i ty, and t i m e-
27 con d i t ions i n a l l . The fade detector was i n c u bated aga i n s t inert fi lter
paper, and the fad i ng, as meas u red by the c h a nge in b l u e density From a n
origi n a l 1 . 70, i s given i n Ta ble 2 .

1 59
Part II S I LV E R I �I A G E S T H U C T U H E 1\ N D ST 1\ ll I L I T Y

Table 2
B l u e density changes in colloidal silver fade detector i n
contact with fi lter paper.

Days
Temperature RH
("C) (% ) 15 30 60
50 75 -o.33 -0-44 -0.54
50 86 -o-48 -0. 6 1 --0 . 72

50 95 -0.87 -1 .04 -1 . 1 3
60 75 -o.66 -0.92 -I . I I

60 86 -o.88 -I.OJ -1.13

60 95 -J .02 -1.12 -1.19
70 75 -0.98 - 1 . 14 -1 .30
70 86 -1 .08 -1.21 -1 .33
70 95 - 1 .23 - 1 .28 -J -48

l n n o case was the fad i ng of t h e Carey Lea d etector complete, b u t t h e

density changes after 6 0 days i n c u bation at 7 0 ° C were very severe. Severe
conditions can res u l t i n l oss of i n formation d u e to total b leac h i ng of t h e
col loidal s ilver. H owever, 1 5 clays a t 70°C, 8 6 % R I-I, s ti l l al l owed s ufficient
u n b leached col loidal s ilver to detect additional i mage fad i n g cau sed by poor
enc losu res.
A second factorial experi m e n t i nvolved both the colloidal s ilver fade
detector and a l ightly gold toned p ri n t i ng-o u t paper as the stain detector.
Both detectors were incubated in contact with a negative storage envelope
known to have caused severe m i rroring and fad i ng u nder real - l i fe condi tions.
F i lter paper was agai n u sed as a contro l to determ i ne the e ffec t of i n c u ba­
t i o n alone on the detector. The blue density d i ffe rence (Ta b l e 3) between t h e
"bad,. enclos u re and the fi l ter p a p e r contro l i s considered a good measure of
t h e e nc losure effect, because i n here n t c hanges i n the detectors are removed.
A p os i t i ve nu mber i n d icates that t h e "bad" envelope faded or stained
t h e sample m o re than t h e fi l ter paper, whereas a negative n u mber i n dicates
t h e opposi t e . The i nc u bation condition of 70°C, 86% RI-I, gave the great­
est visu a l and dens i ty d i fferences between the f i l ter paper contro l and t h e
" bad" e nvelope i n the s hortest t i m e period. M athematical mode l i ng and s u b­
sequent optimization u s i n g a t h ree-factor s i m p l ex m e t hod produced a very
close set of opt i m u m i n c u bation conditions.
It i s of i nterest to note that an a n a lysis of variance (Tables 4 and 5)
of the resu lts i n d icated that tempera t u re had the l a rgest effect, followed by
h u m id i ty and t i me. A t h i rd expe r i m e n t was cond ucted at the 70° C , 86% R H
condition t o determi ne i f t h e 1 5-day period cou l d b e s hortened. Four enclo­
s u re materi a l s were i nc u bated aga i nst both detectors for 1, 3, 7, a n d 15 days.

1 60
Table 3
Effect of i n c u bation conditions on PAT for "bad" enclosure: blue density c hange from
fil ter paper.

Colloid a l si lver fade Printing-out paper

Detectors detector stain detector

Temperature RH 15 30 60 15 30 60
(" C ) (%) day day day day day clay
50 75 0.04 0.06 ---0 . 0 1 0.01 0.01 0.03
50 86 0.07 0. 1 1 0.13 0.02 0.02 0.02
50 95 -0.07 0.03 0.1 1 0.01 0.04 0.05
60 75 0.05 -0.02 -0.03 0.03 0.04 0.06
60 86 0.07 0.22 0.32 0.03 0.04 0.06
60 95 0.02 o.33 0.32 0.05 0.05 0.08
70 75 -0.06 -0. 1 1 -0. 1 9 0.03 0.05 0.08
70 86 0.24 0.20 0.11 0.07 0.09 0.10
70 95 -0.05 0.29 0.10 0.05 0.04 0.06

Table 4
Analysis oF variance for effects of time, temperature, and h u midity on fade detectors in
contact with "bad" envelope.

Sum of Degrees of Mean Variance S ignificance

Sou rce Squares Freedom Square Ratio Level
T(emperature) 70879.6 2 35439.8 29 1 . 1 3-4 x 1 0-8
H (u m idity) 229 1 9. 5 2 1 1459.8 94 · 1 0.000003
D(ays) 22054.3 2 1 1027.2 90.6 0.000003
T X H 2687.6 4 671.9 5· 5 0.03 1 1 74
T X D 382 1 . 5 4 955 · 4 7·9 0.012991
H X D 3 10.6 4 77.6 o.6 0. 5533 17
TX H X D 973 · 9 8 1 2 1 .7
Total 1 23647.0 26

Table 5
Analysis of variance for effects of t ime, temperature, and h u midity on stain detectors i n
contact with "bad" envelope.

Sum of Degrees of Mean Variance S ignificance

Source Squares Freedom Square Ratio Leve l
T(cmperature) 14587.0 2 7293.5 269. 8 4.6 x 1 0-8
H ( umidity) 10575.6 2 5287.8 1 95.6 1.6 x 10-7
D(ays) 49 4 1 .0 2 2470.5 9 1 .4 0.000003
T X H 6 1 3.0 4 1 53 · 3 5· 7 0.029296
T X D 387.0 4 96.8 3.6 0.077597
l -I X D 469.7 4 1 1 7-4 4-3 0.052835
T X H x D 216.3 8 27.0
Total 3 1 789.6 26
Part II s I L v E n I �I i\ G E s T n u c T u n E i\ '" I) s T f\ 13 I L I T y

Table b
Effect oF i ncubation l i me oF PAT: bl ue density cha nge l'rom filter paper.

M aterial Fade Sta i n Mott l i ng

One Day
" Poor" envelope paper --0.06 0.02 No
r-,11at board II 1 0.02 o.oo No
Mat board If 2 0.02 0.00 No
" Poor " qual ity black paper album page 0.07 0.02 No

Three Days
" Poor" e nvelope paper -
0 . 08 0.02 No
Mat board If 1 -0.02 0.00 No
Mat board II 2 0.0 -j 0.00 No
" Pour" quality black paper album page 0.08 0.05 Yes

Seven Days
" Poor" envelope paper -0.07 0.03 No
Mat board If 1 -0.05 0.01 No
i\ lat board If 2 -0.00 0.02 Nu
" Poor " quality black paper album page 0.03 0.08 No

Fifteen Days
" Poor" envelope paper -0. 1 8 0.05 Yes
r-. lat board If 1 -0.06 0.03 No
r-. hit board I/ 2 0.17 0.03 Yes
" Poor" quality black paper a l b u m page 0.07 0. 1 9 Yes

I n add ition to changes in b l u e density, visual observations were made for

mottl i ng. As shown i n Tab l e 6, broad d i ffere n t iation between good and bad
materials was not ach ieved u n t i l 15 clays of i nc u ba t i o n .

Development o f Col loidal S i lve r

Fading of t h e col loidal s i lver fade detector as a res u l t of i nc u bation with

poor enclosure materi a l s is presu mably caused by oxidation of the metal­
l i c si lver to the ionic form. Photographic development of the fade detec­
tors after i n c u bation wou l d , therefore, red uce the ionic s i lver to visible (and
more stable) meta l l i c si lver. Th is approach has been u sed for t h e Carey Lea
si lver detector used in the hydrogen peroxide test and was stud ied with the
photographic act ivity test.
To test this hypothes is, 30 enclos u re materials were i n c u ba ted with the
col loidal si lver detectors for 15 clays at 70°C, 86% R H . Blue density meas u re­
ments were made before i ncuba t i o n , a fter incubation, and after development
 Reading 19 N I S l-l l 1\ I U B A ) H E I L L Y , A N D A D E L S T E I N

12

10
Fade detector developed

0 2
f

� 1.6

l 12

10
� 2
n
l.
Fade d e t e c tor not d e v e l oped

n
o.e

: 0.6
oO
a o
\I 0 . 4

0 0
0
0
p 0.2

t 0 . 0-1"-��+-��+-��1--�__,r-�__,��-+��---< 0.2 0.4 0 .6 0.8 !.0 !.2 1 4 I .6

o.o

Blue Density Loss from tncutietlon Blue De n s i t y of Co l l o i d a l S i l ver Fade Detector

Figure 1 Figure 2
DcnsiLy loss From i ncubation versus density gain rrom dcvelopmcnl. Hi s togram showing the effect of' developing the fade detector
after incubation. Enclosure materials total is 30.

of the col loidal s i lver i n Tech n i clol for 10 min at 63° C . Development of t h e
s a m p l e s red uces ionic s i l ver, b u t wou ld not reproduce the origi n a l col loidal
si lver morphology. Therefore, i t was expected that the faded samples wou l d
recover some, b u t not a l l o f their origi n a l b l u e densi ty after development.
This was experimentally verifi ed in Figure 1. I n genera l , the density rega ined
by development i s proportional to the l oss clu e to inc u bation. It is concluded
that the fad i ng effec t was m a i n l y clue to oxidation of the coll o id a l s ilver a n d
not the morphological c ha nges i n the s i lver, because the l atter wou l d s how
very l i t t l e density change after development.
H owever, i t was a l so noted that t h e spread of data between t h e 30 enclo­
s u re materials decreased after development, as shown in t h e histograms ( Fig­
u re 2). I t was therefore decided t h a t the l oss in d isti nction between m a teria l s
Part II S I LV E R I M A G E S T R L C TU R E A N D S T A B I L I T Y

outweighed the stabil ization of the detectors . Consequently, development of

the fade detectors was not clone i n subsequent experiments.

Pass/Fail L i mits

The u sefu ln ess of the PAT i s its ability to determi n e whether a n enclosure is
acceptable for p hotographic materials. Consequently, pass/fai l l i m its had to be
set. Even good enclosure materials are not expected to perform as wel l as fi lter
paper and, t herefore, pass/fai l l i m i ts have to a llow changes greater than that
observed with fi l ter paper. There are three criteria for passi n g the test: (i) the
maxim u m stain , (ii) the maximu m fade, and ( i i i ) the absence of mottling.
I n criterion (i), the stain detector consistently had very even changes
across the whole strip. The pass/fai l criteria for stain was set at the mean
stain cau sed by the fi l ter paper control plus 0.05 density u nits. In other
words , a "good" material was allowed to cause 0.05 density u ni ts more stain
than fi l ter paper. Regardi ng criterion (ii), the fade detector had a s l ight vari­
abil i ty in silver density over i ts 2 X 1 2 cm area, which caused small variations
in the amount of density lost during i ncubation. The l i m i t for fading was
therefore based on the standard deviation of fou r l ocations for each of two
fade detector strips. The pass/fai l criteria was set at the fade caused by fil­
ter paper p lu s two standard deviations of this fil ter paper control. Regarding
criterion (iii), poor enc losure material genera l ly exhi b i ted a mottling of the
colloidal silver fade detector, whereas filter paper showed none. The absence
of such mottling was made a nother criteri[on] of this test.
In some cases, the fade detector i n contact ·with poor materials did
not fade, b u t actually gai ned density. H owever, because such materials also
failed either the sta i n i ng or the mottli n g criteria, no l i m i t was set on density
increase i n the colloidal si lver detector strips.

S pecimen Conditioning

Good scientific method suggests that both the test samples and detectors
should be conditioned to the 86% R H of the incu bation condition before the
test i s started. I n theory, if harmfu l materials in the enclosu res are carried
by moisture to the detectors, then preconditio n i ng of samples would ma ke
the test even more sensitive to harmfu l products. H owever, a n e nclosure­
cletector sandwich will certa inly obtain complete moisture condition i ng
within a fraction of the 1 5-day i ncubation time. N evertheless, a condition­
ing ex'Perim e n t was done in which 1 0 differen t enclosures and detectors
were conditioned to 86% R H before assembly i nto sandwiches. Ex1Jeriments
showed that condition i n g made the test less sensitive (Table 7) to the differ­
ent enclos u res. Possibly deleterious m aterials escaped during the condition-
 Reading 19 N I S H I M U R A , H E I L LY , A N D A D E L S T E I N

Table 7
Effect of conditioning enclosure materials in PAT: density change from filter paper.

Fade detector Stain detector

E nclosure U nconditioned Conditioned Unconditioned Conditioned

o.oo -0. 0 1 o.oo -0. 0 1
2 0.03 0.04 0.00 o.oo
3 0.01 0.07 0.01 0.00
4 0.08 0.12 o.oo 0.01
-0.07 -0,02 0.02 0.02
6 -0.04 -0.02 0.03 0.03
7 -0.08 0.01 0.06 0.03
8 -0. 1 1 -0.07 0.04 0.03
9 -0.0 9 -0 06. 0.04 0.02
10 -0. 1 4 -0. 1 1 0.03 0.02

i ng period. H owever, because conditio n i ng the m aterials prior to sandwich

assembly is difficult a n d i t d id n o t give greater differen tiation between e nclo­
sures, this procedure was not followed.

Specimen Thiclmess

A question similar to that of conditioni ng was whether or not the thickness

of the enclos ure wou ld affect the test result. If a thick materi a l provides
enough of a barrier to moistu re p enetration, then thick mat boards would
be e,\'Pected to perform better than t h i n mat boards. H owever, if moisture
penetrates any thickness sufficiently i n 1 5 clays, then thick boards would
p erform worse than t h i n boards because they should contain more h armful
material . Resu lts showed that the thicker boards tended to perform slightly
better than the thinner boards (Tables 8 and 9 ) , but the d ifferences were
very small. H owever, these small differences cann ot be attributed to lack
of moisture condition, because conditioning did not make thick and t h i n
boards perform more evenly (Table 9 ) . T h e relative differences betwe e n t h e
t h i c k a n d t h i n e nclosures were small a n d inconsistent.

Sandwic h Pressure

Pressu re in the enclosure-detector san dwich was the final variable that was
studied. H igh pressure made more materials fai l due to mottli ng a nd fad ing,
but also caused a greater problem with fibers stickin g to the colloidal silver
detector (Table w). Low pressure allowed even very poor materials to pass
the fad i ng and mottling criteria. Based on the e,\'Perimental results, a pres­
sure of 5 g/cm 2 was selected for the test method .
 Table 8
Density change From riltcr paper laminated w i t h various adhesives.

P l ies Adhesive Fade Detector Stain Detector

Polyvinyl acetate -o.97 0.08

4 Polyvinyl acetate -0.94 0.09
8 Polyvinyl acetate -0.96 0.08
2 Wheal starch -0.96 0.08
4 \"1heat starch -o.93 O.JO

8 \�/heat starch -o.88 0.09

2 Methyl cellu lose -0.96 o. [ Q
4 M ethyl cellu lose -o.93 0.08
8 M ethyl cellu lose -0.89 0.08
2 No adhesive -0.9 5 0.08
4 No adhesive -0.93 0.09
8 No adhesive -0.89 0.09

Table 9
Dens i ty change of conditioned and unconditioned mat boards (without adhesive) in PAT.

Condi tioned U ncond i tioned

Fade S tain Fa d e S ta i n
Material Plies Detector Detector Detector Detector
Fi lter paper -1.01 0.08 - 1 .00 0.09
2 -0.96 0.09 -0.97 0.09

-! -o.93 0.09 -o.99 0. 1 0

8 -o.88 0. 1 [ -0.92 0.09
Mat board II 1 - 1 .02 0. 1 1 -1 .07 0. 1 I
- J .02 0.12 - 1 .04 0.12
-! -o.99 o. 1 2 - 1 .08 0. 1 5
M a t board II 2 - 1 .07 0.12 -I . I I 0.13
-1 .06 0. 1 1 - 1 .09 0.13
-! -I.JI 0. 1 1 -1 . 1 4 0.12

Table 10
E ffect of pressure on PAT.

Fade Fade vs. Stain Stain vs.

Pressure Detector F i l ter Detector F i l ter Pass/Fa i l
M a teria l (g/cm2) Blue Density Paper Blue Dens i ty Paper M ottl ing PAT
F ilter paper o.66 -I.OJ 0.10 No
5-42 - J .00 0.09 No
50.00 - 1 .04 0.09 No
" Bad" envelope paper o.66 -o.99 -0.02 0. 1 4 0.04 Yes Fa i l
5 - 42 -1 . 1 4 0. 1 4 0 . 14 0.0 5 Yes Fa i l
50.00 - 1 .29 0.25 0.19 0.10 Yes Fa i l
M a t board I/ I o.66 -1 .03 0.02 0.13 0.03 No Pass
5 - 42 - 1 .03 0.03 0.13 0.04 Yes F ai l

50.00 -1.18 0. 1 4 0.13 0.04 Yes Fail

Mat board I/ 2 o.66 -o.94 -0.07 0.13 0.03 No Pass
5-42 -0. 9 1 -0.09 0.13 0.04 No Pass
50.00 -0.90 -0. 1 4 0.13 0.04 No Pass
 Reading 19 f\ I S l l l M U H A , H E I L L Y , A N D A D E L S T E I N

Test Procedure

The test met hod i nvolves i nc u ba t i ng two strips of each d etector i n contact
with t h e enc losure test spec imen in a sandwich . Status A blue d i ffuse den­
s i ty meas u rements a re made at fou r locations o n each detector: transmission
density on t h e fade detectors a n d reAection density on the stain detectors.
Jn addition to the detectors and the specimens, u ncoated polyethylene
terephthalate, glass, a n d sta i n less steel weights are req u i re d . The detectors,
specimens, and polyester a re a l l cut to 2 X 1 2 cm strips. The fade detec­
tors are a l te rn a ted with the test spec i m e n i n the fol l owing order from top to
botto m : fade detector ( face clow n ) , test enclos u re speci men, fade detector,
test enclos u re spec i m e n , and polyester. The polyester strip prevents harmfu l
components of t h e e n c l os u re sample from d i ffu s i ng t h rough t h e back of the
bottom test specimen . Note that the fade detector i s on a polyester su pport
and, therefore, an extra polyester strip is needed on the top. S i m i larly, t h e
s t a i n detectors are paired w i t h t h e test spec i m e ns s u c h that e a c h p a i r i s iso­
l ated between polyester: polyester, stain detector, enclos u re spec i m e n , poly­
ester, stain d etector, enclosure, a n d p olyester. S i m i l a r stacks are made u s i ng
\i\lhatman # 1 f i l ter paper i nstead of t h e e nclosure m ateria l . Glass stri ps are
u se d a t the top and bottom of each sandwich. Finally, sta i n l ess steel weights
supplying a pressure of 5 g/c m 2 a re added at the very top of each sandwich.
The sandwiches are i n c u bated for 1 5 clays at 70°C, 86% R H .

Practical App l ication o f the New PAT

To i l lustrate the use of the PAT method in the selection of enclosures for use
in archival col l ections, an experi m e n t was performed in which 90 different
enclosures were eva luated. This i n c l u ded 66 commerc i a l ly avail a b l e materi­
a l s t hat could be considered "arc h iva l , " not by any strict scientifi c defi n i t ion,
b u t because t hey were sold by s u p p l i e rs speci a l izing in t h i s line of prod­
ucts. The 66 arc h iva l materia ls i nc luded 36 rag boards, 9 nonr a g boards, a n d
2 1 papers; n u m bering a m o n g t h e m w e r e i n terleavin g tissues, Japanese repair
tissues, barrier papers, enve lope papers, glassines, and slip sheets. These
materials were obtai ned From a n u mber of m a n u factu rers and distribu tors,
and are representative of the kinds of prod ucts that m ight be used in a rc h i ­
va l col l ections in contact w i t h photogra p h s . A l s o i n c luded were a n u mber o f
known good and b a d "bench mark" materials t o p u t the performance of t he
archival p roducts i n perspective.
The outcome of the test for the 66 arc h ival products is given i n Ta ble 1 1 .
Th i s ta ble shows how many o f t h e p roducts fai l e d i n each o f t h e t h ree pass/
fai l criteria. Overa l l , 29 (44%) of t h e a rc h ival products passed the PAT. The
most common cause of products fai l i ng t h e PAT was mott l i ng ( u neven
P a rt I I s I L \I E n I 1\I A G E s T n L' c T L' n E A N I) s T A B I L I T y

Table 11
Su mmary oF PAT resu lts on 66 a rch ival prod ucts.

Fade Stain Mottle No. %

Fail Fail Fa i l 2
Pass Fail Fa i l -j 6
Fail Pass Fa i l 8 12
Fail Fail Pass 0 0
Pass Pass Fail 12 18

Fail Pass Pass 7 II

Pass Fail Pass 8

Pass Pass Pass 29 H

b lotchy fad i ng of the colloidal si lver detector) . M ost of these fa i led products
were 2- or 4-ply boards. In a l l , 25 p roducts (38%) fa i led the mott l ing criteria.
Mottling represents the presence of l ocal " hot spots " o f fad i ng a n d genera l l y
i nd icates i n ho mogeneity i n a n enclosure prod uct.
F igure 3 s hows a freque ncy h istogram o f the performance of t h e 66
a rc h ival p roducts in the fad ing cri terion . The horizo n tal axis val ues are t h e
m e a n fad i ng o f the prod ucts relative to the fi l t e r p a p e r contro l s . The pos i t ive
va l u es on t h e horizo ntal axis ind icate less fad i ng than the controls, whereas
the negative va l u es i n d i cate more fad i ng than t he contro l s . The t a l l es t bar
of the h istogram occ u rs near o.oo, mea n i ng that most prod ucts caused about
the same amount o f fad i ng as the controls. Note that the d istri b ut i o n of
fade data i s approximately normal and that a nu mber of prod ucts caused sig­
n i ficantly l ess fad i ng than the contro l s . Often, prod ucts that fade m u c h l ess
than the contro l s a lso de monstrate a p ropensity for heavy stai ni ng. Overa l l ,
1 6 (24%) o f t h e arc h iva l products fai l e d t h e fad i ng criteri o n .
Figure 4 shows a freq u ency h i s togram o f sta in d a t a for t h e 6 6 arch iva l
p roducts. T h e horizo ntal axis va l ues a re t h e meas u re stain relat ive t o t h e filter
paper contro l s . None of the prod ucts stained l ess than the controls, but m os t
were l e s s than t h e 0.05 l i m it for passage of t h e t e s t . T h e majority of products
stai ned just s l ightly more than f i l ter paper, but a few stained q u ite heavily.
Overa l l , 10 ( 1 5% ) of the a rc h ival products fai led the sta i n i ng criterion.
The res u l ts o f t h is evaluation of 66 commercially ava i lable archival
prod ucts have an i m portant l esson for arch ive ma nagers: not a l l enclosures
offered i n the ma rket p lace are safe to use with photographs. Vague descrip­
tors, such as "acid-free . . ( most o f the fai led prod u cts were so described), do
not guarantee i nertness toward photographs. ln some cases, the h igh p rices
paid for "arc h iva l" enclosures are actu a l ly buying mate ria ls more harmful
than grocery bags or newsprint. It is essential that consu mers of photographic
enclos u res take steps to ensure the inertness of the a rch ival products they use
i n collections. By insisting that enclos u re manufactu rers demonstrate com-
 Reading 19 N J S ll l M U H A , H E I L L Y , A N O A D E L S T E I N

26

24

22

20

18

16

u 14

12

10

o-1-_,,.___,_
-o 40 -o . 30 -0 20 -o . 10 0 . 00 0 . 10 0 . 20 0 . 30 0 . 40 0 . 50
Density Change vs Fi lter Paper Density Change vs Fi lter Paper

Figure 3 Figure 4
Histogram showing the distribution or fade data for H isLOgrnm showing the distribution of stain data f'or
66 archival products relative tu filter paper. 66 archival p ro d u cts rela t i ve LO filter paper.

p l i a nce w i t h A N S I lT9.2-1 988 and, specifica l ly, passage of the PAT, they can
provide themse lves with reasona b l e assu rance of satisfactory performance.

Performance of Arch iva l Prod ucts i n Perspective

The performance of t h e 66 a rch iva l prod ucts can be p u t i n to perspective by

comparing them with t h e behavio r of some of the 24 known good and bad
"benchmark " materia l s a l so incl uded i n t h i s test. This data i l l u strate that,
by and l a rge, photogra p h ic materials have come a long way from the t ru ly
d readful materia l s that were so c o m mo n i n the past. For exa m p l e , two 1 930s
portra i t studio folders (one gray a n d the other dark gree n ) were tested. The
pri n ts i nside t hese fol ders s h owed fad ing and m i rroring where they had been
in contact w i t h the overmat part of the folder. Both fai led a l l t h ree PAT cri­
teria by l a rge margin s . The fad i ng t hey caused was among the worst o f a l l
Part II S I L V E H I � I fl G E ST H U CT U H E A N D S T 1\ B I L I T Y

90 materials. Their sta i n i ng was about seven times the maxi m u m acceptable
l i m i t , and t hey were heavily mottled. But i t i s also i m portant to note that the
fo u rth worst fad i ng perfo rmance o f all 90 materials was given by an ' 'arc h iva l "
prod uct, a 2-ply w h i te rag board . Two of t h e t h ree J apanese repa i r tissues
tested fa i l ed t h e fad i ng c r i teri o n . There appeared t o be no d i ffere nce i n prod­
uct performance re lated to the p resence o r absence o f carbonate b u fferi ng.
The in teractions between p h otogra p h i c materi a l s and enclosures are obvi­
ously more com plex a nd varied t ha n the commonly used arc h iva l desc rip­
tions, such as "acid -free, " a llow for. An e m p i rical eva l u a t i o n , such as the
PAT, is a vital check for u n foreseen harmfu l effects. Although i t i s a demand­
i n g and rigoro us test method, there a re n u m e ro u s products o n the market
that meet its req u i rements a nd are demonstrably safe to use i n arch ives .

Conclusions

An im proved PAT was developed based o n the use o f both c o l loidal s i lver
o n a polyester film base and fixed-out fiber-base prints as detectors o f fad e
and sta i n , respect ive ly. The i n c u bation cond i t ions are 1 5 days at 70°C, 86%
R H , with a sandwich pressu re between enclosure materi a l s a n d detector of
5 g/c m2. The b l u e f i l t e r density c h a nge was mea s u red in both t h e c o l l o idal
si lver and i n t h e fiber- based print paper. I n add i ti o n to fade a n d stain l i m i t s ,
the enclosure must not cause any mottl i ng i n the col loidal s i l ver. T h e d e t a i l s
o f this new PAT a r e n o w stan dardized i n A N S I Standa rd I T9 .2-1 988.

Acknowledgments

The a u t hors t hank the National E n dowment for the H u ma n i t ies, t h e

N a t i o n a l H istorical P u b lications a n d Records C o m m ission, and the National
M u seu m Act for fu n d i n g t h i s researc h . \11/ e are gratefu l to Agfa-Gevaert and
t h e Conservation B ra n c h , Nat ional Arch ives and Records Ad m i n i stra t i o n
(espec i a l l y C onstance M cCabe ) for h e l p w i t h the project.

Reference and Note

I E. vVcydc, "A si mple test to i d e n t i fy gases which harm si lver i mages,"

Phot.ograpli . Sci. Eng. 1 6 : 283-286 ( 1 972).
2 J\'1 . I<. Porter, private commu nication, 1 983 .
 R e a d n g 20

T I M OT H Y F . P A R S O N S , G L E N G . G RAY,
A N D I RW I N H . C RAWF O R D

To RC or N ot to RC ( 1 979 )

Polyethylene-coated or RC ( resin-coated) paper was introduced to t he photo­

graphic i ndustry in the late 1 960s. H C papers dranwtically reduce the amount
of 1noistu re absorbed by th.e paper base, resulting in reduced washing and dry­
ing times and ·1 n i ni ·ma l print c u rl and coclde. S u c h papers were (and remai n )
exceptionally popular on th.e amateur marlwt. Th.is reading, coauthored by
Eastman Kodalz research scient i.st;s Tiniothy Parsons, Glen Gray, and I rwin
C rawford, clearly o utlines the c hemist ry of polyet hylene and t he oxidation
Tnechanism11eroxide formation promoted by the presence of titaniwn di.ox­
ide incorporated in t he layer st ructu re to improve i ·mage sharpness and bright­
ness. Unfort u nat ely, the i nclusion of titanium dioxide led to irreversible and
destructive c hain scission, entbrif; tlem.ent, an.cl cracbn.g of the polyet hylene
layer in. these early RC photographic papers. Parsons, G ray, and Crauiforcl 's
lanclmarlz researc h reviews clarlz st;orage and display conditions; describes how
incorporated stabilizers will greatly improve product life; and concludes t h a t
with proper care, storage, an.cl handling, RC papers (when stored in t he darlz)
will last as long as their convent:ional fiber-base counterparts. The long-t;erm
clarlz and lig h t stability of RC papers is still debated f;oday; t h i.s inspired study
and its conclusions remain an essen./;ial point of reference.

T I M OTHY F. PAHSONS, G LEN G. G nAY, and I HWIN 1-l. C HAWFO B D , "'To R C or Not to n c . ..
jo11rnal of Applied Phologrnpliic E11gineeri11g 5, no. 2 ( S p r i n g 1 979) : 1 1 0- 1 7 . © 1 979, Soci­
ety of Photogra p h i c Sciences and E ngineers. Text and i mages re pri n t e d by p e r mis s i on of
I S&T: The Society for I maging Science and Tec h n o logy, sole copyright owners of.Jo11 rnal
ofApplied Pliot:ographic Erigineering.

171
 Part II S I L V E H I M t\ G E S T l1 U C T U R E t\ N D S T A B I L I T Y

G E N ERAL, n = 50-5000
PAPE R , n = 200- 1 0 0 0

C H ,O H H OH
I I I
c -o c-c

-o-c
�/� \� c - o-c
�/J H �\� c-

'e �/ \� I
H
Figure 1 ·
c -c c -o
I I I
Struclure of c e l lulose showing
hyd roxyl groups available For
hydrogen bonding between fibers. H OH CH20H

I n troduction

The chem istry of c e l l u losic fibers i s bas ica l ly the same as i n t h e trees from
which t h ey came. As shown in Figure 1 , 1 the molecule i s a l a rge one w i t h
t h e repeat i ng glucose u n i t appearin g u p to 1 ,000 t i m es i n the molec u l e . The
p r i m ary and secondary hydroxyl groups on the molecule associate with water
and make fi bers s u ffi c iently Flexible to be formed i n to paper. During the d ry­
i n g process on a papermaking machine, water is driven off, a n d hydroxyl
groups on a djacent fi bers u ndergo hydrogen bondi ng. I t is t h i s hydro­
gen bon d i ng t h a t accounts for the major portion of pape r's strengt h . The
hydroxyl groups do not lose t heir affi n ity for water, and wi l l reabsorb mois­
t u re at every opport u n i ty. Ever since paper was i nvented about roo A.D.,2
papermakers have been searc h i ng for methods of m in i m i z i ng the effects of
moisture exc hange i n their p roducts.
In the photographic i nd ustry, extended fixing and was h i ng t imes, limp­
ness of paper in p hotographic solu tions, and prolonged d rying t i mes for
p r i n ts were the d irects res u l t of papers' aff i n i ty for moisture . Significant a n d
disproport ionate c hanges i n t he l ength a n d width of p a p e r w i t h wetting or

�be\based prints. D ifferences in

c hanges i n h u m i d i ty, roughe n i n g of s u rfaces and an noyi ng problems w i t h
ferrotypi ng a r e additional problems with
m o i s t u re absorption between the paper base and the emu l s i on layer, and
d i fferences in s h ri n kage of t hese layers in d ry\ a i r, c reate the additional p rob­
lems of c u rl and cockle.

History of Water-Resistant Papers

Many methods have been tried to e l i m i nate or m i n im ize these problems with
photogra p h i c paper. During \i\forld \Var I I, waterproof aero mapping papers
 R eading 20 P J\ H S 0 N S , C H AY . A N D C H A \V F 0 H I)

were prod uced for the a rmed services by mel t i ng a c e l l u lose de riva tive s i m i ­
lar t o that use d f o r f i l m base, and coating the hot melt on paper. These
coati ngs were d i ffic u l t to make and were e>qJens ive. After \;\/oriel \;\fa r 1 1 ,
t h e hot m e l t method was replaced by coati n g paper with a solvent solution
o f cel l u lose acetate, b u t t h i s was also a n e>qJens ive method that met with
l i m i ted s u ccess.
1n t h e 1 950-1 960 e ra, a n u m be r of other methods were t ried to produce
waterproof o r water-resista n t papers. These i n c luded coating o r i mpregnat­
ing paper w i t h latex and with s i l icones, partia l l y acetylating fi bers before or
after formation of the paper, using synthetic fi be rs as part ial replacement for
eel I u Josic fibers, a n d extrusion coat ing of various polymers. I t soon became
appare11t that extrusion coat i ng with polymers had many advan tages over
other methods.

Polyethylene as a Material of Choice

A l t hough a n u m be r o f polymers can be coated on paper with a n extrusion

process, the u ni q u e p roperties o f polye t hylene make i t part icu larly s u i ta b l e
for photographic paper. Polyet hylene i s easi ly ava i lable, is relatively s t a b l e
therm a l ly compare d with other polymers, and has a low viscos i ty change
with temperature. I t exh i b i ts exce l le n t coatabi l ity by extrusion, is i nert to
most c h e m i cals and solve n t , i s i m pe rmeable to water, a n d i s q u i te flexi b l e .
Polyethylene can b e made to adhere wel l t o p a p e r and t o p hotographic e m u l ­
sion layers, a n d i t provides a good m e a n s for contro l l i ng c u r l . Th rough t h i s
combination o f advantageous properties, polyethylene provided for t he f i rs t
t i me a water- resi s ta n t paper su pport f o r general photographic u s e .

I ntroduction of RC Products

Polyethylene coated pape r, or RC ( Re s i n Coated) paper as i t became known,

was in t roduce d to the p hotographic i n d ustry in the early 1 96o's t h rough d i s­
posable i n termediate office copy matrices and p r i n t i n g plate masters. Verifax
Matrix on an RC base was int ro d uced in 1 962, u t i l izing the advan tages of
smooth ness and wet s t i ffness to i m p rove i mage q u a l ity and hand l i ng ease of
this produ c t . F o llowi ng t h is, a l i t h ograph i c paper plate cal led Veri l i t h was
i n t rod uced on a n RC base. I n t h i s case, the RC base provided the d i men­
sional stabi l i ty necessary to make the produ c t fu nction. A short ru n , i nexpen­
sive l i t h o plate would have been u n l i ke l y without R C paper. The tec h n i q u e
w a s l a t e r applied t o a m a t e u r a n d com merc ial papers, a n d the advan tages
were very wel l received .

1 73
 Part II S I LV E B I �I ;\ G E S T H U C TU H E i\ N D S T A ll I L I T Y

U) 40 6�....• •
Q � ...
!:
•
-
Cf)
P o l y c o n t rast R a p i d R C
Q.l
"CJ
� 30
E:
()
I.()
....
Q.l
Q
U) 20
E:
Ct!
....
Ol

g
"<'.
10
. ::
Q.l P o l yc o n t ra s t
()
....
Figure 2 0
LL
Strength in kilograms/5 cm wid t h
0
For slrips of HC and n o n - H C photo 10
0 20 30
papers vs. soaking t i me in water
containing )% Aerosol OT. S o ak i n g T i m e I n M i n u tes

Advantages of RC Paper

Faster process ing was achieved primarily as a res u l t of redu ced was h i ng a n d
d rying t i mes. I n many i nstances, b o t h fi l m and RC p a p e r could b e processed
in the same eq u i pment. S i nce the paper fi bers were no l o nger wetted d u r­
ing photographic processi n g, the h igher d ry stre ngth and s tiffness preva i led
d u ring processi ng, a n d d imensional s ta b i l i ty was greatly i m p roved. Flatter
prints res u l ted by avo i d i ng d rying cockl e , and because curl control could be
built i n to t h e products. S i n c e smooth s u rfaces a n d gloss could be i mparted
i n to the RC layer, ferrotyping was no longer necessary. Perman e n t matte or
textu red su rfaces were poss i b l e by b u i l d i n g texture i n to the RC l ayer.
Some basic advantages of HC paper are i l l u strated in Figures 2 and
[ figu re not re produced h e re ] . In Figu re 2, brea king stre ngth i n ki logra ms
per 5 cm of width a re p lotted on the ordi nate, and the soaking time ( m i n­
utes) in water conta i ning a wett i ng agen t are shown on t h e abscissa. Note
how q u ickly the fi ber-based product loses strength as i t is penetrated by
water, w h i l e the RC produ c t retains al most all of its d ry strength in the wet­
t i n g so l u t i o n . This characteristic not o n ly yields m u c h greater resistance to
tearing in processing m ac h ines, but exp l a i ns how faster processi ng can be
ach ieved by preven t i ng wetting of t h e paper fi bers.
The photograph in [figure not reprod uced here] demonstrates the
advan tage RC pri nts have over fiber base prints for curl. . . . [ Prints] from the
wash tray were d ried in 20% relat ive h u m i d i ty without mechanical restra i n t .
Force developed w i t h i n the emu lsion layer i n l o w h u m idity air t h a t tends t o
make p r i n t s c u rl c a n b e counter bala nced b y using d i fferent density polyeth-
 Reading 20 I' A n s 0 N s ' G n A y ' j\ N D c n 1\ \V 1: 0 H D

ylene and u nequal coverages on the two s ides of the paper. Th i s c haracteris­
t ic of RC paper yields pri n ts that are easier to h a n d l e and to store.

N eed for Ti02 in the Prin t Side RC Layer

l n addition to waterproofi ng the paper base, the p r i n t side RC l ayer has two
additional fu nctions. It m ust provide i m age s harp ness and reflect ive w h i te­
ness i n h ig h l ight a reas of the print. These propert ies are obtained by com­
pounding pigments, colorants, a n d dyes with polyethylene. The i m portance
of opacity in the pri n t side R C layer i s i l l us t rated in [ figu re not reprod uced
here] . [One] i mage . . . was made from a black-and-wh i te print with pigment
i n the RC l ayer, and . . . [another] was made from a print without p igment i n
t h e R C layer. The sign ificant i mprovement i n i mage sharp ness w i t h pigmen t
i n the R C layer is q u i te apparent. . . .
R a n k i ng of the ava i l able p igme nts for refract ive i ndex a n d relative
reflectance are shown i n Table 1 . 3 The latter is defined by Fresn e l 's law
shown at the bottom of Table 1 . The r u t i l e form of Ti02 at the top o f the l i st
is the best p igment avai lable for i m age s harpness w i t h RC for m u lations.

Polyethylene

Polyethylene i s formed by polymerization of e t hylene and t heoreti c a l ly s h o u l d

have t h e struct u re as shown i n Figure 3 .4·5 I n com merc i a l processes, l i near
polymerization does not a l ways occ u r, a n d some side chains or b ranches a re
presen t which i nc reases reactivity of t h e molec u les. 4 5·6 The tert i a ry carbon-

Table 1
Optical properties of pigments.

RI Rel. ReA., %"

Ti02
Ru tile 2.76
f\natase 2.52
ZnS 2 . 37 5.0
Sb,03 rhom bic 2· 3 5 4.8
Zr0 2 2.17 3·3
Sb203 cubic 2.09
ZnO 2.02 2.0
Ba SO, 1 .64 0.2
Polyethylene 1 . 50

.. Binder RI = 1.5 Hcl. lkn.

- ( N, - N,N,)'
N, +

175
 P a rt I I S I L V E B 1 1\ 1 /\ G E S T H L! C T U H E t\ N D S T 1\ l3 J L I T Y

T H E O R ETI CAL

ACTUAL
light,

I H I I N I T I AT I O N : RH- R• + H•

i I � heat etc.

· · · · · C -C •C · · · · · c - c -c · · · · · · c - c -c - c -
I
• •
P R O PA G AT I O N : R• + 02- R O O •
H H
+ +
c
ROO• RH- ROOH R•

I
c CHAIN BRANCHING: ROOH-RO• + HO•

I RO• + HO• + 2RH­

+ +
c
ROH HOH 2R•

I T E R M I N AT I O N : R•

c
I
ROO•

RO• l - I N E R T P R O D U CT S

Figure 3 Figure 4
Theoretical structure of polyeLl1ylcnc. and example OxidaLion nH:c: hanisms oF polyethylene.
of structure rrom commercial process.

hyd rogen bond is the most easily a ttacked, and s i nce com mercial polyethyl­
ene has some tertiary carbons, polyethylene is read i l y oxi dized. The oxidation
m ec h a n i s m is shown i n F i g u re 4.7·8 The oxidation is a free radical c h a i n
reaction i n which t h e p roducts of reaction i n t u rn react with polyet hylene
to p rovide additional oxidation. The reaction can be i n itiated by l ight or by
heat, and i m p u ri t ies i n the res i n can hasten t h e reaction. The oxidation o f
polyethylene is fu rther promoted b y t h e prese nce of Ti02•
\!\Then Ti02 is exposed to l ight, Ti 2 0.1 and a n active form o f oxygen a re
formed primarily on t h e s u rface as s hown in Figu re 5.9· 1 0· 1 1 I n the dark, t h e
reaction reverses. T h e active form o f oxygen fo rmed i n t h e presence of l ight
can attack an oxidiza b l e material c lose by-such as polyethylene in RC lay­
e rs . C h a i n scission occ u rs, molec u l a r weight i s reduced, and t h e R C layer
becomes l ess p l iable.

Phys ical Effects

I n add ition to t h e c h e mical effects j u s t described, d i ffere nces in physical

effects between RC a n d non-RC base can i n f l uence [the] useful l i fe o f prints.
As s hown i n t h e schematic d i agram for non-RC pri n ts i n Figu re 6, paper a n d
e m u lsion layers b o t h a bsorb or desorb moisture w i t h changing h u m id ity, a nd
cha nge d i mensions accord i ngly. The paper, baryta, a n d e m u lsion l ayers a l l
expand i n h igh h u m i d ity, a n d s h r i n k in low h u mi d i ty. l n very low h u m id-
 Reading 20 P t\ H S O N S , G H A Y . A N D C H A \V F O H D

11! -------
.,.1111� it ---
E m u l sion
Low H u m i d i ty
-a r y t a - Dim
1-� ..__,_..;."------ -t1 -
Paper Shri n kage
hv
2 Ti02 Ti203 • O• High H u midity
-
d a rk
Expansion

P O L Y ET H Y L E N E - O • V e r y Low H u m i d ity

Greater Shrinkage
of Emulsion Layer =
O X Y DATI O N P R O D U CTS Curl
CHAIN SCISSION
I N C R EA S I N G B R I TT L E N E S S

Figure 5 Figure 6
Hcaction of Ti01 w i t h radiant energy. Schematic or dimensional changes in photo paper wiLh
cha nges i n ambient h u m i d i ty.

ity the e m u l s i on l ayer can shrink more than t h e paper base, t h e reby caus­
ing curl. These dimensional changes that occ u r i n u nison , a n d c u rl i n low
h u m i d i ty, m i n i m ize stress between l ayers .
As show n in the schematic d iagram for RC prints i n F igu re 7, the
e m u lsion l ayer i s also free to lose moisture i n low h u m i dity, b u t t h e RC layer
significa ntly delays m o i s t u re loss from the paper base, and appreciable stress
can arrive w i t h i n the e m u lsion layer as i t attempts to shrink but i t restra i ned
by the s lower d rying base. In h igh h u m i d i ty absorption o f moisture i s a l so
more rap i d i n t h e e m u l s ion layer, b u t i ncreased vo l u m e is accom modated by
vertical swe l l of the e m u lsion layer a n d very l i ttle stress develops.
The more rap i d the c hange from h igh to l ow h u m i di ty, and the greater
t h e pote n t i a l d i ffere n t i a l s h r i n kage between t h e e m u lsion layer and the
paper base, t h e greater t h e chance of c racking the e m u l s i o n l ayer. C racks
that develop u n der very harsh cyc l i ng conditions are s i m il a r in a p pearance to
mosaic c racks that someti mes appear on conve n t io n a l dry-mou nted non- R C
p h otograp h s , a n d on o i l p a i n t i ngs that have b e e n s u bjected to severe or repe­
t i t ious h u m i d i ty cyc l i ng. \,\/hen the d ry- m o u n ted non-RC photograph shown
in [ figure not reproduced here] was i l l u m i nated and viewed normal ly, the
su rface appeared u n i form . However, when the su rface was i l l u m i na ted a t
a low a n g l e , i t i s apparent from t h e c lose u p v i e w i n [figu re not reprod uced
here ] , that t h e s u rface has mosa ic c racks.

1 77
 Part II S I L V E H I J\ I A G E S T H U C T U H E A N D S T A B I L I TY

H2Q

I
E M U LS I O N

RC E mulsion 1s
Preve n t e d b y
0 1 mens1onal
S t il b 1 l 1 t y

PAPER of RC Layer

Figure 7
Schematic or stress developed in
emul sion la yer as moist u re is losl
From t h c i t layer more rapidly than RC
From paper base in low h u m id i t y.

R C layers are i n it i a l l y very Aex i b l e and can withstand normal l evels

of stress ge nerated in the e m u lsion layer. As a res u l t , should R C pri nts be
s u bjected to excessively rapid and/or extensive h u m i d ity cyc l i n g su fficient to
cause c racki ng, the c racks w i l l exte n d o n l y t h rough the emu lsion layer. Tem­
pera t u res near the m e l t i ng point of polyethyl ene ( 1 05°C) s h o u l d be avoided
d u r i ng d rying of HC p h o tograph i c prints.
When RC prints have been s u bjected to d isplay condit ions for long
periods, rad iant energy absorbed by the RC layer can start the c hemical
reactions descri bed earlier, and eve n t u a l ly cause the print side polyethylene
layer to become less p l iable. \!V ith levels of i l l u m i nation norma l l y used i n
viewing and d is playi ng prints, t h e p r i n t s i d e R C layer w i l l , for many years,
remain adequately p l i a b l e to withstand s t resses created by normal h u m i d ­
ity cycl ing. H owever, i n tense leve l s of i l l u m i n ation, h igh tem pera t u re , a n d
severe h u m i d i ty cyc l i ng wi l l increase t h e c h a n c e of c racking t h e pri nt side
R C laye r. A closeup view of a pri n t t reated in t h i s fashion i s shown in [ figu re
not reprod uced here ] . Magnification and i l l u m i n ation angles e m p l oyed were
t h e same as used for the closeup view of mosaic cracking on the non- R C
print i n [figure n o t reprodu ced here ] . S i nce the HC l ayer on the back o f pho­
tographic prints does not contain Ti0 2 a n d is not normal ly s u bjected to rad i ­
a n t energy even i n display s i tuations, cracking of t h i s laye r d o e s not occ u r.

Methods of Stabil ization

H aving recognized oxi dation as a characterist ic of polyethylene, t h e plastics

i n d ustry has in tensively s t u d i ed methods of stabi l izing the polymer. Most of
the successfu l methods a re l isted in Ta ble 2 . 1 2· " All of these materials are
des igned to in te rfere with t h e oxidation mecha n i s m descri bed earl ier. W h i l e
much of t h i s technol ogy can b e appl ied to ge neral u s e s for polyethylene, J i m-
 Reading 20 P A H S O N S , C H A Y , A N D C H A W F O H D

Table 2
Po lyethyle n e sta b i l izers.

Light scrceners
Antioxi dants
Energy que nc h e rs
Peroxide scavengers
Metal chelators
Synergistic combinations
Pigment moclirication

RC
* t-t-t.
0 0
0 0
0 0 0 0
PAPER 0 0
0
0 0 0
o o o o

�--:!-!-�
Q = St a b i l i z e r M o l e c u l e s
Figure 8

!t = M i g rat i o n i n t o R C Layers
Schematic oF stabilizer
incorporated into paper base and
migration into resin-coated layers.

i tations i n t he coati ng process, a n d sens itometric considerations p reven t full

u t i l ization for photographi c paper. F o r example, concentration of a ntioxidant
in the res i n is l i mi ted to a l evel consistent with good adhesion to t h e paper
base and e m u lsion layer, a n d stab i l izers that i m part col or, cause odor, or
i nterfere with the extrusion process a re u ns u i ta b l e . By t h e proper com b i na­
tion of stab i l izers a n d w h i te pigm e n ts, stab i l i ty of the RC layer can be made
adequate for many uses. \Vh e n stored in t h e d ark, the l i fe of p r i n ts made on
R C papers with such stab i l i zed res i n i s exce l l e n t w i t h no fai l u re in o u r tests.
R ec e n t ly another method of stabil izat ion deve l o ped by Kodak provides
stabi l i ty far exceedi n g t h a t achieved by normal res i n addenda. It has been
fou n d that certain stabilizers can be i ncorporated i n to the paper base as
shown in the schematic d i agram i n F igure 8. The stab i l izers m i grate from
the paper i n to the res i n coats. S ince greater a m o u n ts of stab i li zer can be

1 79
Part II s I L v E n I J\ I A G E s T H u cT u n E A N D s T A 13 I L I T y

added to the paper than to the RC layers, the paper acts as a reservo i r for
these addenda, and t h e RC l ayers are stabilized for exceed i ngly long periods
of time as w i l l be shown s u bsequen tly.

Accel e rated Aging Studies

Dark Ovens. Before exte n d i ng the use of R C paper from disposable office
copy matri ces and pri n t i n g p late material to amateur and commercial pho­
tographic papers, deta i l ed accelerated agi ng s t u d ies were conducted. S pe­
cial ovens were asse mbled to control temperat u re, h u m i d i ty, a n d con t i n u ou s
flow t h rough of fres h a i r. Construction of the ove ns are d escribed i n earl i e r
p u b l ication s . 1 4 · "
The basis o f these s t u dies was t h e well-known Arrhe n i u s equations
that can be used to express t h e relationship between the rate of chem ical
reactions and absolute tem peratu re . 1 6· 1 7

(1)
d I n lz A
� RT2

where
lz = rate of react i o n
T = absolute temperature

A = activation energy
R = gas law constant

I f A is i n d ependent of temperature in the range o f i n terest, Eq. (1) can be

i ntegrated to t h e fo l lowing for m :

(In) h = R� + C (2)

where C i s a n i n tegration consta n t .

For convenience Eg. (2) can be converted to a form u s i n g logari t h m s
to the base 1 0 as fo l l ows:

loo lz
"'
= - ( 2 . 303R )
A x _L
T
+ _ C_
2 . 303
( J<. )

S i nce cha nges i n physical p roperti es occ u r as a res u l t of chem ical c hanges,
t h e Arrhe n i u s re lations h i p can in many i nstances be used to p redict rates
of change in p hys ical properties. In the i n itial study, 1 4 tempera t u res of t h e
ovens ranged from 6 0 t o 1 1 2°C when operated u nd e r arid conditions and
from 60 to 90°C with h u m i di ty within each oven adj usted to yield a constant
m o i s t u re content of 5% in the samples. Rates of cha nge were determ i n e d
a fter 1 2 w i t h d ra wal t i mes with e a c h oven tempera t u re . Dwe l l times varied
with each tem perat u re but range d up to a fu ll year i n the 6o°C ove n s .
 Reading 20 P A H S O N S , G H A Y , t\ 1'\1 D C H . t\ \V F O H D

k.
l oss
1 0'
pe r • • R C C o a te d
10·'
hr
1 0° 1 0·· 1 0 ·1
k, Loss
Folding
E n d u rance 1 Q·1 1 0 ·3
Per Hour
10 ,

1 0·3 1 0·'

1 0·2
10' �#.• 1 0 ·5
•#,,
�'I.••
•• ••
1 0' 3 · ·
1 0·5 =
·· ··
•• ·•• 1 0 ·6
•• ••
••
••
•
1 0 ·' ..______________... 1 0· 5
1 00 80 60 40 20 1 00 80 60 40 20
T e m perature,° C Tem perature, ° C

2.6 2.8 3.0 3.2 3.4 2.6 2.8 3.0 3.2 3.4
1 /o K x 1 Q i 1 /° K x 1 0·3

Figure 9 Figure 10
Loga rithm oF h v s . i / T for Fol d i ng endurance Log:irithm of h vs. i /T for residu;il tensile breaking
of BC an d non-HC 1rnpcrs in dry and strength ol' RC and non-R C papers al'ter 2 5 zero tension
moisture-controlled ovens. pressure folds in dry and moistu re-controlled ovens.

Tests conduc ted on RC a n d n o n - R C spec i m en s i n c u bated in t h e dark

between each ope n i n g of the oven s i n c l u ded ten s i l e strengt h , 1 8 M IT fol d i ng
e n d u rance, 1 9 resid u a l tensile stre ngth after 25 fol d s u nder pressure ,20 a n d
reflective brightness.2 1 A l though t e ns i le brea king strengt h c h anged very l it t l e
on these papers u n d e r these h a r s h conditions, reasonably l i near re lationships
were fou n d when l ogarithms of t h e average M D ( machine d i rection) and CD
( c ross direction) M IT fol d i ng e n d u rance va l u es were plotted versus i n cuba­
tion t i mes. Linear re lationships were also fou n d w h e n residual tensile stre ngth
a fter 25 pressure folds and reflective brightness were p l otted versus i n c u ba­
tion t i mes. Rates of c h ange establ i s h ed with t hese d a ta were l i near with t h e
rec i p rocal of absol ute t e mperature, consistent w i t h t h e Arrh e n i u s equation.
A lthough calcu lation s were made with a compu ter, Arrh e n i u s type
graphs are shown in F igures 9-1 1 for average val ues on the RC and n o n - R C
papers i n t h e study.
Data i n F igu re 9 i n d i cate that l oss of M IT fol d i ng e n d u rance was more
rap id i n the moist ove n s , and a t the h igher te m peratu res, loss of fol d i ng
e n d u rance was more rap i d o n t h e RC papers. Note, however, that the l i nes
for RC papers cross t hose for non-RC papers near 6o°C, a n d at room tem­
pera t u res, loss of folding e n d u rance o n t h e RC papers wou l d be less rapi d
t h a n o n t h e n o n - R C papers f o r b o t h a r i d and m o i s t conditions.
 P a rt I I S I L V E fl I M A G E S T H U C T U fl E A N D S TA B I L I TY

1 0°
• • R C Coated
o- - -o Non-RC Coated

1 0 ·'
k. L o s s
B r i g h t ness
Per Hour
1 0"

Figure 11
Loga rithm oF h vs. 1/T for 1 0"
reflective brightness of' HC 1 00 80 60 40 20
and 11011-HC papers in dry and Tem perature. ° C
moisture-controlled ovens. I I I I I
2.6 2 8 3.0 3.2 3.4
1 /° K x 1 0"

Loss in res i d u a l ten s i l e strength after 25 double folds u nder p ressure

was only s l igh t l y more rap i d in t h e moist ovens t h a n in the arid cond i t ions;
therefore in F igu re 1 0 the two sets of data have been d ispl aced by a factor of
10. Aga i n t h e loss of res i d u a l tensile strength after pressu re fol d i n g was more
rap i d on t h e RC papers at the higher tempera t ures, b u t aga i n t h e l i n es cross
near 6o°C , and at room tempera t u res the loss of strength w o u l d be less rapid
on the R C papers.
Loss of re flective brigh t n ess was more rapi d i n the moist oven s as shown
in Figu re 1 1 . In both t h e moist and arid oven s , loss of reflective brightness on
R C paper was l ess rapid than on non-RC paper over t h e e n t i re t e m pera t u re
range. F ro m the res u lts of t hese dark ove n studies publ ished earlier, 1 4 i t was
concl uded that when s tored in the dark between occasional viewings, pri nts
on RC papers wou l d l as t at l east as long as pri n t s on non-RC papers.

Lighted Ove n s . When it was d iscovered t hat light absorbed by t h e print side
RC l ayer cou l d trigger chemical reactions caus i ng that layer to become l ess
p liable, windows were i n s ta l l ed i n the ovens. F l uorescent l a m p s m o u n ted
outside o f these w i ndows perm itted rad i a n t energy to reach speci m e ns i ns i d e
the ove n s . Figu re [not reprod uced h e r e ] is a photograph of a n oven w i t h
the door open, and t h e d o o r of t h e i n ner cham ber removed. L i g h t pass­
i ng t h ro u gh w i n dows a t the back of the oven i l l u m i nate the p r i n t side of
the spec i m e n s .
Stud ies conducted i n these l ighted oven s i nd icated that u nder d i s­
p lay conditions loss o f flexib i l i ty in the p r i n t side R C layer is hastened by
 Reading 20 1 • 1\ H S 0 N S , G H AY , A N I) C n /\ W F 0 H D

Flex i ble High

A
S t ress
C reated
By
H u m i d i ty
Cycl i n g

1 /E
s,

Figure 12
S, Schematic i llu s t rating t i me l O crnck
print side H C layer (T 1 to T.�), varies
with level of display i l l u m ination
(A/3 or A C). and stress applied by
Brittle level oF hu midity cycling ( S 1 - SJ.
Display Time T, T, T3 T,

i nc reased levels o f temperature, h u m i d i ty i l l u m i nation, a n d d u ra t ion of the

i 1 1 u 111 i nation.
S i nce both flex i b i lity of t h e print side R C layer, and magnitude of
the stress a p p l i ed t h ro ugh h u m id i ty cyc l i ng, determ i ne t h e t i m e req u i red
to cause eve n the s m a l l es t of cracks i n the R C layer, and since add i t ional
loss of flexi b i l i ty and contin ued appl ication of stress are req u i red to c reate
more noticeable cracks, it is d i ffi c u l t to estimate the u sefu l disp lay l i fe of RC
prints u nder the wide variety of customer con d i tions. The schematic diagram
in F igure 12 wi l l i l l u strate the complexity of making these esti m ates. D i splay
time i s shown on the abscissa; l oss of flexibi l i ty of t h e R C l ayer ( reciprocal
of the elastic mod u l u s ) i s shown on the left side ord i nate, and i ncreas i n g
amounts of stress a p p l i ed to the pri n t s i d e R C layer i s shown on the righ t
side ord i nate.
C u rve AB in F igure 12 i l l u st ra tes that at h igh levels o f i l l u m i nation,
tempera t u re, or h u m i di ty, the loss i n flexib i lity of the p r i n t side RC layer
wou l d be more rap i d t h a n a t lower l evel s of t hese va riables i l l u st rated by
c u rve AC. H owever, loss in f l exi b i l i ty alone does not res u l t i n cracks in the
print side R C layer; applied stress is also requ i red. D i ffere nt leve ls of stress
appl ied by d i m ensional changes of the paper base e m u lsion l ayer are i l l us­
trated at two l evel s S 1 and 5 2 • Both magnitude and frequency o f h u m id ity
cyc l i n g can i n fl uence the l evel of stress a pp l ied to the R C layer. As a fu nc­
tion of d i s play condi t ions in this i l l ustration, the time req u i red to crack the
pri n t side R C l ayer can be from Time to Ti me4•
1
The time req u i red to crack t h e R C layer u nder d isplay cond i t ions i s a
rec i procal of the ''h" factor i n the Arrh e n i u s equations. Data generated at a
n u mber of d i ffere n t temperatu res u s i ng commerc i a l s tabil izers in the print
side R C layer, and a rather severe set of i l l u m i n ation and h u m id i ty cyc l ing
conditions, were plotted o n a n Arrhe n i u s type gra p h . As shown i n F igu re 1 3 ,
 Part II S I L V E H I M 1\ G E S T H U C T U H E A N D S T A B I L I T Y

75° F 75° F
10 1 05
Y e a rs Years
- 1 00 - 1 00
• I nitial Formulation 75 • I n i t ial Formulation 75
D Mod ified P i g m e n t
50 50
1 04 25 1 0' 25
k. k,
Days t o Days to
Crack Crack
5 5
1 03 1 03

1 0' 1 02

10' 1 0'
80 60 40 20 80 60 40 20
T e m p e ra t u re . ° C Tem perature,° C

2.8 3.0 3.2 3.4 3 2 3.4

2.8 3 0
1 10 K x 1 Q ·' . 1 10 K x 1 0 ·3 .

Figure 13 Figure 14
Time to crack print side R C layer in lighted ovens vs. 1ff Time lo crack print side BC layer i n lighted ovens vs. 1/T p rojected to
projected to room temperature display life ( 1 00 footcandles1 room temperature display l i fe ( 100 footcandles, 10 h r/day) for initial
10 h r/day) for initial RC color Formulation. RC color formulation and w i t h modified pigment i n the RC layer.

a l inear relations h ip was fou n d . S in c e the time requi red for t h e first sign of
c racking to appear is p lotted as " log lz," rather t h a n the c h a nge with time,
the graph has a positive slope rather t h a n the negative s lopes of F i gu res 9- 1 L
Computer estimates of t i m e for t h e first c rack to appear with these i l l u m i na­
tion conditions was abou t five years for i n i t i a l RC color paper formu l ations.
These estimates were later ver i fied w i t h natural agin g display conditions,
and l e n d c o n fidence to d i s play l ife estimates determined for i m p roved RC
formulations.
Color prints made w i t h a c o m b ination of stabilizer a n d a modified p i g­
ment i n t h e RC layer w i l l requ i re a n average of 35 years to develop the fi rs t
crack w h e n contin u o u s ly displayed u nder 1 00 footcandles for ro h r/day, as
i ndi cated i n Figure 14. Samples u n der t h e same i l l u m ination cond itions but
a t room temperature s how n o indication of cracks after eight years to date.
Color p r ints made o n RC base that also contain stabi l izer in the paper
between t h e RC layers have not yet cracked u n de r the same accelerated aging
condition. The t i me periods s hown in F i g u re 15 p roject to 1 00 years ; however,
s i n c e c racking has not yet occurred, these RC p ri n ts should req uire in excess
of 1 00 years to develop t h e fi rst c racks when continuously displayed u n der
1 00 footcandles for 10 hr/day, every day. B lack-and-white papers that m ake
 Reading 20 P A R S O N S , G R A Y , A N D C H A \.V F O R D

75°F
1 0' • I n i t i a l F o rm u l a t i o n Years
D M o d i fied P i g m e n t _1 00
- 75
!:!,. S ta b i l i z e r i n Base
- so
••
1 0' ...
- 25
•
•••
k. ••
••
••
...
Days t o
•
Crack ••
• ·-
1 03 ••
••
5

• ••
•

1 02 Figure 1 5
Time to crack print s i d e HC layer
in lighted ovens vs. 1/T projected
to room temperature display life
( 1 00 footcandles, 10 h r/day) for
80 i n i t ial RC color formulaLion, with
T e m p e ra t u re , ° C modified pigment in the RC layer,
and time periods to date with
stabil izer in the paper base.
2.8 3 . 0 1 ;o K x 1 Q · 3 3.2 3. 4

u se of this new tec h nology l i kewise project i n excess of 100 years to develop
the first crack when displayed u n der the same i l l u m ination conditions.

Availabil ity of Fiber Base Black-and-White Papers

Editorials i n photograph i c l i terature have expressed concern that fiber base

b lack-and-whi te papers are beco m i ng an endangered species. Conc u rrent
with the m a nufacture of b lack-and-wh i te RC papers, Eastman Kodak Com­
pany suppli es a n um ber of b lack-and-white fiber base products that i nc l ude
graded a n d selective contrasts, contact and projection speeds, various sur­
face fi nishes, and i n d ifferent basis weights. New i mp roved b lack-and-white
fiber based products have recently been annou nced, and additional black­
a nd-white fi ber based papers are being developed. C ustomer needs for pho­
tograph ic papers are widely diversi fied. Many customers needs are more
efficiently met with RC papers, but others might prefer fi ber base products.
Eastman Kodak Company h as therefore tried to supply both and wi l l con­
tinue in that e ndeavor as long as the need for both types i s apparent.

Recommended Treatment for A l l Photographs

The u seful l i fe of a l l p hotographs whether on RC or non-RC base can be

extended by exerc is ing care i n their handling an d storage. American National
Part II S I L \I E H I � I 1\ G E S T B U CT U H E 1\ N D S T 1\ ll I L I T Y

S ta ndard s I ns t i t ute, l nc . ( A N S I ) Standard P l- I 1 .48- 1 974 offers recommenda­

tions for print enclosures, storage housi ng, storage rooms, print hand l i ng,
and envi ronmental conditions. The i r suggestions o n tempera t u re, h u m i d i ty,
and l ight a re worthy of review here:

1 . A tempera t u re in the range of 59-77° F is acceptable, but daily cycl i ng

greater than 7 ° F s h o u ld be avoided .
2. E m u lsion layers become brittle below 30% R H and mold growth i s
promoted above 6 0 % R I- I . O p t i m u m l i m i t s a re 30-50% R H , b u t daily
cyc l i ng between t hese ext remes s h o u ld be avoided.
3 . Exposure to d i rect s u n l ight or l ight sou rces contain i n g h igh level s o f
u l t raviolet rad iation s h o u l d be avo ided . Tu ngsten and u l t raviolet-free
A u orescent lamps are reco m mended for viewing and exh i b i t i ng.

Summary

RC base papers have h e l ped to solve many t rad itional prob lems in the pho­
togra p h i c i nd u s t ry, a n d have been e n t h u s iastica l l y received by many custom­
e rs . 'With proper care in handl i ng a n d storage, RC papers w i l l meet most
needs for u sefu l l i fe. When stored i n the dark between occasional viewi ngs ,
prints on R C paper wi l l l a s t at least as l o n g a s prints on n o n - R C paper. Tec h­
nological advances have been made to sign i ficantly pro long the usefu l l i fe of
RC pri nts u nder display conditions, b u t fiber base b lack-and-wh i te photo­
graphic papers w i l l sti l l be ava i l a b l e for as long as they are n eeded.

Acknowledgments

The assistance of several members of t h e Paper Service Divi s ion Staff is grate­
fu l l y acknowledged ; in particular a special note o f t h a n ks is cl ue Vli l liam J .
Dora n for su pervising operation o f the ove ns, and m u c h o f the physical test i ng,
and to Thomas A. We ber who handled most of the statistical calcu lations. The
a u t hors are a l so indebted to the Paper M a n u facturing and Eastman Kodak
Company management for permission to p u b l ish the results of t hese studies.

References

1 Ott, E., and H. M S p u rl i n : Ce/111/ose r111cl Ce/111/ose Deri11ati11es, Part I,

l ntcrscicncc P u b lishers, I nc .• 1 954, p. 66.
2 B r i t t , K. W.: /-/anclbooh o.f Paper and Technology, Reinhold P u b l is h i ng C o r p . ,
1964, p. I .
3 ,
Kampfer, W . f\., a n d F . Stie g J r. : 'Tit a n i u m Dioxide a s a Colora nt- Profile ol'
a Pigment," Color Engineering 35 (J u ly-August, 1 967).
 Reading 20 jl A H s 0 N s ' c n i\ y ' A N D c B Aw F 0 n D

4 Renfrew, f\ . , and P. Morgan: Polyet.hylene, I l i ffe and Sons, London, 1 960,

p. 87.
Sanders, K. J . : Organic Poly111er Chemist1y, C hadman and H a l l , London, 1 97.'\ ,
pp. 22, 40.
6 Smith, W. i\11 . : Manufacture of Plastic, Vol. I , Reinhold, New York, 1 964,
pp. 70, 9-b 138.
7 Ran by, 13., and J. F. 11abek: Photodegradation, Photo-oxidation and Photo
Stabili:ation of Pofyll'lers, J. W i l ey & Sons, New York, 1 975, pp. 45-48. 97- 1 02.
8 Hawkins, W . L. : "Mechan isms Contributing to the Autoxidation ol'
Hydrocarbon Polymers," Society oF Plastics Engi neers, Prepri n t , S tabil ity ol'
Plastics Con Ference, J u ne 1 965, p. 39.
9 \t\ley l , W. S . , and T. Farland: " Photochemistry oF 11utilc," Ind. Eng. Cliell'l . , 42:
257-163 ( 1 950).
1 0 Castor, W. S., and L . A. M elsheimer: " Optical Effect of Ti02 Upon I ndustrial
F i n ishes," Paint-Varnish Prod. , 47: 1 0 ( 1 957 ) .
11 Hanby, 1 3 . , a n d J . F . Rabek: Paint Varnish Prod., 4 7 ' 290-29 1 ( 1 957).
12 Hanby, 13., and J. F . Rabek: Paint Varnish Prod., 362-4 1 8 ( 1 957 ) .
13 I - l e i lei·, J . : " P rotecti on o l ' Polymers Against Light I rradiation," Eur. Polym. J .
(S11'f'pl. ) J 05- 1 32 ( 1 962).
14 Gray, G . G.: "An Accelerated Agi n g Study Compari ng Kinetic Rates vs. TAPPI
Standard 453," Ta'f'pi } . , 52: 325-334 ( 1 969).
15 G ray, G . G . : "Determi nation and S ignificance ol' Activation Energy in
Permanence Tests," Advances in Che·m ist1y Series No. 164, 286-3 1 3 ( 1 977 ) .
16 Arrhenius, S . Z.: Phys. Cfw·1n., 4 : 226 ( 1 98 9 ) .
17 Perry, J . 1-1 . : Chemical Engineers 1- /anclbooft, Third Ed., 1 950, pp. 323-324.
18 TA P P ! Suggested Method T- 494 S U 64, 'Tensile Energy Absorption oF Paper."
19 TAP P ! Suggested Method T- 5 1 1 S U 69, " Fold i ng Endurance of Paper ( M IT
Tester) . "
2 0 Brecht, v\/. , a n d A. We sp: Papier ( Darmstadt ) 2 1 /22: 4 4 3 ( 1 952) 23h4: 496
( 1 952).
21 TAP P ! Standard M e thod A-452m 58, " Brightness oF Paper and Paperboard.''

187
 R e a d n g 21

L A R RY H . F E L D MA N

Discoloration of Black-and-White
Photographic Prints ( 1 98 1 )

In this pioneering study, Larry Feldman, a researcher at Eastman Kodah Com­

pany, examines the effects of different types of house paints on the discoloration
of gelatin silver photographic prints. In doing so, he found that, while drying,
alhyd oil-based paints produce peroxides, which may react with filamentary
silver; latex-based paints were shown to be harmless. T1iis research further
demonstrated that fiber-base prints were generally more resistant to image deg­
radation than those on resin-coated paper base owing to the superior absorbent
quality of the uncoated paper base. Feldman's study cautioned generations of
photographers, scholars, curators, conservators, dealers, collectors, and sci.en­
tists about the imminent clangers of photographic collections exposed to sur­
faces freshly painted with alhyd oil-based paints in galleries and in shipping
c rates. His research is frequently cited in 11ollutant studies today and continues
to inform conservators about th.e immense susceptibility of filamentary silver
images to oxidizing atmospheres-and yet, we still frequently encounter photo­
gra11hs displayed in galleries freshly painted with this type of paint.

LARRY 1-1 . FELDMAN, "Discoloration of B lack-and-White Photographic Prints," Journal of

Applied Ph.ot.ograpliic
Engineering 7, no. 1 ( February 1 9 8 1 ) : 1-9. © 198 1 1 Society of Photo­
graphic Sciences and E ngineers. Text and i mages reprinted by permission of I S &T: The
Society for I maging Science and Technology, sole copyright owners ofjournal of Applied
Photographic Enghieering.

1 88
 Reading 21 F E L D !vl A N

figure 1
- Transmission electron micrographs
0. 1 µm 0. 1 µm of developed silve r filaments al
high magnification.

I ntroduction

Residual processing chemicals or chemical reactions triggered by l ight, heat,

h u m i dity, or oxid izing gases can affect the stabi lity of si lver i mages- i n black­
and-whi te photograph i c prints. The effects of the most common res i d ua l
processing chemicals-fixing agents, si lver salts, and developing agents-are
wel l known i n the photographic l iterature, 1 and Standards Organizations have
published methods to address this aspect of p hotographic print stabi l i ty. 2
Attack of s ilver i m ages by various chemical agents present in the envi­
ronment was wel l known with early photographic materials,3 but even pri nts
from modern emulsions are subject to attack. 4 Weyde5 has studied the effect
of a variety of oxid izing gases on black-and-white photographic films and
papers. Freshly produced plastics, engine exhaust fumes, or other sources
of strong oxidizing agents, such as peroxides or n i tric oxides, were shown to
seriously damage s ilver i mages.
The formation of microscopic blemishes i n rol ls of m ic rofi l m held i n
archives has been widely d isc ussed i n the l iterature.6 ·7 I t is general ly accepted
that the small, colored spots are formed by oxidation of the silver i mage, fol ­
lowed b y diffusion of t h e resulting si lver ions, and subsequent reduction to
colloidal si lver.
This paper will briefly review the effect of residual processing chemi­
cals on a s i lver photographic pri nt. The main p u rpose, however, i s to d iscuss
environmental factors leadi ng to the d iscoloration of black-and-white photo­
graphic pri nts and measu res that can be taken to prevent such d iscoloration.
M ethods for the restorat ion of d i scolored prints will be outlined.

F i lamentary S ilver

Filamentary s ilver is normally produced dur i ng the development of photo­

graphic emu lsions. The types of structure shown in the transmission elec­
tron micrographs in F igu re 1 are typical. I nstabi l ity of such filaments, with
Part II S I LV E H I 1\ I A G E S T H U C T U H E A N D S T A H I L I TY

t h e i r large su rface-to-vo l u m e rat i o and correspo n d i n g high su rface e n e rgy,

may be expected u nder certa in conditions.
James,8 for example, has s hown that f i l a ments in u n fixed s i lver halide
films recryst a l l ize i nto s horter, t h icke r filaments or roun ded part i c les a fter
h igh-h u m i d i ty or h igh-tempera t u re storage. U nder more p ra c t ical c i rc u m ­
stances, i n s p i t e of the p rotection afforded b y the gelatin matrix, c hanges i n
density a n d i m age color have been observed i n filam e n ts from a hardened
si lver c h loride e m u lsion dried at h igh tempera t u re.9

Process i ng

Re mova l of u ndeve loped s ilver hal ides a n d t h e res u l t ing soluble s i lver com­
pou nds from the e m u l s io n i s of fa r more practical significance to the s tabi l ­
i ty of a s i lver i mage t h a n any other factor. Fai l u re to d o so adequately may
res u l t i n darke n i ng, d iscoloration, or fad i ng.
Conseq u e n t ly, fol l ow i ng t h e deve l opment s tep, s i lver h a l i de p hoto­
graphic papers are us ually subjected e i ther to fixjng and was h i ng or to a
"sta b i l ization " t reat ment. Fixing converts the u n used s ilver hal ide to sol u­
ble si lver complexes. These, along w i t h the fixing chemicals, can then be
rem oved from the e m u lsion and its su pport by t horough wash i ng. In some
cases, a c h e m i cal was h i n g aid or a hypo e l i m i nator may be employed between
the fixing and was h i n g steps. Stabi l iza t i o n , however, usually consists of bath­
i ng the devel oped print in a sol u t i on conta i n i ng, for examp l e , t h i o s u l fate or
.
th iocyanate to co nvert any u n u sed s i lver salt to a chemical com p l ex. Drying
usually fol lows without any was h i ng. The degree of s ta b i l i ty attainable by
sta b i l ization i s u s u a l ly l ess than that attainable by fixing and was h i ng, but i s
adequate f o r s o m e applications.
A N S I P H 4.32- 1 9742 speci fies tests for deter m i n i ng the relative sta­
b i l ity of processed conve ntional si lver hal ide p hotographic papers. This
standard does not d e fi n e a fi nite time for the usefu l l i fe of processed pho­
tographic papers, but rather, foc uses on levels of stab i l i ty of a test process
compared to a reference process. The emphasis of ANSI P I-I 4 .32- 1 974 i s on
t hose factors that are i n ternal to the sa m p les being eva l u ated . In addition to
s i lver salts and fixing age n ts, developing agents a n d e m u lsion or base com po­
nents may be i m porta n t .
Two t e s t met hods a r e specified i n the standard : ( r ) a t e s t for the effects
of acce lerated agi ng, and (2) a test for stabi l i ty to l ight. Th ree l evels of pro­
cess stab i l ity are also d e fi n e d : opt i m u m , commerc i a l , and s hort-term . The
test methods and the levels of sta b i l ity a re used to compare a test process to
the reference process.
For i l l u stra tive p u rposes, the res u l t s from test processes a re shown in
Figures 2-6. Figu re 2 shows a sta b i l ization-processed print that has faded
 Reading 21 F E L D 1\ I t\ N

Comparison 30 Days 24 Hours

Sample °
38 C/94% R H • 5400 Fe•

Comparison 1 Day 24 Hours

°
Sample 38 C!94% R H • 5400 FC• Developer·
I ncorporated,
F i ber-Base
Paper

Developer­
I ncorporated,
Resin-Coated
Paper

• A NSI P H 4.32- 1 974

• A N S I P H 4.32-1974

Figure 2 Figure 3
SLabilizatiun-pruccss1:.·d prints. Activati(Jn-convenlionally proccsscd prints.

Comparison 30 Days 24 Hours

5400 FC•
° Comparison 20 Days 2 4 Hours
•
Sample 38 e/94% RH • °
Sample 38 e/94% RH 5400 Fe•

Fiber-Base Silver
Paper Retention

Aesln·Coared Hypo
Retention
Paper

• ANSI PH 4.32-1974 " A N S I P H 4.32- 1 9 7 4

Figure 4 Figure 5
Conventionally prrn.:essed prinls. Con\'t'ntionally processed r-lbcr-b;1sc paper
print s-silver and hypo rctcntion.

Comparison 20 Days 24 Hours

Sample
°
38 e/94% R H · 5400 FC •

Silver
Retention

Hypo
Retention

• A N S I P H 4.32-1974

Figure 6
Conventionally processed resin-coaled paper
base prinls-silvcr and hypo retention.
P a rt I I S I LV E B I 1\ I A G E S T B L C T U ll E A N I) STA B I L I T Y

a l most completely after o n ly one day u nder the 38°C ( t 00°F )/94% R H accel­
e ra ted aging test of t h e standard . Jn Figure 3 , two deve loper-i ncorporated
papers-one on a fiber base and one on a res i n -coated base-are shown
to ach ieve opt i m u m process stability with respect to both accel e ra ted aging
and ligh t . Figu re 4 shows that opti m u m process stability with respect to
acce lerated aging a n d l ight can be achieved with conventionally p rocessed
papers. The res u lts from two nonstandard test processes a re shown i n Fig­
u res 5 and 6 . S i lver retention, obtained by u s i ng an exh a u s ted fixing bath,
a n d hypo retention, obtained by i nadequate was h ing, will yield prints o n
b o t h fiber- base and res i n -coated papers L hat d i scolor u n d e r t h e conditions
shown .
I n the a bove figu res, the compa rison sample is one that has been pro­
cessed in t h e test process, but not s u bjected to accelerated agi ng or l ight
sta b i l i ty testing . \t\/i t h the exception o f the samples shown in Figu re 2, refer­
ence samples were processed in t h e refere nce process and s u bjected to t h e
same accel e rated a g i n g and l ight t e s t s as the t e s t samples that h a d been
processed i n their respect ive test processes. The p rocess stab i l ity level was
determined by comparing the test samples to the reference samples as speci­
fied i n the s ta ndard.

Storage and Display

I n add ition to residual chem icals, storage condi tions after proper p roces s i ng
can have an i mporta n t bearing on t h e practical l i fe of a p hotographic paper
print. The u se fu l l i fe of a l l p hotographic pri nts, whether o n resi n -coated or
fibe r-base papers, can be extended by exercising care i n t h e i r h a n d l i ng a n d
storage. A N S I P H 1 .48- 1 974 1 0 offers recommendations f o r print enclosures,
storage housi ng, storage rooms, print h a n d l i ng, and enviro n mental cond itions.
Parsons, G ray, and C rawford 1 1 have s u m ma rized t h e A N S I P l- I 1 .48-1 974
suggestions regard i ng temperatu re , h u m idity, and l ight as fo l lows:
1 . A tem perature in the range of 1 5-25°C ( 59-77°F) is acceptab le, b u t
daily cyc l i ng greater than 4°C (7° F ) s h o u l d be avoided.
2. E m u lsion layers become brittle below 30% R H and mold growth is
p romoted a bove 60% R H . Optim u m l i m i t s are 30-50% R H , but dai.ly cyc l i ng
between t hese extre mes s h o u ld be avoided; seasonal drifts within t hese l i m ­
i t s a re of lesser im porta nce.
3 . Exposu re to d i rect s u n l ight or l ight sources conta i n i ng h igh leve l s of
u l t raviolet rad iat ion should be avoided. Tu ngsten a n d u ltraviolet-free f l uores­
cent l a m ps a re recommended for viewing and exh i b i t i ng. F l u orescent l a m ps
with low levels of u l t raviolet output are available from companies such as
Ge nera l E l ectric and Sylva nia E lectric.

1 92
 Reading 21 F E L D 1\ I A N

I nformation on protection of stored or display prints is also i ncl uded i n

" Preservation of Photographs, " Kodak Publ ication No. F-30. 1 2

Print D iscoloration

M i.crofi.lni

D u ring the 1 96o's, m icroscopic blem ishes were d iscovered on stored rol ls of
microfi l m . 1 3 These spots, which were general ly red or ye l low in color, often
appeared at a scratch , d i rt speck, or d rying residue. They appeared bot h ran­
domly and along density grad ients. The absence of developed s i lver i n the
central areas, the reel or ye l low color i n the c l ear area and surroun d ing areas,
and the frequently observed dense su rface deposit were consistent with the
mechanism of attack by oxid izing agents.

Photographic Papers

Displayed black-and-white pri nts on resi n-coated paper base that are sub­
jected to active oxidants at low concentrations can, over a period of t i me,
develop colloidal silver spots or l ines along i mage density gradients, i n a
fashion s im ilar to that just described with microfi l m . When the aged pri n t
reproduced i n Figu re 7 is i l l u m i nated normal ly, orange-red spots are c lea rly
visible. When the angle of i ncident i l l u m i nation is lowered to prod uce spec­
u lar reflections, the si lver mirror effect at the su rface of some spots and
along abrupt changes in i mage density is c learly visible as shown in Figure 8.
On reflection prints viewed normally, these discolorations can be ye l­
low, orange, or red, depending u pon the size and nu mber of col loidal si lver
parti cles per u n i t vol u me that are d ispersed within the emu lsion layer. Photo­
m icrographs of a spot area are shown normal to the surface and i n cross sec­
tion in Figures 9 and 1 0 , respectively. When the colloidal si lver particles are
c l u stered near the e m u lsion su rface as shown i n the transm ission electron
m icrograph cross sections of Figure J J , the effect is that of a si lver mirror.
As discussed i n the introduction and i n re lation to micro fi l m , this effect
is we l l known and has been described by others; however, a brief review of
the mechanism is in order here. As shown previously, and as represented
schematically in Figure 1 2, image silver is in the form of filaments. \Vhen
act ive oxidan ts are present (represented by hydrogen peroxide in this i l lus­
tration ) , metallic silver ( i n d icated by the symbol Ag0) can be converted to
si lver ions ( i ndicated by the symbol Ag+ ) . These silver ions can then migrate
away From the parent fi lament, part i c u larly when the moisture content of
the i mage layer is high as duri ng h u m id weat her. These si lver ions can then

1 93
 Part II S I L V E B I i\ I A G E S T H L' C T l' H E A N D S T ,\ B I L I T Y

Figure 7 Figure 8
Normal i l l u m i nation of print showing spots. Low-angle illumination of' print showing spuls.

Figure 9 Figure 10
Photomicrograph of a spot area-normal to t he surf.ice. Photomicrograph or a spot area-swollen cross section.

H �

0 . 1 µm O . l µm

Figure 11
Transmission electron micrographs of' a spot
area-low and high magnificat ion.

' 9-f
 Reading 21 F E L D M A N

EMULSION SURFACE EMULSION SURFACE

OXIDATION-

Resin Layer
t-t-t-t.
00 0 0
+ 0 0 0 0
0
MIGRATION

EMULSION SURFACE EMULSION SURFACE PA P E R 0 0

0 0 0
8 o o o o
DEPOSITION

!-¥--!-!�
REDUCTION­
LIGHT
H2S, ETC.
Resin Layer

+It
· Q Stab i l i ze r
Molecules
Migration into
Resin Layers

Figure 12 Figure 13
Schema! ic representation of silvcr oxidation, Stabilizers i n paper s t o c k (after Parsons cl a l . . r e L 1 1 ) .
migralion. and depos itio n .

be red uced to metal l i c silver (as i l l u strated in this schematic d iagram by the
action of l ight), or converted to si lver su lfide (as i l l ustrated i n this d iagram
by the action of hydrogen sul fide, that is often present in ambient air) . Since
these m in u te particles refract l ight, groupings of these particles have a c har­
acteristic yel low, orange, or red appearance. \Nhen concentrated near the
su rface, the metallic silver or si lver su lfide particles can reAect l ight as a
s i lver m i rror.
As described in a p revious publication, 1 1 Eastman Kodak Company pat­
ented a process of incorporating a stabilizer in the paper stock of res in-coated
paper base as represented in the schematic d iagram shown i n Figure 1 3 .
The stab i lizer m igrates i nto the resin l ayers and s ignificantly prolongs the l i fe
of resi n -coated papers u n der d isplay conditions. I t h as been foun d , however,
that u n der certain u nusual environmental conditions to be descri bed later,
overall ye!Jowing of i m age areas can occu r on fiber-base paper p 1·ints and
on resi n-coated paper base prints, even those prints on resi n -coated paper
base that i ncl ude this added protection. F igures 1 4 and 1 5 s how this type of
d iscoloration of fiber-base and resi n-coated paper base prints, respect ive ly.
Note that only the i mage areas are d iscolored.
F igure 16 is a photomicrograph of a d iscolored e m u lsion area, on the
top, compared to an u naffected area. The cross sections are mou nted emul­
sion to emulsion. The same phenomenon i s shown i n Figu re 1 7 via a trans­
mission el ectron m icrograph of a d iscolored emu lsion area, on the right,
compared to an u naffected emulsion area. The col loidal s ilver p resent is d is­
persed both in the emulsion and near the s urface, top right .

1 95
 Part II S I L V E H I M A G E S T n U C T U B E 1\ N D S T A B I L I TY

·· ' • · ' .
, ,. ·

,. ....

' -.

!·
Reference Discolored

Figure 14 Figure 15
Discolored print on fiber-base paper Discolored print on resin-coated paper base.
( Kodak Athena paper, circa 1952).

.I
- - -
..
- -�
-. ,, - - .. �;:-�· · :. .
. ,.. _-,- -·� --.:::
- -
.
.. - - -
&.;..;:-;;; �,f'.;.l!;,,...:""M;
. h-,. �- ;...r - •�
1-4 h

B 0.1 µm 0.1 µ:n

Figure 16 Figure 17

e
Photomicrograph of a discolored e m u lsion area (;\) compared Transmission electron micrograph of a discolored emulsion area
t o an u naffe ct d e m u lsion area (1 3 ) . (righ t ) com pared to a n u naffected emulsion area.
 R e ad i n g 21 r E L D M A N

I 10.8 cm
-/ t

;/
T
Alkyd Alkyd
Point A Paint B
Activity J
8.3 cm
(Signi:i�anJ (Significant
\

j
Act1v1ty

Alkyd
) /f__tJI
Latex

Painted
(LowerJ
Paint
Activity
C Paint
(Ac��itv)
Surface
Facing = ? Print Glass Plate1
Print
( Face-up)

Figure 18 Figure 19
Paint test configuration. Examples of' parallel-plate paint test results.

Environmental Effects

I n some i nstances, these discolorations appeared after prints on resin-coated

paper base had been displayed i n freshly pain ted areas, and in other cases,
the prin ts had been displayed in areas where cosmetics had been used. The
former observation prompted a l aboratory i nvestigation to study the effects
of pain t fu mes on the stab i l i ty of black-and-white p hotographic prints.
A random sampl i ng of 32 paints from d i fferen t manufacturers was
obtained by over-the-cou nter purc hases. Ni neteen alkyd oi l-base and t3 latex
paints were p u rchased and eva luated using the test configuration shown
in F igure 1 8 .
G lass plates l0.8 X 8 . 3 X 0.32 cm (41/4 X 3 1/4 X 1/s i n . ) are used with
0.64 cm ( 1/4 i n . ) Teflon spacers. The p r int to be tested is placed face-up on the
upper side of the bottom plate. The pai n t to be tested is applied uni form ly
about 0 . 0 1 1 g/cm2) to the bottom side of the upper p late and allowed to dry f-ive
hours before assem b li ng the upper and lower plates with clamps or ru bber
bands. The assembly is put i n to a polyester bag to prevent contam ination From
adjacent samples, and stored for one or two weeks at room temperature and
50% R H . A comparison print is stored i n the same manner as the test pri nt, but
without paint on the u pper plate. After the one- or two-week period, the prints
are removed, exam ined for d isco loration, and then treated with a 2% sod i u m
borohydride solution for 2 m i nutes. The sod i u m borohydride reduces any oxi­
dized silver to colloidal s i lver, and gen eral ly produ ces a visi bl e d iscoloration.
None of the 13 latex pai n ts tested by this technique discolored black­
and-whi te p hotograph i c prin ts. These latex paints com prised vinyl acetate,
acrylic, and vinyl acetate/acrylic res i ns. The 19 al kyd oil-base pai n ts, however,
showed varying degrees of activity. Exa mples of prin ts after a one-week parallel­
p l ate pai n t test and sod i u m borohyclride treatment are shown in Figu re 1 9 ·
Part II S I L V E H I J\I 1\ G E S T R U C T U R E f\ N D S T A B I L I T Y

Table l
M a n u facturers' paint composition data.

Latex Type

S igni ficantly Active Low Activity Non-active

Com p onent A B c

Ti0 2 27.0% 25 . 1 %
ZnO 2.0
Ca CO, 1 3.0 1 3.0
S i l ica or s i l icates 3.0 o.8 21.5
A lkyd res in 20.0 23 . 1 :t
Vi nyl acrylic l a tex
M i neral spirits 34.0 34 · 2
'Nater 22.0
Colorants and driers 1.0 3·7
Phc nyl merc u ric 0 . 005
propionate
1 00% 99. 9 % 1 00 . 1 % 1 00%

·' Resin mixture: tall alkytl 1 6.7%. safflower a l kyd 6.4% .

hIncludcs driers.

Manufacturers' compos ition data for these paints are l isted in Table 1 . The
data are not i n te nded to e>.']Jlain the relationship between activity levels, b u t
rather t o i l l ustrate the general characteristics of t h e paints u nder discussion.
I n order to eval uate the activity of paints as a fu nction of drying time,
the paint on the upper pl ate was all owed to dry for increasing periods of time
before assembly with the test print for a two-week reaction period. Three of
the a l kyd oil-base pai nts that fell i n to two categories-sign i ficantly active
an d slightly active-were selected . I mage d iscoloration was m inimal after
7 days with the slightly active paint; but i mage d iscoloration was still evident
with the sign i ficantly active paints, even after the paints had been dried for
29 clays as shown i n Figure 20.
AN S J P H 1 .43- 1 979 1 4 cautions that processed film should be removed
from a storage area for a two-week period when the area is freshly pai n ted,
and Ostroff1 5 has stated that p hotographs may be damaged within the f irst 3
to 4 weeks after an area is painted. A practical test was undertaken to verify
these reports an d to confirm the para l lel-plate pa i n t test results.
Three walls of a room approximately 3.35 m ( 1 1 ft. ) wide X 3.66 m ( 1 2 ft)
long were pai n ted with pai nt A. Approximately 5 hours later, test prints on
both fi ber-base and res in-coated papers were placed in the room . Although
photographs wo uld not normally be rehung on freshly pai nted walls this
soon, i n most i nstances they wou ld be stored i n prox i m i ty to the painting
 Reading 21 F E L D M A N

10 .

C=:J
�L u -
Significantly Aclive

8 .
(Paints A and B)

� Low Activity
(Paint C )
6 .
I ncreasing
Activity
4 .

0 .
0-2 3-6 7-9 10-15 16-20 21-25 26-29
Days Paint Dried Before Two-Week Parallel Plate Test

Figure 20 Figure 21
Rclalivc activity vs. paint drying time. Photograph oF pai nted-room experimenl.

site. A photograph of one of the walls showing the arrangement of test prin ts
at two elevations i s shown i n Figure 2 1 .
Th is painted-room test did substantiate laboratory findings i n that cer­
t a i n test prints on both fiber-base and res i n-coated papers d iscolored within
7 days. Also, other test prints discolored when p laced in the room up to four
weeks after pa i nting was completed. Total oxidant concen trati ons i n the
painted room never exceeded 30 parts per bill ion as determ i ned by nonselec­
tive a nalytical tec hniques. Pai n t-tech n ology l i terature 16 descri bes au toxida­
tive polymerization where drying oils absorb oxygen and form hydroperoxides.
Both water and hydrogen peroxide h ave been fou n d i n the volatile products
of the cross l i nking reactions.
Further laboratory studies were undertaken to establish that hydro­
gen peroxide was the active species in the discoloration of black-and-whi te
photographic prints by oil -base paint fumes. It was s hown that catalase, a n
enzyme that catalyzes the decomposition of hydrogen peroxide, 1 7 ca n preve nt
i mage discoloration when used to treat a potentially su sceptible print before
exposure to an active paint.
A chem i l u m i nescence tec h n i que, based o n the oxi dation of luminol by
hydrogen peroxide, 1 8· 1 9 was used to m easure the evolu tion of hydrogen perox­
ide from drying pain ts as a fu nction of t i me as follows.
Two m i l l i l iters of 0.00 1 M sod i u m ethylenediamine tetraacetic acid
( E DTA) solution were added to a 1 30-ml bottl e. (The EDTA forms complexes
with metal ions, which m ight otherwise catalytically decompose hydrogen
peroxide.) Pa i nts A, B, and C and a latex pain t were pai nted on 2.5 X 7.6
c m (r X 3 in) m icroscope sl ides, and allowed to dry for various times. The
s lides were then suspended over the solution in capped bottles for 1 2 hours.
The E DTA sol u tion was then m ixed with a l um i n o l solution to determ i ne

1 99
P a rt I I S I L V E H I M A G E S T H U C T U R E A N D S TA B I L I T Y

Table 2
Che111 i l u 111 i n escence una lysis oF hydrogen peroxide evo l u t i o n as a Fu nction oF paint
d ryi ng time.

Nanograms of hydrogen peroxide

absorbed" in 2 111 i l li l i ters reagent
Dryi ng t i m e

Paint 6 H ours 4 Days 9 Days 21 Days

f\ l Sign i ficant + -1 3·3 1.7

B _J acllv1Ly 36.9 1 .7 1 . -1
C )-- Low activity 8.5 o.6 0.7

Latex J-- N o activity 0 0 0

·' Boule technique.

Table 3
Quanti lal ivc analysis of oxi d i zed si lver in med i u m
density i m age a reas.

Paper Post-process Nanograrns of ,,vater-

treatn1ent soluble s i l ver/cm2 "
Paint roo111 II
2 P a i n t room 1 000
, Peroxide l"u 111ed 1 60
.)

-I Peroxide l"u 111ed 1 500

·' Background range = r-12 nanograms of si lvcr/cm2.

d issolved hydrogen peroxide concentration by chemil u m i nescence. The

resu lts presented in Table 2 show that no hydrogen peroxide was evolved
from the latex paint sample, but that hydrogen peroxide was evolved from
the alkyd oil-base paint samples. Although the active pai n ts A and B d i ffer
from one another, they evolve more total hyd rogen peroxide than the less
active pai nt C. The levels of hydrogen peroxide reported here are consistent
with the 1 0 -9 mol/l itre level suggested by Kolf.10 Another result of the oxida­
tion of s ilver by hydrogen peroxide is the presence of sol u ble s i lver salts i n
the emulsion o r base.
Papers were se lected that had varying susceptibi l i ty to post-process oxi­
dative treatments. S mall sam ples were taken from mediu m-density areas of
these papers that had been subjected to pai nt or hydrogen peroxide fu mes.
Soluble si lver was extracted with d istilled water and determ i ned by a carbon­
rod atomic-absorption analytical procedu re. Typical res ults for the levels of
su sceptib i l i ty encountered, which support the mechanism of si lver oxidation
and m igration d i scussed earl ier, are shown in Table 3 .
The data generated d uri ng this invest igat ion provide good support to
the general mechanism of attack by oxid izing gases on si lver i mages. The

200
 Reading 21 F E L D 1\ I J\ N

K O D A K Rep;d KODAK KODAK KODA !$

Rap;d KODAK KODAK
Un treated Selenium Toner POLY-TO N E R Sepia Toner Un treated Selenium Toner PO L Y - TO N E A Sepia Tonor

Reference
Reference
Print
Print

Peroxide Peroxide
Fumed Fumed

Figure 22 Figure 23
Post-process treatments-peroxide fumed. C(>11vcntionally Pust-process treatmen ts-peroxide fumed. com·cntionally
processed prints on resin-coated paper base. processed prints on fiber-base paper.

specificity of attack by the hydrogen peroxide produced as a by-product of

alkyd oil-base paint drying has been established q u al itatively and semiquan­
t i tatively. Whether hydrogen peroxide is the o n ly active species, or whether
other volatiles are also sign i ficant is still u nder study.

Protective Treatment

U nderstanding that the silver i n wel l processed black-and-white photo­

graphic prints may be s u bject to environ mental attack suggests that prints
of more than ephemeral va lue should be protected in some man ner. Proper
storage, as d iscussed earlier, will extend the usefu l l i fe of a l l prints. Post­
process treatment may also be appropriate. Typical treatments i n c l ude toner
solutions, proprietary baths, various chem ical solutions, or lacquers.
The use of toners to convert metallic s ilver i mages to si lver sulfide or
si lver selen ide is well know n ; 1 2 and the protection afforded by such treat­
ments to hydrogen (both gaseous and i n sol ution) and other ox idants has
been documented. 4 ·2 1 Treatment with gold toners4 · 1 3 · 1 5 also a ffords protect ion
and, i n many cases, with less change i n i mage color.
The usefu l ness of several toners as protective treat ments for pri nts on
bot h resi n-coated and fi ber-base papers was exa m ined i n laboratory hyd ro­
gen peroxide fu ming tests. The d iscolora t ion observed from such a test on
a n u nt reated print compared to a nonfu med reference pri nt and the pro­
tection afforded by Kodak Rapid Selen i u m Toner, Kodak Poly-Toner, and
Kodak Sepia Toner u nder the same test conditions with conventionally pro­
cessed, resin-coated paper base pri nts are illustrated in Figu re 22. A si m i lar
d isp lay for conventionally processed, fi ber-base paper pri nts is shown i n Fig-
ure 23.

20 1
Part II S I L V E H I 1\I A ( ; E � T H L' C T L' H E A N D S T 1\ IJ I L I T \'

The use of post-process t reatments other t han toners has been d is­
cu ssed i n the l i terat u re. S i stan, a proprietary Form u lation of Agfa-Gevaert
A. G . , is recom mended by Kolf. 20 This material is said to contain potassi u m
thiocyanate, which can precipitate any soluble si lver resulting from the oxi­
dation of i mage s i lver.
Treatment with s u l fur-containing orga nic compounds l i ke thiourea
was shown by Luckey, James, and Va nselow2 1 to i n h i b i t the catalyt i c decom­
pos ition of hydrogen peroxide by i mage s ilver. In a recent patent appl ication
by C i ba-Geigy A.G. ,22 the treat ment of black-and-white photographic prints
on res i n-coated papers with compounds conta i n i ng both a free thiol and a
free amino grou p is d isclosed . Thiourea is spec i F1cally clai med to be of value
in protecting s i lver from d iscoloration.
Laboratory tests u n dertaken d u ri n g the course of this i nvestigation
are in general agreement with the a bove reports . These laboratory tests
also showed that lacq uers were of l i mited effect iveness fo r the protection of
i mages from d iscolorat ion.

Restoration

Prints that have discolored can often be restored . The degree to which resto­
ration can be accompl ished depe nds upon many factors-the most im portant
o f which is the degree of dete riorat ion. Photographic copying i s often the
method of choice, but frequently c he mi cal restoration can give good res ults.
General i n formation on photographic methods may be foun d i n Kodak
P u b l ication F-30. 12 Good restorations of d iscolored pri nts have been ac hieved
using the b leach-redevelop proced ure described there . An example of a print
partially restored by this method is shown i n Figu re 2 +
Pri n ts that have developed colloidal si lver spots can not usually be
restored by this method; however, Weyde 5 has described a method of restora­
tion using iod i ne sol ution. Some su ccess has a lso been ach ieved by copying
an affected print with polarized l ight through a deep blue fil ter, such as a
Kodak Wratten Fi lter, No. 4713.

Su mmary

I t has been s hown that black-and-white photographic prints may d iscolor

from residual processing chemicals or environmental factors such as oxi­
dizing gases. Prints on both resin-coated and fiber-base papers have been
shown to be su scepti ble to d iscoloration from ox idizing gases in la boratory
and practical tests. It is esti mated that this occ urs under actual usage condi­
tions, with prints on resi n-coated paper base, at a frequency of less than one
in a m i l l ion. That field experience has shown fi ber-base paper prints to be

202
 Reading 21 F E L D l\l I\ N

Figure 24
Parlially restored pri n t .

more resistant may be cl ue to the paper base itself acting as a sump for any
sol u ble salts generated by the effect of oxidizing gases on the si lver i mage, as
suggested by Kolf. 2 0
A N S I P I-1 1 .48- 1 974 , 1 0 as discussed previously, provides stringent tem­
peratu re, h u m i di ty, and handling recom mendations for the storage of those
processed black-and-white prints i ntended for record pu rposes. f\ distinct,
but larger body of prints is in tended for use as "work" prints, while others
are in tended for display. S i nce display conditions vary over a wide range,
postprocess treatment with toners, such as Kodak Rapid Selen i u m To ner,
Kodak Poly-Toner, Kodak Sepia Toner, or equ ivalent may be advised . I n
particu lar, black-and-white prints o n res i n-coated paper base that may be
s u bjected to i ntense or extended i l l u mination, exposed to oxidizing gases. or
framed u nder glass or plastic should be considered for treatment with toners
to extend i mage l i fe. The ton ing ol' prints on fi ber-base papers is l i kewise rec­
ommended for those applications req u i ring long-term keeping u nder adverse
storage or display conditions.
Black-a nd-white photographic papers on resin-coated supports have
enjoyed excellent acceptance by the photographic i ndustry. The shortened
processing t i mes and i mproved handling characteristics of these materials
Part II S I L V E H I M A G E S T H U C T U H E A N D S TA B I L I TY

are but two of the benefits to the i n d u stry of this technology. Resi n-coated
papers have been accepted to such a degree that concern has been expressed
in various media for the future of fiber-base black-and-white papers. East­
man Kodak Company su pplies a nu mber of black-and-whi te papers-on
both resin-coated and fiber-based supports. These i nclude many combina­
tions of graded and selective contrasts, contact a nd projection speeds, vari­
ous surface textures, and basis weights for a wide range of applications a nd
cu stomer needs. I mprovements have been annou nced i n both the resi n ­
coated an d t h e fiber-base paper product l i nes, and future i mprove111ents 111
both product l i nes to meet changing custo111er needs are a nti cipated.

Acknowledgment

I wish to express my thanks and appreciation to 111y colleagues in the East­

man Kodak Co111pany for their i nvaluable assistance. The support of Kodak
Park and M arketi ng 111anage111ent is also gratefully acknowledged. My special
thanks to the secretaries and vis ual aids spec ial ists who worked so patiently
with me d u ri n g the many revisions of this report.

References

1 James, T. H . : Theo1y of I. he Photographic Prncess, M a c m i l l a n Publish ing Co.,

I nc . , New York, 1 9 77 , pp. 455-458.
2 See for example, "American N a t i onal Standard M e t hod for Eva l uating the
Processing oF Black-and-White Photographic Papers with Respect to the
Stabil i ty oF the Resultant I mage," A N S I PH +32-1 974, American National
Standards I nst it ute, I nc., 1 430 B roadway, New York, NY.
3 J ames, T. 1-1 . : Op. Cit . , p. 458.
4 Henn, R . W., N . 1-1. King, and J. I. C rabtree: "The Effect oF Salt Baths on
Hypo and S i lver El imination," Photogr. Eng . , 7 : 1 53-1 64 ( 1 956).
\h/eyde, E.: "A S i mple Test to I d e n t i fy Gases which Destroy S i lver I mages,"
Pliotogr. Sci. Eng . , 1 6 : 283-286 ( 1 972) .
6 J ames, T. 1- 1 . : Op. Cit., p. 458.
7 Adelstein, P. Z. : " Preservation of M icrofil m , " ). f\il icrogrnpliics, 1 1 : 333-337
( 1 9 7 8).
8 J a mes, T. H.: "The Stability of S ilver F i laments," Photogr. Sci. Eng., 9 : 1 2 1 - 1 32
( 1 96 5 ) .
9 J a mes, T. 1-1 . : The Theo1y of the Photogmphic Process, pp. 392-393.
10 "American National Standards Practice for S torage o f B lack-and-\h/hite
Photographic Paper Prints," A N S I P H 1 .48- 1 97+
11 Parsons, T. F . , G. G. G rav, and I. H. Crawford: "To RC or Not to RC," . J . Appl.
P/101.ogr. E11g . , 5 : 1 1 0-1 1 7 ( 1 979).
12 " Preservation of Photographs," Kodak Publication No. F-30 ( 1 979), Eastman
Kodak Company, Rochester, NY.
 Reading 21 F E L D M A N

13 H e n n , R . VV. and D . G . Wiest: " M icroscopic Spots i n Processed M icro f i l m :

The i r Nature and Prevention , " P110togr. Sc-i. Eng., 7: 253-261 ( 1 963).
14 "American National Standard Practice for Storage of Processed Safety
Photographic F i l m " A N S I P H 1 -43- 1 979.
15 Ost roff, E.: ''Preservation o f Photographs," Photogr. ) . , 107: 309-3 1 4 ( 1 967).
16 Sec for example, Payne, H. F.: Organic Coat ing Tech.110/ogy, Vol . I , J o h n
Wiley & S o n s , I n c . , N e w York, 1 954, p p . 1 1 6-1 1 7 .
1 7 Fruton, J . S. and S . S i m 111onds: General /3iochen·i istry, J o h n W i l ey & Sons, I nc .
N e w York, 1 958, p . 365.
18 Cooper, \�I., Kodak Research Laborntories, private com111 u n ication.
1 9 Sec also, Kok, G . L . , T. P . H o l l er, 1\1 1 . B . Lopez, H . A. Nachtrieb, and i\1 1 . Yuan:
"Chemil u 11 1 inescent Method for Determ i n ation of Hydrogen Peroxide in the
Ambient At111osphere, " En.vimn. Sci. Tech . , 12: 1072-1076 ( 1 978).
20 Kolf, C . : '' Modern Photographic Papers," B rit. ) . Phut.ogr., 1 2 7 : 3 1 6-3 19 ( 1 980).
2 1 Luckey, G . \�I. , T. H . J ames, and W. Vanselow: 'The Effect o l" Various
Pretreatments o n the Reaction of H ydrogen Peroxide with a S i lver l 111age, "
Photugr. Sci. Tech ., (2)2: 130-134 ( 1 955).
22 U . K. Pat. Appl icat ion, C B 2,019,024A (April 6, 1 978).
 R e a d i n g 22

M A S A A K I T o R I G O E , K u N I O K I O tt M U R A ,
S H U N Z O YAG A M I , A N D H A R U H I K O I WA N O

Long-Term Preservation of B lack­

and-White Photographs ( 1 984)

This excerpt, wriJ ten. by Fuji. research scient ists Masaaki Torigoe, J<.u n:iohi
0'1:1n u ra, S h u n=o Yagam i , and 1-laruhilw Jwan.o, was originally p ublished by
Fuj i. Photo Filrn Co., Ltd., in Japanese in. 1 984 and is translat:ed in.to E nglish
here for the fi rst t hne. The a rt icle addresses t he clegraclat ion. offilamentary sil­
ver (through su lfi.ding and oxidation) in gelat in. silver p hotographs. Although
t here has been li mited access to the text of this reading, many will recognize
the frequently cited schematic of the oxidat ive disintegration. of develo11ed
silver particles into colloidal silver. The portion of th.e paper not reproduced
here focuses on. t he clevelopm.en.t of post-processing p rotective treatments, spe­
cifically AgGuard, a proprietary solution. of a su lfu r-contain i ng organic com­
pound, ( 2-(cnnidin.othio )ethan.osulfon.ic acid), an.cl reiterates the importance of
a con. t rolled environ ment and h'l.at storage enclosu res i.n t h e preservation. of
p ublic an.cl p rivate p hotographic collections.

I ntroduction

Alt hough i t has been 1 40 years since the advent of daguerreotypes-the P1rst
type of photograph-these i mages are sti l l in good condition. On the other
hand, as early as 1 879, the B ritish journal of Photography mentions the dete­
rioration over t i me of silver-i mage p hotographs (on albumen paper), and
perhaps this was the first mention of the specific problem of i mage preserva-

From i\IASAA1<1 To 1 1 1 G o E , l<U N I O K I 0 1 1 ,\ I UHA, S1·JU NZO Y1\GA� 1 1 , and H,\B U l l l KO IWANO.
" Long-Term Preservation of B l ack-and-'vVhite Photographs," Scientific Publ ications oF
the Fuji Photo F i l m Co. Ltd. 39. no. 29, 3 1 (J anuarv 1984): 3 1-36 (31-33 excerpted here).
© FUJ I F l L i\11 Corporation.

206
 Reading 22 T O ll l G O E E T /\ L .

tion. 1 The original p u rpose of the photograph is i nseparable fro111 i ts perma­

nence, so the problem see111s to have been ra ised surpri singly late.
Nowadays the p hotograph is more inti111ately connected to daily li fe
than i t was then, so there is increased i nterest in the preservation of p h oto­
graphic i 111ages. There is a wide range of needs for such preservation, fro111
social needs such as leaving to later generations records representing cultu ra l
assets, to personal needs su ch as leaving one's i 111age t o one's descendants.
Besi des si lver halide photography, n u 111 erous i mage record i ng means
have appeared recently, such as 111agnetic and optical 111e111ory record i ng.
However, the reality is that for re l iable, practical, long-term preservation, sil­
ver halide photography remains u nsurpassed. Therefore, we 111 ust acknowl­
edge that the public expects these p hotographic i m ages to be per111anent.
Per111a nence i 111prove111ent i s one of the 111ore i 111portant tasks of our
co111pany. H owever, three other qualities 111ust also be addressed: photo­
graphic m aterials, i 111age processing, and preservation environ 111en t . The
a uthors of this paper i ntend to provide users with the appropriate i n for111a­
tion rega rd ing 111ainly the two latter topics, and they hope that, in collab­
oration with others, this will contrib u te to the longer life of photographic
i 111ages.

D ilemma of Increased Image Longevity

The Osaka Expo time capsule, which is to be opened in 5,000 years, also con­
tains photographic i mages. These i m ages were su bjected to the best preser­
vation tec h n iques ( i . e . , they were placed in an argon gas atmosphere after
being strengthened with gold toni ng). Some m ight wonder why so muc h
effort was exerted to ensure t h e preservation of present-day photographs for
posterity, when ancient m u rals rem a i n beautifully preserve d .
S ome may s i m ilarly wonder wh y discoloration occurs i n modern p hoto­
graphic i 111ages, when daguerreotypes remai n preserved. In a daguerreotype,
both the i mage and the backgro u n d consist of silver that contains mercury
and gold, and differences in surface roughness create con trast.23 That is,
they are com posed of aggregations of elements that are very expensive and
resistant to change. By contrast, even t hough the image in a black-and-white
pri n t i s composed of s ilver, its su rface contacts gelatin and the base is paper
or polyethylene, so the drop in stability i s considerable. However, consider­
i ng the fact that its h i gh i mage q u al ity, low price, ease of use, and mass p ro­
duction capabi l i ty a llow it to be used widely in daily l i fe, it is undeniable that
the p hotographic i mage has become avai lable to ordinary people, at the cost
of slightly redu ced permanence.
Such a permanence d i lemma i s evident i n many aspect s . For example,
the world of photography was enriched by the wide palette of col ors resul t-

207
P a rt I I s I L vE n I J\ I /\ c E sTn uc T u n E I\ N D s TA B I L I T y

ing from photograph colorization. On the other hand, i t ushered in such

problems as d iscoloration, which is believed to be u navoidable as long as
organ ic dyes are used .
Moreover, after the transition from baryta paper to res in-coated
paper ( RC paper), considera b le progress occu rred with respect to quality,
affordab i l i ty, and speed, such as the shortening of processing ti me, water
conservation, energy conservation, enhanced su rface quality, and su l fide d is­
coloration. At the same time, in exchange for these advantages, RC paper
has the drawback of a l ower resistance to an oxidizing atmosphere.
Th us, alt hough past techn ical advances have many merits, they fre­
quently entail such d i lemmas as red uced i mage stability. Si nce the advent of
such tec hnology, steady efforts have been made to e l i mi nate this drawback.

I m age Deterioration Process

The deterioration of a black-and-white photograph i nvolves serious physi­

cal and b iological problems, such as base ( i . e . , paper) embrittlement and
breakage, as wel l as i m age-layer cracking, film peeli ng, foxi ng, wo rmholes,
etc. However, this can be prevented eas i ly by taking into consideration the
environ ment, which will be discussed later. Somewhat more trou blesome is
the d i scoloration of the i mage itself.
There are two types of si lver-i mage d iscoloration, with different char­
acteristics and causes: s u lfide discolorat ion4 and yel low cliscoloration.5 Sul ­
fide discoloration occu rs because t h e su rfaces of the silver particles forming
the si lver i mage change continually to si lver s u l fide, thereby changing their
spectral re flect ivity.4 One material that causes s u l fu ration is residual thiosul­
fate introduced duri ng the development process, and the other is the min­
ute quant ity of sulfur-contai n i ng gases in the a i r, as for example, sul foxicles,
perfu mes, and food vapors. As for ye l low discoloration, on the other hand
(shown in Figu re 1 ) , the s ilver particles of an i mage are broken down by
oxidation; the result i ng silver ions are local ly reduced and aggregate, thereby
formi ng m i nute particles that scatter l ight and, as a result, give off a ye l low
color. Consequently, the causative materials are: an oxidizing atmosphere,
such as atmospheric n i trogen, sul foxides, peroxide vapor from fu rniture
paint, etc. (Table 1 [ ]) • • • •

Ordinary Deve loped S ilver Particles

U ntil just recently, su lfide discolora t ion that t u rned old photographs
b rownish-reel was a concern , and yel l ow di scoloration was a problem in
particular fields, such as m icrofi l m preservation, etc. At present, however,

208
 R e a d i n g 22 T O H I G O E E T t\ L .

\
;-- Silver ions
\\ '""
Colloidal s i l ver
brownish yellow)

. .
•
\-.
I •
. ti
.
.
• . .
,. •
. . � .
t

Figure 1
Schemali<..: demonstration of yellow
discoloration caused by oxidative
d i s i n tegration of developed silver
followed by formation oF fine silver.

Developed silver Genera tion of silver Generation and Reduction of diffusing silver ions -
particles after ions from developed diffusion of silver ions Formation of silver atoms - Concentration
development process silver particles from developed silver of silver ions at silver atoms - Reduction -
particles Colloidal silver formation

Table 1
Two t�1>es of d i scoloration of si lver i m age.

e
D ta i l Ph e n o m e no n Cause Mechanism

S u l fide
a
d iscolor t i o n
The s u rface ol' a s i lver
i mage colors after
changing to s i lver
S u l f'uration caused
by res idual t hiosul­
f�ides, etc., a n d envi­
Oxygen
Ag + S,0,-2 -7 Ag2S

s u l fide. ronmental s u l fides.

Yellow The s i lver i mage Oxidation and Oxidizi ng
d iscoloration decomposes i n to frag­ m igration of s i lver agent
( b l emishes) m e n ts and becomes caused by environ­ ( hu)
( m i croscopic yellow, and the image mental oxidizing Ag -----? Ag+
spots) va nishes in spots. atmosphere. Ag ' --7 Ag colloid
( local reduction)

the situation is the reverse. \i\lith the development of c ivilization increased

oxidizing atmospheres are presen t i n our ambient environ ment.6·7 There­
fore, yellow d iscoloration occ u rs read i ly. Moreover, with the advent of the
resin-coated paper mentioned previously, the amount of residual th iosul­
fate dropped s harply, thereby i n hibiting s u l fide d iscoloration . On the other
hand, yel low d iscoloration now occ u rs readily. In the case of baryta paper,
the residual thiosulfate prevented yel l ow discoloration by blocking the attack
of the oxidizing atmosphere. Thi s point will be discussed in fu rther detail is
the next section.
Part II S I L V E H I M 1\ G E S T R U C T U H E A N D S TA B I L I TY

E ffects of Residual C h e m i cals after Development Processing

Figure 2 [ not reprod uced here] shows the level of yel low d iscoloration after
letting F u j i bromide printing paper developed with Papitol stand in atmo­
sphere in the presence of hydrogen peroxide solution ( 1 % ) , versus the
amount of res idual th iosu l fate, and both the baryta paper (broken li nes) and
RC paper (solid l ines) fal l wi thin the respective hatched regions, accord­
i n g to the fixing and washing times. The fact that they rise to the left i ndi­
cates that yellow discoloration occurs more readi ly as the res idual amount
decreases. Also, although the thiosu lfate wash es out of the RC paper faster,
the figu re indicates that i t i s suscept i ble to yellow d iscoloration, even at the
same residual amount leve l .
Figure 3 [not reproduced here ] shows t h e exa mple o f m icrofi l m . For
m icrofi l m , it is recom mended that the fixing solution contain K I to extend
the life span of an i mage,8 which is also mentioned i n the ISO and ANSI
standards.9 Th i s i s u ndou btedly correct i n a c lean environment. However,
Figure 3 shows that the res idual thiosulfate decreases as the result of KI addi­
tion, and this almost corresponds to the ye ll ow d iscoloration in the oxid izing
atmosphere . l n developed countries, oxidizing atmospheres will continue to
i ncrease i n the fu ture; as a result, i t is necessary to revise the conventional
rule that states that the greater the red uction in the residual amount of thio­
s u l fate, the more stable the i m age. Therefore, studies are being conducted
at present. The prob lem is how to determine the optimal level of resid ual
thiosu lfate. I ts va lue varies with the environment. In a clean, dark place, a
low va lue is preferable, as is to be expected. I f an oxidizing atmosphere is
anticipated, it is safe r to set the level high, even though su lfide d iscoloration
occ urs read ily. In other words, because of differing environmental cond itions
i t is d ifficult to u n i form ly determ i ne t he optimal residual leve l .
U l timate ly, t h e solution t o t h i s problem is t o provide s u l fu ration o r oxi­
dation resistance to the i mages themselves. Si lver i mage toni n g originally was
a post-processing method for changing the tone. H owever, it was fo und that
some types of toning prevent image oxidation and deterioration; as a result,
gold ton i ng is u sed to en hance the d ura b i li ty of micrograph i c i mages . 1 0· 1 1
Also, s u l fide toni ng and seleni u m ton i ng are recom mended for R C paper. 1 2
The aut hors developed a post-process i ng method m u c h more practical than
ton i ng techn iques , thereby solving t h e d i lemma of having to adopt two cou n­
termeasures for these two types of d i scoloration. This method is Ag-guard .

References Cited

1 B rit . ) . P/10tograpl1y, Sept. 19, issue ( 1 879).

2 M. S. Barger, H. M essier, and \•\/. 13. V\lhite. Pl10tog1·. Sci. Eng., 2 7 (4) 1 4 1-146
( 1 983).

210
 Reading 22 T O ll l G O E E T A L .

3 J\ I . S . Barger, R . J\ l essier. a nd W . B . W h i te, P/10togr. Sci. E11i;:., 2 6 285 ( 1 982).

4 R . W . H e n n a n d N . H. Ki ng, P/10togr. Sci. E11g . , 5 46-47 ( 1 96 1 ).
a) i\11 i nagawa-Presentcd al 1 nternational Sy111 pos i u 111 on Preservation a n d
Stab i l i ty of Photogr. I m ages ( S P S E ) 1 982 (Ottawa ) .
b) L. H . Feldman , ) . Appl. Pliotogr. Eng . , 7 , 1 - 9 ( 1 98 1 ) .
6 F u k u i . A11al)'sis. 849/853 ( 1 983).
7 ISO 605 1 , An nex C, An nex E .
8 R. W. H e n n , D . G . Wiest. a n d B . D. !\ l ack, Pliotogr. Sci. Eng . , 9 1 67- 1 73
( 1 965) .
9 a) I S O 2803; b) A N S I PH q 1 ; c) I S O 4332.
10 R . W . Henn a n d D . G. \Niest, Photogr. Sci. Eng . , 7 253-261 ( 1 963).
11 Kodak P u b lication F-30, p . 23.
12 'v\I. E . Lee, S PS E 34th /\ n n u a l Conference ( M ay 1983).

211
 R e a d n g 23

G E O R G E T . E AT O N

History of Processing and

Image Stability ( 1 987)

George Eaton ( 1 9 10-1 995) worhed i n the J<odah Research Laboratories fro-in
1 93 7 lo 1 975. I-lead of t:h.e Ph.otograph.ic Che1nist ry Departn'Lent a nd assistant;
head of the A71pUed Photography Division, Eaton was a research chemist, tech­
nical editor, Fellow of the Society of Ph.otogrnphic Scientists a nd E ngineers,
an.cl product ive au t hor of scien t ific papers relat:ed to 71hotogrn11hi.c chemist ry.
Eaton 's 1 9 57 Photographic Chemistry in Black-and-White and Color Photog­
ra phy is an introductory primer in. silver haf.ide and image processing c he'l'nistry.
In 1 985, Eaton authored the Conservation of Photographs, a comprehensive
overview of conteniporary collect ion incm.agenienl, 7neservation, and (some­
what radical) t real·me n t practice. The present reading is a ch.apter t:ahen. fro·m
P ioneers of Photography: Their Achievements in Science and Technology,
a compilation of papers 111-eparecl for the First ln t:ernat i.onal Congress "Pi.o­
neers of Photographic Science and Technology, " held ) ime 22-25, 1986, at t he
Internat ional Nhiseum of Photogra11hy, George East man House. This superb
booh recou nts t he history of ph.otograph.y t h. rough. its technical ch.anges an .cl
aclva nce·f'n.ents. George Eaton 's reading offers a comprehensive resou rce t hat;
s11 m mari::es the challenges of silver hn.age stability from. photogenic drawings to
resin-coated pa71ers. Of va rticular note is the t horough. discussion on advances
in image vrocessingfrom 1 9 1 0 t h.rough. 1 986 to ach ieve image stabili.ty .

G EOHGE T. EATON , " H istory of Processing and I mage Stabi l i ty," in Pioneers i11 Pho1ogra­
p/1y: Their Acliieve111e11ts in Science a11d Tech notog)'. eel. Eugene Ostroff ( S pri ngfield, VA:
S P S E-The Soc iety l'or I maging Science and Technology/Northeastern U n iversity Press,
1 987), 87-93. Hcprinted by permission of I S&T: The Society for I maging Science and
Technology, sole copyright owners of Pio11eers in P/10tography: Tl1eir Acliieve111e11ts in
Scie11ce a11cl Tech 11ology.

212
 R ea d i n g 23 E A T 0 N

Photography was first i ntroduced in 1839 by Louis Jacques Ma nde Daguerre

in France and Wi l l ia m H e n ry Fox Talbot i n England. The daguerreotype wi ll
n o t b e discussed in t h is paper s i nce the i m age formation process is so di s­
ti nctly different from t h e other pri nt processes. Th e emphasis wil l be on t h e
silver negative-positive system t h at h as endured to t he present.
The a b i l ity to make pictures by e;..'Posing a piece of paper to s u n l ight
was i ntrigui ng. There was an i mmediate enthusiastic response by both ama­
teur hobbyists and professionals such as teachers, m i ni sters, doctors, and
chemists. It was soon evident that some very carefu l research was requ ired
to i mprove i mage c haracteristics and i m age stabil ity or permanence. It was
also soon evident that m u c h non-scientific "ldtchen" c h e mi stry occurred.
The encl result of all this, as seen today, was the production of a relatively
few stable p hotographs.
A c hart s howing the periods of predomi n ance of the various negative
and print processes will provide a ready appreciation of the h i story of si lver
photographic processes. It also provides a base for a quite logical review of
processi ng and image stability. This history has been d ivided i n to three peri­
ods; 1 839-1 880, 1 880- 19 w, and 1 9 1 0-1 986.

Although Fox Ta l bot's earliest experiments began i n 1 834, h i s photoge ni c

d rawin g process was anno u nced by Michael Faraday on January 2 5 , 1 839. 1
Process i ng i nvolved these steps: ( 1 ) soak a s heet of paper i n sodi u m ch loride
solution and dry; (2) treat in strong s i lver n itrate solution to make l ight sensi­
tive; and (3) fix in concentrated salt solution. The pri nt remai n ed somewhat
sensitive to l ight because the u n exposed s i lver c hloride was not removed but
only i nactivated .
Almost i m mediately there was concern over faded i mages, and i n fact,
Ackerman's manual p u b l i shed in 1 839 warned there was "no method d i scov­
ered by which a photogenic drawi ng can be absolutely fixed, so as to be able
to resist the action of the direct rays of the S u n . " 2
J n 1 84 1 Fox Talbot annou nced the calotype process, 3 which produced
a paper negative. The calotype negati ve was processed by development and
then fixed i n hypo rather than sod i u m chloride solution. In this case the
u nexposed s ilver ch loride was d issolved by the hypo and then removed by
washi n g to provide a more stable i mage. The ca lotype process was the fore­
runner of m odern photography and was i n use u n t i l the i ntroduction of Scott
Archer's wet p late process in 1 85 1 .4
The a l bu men process was in t rodu ced by Louis Desire B l anquart- Evrard
on M ay 27, 1 8 50. The a l b u men sizing was hen's egg wh ite and was appl ied to
the paper s u rface to provide a non-poro u s layer upon which the si lver i mage
P a rt II S I L V E B I M A G E S T H U C T U H E A N D S TA B I L I TY

was formed with improved photogra ph ic characteristics such as contrast,

sharpness, and tone. Many experiments were made to change and improve the
albumen layer, such as the addition of citric acid to i m p rove shelf-life. H a nd­
coating caused variations i n u n iformity and thickness with some obvious
effects upon the si lver i mage. The general situation was improved when manu­
factured albumen paper became available i n 1 86 1 . The processing of albu men
paper i n c l u ded flxing, toni ng, and was h i ng. Sod i u m thios u l fate had become
the universal flxing agent and practically all a l b u men prints were gold-toned.
Fro m 1 840 until about 1 854 the situation was chaotic, with little seri­
ous scientiflc exploration. Many practitioners began to experiment, flrst by
followi ng i nstructions and then by attem pting i mproveme n ts in some or a l l
components o f t h e p rocess. I mage deterioration was more common t h a n not
and changes occurred relatively rapid ly. During the early 1 85o's there was
i nc reasi ng i nterest i n the possible solution to the problems of permanence.
The flrst organized and lo ng-range attempts at u nderstandi ng the problem
were probably i n i tiated because of the ge nera l acceptance of the wet col­
lodion process and the a l bu men pri nt ; the need for m ore guali fled practi tio­
n ers; and the better communication and i n teraction provided by the number
of photograph ic societies.
The Societe Frani;aise de P hotogra p h ie began to study the fadi ng of
prints i n 1 855, and on May 1 8 orga nized a com mission for t he purpose.5 The
Photographic Society of London , a few days earlier, estab l ished a Comm i ttee
on Positive Prin t ing.6 The objectives were: (a) the refinement of current flxing
processes, and ( b ) the investigation of restorat ion methods for faded prints.
It is of i n terest that Prince A l bert, the Royal Consort, is said to have i n sti­
gated the Photographic Society's Committee and donated £50 to the task. " I t
i s wel l known that h e r Majesty a n d t h e Prince are much devoted t o the Art
of Photography; not merely are t hey purchasers of the best photographs, but
h is Royal H igh ness is h imself, a p hotographer. H aving observed that many of
the pictures in the extensive col lection in the palace are fad i ng out, Prince
Albert at once determ i ned on i nvestigating the cause of this, and on enlisting
a com m i t tee of p ractised photographers to examine the subject."7
Pri nts processed i n d i fferen t ways were collected from prominent
p hotographers. The details of processing and the date of production were
provided in each case. Arra ngements were made to carry out keepi n g experi­
ments in the expansive gal lery of the Crystal Palace.8 One member of the
com mittee later stated t hat most of the prints at the Crystal Palace faded
while h is personal pictures did not. ( N ote: probably due to l ight expos ure,
h u m id i ty, and temperature . ) Fou r suggestions were made by the committee
as fo llows: (a) take greatest care i n wash i ng o u t hypo; (b) use gold in some
form; (c) keep p hotographs d ry, and (d) determi ne su bstances that can pro­
tect the photograph from air and moisture .
 R e a d i n g 23 E A T O N

The i ntroduction of the wet plate process i n 1 8 5 1 had a great effect on

the enthusiasm for photography. The qua lity of the positive i mage was greatly
i mproved and m u l tiple prints were easily made. Consequently much experi­
mentation occurred and even some com mercial production of prints began .
The origi nal wet collodion process was partially rep laced b y t h e dry collodion
process by 1 855. The origi nal fixing agen t-potassium cya n ide-was soon
replaced by sodium th iosulfate ( hypo) for both processes. About 1 860, col­
lodion was being manufactured on a large scale,9 thereby making available a
more u n i form product. There were tests of various su bstances used as a sub­
bing layer for the collod ion (e.g. albu men and i ndia rubber) . Many materials
were tested and used as preservatives including tan n i n , iodine, milk, coffee,
caramel, I celand Moss, morph i ne, camphor, sugar, tobacco, alcohol arsen­
ite, creosote, honey and acetic acid. G lycerine was tried in both the collodion
and the silver bath. Gelatin in alcohol, 1 0 arseni te of soda, and cad m i u m 1 1
were also tried. There were many named processes and mod i fications of
them, such as Ta upenot, Oxymel, \l\fh ipple, Fothergil l , M c N a i r, and Sutton.
Duri ng this period an i nc reas ing f lood of articles or sections of hand­
books approached the issue in various ways. Many articles provided i nstruc­
tion i n the use of various "arc h iva l" processes for making prints more
permanent. There were approxi mately 1 50 papers that attem pted to expla i n
the l ac k of i mage stabi lity. S o m e of the more objective scienti fic writers
i ncluded T. Frederich Hardwich , 1 2 Col i n S i nclair, 1 3 Thomas Seto n , 1 4 and
H e nry Pol lock. 1 5 Other artists and scientists continued to look for solutions
to the i mage stabil i ty problem including M athew Carey Lea, Desi re C harles
Emanuel van i\/ l onckhoven, John Spiller, \l\filliam E ngland and Thomas
M a lone, to name a few.
There were few positive answers but i n n um erable suggestions that
conti nued to confuse the issue. In fact, the si tuation beca me so serious that
some prominent practitioners gave up their i n terest in photography, i nclud­
ing Roger Fenton i n 1 862. 16
Neither time nor space permit del i neation of all the tec hnical aspects
involved i n the struggle for i mage stabil ity and the elimination of the chaos.
I mage stab i l i ty in this period was not the effect of poor process i ng on ly, but
also i nvolved other components of the system , i nc luding the paper support;
the se nsitizing systems; fixing of the i mage with or without ton i ng; and ade­
quate washing to remove residual hypo i n the print.
The h istory of paper manufact uring for photographic pu rposes is cov­
ered el sewhere in these proceedi ngs but a ge neral statement is req uired here.
Basical ly, paper was made for the arts and the printing i ndustry, but an all­
rag, h igh quality artist's paper was best for sens itizing. However, subsequent
changes i n paper manufacture did not help the p hotographic process, e .g.
the use of c hloride of lim e bleac h , rosi n as a sizing agent, the use of grou nd-

215
Part II S I L V E R I M A G E S T H U C T U H E A N D S T A B I L I T Y

wood i n 1 840, and the s u l fi te process i n 1 867. All of these c hanges compro­
m ised paper permanence and in several ways contributed to pri nt i nstability.
Alb u men-s ized paper was the most popu lar. Va rious papers and their meri ts
for photographic purposes were disc ussed by Frederic Townshend in 1 8 55. 1 7
Manufactured albumen papers were avai lable i n 1 86 1 .
Gold toni ng was strongly recommended i n the processing of albu­
men prints to produce more des i rable i m age tones but was often claimed
to increase i mage permanence. 18 Ton ing usually preceded fixing, but some­
times the two were combined i n a si ngle bat h . Both alkaline and acid gol d
ton ing baths were i nvestigated . 1 9
F ixat ion was ge neral ly accomplished with sod i u m thiosu l fate b u t other
potential fixing agents were often retested i n an effort to i mprove i mage per­
manence. The most p rominent one was ammo n i u m su lfocyan ide, but it was
not as practical as hypo. Various formulations and tec h n iques were studied
with both collodion plates and a l b u men prints.
\;\/ashing of glass plates was generally qu ite satisfactory, but not so
with albu men prints. There were at least a dozen washing devices described,
as wel l as hypo elim i n ators and hypo tests, none of which appeared to be
widely accepted. However, h istorically, there a re some e liminators and hypo
tests of i nterest.
Salt water was suggested first i n 1 864 and later in 1 875; sa l i ne sol u­
tions in 1 864; hydrogen peroxide i n 1 866; and at some time i n this period,
alkaline fixing baths. Later, in the m id-20th century, all of these were not
only reco m mended but became part of regu lar processing practices. Other
recommendations i n c lu ded the fol lowing: adequate washing plus a fi na l
r i n se i n ethanol (spiri ts of wine) ( 1 852, 1 855); potassiu m perma nganate
( 1 864) ; sod i u m hypoch lorite ( 1 866, 1 873, 1 877) ; hypochlorous acid ( 1 866),
iodine and potassium iodide for negatives ( 1 874) ; lead acetate ( 1 871 ) ; and
lead nitrate ( 1 874). Excessive was h i ng was said to be i nj u rious to albumen
prints ( 1 872 ) . Adequate was h i ng was recom mended often but determination
of sufficient was h i ng was not readily possible a l though many tests for hypo
were suggested .
Tests for sod i u m thiosul fate i ncluded the use of the fol lowi ng chemi­
cals: mercu ry n itrate with n itric acid; nitroprusside; starch iodide; ruthe n i u m ;
potass i u m permanganate, mercu ric c hloride; si lver nitrate; a n d t urpentine.
Of these, starch iodide, potassi um permanganate, mercuric ch loride and sil­
ver nitrate appeared to be the most sensitive and the most usefu l . The sen­
s i tivity to hypo of silver nitrate solution was noted i n tests by John Frederick
W i l liam Herschel i n 1 8 1 9 and by E.J. Reynolds i n 1 863 .
U n fortu nately, most of the hypo tests were used to determine the hypo
content of the wash water, or col lected drippi ngs from a negative or print.

216
 Reading 23 E A 'f O N

When the concentration became very low, depending upon the sensitivity of
the test em ployed, the negative or pri nt was considered washed. However,
a few i nvestigators s uggested that the res idual hypo in the material itself
should be determined. Although an i mprovement, quantitative measurement
was not poss i ble at that time.
I t is apparent that by 1 880 extensive i nvestigations had been made with
the object ive being "permanent" pri nts and negat ives. Those pri nts in partic­
u lar that have survived in good condition to this clay were carefu l ly processed
but, addi tional ly, were carefu l ly stored dry, in the dark, at a reasonable tem­
pera t ure, and without e>.']Josure to atmospheric poll u tants. Further, mounted
pri nts were attac hed to h ighest grade rag stock mou nt boarcls, probably with
gelatin as an adhesive because it was considered safest.
Some attempts were made to explain pri nt deterioration. Studies s uc h
as those conducted by t h e London Photographic Society Committee clearly
i nd icated the conditions causing deterioration. Exactly what took place
chemica l ly often differed from one investigator to another or ind icated an
u nsolvable situation. H ardwich clai med fad i ng was due to excess of sul fu r­
ization or the effects of sulfurization and oxidation combined. 20 Malone con­
te nded "we have no data for stating with certainty that pictures prepared
according to our present m ethod are secure; and si mply for the reason that,
not knowing the natu re of the i mage, we cannot d iscuss the exact i n fl uence
of atmosphere and moisture." 2 1 On the other hand, Shadbolt22 theorized that
s u l fu rization of pri nts occ u rs from the decomposition of hypos u l fite of sil­
ver left in the paper, but Thomas S u tton disagreed . 2 3 Adequate or thorough
was h ing was one widely accepted req u i rement for permanence because hypo
is a cause of image sulfiding. George Mathiot, however, claimed that the real
cause was u nknown and ·' wou ld remai n so until more is known about the
i mage const itution."24
M athew Carey Lea suggested another factor con tributing to i mage sta­
bil ity. H e attri buted fading to the formation of "trithionic acid," which he
clai med grad ually changes to "su l fu ro u s acid, " the real cause of fading. True
or not, his last statement was sign i ficant: " Perhaps too muc h stress is laid,
at present, u pon the wash i n g and too l ittle upon the necessity of the most
l i beral use of h)rposulfite ( hypo ) . "2'
I t is also of interest that one i nvestigator suggested the paper su pport
as a cause of fad i ng because the fi bers retained hypo and a paper i mpervious
to water should be ava i lable for photography. 2 6
Albumen prints generally tu rned yellowish in the h ighlights qu ite soon
after pri nting and processing. For some time this yellowing was attributed
to various sources of s u l fu r, until about 1 866, when John S p i l ler incl uded
among four causes of fad i ng the formation of a l b u men and silver compounds
Part II S I L V E H I J\ll f\ G E S T H U C T U H E A N D S T A B I L l 'f Y

in the whites of pri nts n Carey Lea discussed this poss i b ility i n 1 86628 and
1 868,29 at which time he stated that si lver in the wh ites of a l b u men pri nts
was converted to a less colored component than si lver sul fide. James Lamb
in 1 876 ascri bed the yel lowing of wh i tes to "al b u m i nate of s i l ver. "30

Period 1 880- 1 9 1 0

The ge latin-bromide d ry plate descri bed by Richard Leach Maddox i n 1 871

provided, for the first time, a successfu l ge latin emulsion and the capability
of presensitized plates that coul d be packaged and kept on the shelf ready
for use.31 An expanding market developed that awaited tech ni ca l i nnovations
and fostered the evo l u t ion of new pri nt materials.
The collod io-c hloride and gelati n-chloride pri n ted papers i n trod uced
in the early r89o's consisted of the sensi tive silver salt suspended in collodion
or gelatin and coated over a subcoat of bari u m s u l fate in gelati n . These were
known as baryta papers and gave extra bri l l iance and contrast to the print.
They were used pri marily for portraiture u nt i l about 1 9 10. I mage sta b i l i ty
was obtained by double toning i n gold fo l lowed by plati n u m . Many of these
prints are stil l i n excellent condition.
Although earl ier attempts to produce i mages on alb umen paper by
development, rather than by pri ntout, were descri bed,3233 i t was not u n t i l
1 873 that a gelatin- bromide developi ng-out paper was ava i l able. H owever, i t s
greater sensitivity was actually a n inconvenience a n d it was n o t u sed m uch
u n t i l ab o u t 1886, and t h en primarily for prin t i ng by en largement. The i ntro­
duction of "gasl ight" paper i n 1 893 provided a less sensitive paper that cou ld
be exposed and then processed i n su bdued l ight . This was a developing­
out con tact speed gelatin-silver ch loride emu l sion coated on baryta paper
that supplanted the pri ntout emu lsion papers by 1 905. Both of these papers
had improved stabil ity compared to albumen paper a nd gave neu tral black
i mages. After e>q:>osu re, the i mages were formed by development, then the
print was fixed in hypo fixer and washed, but no ton i ng was requi red to con­
trol i mage tone or for image stability.
During this period, amateu r photography expe rienced m ajor growth,
primarily because of the greater si mpl icity of the system and the reason­
able costs i n volved. The dry p late made "snapshot" photography possible,
but the rol l fil m systems i ntroduced by Eastman s i m p l i fied the system even
more-especially when the first Kodak camera ( 1 888) and daylight-loadi n g
fil m ( 1 89 1 ) became available. Gaslight paper (Ve l o x 1 893) provided t h e ama­
teur with a simple pri nting procedu re .
Als o d u r i n g t h i s period, conti nuous rol l coati ng of photographic papers
and large volu m e production of dry plates provided reasonably priced m ate-

218
 R e a d i n g 23 E J\ T 0 N

rials. Other manufacturers provided processi n g chemicals, apparatus, and

services such as negative development and printm aking. Commercial p hoto­
finishing was u nder way.
H istorical ly, i t m ight be concluded that the decade 1 900- 1 9 1 0 had seen
the replacement of the n ineteenth century processes by the new, versatile,
s i m p l i fied, develop ing-out photograp h i c techniques; that few problems of
image permanence had been solved; and that the same problems must be
resolved for the modern materials.
Most of the 1 9th-century i nvestigators described the causes of negative
and print image instab i li ty and offered many good suggestions for proper
processi ng, storage and fram i ng. Many attempted technica l explanations for
fading b u t no consensus was evident except for the recom mendation of ade­
q u ate was h i ng and the s u l fiding of the i m age by some mechanism.

Period 19 10-1986

Compared to 1 839, the i nvestigative environ ment by 1 9 1 0 was much better

suited to the solution of p roblems because of the great i nc rease and avail­
ability of new knowledge i n chemistry, physics, and engi nee ri ng. In pho­
tography it can be said that the p rogress in modern photographic science
and man u facturi ng was i n it i ated and developed as a result of many factors,
i nc l uding the introduction of sensitometry in 1 890;'4 the roles of organic
chem istry and p hysics; the use of a variety of accelerated test procedures
to study reaction effects; and the establishment of i ndustrial research and
development la bora tories.
Each component part of the p hotographic process has been, and con­
ti nues to be studied in order to achieve long-lastin g records of all kinds on
glass, film and paper s upports. In this paper on processing it is assumed that
the sensitive material has been properly handled up to the stages of fixation
and wash i ng. The sign i ficant advances i n processing to ach ieve i m age stabil­
i ty will be outlined.
Two major photographic product problems remai ned at this time
relative to i mage stabili ty: the need for a paper made spec i fically for pho­
tographic prints, and the replacement of cel l u lose n itrate f i l m base with a
safety fi l m . A specially des igned paper was in troduced in 1 926 by Eastman
Kodak Compa ny.35·36•37 Safety fi l m was fi rst described in 1 923, and by 1 9 5 1 all
n itrate-base fi l m had been replaced with a safety fi l m .
Although thorough was hing h a d been recommended often, one o f the
first sign ificant studies i nvolving the modern fil m and paper products was
reported by \l\larwick i n 1 9 1 7 . '8 Probably the m ost extensive early i n vest iga­
tion of washing was reported in 1 92 5 by K. C. D. H ickman and D. A. Spencer
Part II S I L V E H I M A G E S T H U C T U H E A N D S TA B I L I TY

i n England .39 Residual chemicals were readily removed from fi l ms b u t not

from paper, p r imari ly because the paper structure and baryta u ndercoat vig­
orously retained hypo.
In the meanwh i le, 111 otion picture fil111s, 111i crofil111s, and amateur roll
fi l 111s were being p rocessed in 111ore or less a uto111atic continuous machi nes
in which satisfactory was h i ng and hypo re111oval were in doubt because of
the lack of a dependable q uantitative test. The C rabtree-Ross 111ercuri c ch lo­
ride test for residual hypo i n films was described i n 1 93040 and soon became
a spec i fication i n processing standards on the National Bureau of Standards
and the American Sta ndards Association (now the A111erican National Stan­
dards I nstitute). This test e nd u red for forty years until rep laced with the
ANS I Methylene B l u e M ethod-A N S I Sta ndard PH 4 .8- 1 978. 4 1 42
As in the past, various qualitative hypo tests were suggested during the
period 1 9 1 0 - 1 940. A quantitative test for residual hypo i n prin ts was pub­
l ished in 1 943 and beca111e an ASA and ANS I standard . 4 3 The significance
of this test was the fact that it measured the residual hypo " in-the-print, "
not in the drippings or was h water which had been the general practice.
The si lver nitrate reacts co111pletely with all of the residual hypo in situ., to
produce silver su lfide in q u antities d i rectly proportional to the hypo content.
The i ntensity of the si lver sulfide stai n also i ncreases i n d i rect proport ion
to the quantity of s u l fide produced so that a quantitative measure of the
transm ission densi ty produced by the silver su lfide wou ld i n di cate a corre­
spond i ng quantity of residual hypo. The si lver n itrate test can be used as a
qualitat ive 111easu re of residual hypo in both Fd111s and prints and is read ily
acco111 pli shed using the Kodak Hypo Esti111ator first i ntroduced about 1 952.
Even though quantitative measurement of hypo is possible i n both
processed fi lms and prints, i t is i 111 portant i n practice that the re111oval be
acco111pl ished completely and as q u ickly as possi ble. This i nvolves the role of
fixation, the design of the washing apparatus, a n d the use of washing aids.
The composition of fixing baths is an i 111portant factor rela tive to effi­
cient rapid p rocessi ng. The use of two fixi ng baths is advantageous both
econo111 ically and che111 ical ly. 44 Aci d-hardeni ng fixing baths are commonly
u sed, and usually have a pH of approxi 111ately 4 . 3 . Hypo is reta ined 111ore
tenaciously at this p H va lue than at a p l-I of 5.5 or h igher or than in a non­
hardening fixer at p l- I 5.6 or h igher. The e m u lsion gel atin usually has an
iso-electric poin t about p l-I 4 . 9 and when the fixer pH value is above 4 . 9 hypo
is more read i ly re111oved by wash ing. However, emu lsion hard e n i ng may be
i nadeq uate at p H values above 4.9.
The exhaustion or extent of use of the fixer has a signi ficant effect
with respect to image stab i l i ty. A print fixing bath i s exhausted when i t con­
tains 111ore than 2.0 gra111s of s ilver per li ter and a film fixing bath contai ns
111ore than 6.o grams of si lver per l i ter. 4 ' \Vhen exhau sted baths are used, the

220
 R ea d i n g 23 E A T 0 N

si lver-thiosu lfate co111plexes beco111e i ncreasi ngly 111ore i nsoluble as the d is­
solved si lver i ncreases, and are not read i ly re111oved and 111ay eventually give
rise to s u l fide stains in the non-i111age areas of negat ives and prints.
Another i 111portant aspect of fixation with respect to prints is the le ngth
of t i 111e in the fixing bat h . Ti 111es in excess of those recom111ended perm i t
more absorption a n d adsorption of hypo in t h e fibers a n d baryta layer o f
fiber-base papers. M uch i ncreased washing 111ay n o t remove t h i s hypo a n d
silver-hypo co111plex salts.
Efficient washing also req u i res a well-designed was h i ng apparatus.
'vVhatever its design, the degree of efficiency can always be determi ned by
continuation of was h i ng until the fil 111 or prin t has reached the 111 i n i m u m
level of residual hypo considered essential for good i mage sta b i l i ty. The rate
of Aow and turb ulence of the water are i 111portant factors, and of cou rse the
p H and the temperatu re, which should be a 111oderate 65-70°F ( 1 8-2 1 °C ) .
\Vash i ng i s the most ti111e-consu111i ng step i n t h e processing cycle and
111a ny, 111any efforts have been made to reduce the time. M a ny compounds
have been suggested, i nclud ing hypo e l i m in ators which are oxid izing agents,
and washing a ids which change conditions so that hypo is not retai ned. H is­
torically, not 111any satisfactory substances were fou nd. An dre Charriou sug­
gested 5% bicarbonate so lution in 1 923; Edith Weyde i n 1 935 reco111mended
1 % sod i u 111 carbonate for one 111 i nu te between the fix and wash; and in 1 950
]. I . C rabtree described the use of 2% Kodak solution. These were all alka­
line sol utions, and probably changed the p H of the ge latin i n the processed
111aterial and thereby assisted wash i ng to so111e degree.
Sea water was suggested several ti 111es between 1864 and 1 904, but d id
not receive a ny attention u n t i l its use was of possible i n terest in \Vorld \Var 1 1
i n areas short of fresh water. The fact that sea water or salt water was a very
effective was hing aid46 led to the study of a variety of salt sol u t ions. Sod i u m
s u l fate h a d a particu l a rly high efficiency i n re111oving adsorbed th iosulfates. 47
Co111111e rcial products such as Kodak Hypo Clearing Agent are in co111111on
use today in the processing of both films and prints.
Eve n with the use of washing aids it is not poss ible to remove the last
t races of hypo from fiber-base prints. The peroxide-ammonia hypo e l i m i na­
tor was form u lated to be used after the recommended washing t i me, thereby
provid i ng pri nts completely free of residual hypo.48 The peroxide-ammonia
e l i m i nator 111ust be adju sted to a p H of 9 . 8 or h igher i n order to oxid ize hypo
co111pletely to sodiu m su lfate.
Although the procedu res were avai lable to prod uce completely fixed
and washed fil ms and pri nts, it was recogni zed that the pure si lver i mage
was very sensitive to external contami nants. Consequent ly, the treatment of
processed prints i n a d i l ute gold ch loride solution was recommended i n 1 940
to p rovide improved i mage stabi l i ty. 49

221
P a rt II S I L V E H I �I A G E S T H U C T lJ H E A N () ST A B I L I TY

U n fort u n a tely the emphasis o f the industry, processing labora tories,

and popu lar photogra p h i c l i tera t u re was on t h e complete removal of hypo
and hypo-s i lver salts, w h i l e a l most completely overlooking the i nsta b i l ity
of we l l - fixed and we l l -washed i mage s . This situation existed for a period of
nearly twe n ty years u n t i l the early 1 96o's.
At that ti me, the occu rrence o f m i c roblem ishes or red spots in m i c ro­
fi l m records50 caused great concern over the sta b i l i ty o f valuable gove rn m e n t ,
business a n d h istorical records. Li braries, museu ms, ga l l e ries and other
orga n iza t i ons beca me concerned about other photogra p h i c records such
as 1 9th century art i facts, val uable a n d h istoric photograph ic pri n ts , n it ra te­
base fi l ms, wet plate negatives , as we l l as contempora ry b lack-a nd-white
and color i mage s .
S i m i l a r and re lated b l e m i s h e s have appeared o n processed photograp h i c
p r i n t s , astronomical plates, and aero negatives. H owever, a word of warn i n g
i s i n order: prevent ive treatments u sed i n micro f i l m processing do not neces­
sari ly apply to other produ c t types.5 1 ·52 All of t hese type defects appear to be
the res u l t of the oxidation of the s i lver i mage'3 by some identi fied external
con tam i nants or environmental p o l l utants. These i ncl ude reactants such as
hydrogen s u l fide, s u l fu r d ioxide, ni t ro u s oxides, and other toxi c gases; perox­
ides From any source; p a i n t fu mes, and deco m position p roducts from enclo­
s u res, such as paper cartons for storage of micro fi l m rol l s . A mere trace is
s u fficient to i n i t iate deterioration which may not be apparent for a consider­
a b l e t i m e after exposure. The deterioration may appear as m icrob lem ishes,
s i lver m i rrors i n specific dens i ty areas, tarnishing along the edges o f plate and
fi l m nega t ives, or as yel lowing of t h e i mage a rea o f a p r i n t or negative .5 4
Recent i nvestigations on t h e sta b i l i ty of blac k-and-white photographs
revealed that a trace of residual hypo provided some protection against
oxidat i o n . 55·56 H owever, t h e opt i m u m amount va ries from p roduct to prod­
uct and i n any case wou ld be d i ffi c u l t to determine and control i n prac­
tice. There fore, the best reco m m e ndation is to wash thoroughly and then
t reat t h e i mage in a stabi lizing bat h . The c u rre n t l y recom m e nded bath for
negatives and prints is a 1 to 20 d i l u t io n of Kodak S e l e n i u m Toner used for
2-3 m i nutes fo l l owed by a s hort was h . 57
I n l ieu of the above sta b i l iz i ng reco m mendation a n d t h e poss ible
e ffects of a m i n u te concentration o f hydrogen peroxide, the use o f the hydro­
gen peroxide hypo e l i m i n ator is no longer recom mended except when a
trace of h)1JO m ight i nterfere i n an i m age ton i ng procedure. For reasons s t i l l
u n known, the adsorption of hypo b y paper fibe rs c a n interfere w i t h toning
reactio ns. The e l i m i nator should never be used with plates or fi l m negatives .
Another cha nge i n recom mendations d iscussed previ ously m u s t be
brought to t h e attention o f the reader. Resi n-coated ( RC ) papers are widely
used and permit more rapi d p rocess i ng. Some o f t hese have t h e deve lop-

222
 Reading 23 E 1\ T 0 N

i ng agents incorporated i n the e m u lsion. \Nh ile such papers provide ma ny

advantages in processing, residual hypo cannot be measu red using ei ther
the Methylene Blue or S i lver Densitometric methods. Therefore, the l od i ne­
Amylose method has been designed;8 to measure residual hypo i n RC
papers. This method also works we ll for fiber-base papers, films, plates and
color materials. ; y

Color Products

The processing of color materials is more complex than processing of black­

and-whi te materials. Carefu l adherence to the manufacturer's processing
i nstructions is mandatory for i mage stab i l i ty, which can be seriously threat­
ened by proced u ral or chemical changes . The th ree dyes in the color i mage
have d i ffe rent aging behavior in dark as we l l as in light storage. The data
obtained in accelerated dye fad ing tests are u sed i n an Arrhenius equation to
predict the dark storage dye stability of color products.60

S torage

Carefu l and complete processing alone will not provide m axi m u m stabi l i ty
for either black-and-white or color i mages. The processed materia ls must be
properly stored in an arc h ival storage area away from light, excessive tem­
peratu re, moisture, a n d any environ mental or atmospheric contam ination .
The accessory materials u sed as enclosures, envelopes, i n terl eaving layers,
storage boxes, mountboards, adhesives, frames and even storage cabinets,
Aoor coverings, paints and l ight fixtu res must be carefully selected to i nsure
long keepi ng. 6 1
The recommended storage temperature and h u midity for long-term
keeping of black-and-whi te and color i mages are:
[ . . . ]
Temperature : u °C (7o° F)
Relative H u m id ity 30-50%

References

1Ostroff, Eugene, "Tal bot"s Earl iest Extant Prin t . J u ne 20, 1 835, Rediscovered,
..
Pliot . Sci. 1111d Eng. 1 0(6): ( 1 966)
2 f\ckcrrnan, Rudolph, Achern1c111"s P/1otoge11ic Drawing Apparnt us, f\ckerrnan
and Co., London, 1 839, p. 8
3 Talbot, W i l l iam H e n ry Fox, The Process of Calolype Photogenic Drawing,
(com m u n icated to the Royal Society, J u n e 1 0 , 1 84 1 ) J. L. Cox & Sons,
London, 1 8 4 1

223
Part II S I L V E H I M A G E S T R C T U H E 1\ N D S T A B I L I TY

4 Archer, Frederick Scotl, 'The Col lodion Process on Glass," The Chemist. ,
M a rch, 1 8 5 1
Aeiel, " O n Davanne a n d G i rard's I nvestigation o f the Causes o f Fading of
Paper Prints," /-lu.1nphrey's Joumal, 7: 233-235, 249-250 ( 1 8 55)
6 Journal of the Photographic Societ:y, 2(30): 1 59 ( 1 855)
7 H u n t , Robert, "On the Fading of Photographic Pictures," /-111 111. ph.rey's jo'llrnal,
7 ( 1 6 ) : 251 ( 1 855)
8 " F i rst Report of the Committee Appointed to Take Into Consideration the
Question of t he Fading of Posit ive PhoLOgraphic Pictures U pon Paper,"
}. Pliot .. Soc . , 2(36): 252 ( 1 855)
9 H ardwich, T. F . , "On the M a n u factu re of Photographic Collod i o n , " Ph.ot .. J . ,
6 : 1 73- 1 77, 209-2 1 5 ( 1 860)
10 Long, C harles, "The Dry Collodion Process," /-/ uniplirey'sjournal, 9(9): 1 3 1 - 1 32
( 1 857)
11 H ardwich, T. F., "On Collodion for the Dry Process," Phot. ) . , 6(93): 1 1 7- 1 27
( 1 860)
12 H ardwich, T. F., " Remarks on t he Fad i ng of Positive Proofs," (extracted from
the 2nd ed. of Hardwich 's Man.11al of Photographic Chemist 1y) ]. Pliot. Soc. ,
2(35) : 240-242 ( 1 855)
13 Proceedings of the Phot. ographic Society of Scotland, 60( 1 1 ) : 1 66-167 ( 1 857)
14 S u tton, Thomas, "On the Fadi ng of Positives," /-lmnphrey's jo11rnal, 9 ( 1 6 ) :
245-248 ( 1 857)
15 journal of t he Phot.ograpliic Society, 2(30): 1 59 ( 1 855)
16 Diamond, H ugh Wel c h , The Yearbooh of Phot.ography for 1 88 1
17 Townshend, Frederich , "On the Quality o f Paper Requ i red for Photographic
Processes," Phot . ]. , 2(30): 1 66- 1 69 ( 1 855)
18 S u tton, Thomas, "Gold vs. Old Hypo," J. Phot . Soc. , 2(28): 1 3 3- 1 3 5 ( 1 855)
19 Davanne, Loui s Alphonse and G i rard, J u les, " Researches on Posi tive Printi ng,"
Pliot . News, ' 7' ( 1 863); idem, 8 : ( 1 864 )
20 H ardwich, T. F., "Remarks on t he Fad i ng of Posi tive Prints," Pliot . ]., 2(35):
240-247 ( 1 856)
21 Phot . ]., 3(40): 2-6 ( 1 856)
22 Shadbolt, Pliot . J. , 7 ( 1 1 6) : 324-326 ( 1 8 6 1 )
2 3 Sutton, Thomas, Pliot . Notes, 7( 1 40 ) : 30-33 ( 1 863)
24 Mat h iot, George, "The Fad i ng of Paper Photographs-Wa s h i ng the Prints,"
/-/ urn.phrey's jo'l lrnal, 1 1 : 1-3, 1 7- 1 8 , 34-35 ( 1 859)
25 Lea, M. Carey, "On t he Cause of Fadi ng of S i lver Prints," Phi/a. Phot . , 4(38) :
35-36 ( 1 867)
26 Bovey, W. T. , " I s Paper A Cause of Fadi ng)," Pliot. News, 1 5(625): 277-278
( 1 87 1 )
27 S p i l ler, John, " Fading of Albumen Prin1s, etc.," PhoL i\IG>tvs, 1 0(406): 277-278
( 1 866)
28 Lea, M. Carey, "An Exa m i nation of t he C ircu mstances U nder \i\lhich S ilver Is
Found in the Whites of Albumen Prints," Phi/a. Pl10t . , 3(32): 225-229 ( 1 866)
..
29 Lea, M. C., Phi/a. Phot , 5(57): 3 1 5-3 1 6 ( 1 868)
30 Lamb, James, "On t he Fadi ng of Si lver Prints,'' B ri t . J . Pho t . , 23(837):
234-235
3 1 Maddox, R. L., "An Experiment with Gelati n Bromide," B rit. ) . Phot . , 1 8 ( 592):
422-423 ( 1 87 1 )

224
 R eading 23 E A T 0 N

32 S u tton, Thomas, " O n an I m proved Process for Printing by Development

Without a Toning Bath," Pho t . Notes, 3(42): 9-1 1 { 1 858)
33 B lanquart-Evrard, L. D., "Gelatin Developing-Out Process," 1-/uinphrey's
Journal, 1 3(23): 36 1-364 ( 1 862)
34 H urter, Ferd i nand, and Driffield, V. C., " Photo-chemical I nvestigations and a
New M ethod of Determination of the Characteristics of Photographic Plates,"
] . Soc. Chem. Incl., 9: 455 { 1 890)
35 Lane, Gerauld T., Pemianence of Paper, Eastman Kodak Co., Rochester, N .Y.,
1 935
36 Woodward, A. I . , "The Evo l ution of Photographic Base Papers , " ] . App. Phol.
Eng., 7(4): 1 1 7- 1 20 { 1 9 8 1 )
37 Rasch, R . H . , and Scribner, B. D . , "Comparison o f Natural Aging of Paper
with Accelerated Aging by Heating," Journal of Research of t.he National
B u reau of St.anclarcls, 1 1 : 727-732 { Dec. 1 933)
38 \l\larwick, A. N., "Scientific Wash i n g of Negatives and Prints," B rit. ] . Phot . ,
64: 261 { 19 1 7)
39 H ickman, K. C . D . , and Spencer, D. A., 'The Washing of Photographic
Products-Part 6-The Washing of Bromide Prints," Phol. ] . , 65( NS49): 443
( 1925)
40 Crabtree, J. I . , and Ross, J. F., "A M ethod of Testing for the Presence of
Sod i u m Thios u l fate in Motion Picture Films," ]SJ\ll P E, 1 4(4): 4 1 9-426 { 1 930)
41 Pryzbylowicz, E. P., Zuelke, C. \1\1., and Ballard, A. E . , " Eval uation of
Crabtree-Ross Procedu re for Residual Hypo i n Processed Films," Ph.at. Sci.
and E ng . , 2: 148- 1 53 (Oct. 1 958)
42 \l\larburton, C. D., and Pryzbylowicz, E. P., "A New Test Method for the
Measurement of Residual Thios u l fate in Processed Film Based on Borohydride
Reduction to S u l fide and Methylene B lue Formation," Phot . Sci. and Eng . ,
1 0 ( 2 ) : ( 1 966)
43 Crabtree, J. I . , Eaton , G. T., and M u e h ler, L. E . , "The Quantitative
Determination of Hypo in Photographic Prints with S ilver Nitrate," Journal of
Franld.in lnst.ilut.e , 235(4): ( 1 943)
44 Crabtree, J. I . , H e n n , R. \1\1., and Edgerton, R. F., "Two Bath Fixation of
Prints," Phot.. Sci. and Tech . , PSA journal, 1 9 B : 10 ( 1 953)
45 Crabtree, J. I . , Eaton, G. T. , and M uehler, L . E., "The Removal of Hypo and
Silver Salts from P hotographic Materials as Affected by the Composition of
the Processing Solutions," ] SM PE, 4 1 : 9-68 { 1943)
46 Eaton, G. T., and Crabtree, J. I . , "\l\lashing Photographic Films and Prints i n
Sea Water," ]SMPE, 40: 380 ( 1 943)
47 H e n n , R . \1\1., Ki ng, N . H., and Crabtree, J. I., "The Effect of Salt Baths on
H)1)0 and Silver E l i mi natio n , " Pliot . Eng., 7: 1 53 ( 1 956)
48 Crabtree, J . I . , Eaton, G . T. , and M u ehler, L . E . , "The E l i m ination of Hypo
from Photographic I mages," Jou.r. PSA, 6:6 ( 1 940)
49 Ibid.
50 H e n n , R. \1\1., and \l\liest, D. G, " M icroscopic Spots in Processed Microfi l m , "
T. Pho t . Sci. a n d E ng . , 7: 253-261 ( 1 963)
51 H e n n , R. W., \l\liest, D. G, and Mack, 13 . D., " M icroscopic Spots in Processed
M i crofi l m : The Effect of Iodide," ] . Phot . Sci. and Eng . , 9: 167-1 73 ( 1965)
52 Henn, R. W., and Mack, B. D . , "A Gold Protective Treatment for M icrofil m , "
] . Pho t . Sci. a n d Eng., 9: 378-384 { 1 965)
Part II S I L \I E ll I 1\ I A G E S T ll U C T U ll E ,\ N D S T A ll I L I T Y

53 Luckey. C . \'\/. , J a mes, T. 1-1 . , a n d Vanselo"" W . , " The Effect of Various

Pretreatments o n the Heaction or H ydrogen Peroxide with t he Si lver I mage, ..

.J . Phot . Sci. and Tecli . , 2(2): 1 30-1 34 ( 1 955)

54 Feld m a n , L. , " D iscoloration or B l ack-and-White Photographic Pri nts," } . /\pp.
P/10 1 . En,g. , 7( 1 ): ( 1 98 1 )
55 Ibid.
56 Lee. W. E., \-\loocl, Beverly, and Drago. F. J . . 'Toner Treatments l'or
Photographic I mages to E n ha nce I mage Stability, " ) . l111ng. Tec/1 ., 1 0(3): ( 1 984)
57 Ibid.
58 Owerback . D., "A Colorimetric Determination or Hesiclual Thios u l fate in
Processed Paper , " ) . App. Phot. E11g . , 9(2): 66-77 ( 1 983)
59 American National Stamh1rd for Photography (Chemicals) Hesicl ual
Thios u l fate and Other Che m i ca ls i n F i l m s , P lates and Papers- Determ i nation
and Measuremen t . A N S I /Ase Ph 4.8- 1985
60 Comerl'{(/io11 of Photographs, Kodak Publ ication F-40 . Eastman Kodak
Companv, 1985
61 Ibid.

226
 R e a d n g 24

K LA U S B . H E N D R I K S

On the M echanism of Image

Silver Degradation ( 1 9 9 1 ) 1

l\laus Hendrihs (see also Readings 9, 58, and 65) was an influential photo­
graphic research scien tist. This readi ng is clear, concise, ancl informative and
serves as an excellent conclusion to Part JI. ft summ.arizes the fading of blaclz­
and-white photographic iniages and exan-r ines experimental evidence current
at the tinie, fu rther documenting the oxidat ion of elemental (filamentary) sil­
ver to highly reactive silver ions.

H i storical Review

The i mage-forming su bstan ce in black-and-white photographs is elemen­

tal silver. It is generated by two fu ndamentally different pathways. The first
occurs by d i rect and s u fficient exposu re of a si lver h alide to light. The silver
halide can be a chloride or bro m ide, or a combination of these, with small
amou nts of silver iodide sometimes present. Upon exposure to l ight, elemen­
tary si lver is formed which is termed photolytic si lver. Exposu re times are
long, typically from 30 to 60 m i n u tes at about 300 footcand les. In practi­
cal ph otography the process of making photographs j ust descri bed is known

KLAUS 13. l-I E N D H l l(S, "On t h e Mechanism or I mage Silver Degradation," i n t<laus B.

/-lenc/1·ihs: A Life Hemem.berecl, ed. iVlogens S . Koch (Copenhagen: School ol' Conserva­
tion, Royal Academy oF F i n e Arts, 2002), 87-90. Originally published in Sauvegarcle et
conservaUon des photographies, dessins, i111pri1116s e/, JJuuu1scrits. Act.es des jour116es i n ter-
11.ationales cl'et11cles de l'AHSA G , Paris 30 Sep t . -I Oct . 1991 ( Paris: Association pour la
-

Recherche Scientifiquc s u r lcs Arts Graphiques), 7 3-77. Text and d iagram reprinted by
perm ission of A R SAG.
Part II S I LV E B I M A G E S T H U C T U R E A N D S TA B I L ITY

as the pri n ti ng-out process, and p hotographic papers operating on the

principle of producing a n image by exposure alone2 are called printi ng-out
papers ( P . 0. P . ) .
Th e second pathway takes place b y t h e chemical reduction of a si lver
hali de crystal that has been exposed to l ight for a period s ufficiently long
to create laten t i mage specks of elemental silver on that crystal. Chemical
reducing agen ts, !mown in p hotographers' l anguage as developers, act upon
these elemental s ilver specks so as to reduce the entire crystal to elementary
s ilver. The exposure times that are necessary to form the developable silver
nucleus are in the order of a few seconds at the same i n tensity as above.
The chemical reaction that converts a briefly exposed silver h alide to ele­
m e n tal silver is called development in normal photograph i c practice. Obvi­
ously, a photograph so produced also n eeds to be fixed, washed and dried
i n order to become a stable i mage. The prin ting-out process was the pre­
dominant, although not the only, process of maki ng photograph i c prints i n
the r9th centu ry.
The elemen tal silver present i n each of the two groups of p hoto­
graphi c prints differs from each other i n i ts respective size and morphology.
S ilver particles present i n printed-out p hotographic prints are smaller by a
factor of a lmost two orders of magnitude than those formed by chemical
development. Although the sizes of s ilver particles in either prin ted-out or
developed p hotographic prints fluctuate widely, the former measu re around
0 . 02 m icrons i n diameter. They are approx i mately spherical i n shape. By

compariso n , the d imension of a developed-out si lver gra i n can vary around

a value of 0 . 5 m icrons. Developed-ou t silver grains can be c u b ic s haped, or
irregularly formed grai n s with numerous edges and corners. Many consist of
filamen tary si lver whi c h m ay be likened i n appearance to steel wool. Experi­
ence h as show n that the i m age-form i ng silver in p hotograph ic prints made
by the printing-out process are more reactive towards aggressive chemicals
than those in developed-ou t p hotographs. This knowledge will be useful i n
u n derstan d ing various observations made throughout the h istory o f photog­
raph y on the stability of b lack-and-whi te p hotographs. The n ature of the
aggressive chemicals that are capable of discoloring black-an d-white i m ages,
an d t h e mechanism b y w h ich they cause t h e i mage to degrade, are t h e prin ­
c ipal subjects o f this article.
The often quoted "Comm ittee Appoi n ted to Take i n to Consideration
the Question of the Fading of Positive P hotographic Pictures upon Paper,"
appointed by the Royal P hotograph ic Society ( R . P. S . ) in London, E ngland,
p u blished i ts first report in 1855. 2 Th e fading comm i ttee presented evidence
that certai n aggressive chemicals, notably "the presence of hyposu lphite of
soda" (sod i u m thiosulphate, the prin c ipal i n gredient of fixing solutions),
and "the continued action of sulphuretted hydrogen and water" can cause

228
 Reading 24 1-I E N D H I K S

discoloration and fading of black-and-whi te paper prints. The sulphuretted

hydrogen is termed today hydrogen su lfide whose devastating effect on b l ack­
and-white photographs can be demonstrated qualitatively under laboratory
conditions in a relatively simple e)qJeri ment. The fad i ng committee noted
that "there are traces of this gas ( i . e . , hydrogen sulfide) at all time present
in the atmosphere," and lamented that "pictu res wil l not remain u na ltered
u nder the continued action of moisture and the atmosphere in London . " The
committee members also observed and noted that pictures may be exposed
to dry hydrogen s u lfide gas for some t i me with comparatively l ittle altera­
tion. The two predomi nant agents responsible for the deterioration of photo­
graphs were thus correctly i dentified: chemical reagen ts capable of reacting
with the black elementary s ilver particles, and moisture whi c h catalyzes such
reactions. The visual resu l t is a yellowed or d i scolored photographic picture .
Further empirical evidence o f the effects o f relative h u m id ity was
reported in 1892 by G ladstone,3 who reported on what he termed the fugac­
i ty of bromide prin ts, m ade on a common p hotograph ic enlarging paper by
the developing-out process . The d i sappearance of i m ages on b romide prin ts
observed by the a u thor i n India was traced to "the instigation by h u midity of
c hemical action in the material or the paper, whi c h converts the silver i n to
a compound that diffu ses and d isappears i n the support . " G ladstone i n ter­
preted h i s o bservations correctly: elemental image s ilver i s converted into a
si lver salt, a process which is aided by h u m i d i ty. While he did not identify,
h owever, the drivin g force for the conversion of elemental silver into a com­
pound, the d isappearance of that compound i n to the s upport is probab ly the
first observation of the m i gration of i mage silver in the process of i mage deg­
radation, even if this ex']Jlains only partially the disappearance of the i mage.
I n 1 923, another photographer discussed the effect of tropical cli mates,
i . e . , persistently h igh relative humidity, on the permanence of p hotographic
prin ts . 4 Reporti ng from the Solomon Islands, that is, "from a c l imate of
the warmth and dampness of that of the South Paci fi c Islands," N.C. Deck
descri bed h u m i d conditions as a very good test of the permanence of p hoto­
graphic pri n ts, q uite i n keeping with contemporary views. The "fading to a
sickly yel low i n a year or so" of bromide prints was attributed "to retained s u l ­
phur or s ulphur compo u n ds i n the pri nt, which i n the presence of moist heat
reacts on the silver i mage. " More detai led i nvestigations on the mechanism
of image silver degradation were carried out in the laboratory by Henn and
V\/iest. 5 This work was triggered by the formation of m icroscopically small
orange-colored spots, known as redox blemishes, red spots, or microspots i n
processed microfilm s . H e n n a n d Wiest s howed that i m age silver had been
oxidized by hydrogen peroxide to form colloidal s ilver as the end product
which h as a n orange-yellow color. The first s tage i n this reaction is an oxida­
tion of image s ilver to silver ions by hydrogen peroxide. The silver ions can
Part II S I L V E R I �I A G E S T H U C T U R E /\ N D S T A ll I L I T Y

migrate to form, a small d istance away, concentric ri ngs of red uced s ilver i n
i t s col loidal form arou n d a now si lver-free a rea. The term redox blemishes
is derived from the oxidation-reduction reactions that give rise to their for­
mation. The formation of redox blemishes is not restricted to m icrofi l m , as
they have been observed on contem porary black-and-white pri nts as wel l . I n
t h e case o f microfil m t h e oxi dizing agent, hydrogen peroxide, was shown to
ema nate From aging cardboard storage boxes that were made from lignin­
contai ning wood pulp.
The m igration of oxidized si lver i n t he gelatin layer had been observed
many years earlier by Weyde.6 ln a paper pub lished in 1 955 on the Agfa Copy­
rapid system (a method to prod uce office copies of l i ne copy originals by
a si lver halide d iffu sion transfer process), she demonstrated the downward
movement of a soluble s i lver salt in the gelati n l ayer of photograp hic prints.
\Nhen the i mage-bearing gelatin layer was stripped off such a print, a s ilver
s u l fide transfer i mage could be seen in the baryta l ayer of a fiber-base print.
The first step to produce "soluble si lver salts" is the oxi dation of elemen­
tal si lver to ions. I t i s apparent that this fi rst oxidation step is more easily
achieved than the classification of s i lver as a noble metal wo ul d i ndicate.
The reaction is l i kely faci l itated by the extremely small size of the individ­
ual processed silver gra i n (which may vary from 5 to 3 5 nm in printi ng-ou t
papers) , a s wel l a s i ts accessible surface area which is large relative t o its
size.7 While the water conte n t of the gelatin, varying from about fou r to n i ne
percent depending on the relat ive h u m idity of the surrounding a i r, may also
play a role i n the i o n ization step, it is definitely responsible for the ability of
the silver ions, once formed, to move aroun d .
Several agents have been foun d capable of oxi d izing i mage si lver to sil­
ver ions. The most n otorious are peroxides. In the form of hyd rogen peroxide
they are also the most common reactants used i n laboratory tests designed
to study the res istance of b lack-and-white photographs to oxidizi ng agents.
Feldman publish ed a paper i n 1 98 1 i n which he described extensive experi­
ments t hat in vestigated the effects of different house paints on the d iscol­
oration o f photograph i c pri nts.8 H e fou n d that d uri ng d rying, a l kyd-based
paints prod uce peroxides that may react with the i mage silver of p hoto­
graphs. Whereas l atex-based paints were s hown to be harmless, photographs
should not be placed on d i splay or stored in rooms t hat have been painted
with al kyd-based paints for at least six weeks after painting.
\Neyde exam ined photograph col lections in several i nstitutions a n d
subsequently described in deta i l new sou rces of aggressive chemicals that
can cause i mage degradation in black-and-wh i te photographs.9 Examples are
certa i n phenolformaldehyde res i ns; ozo ne produced by electrostatic office
copiers; exhaust gases emitted from automobiles; and other industrial gases.
Real izing that colloidal si lver particles in gelatin, because of their smaller
 R e ad i n g 24 II E '' D 11 I I( S

s ize, a re about ten t imes more sensitive to oxidative attack than fi lamen tary
si lver, \i\feyde proposed u s i n g a test s l ide contai n i ng orange-colored colloidal
si lver as a n earl y warni n g system to detect t h e p resence o f harmfu l pol l u t ­
a nts i n t h e e n v i ro n m e n t . 1 0 The colloidal si lver part i c l es react qu ickly w i t h
oxidizing gases a n d s u bseq u e n t ly cha nge color which is not iced eas i l y i n
comparison with a reas o f t h e s l id e that a re protected fro m oxidat ive attack
by a lacq u e r a n d so rem a i n u n c ha nged . The use of these test sl ides neatly
con f i rms t h e h igher react ivity of colloidal s i lver parti c les i n comparison to
t h a t of deve loped s ilver gra i ns, because of their differen t morphologies.
The deterioration o f the i mage structure in albumen p ri n ts, the most
widely used photographic paper in t he 1 9t h c e n t u ry, was exa m i ned by R e i l ly,
Ke n nedy, Black, a n d Va n Dam.7 I mage degradation caused by i n c u ba t i o n a t
50°C a n d 8 6 % relative h u m id i ty occ u rs b y a n oxidative-red uctive chemical
process w h i c h leads to a cha nge i n t h e morpho logy of t h e s i lver particles.
The sma l l s ize o f these partic les makes them thermodynamically u n stable so
that moist a i r at moderate tempera t u re can i n i ti a te an oxidation of i mage s i l ­
ver. The res u l t i s t h e combination of s m a l l particles of si lver to l a rger gra i ns,
with a c o n c u rren t decrease in t h e n u mber of smaller gra i n s .
E m pirical observations obta i ned on hi storical photographs i n arch ives
col lect ions revea l several types of materi a l s which can p roduce d i scoloration
when kept i n c l ose contact with black-a nd-wh i te p h o tograp hs. Some stri k i ng
exa mples i nc l ude newspri n t ; the t ra n s fer of i n k from one p r i n t to the su rface
of an adjacen t p ri n t ; a n d ad hes ives used in the seam of fi l i ng e n c losures. 1 1
The exact i d e n t i ty of t h e o ffe n d i n g s u bstance is n o t known i n any of t h ese
cases. Two wel l-known sources o f aggressive su bstances that can react with
i mage s i lver deserve to be mentioned: residual processing chem ica l s and
n i t rogen oxides. Carro l l a n d Calhou n , i n a classic article p u bl ished i n 1 955,
described the effect of n i t rogen oxides e m a n a t i n g from deteriora t i ng c e l l u ­
lose n i t rate f i l m on t h e i mage s i lver, t h e ge l a t i n b in der, a n d o n safety f i l m
bases stored nearby. 1 2 T h e proces s i n g of b lac k-an d-wh ite photographic f i l m s
a n d papers a l so h a s s o m e e ffect o n i mage stabi l i ty. The vera c i ty of t h i s has
been recognized for about as long as photography has existed . H u n t stated as
early as 1 8 55 that "when properly prepared, a p h otographic p i c t u re w i l l never
fade. The fad i n g of a photograph o n ly marks the wan t of care o n the part of
the photographer." 1 3 \i\!h i l e t h i s may be oversta t i n g the case s i nce even a per­
fectly processed photograph can become di scolored by external sources of
oxidative s u bstances-it is necessary to poi n t out that correct processing is
a prereq u is i te for a stab l e i mage; whether they are u nd erfixed a n d so contain
res idual s i lver salts, or whether t h ey arc u n derwashed-in e i t h e r case, d i s­
colora t i o n and fad i n g of the image w i l l eve n t u a l l y occur. S i nce the l i tera t u re
o n t h i s topic is e ndless, a n d the chemical reactions that are taking place we l l
described, fu rther discussion o f t h i s topic i s n o t necessary here. 1 4 · 1 5
P a rt I I S I L V E B I �I A G E S T 11 U C T U B E A N D S T A ll I L I T Y

Con temporary Work

Four members of t he Fuj i Photo F i l m Co. Ltd ., Torigoe, O h m u ra , Yaga mi ,

and lwano, p u b l ished a schematic representation of t he events leadi ng to the
formation of colloidal silver as a result of i mage si lver oxidation. 1 6 In the first
p hase, a norm a l ly developed ( i .e., unprotected by toning or other treatments)
silver grai n i s exposed to an oxidizing atmosphere. As a result, si lver ions are
formed on its su rface. In the second phase, the si lver ions m igrate away from
t h e si lver nucleus and disperse. l n the third phase, the s ilver ions encoun­
ter an oxidizing-red u ci ng atmosphere, i n which some si lver ions a re reduced
to col loidal si lver which i s ye l low-brown i n color. Transmission electron
m icrographs, showing l arge si lver grains being su rro unded by n u merous
small particles that have m igrated away from them, were publ i shed by this
laboratory. 1 7 The electron m icrographs had been prepared from a naturally
aged and strongly d iscolored pri nt on a chloride paper dated 1 93 5 . 1 7 Trans­
m i ssion electron m icrographs of naturally aged and degraded silver grain s
from black-and-white f i l m were also published . The occurrence o f silver i o n
migration i n h i storical photographs led t o the exa m i nation o f t h e structu re
of si lver grains in sample photographs that had been exposed to oxidizing
conditions in the laboratory. The t hree oxidizing materi als used to reproduce
the type of i mage si lver degradation that had been observed in naturally aged
pri nts and n ega tives were hydrogen peroxide, ani mal gl ue used in mounting
photographic prints, and the components of fingerprints.
An eight percent hydrogen peroxide atmosphere at room temperature
and 75 % relative hum idity is capable of producing si lver ions from processed
si lver grains i n a contemporary slow speed con tact paper within 48 hours.
The ions m igrate away in all directions. Th is is shown in transmission e lec­
tron micrographs. If the exposure to hydrogen peroxide is continued for a
few more clays, si lver particles can be seen to acc u m ulate near the surface
of t he i mage. There they form the fam i l iar blue metallic sheen, convention­
al ly known as silver m irror. The oxi dation to silver ions con tinues u nabated,
i f the presence of an oxidizing atmospheric persists, unt i l the original silver
gra i n is completely destroyed. The loss of the structura l i n tegrity of i ndi­
vidual si lver grai n s is accompan ied by a visual destruction of the i mage: a l l
deta il becomes lost. Th e i mage turns i n to brown muddy zones without any
stru cture or detail.
P hotograph ic prints made i n the first ten years or so of photography
were often m o u n ted onto paper sheets or cardboard . Many of these pictures
are salted paper prints, which are made by a printi ng-ou t process. An obvi­
ous discoloration can sometimes be noted along the edges of such prints. We
investigated the hypothesis that this fad i n g along the edges could have been
caused by an adhesive used to mount the photograph onto a support. Salted
 Reading 24 ll E N D H I K S

paper pri nts prepared i n the laboratory were treated on the back with adhe­
sives of different kinds and either left at roo111 te111perature or kept for a few
clays u nder standard accelerated agi ng conditions. I n all cases, co111 merc ia l ly
available animal gl ue caused severe fading of the i 111age area behind which i t
was applied. After some fu rther experi111ental work, the presence o f thiou rea
in a n i ma l glue was esta b l ished . This compound could be shown to be the
act ive i ngredient i n the a n i 111al glue capable of reacting with both photolytic
si lver and developed-out si lver grains. Trans111 ission electron 111 icrographs
i l l ustrate the result of such reactions.
Literature on the conservation of photographs someti mes 111entions
the presence of fi ngerprints on negatives and paper photographs. They are
111ost often found on the i m age side. The format ion of fi ngerpri nts [ is ] vari­
ously attributed to "acidic o i l ," "oily acids," "sweaty acids" and the l i ke. We
have invest igated the nature of the formation of fi ngerprints on photograph s
a n d their effect on t h e stabi l i ty of si lver i 111ages. T h e princ ipal component
of sweat produced by glands in the known skin is sod i u m ch loride. Minor
components a re u rea and lactic acid. The precise composition varies from
one i ndividual to a nother, and some are known-and described in the 111ecli­
cal literat u re to have more active sweat glands than the 111ajority of people. l t
req ui res a little experience t o produce visible fi ngerprints o n d i ffere nt types
of photogra phs that can be exa111 i necl . A transfer of sweat fro111 the skin of a
fi nger to the su rface of a photograph attracts at once partic les of dust that
settle on the deposi t and so re nder difficult the d i rect observation of the
events that a re to happen. An oxidation of i 111age silver to si lver chloride is
the 111ost l i kely reaction to occu r as a result of a fingerprint. This leaves the
i111age silver 111ore stable than before, probably because a protective layer of
si lver c hloride is formed around an individual si lver gra i n . It is possible to
cle111onstrate such a reaction by bru s h i ng 3% socl i u 111 ch loride on the sur­
face of a fi ne-grain photograp hic paper. After some t i me the areas that were
in contact with the sod i u m chloride solution begi n to t urn l ighter than the
surrounding areas of the print. If the photograph is now exposed to an 8%
hydrogen peroxide atmosphere, the s ilver i n the areas not treated with
sod i u m c hloride reacts guicl ly Lo form yel low and pi n k zones of d i scolor­
ation. The same events take place when potassi u111 bromide and potass i u m
iodide a re used : areas covered b y t h e a l kal i hal ide solutions a re not attacked
by the hydrogen peroxide. The protective effect of the presence of potassiu m
iodide, added to the fixing sol ution, that i s given t o si lver grains i n processed
m icrofi l m was shown by Henn, \l\!iest, and Mack. 1 8 A coating of insoluble
si lver iodide around i n d ividual i 111age partic les is thought to be the reason
for their observed i ncreased stab i l i ty towards oxidizing agents. Ja111es and
Va nselow exa111 ined the reaction of hydrogen peroxide with processed silver
grains and concluded that the silver acts as a catalyst for the degradation of

" '
-.).)
Part II S I L V E R I M A G E S T H U C T U R E A N D S TA B I L I TY

the hydrogen peroxide. 1 9 Thi s ability is destroyed when the su rface of the s i l ­
ver grains becomes coated w i t h a si lver compound, such a s s ilver iodide. The
experiment of b ru s h i ng solutions of alkali c h loride, bromide, and iodide onto
a b lack-and-whi te developed-out print and then exposing i t to a hydrogen
peroxide atmosphere neatly demonstrates the protective effect of the silver
h a l ides towards the oxidizing agent. After prolonged ex')Josu re (approximately
ten clays) this protection b reaks down a n d the regi ons treated with alkali
h a lides begin to fade severely as wel l .
T h e first step i n s ilver i mage degradation is the oxidation o f elemental
si lver to reactive silver ions. Once formed, silver ions can migrate i nside the
i mage layer and towards either of i ts s urfaces. Visible proof of the m igration
of s i lver ions to the upper s urface is the formation of a blue metallic sheen,
particularly i n h igh density areas, of a p hotographic negative or print. The
formation of a transfer i mage in the baryta layer of a fiber-base print, below
the i mage-bearing gelat i n layer, is seen as proof of a downward m igration of
s ilver ions from the emulsion layer, as noted. The s ilver ions, once formed ,
can either form si lver salts, i f suitable anions are ava ilable, or colloidal silver.
This is shown schematical ly in the followin g formula:

Ag salts (oxide, su lfate,

n itrate, s u l fide, etc . )

Exposure Oxidation
i
M igration of s ilver ions to
AgX - Ag - Ag form either si lver salts or
Pro c e ss i n g colloidal s ilver

Silver F ilamentary Colloidal s i lver ( s ilver

halide i mage s ilver m irroring) p l u s s i lver s u l fide

The sign ificance of this mechanism lies i n the conclusion that the preserva­
tion of processed black-and-wh i te p hotographic i mages req u i res a storage
environment free of aggressive oxid izing s ubstances. This means in practice
that p hotographs:

-should be well processed ;

-kept i n chemically stable fi l i ng enclosures; and
-stored in a pol lution-free space.

These requ i rements complement and even su persede [ those] for certai n lev­
els of temperatu re and relative h u m i d ity.

234
 R ea d i n g 24 H E N D R I KS

References

After the i mage has been printed out u pon eJq>osure u nder a negative, prints
are treated i n a fixing bat h to remove u nexposed silver hal ide, washed and
dried.
2 Delamotte, P . H . , et al. 1 855. " Fading of positive photographic pictures on
paper."}. Photog. Soc., 36, 251-252.
3 G ladstone, L.S. 1982. "Fugaci ty of Bromide P r i n ts." Brit ]. Pliot.og. , (29 J u ly),
484.
4 Deck, N . C . 1 923. "The Permanence of Photographic Prin ts as Tested by
Tropical C l i mates." B rit . ]. Photog . , 70 (3284), 222-223.
H e n n , R.W., and Wiest, D . G . 1 963. " M icroscopic Spots in Processed
M icrofilm: Their Nature and Prevention." Photog. Sci. E ng . , 7 (5), 253-26 1 .
6 Weyde, E . 1 955. " Das Copyrapid-Verfahren der Agfa [The Rapid Copy
Procedure of Agfa ] . " Miu. Forsch u ngslab. Agfa, 1 , 262-266.
7 Rei l ly, J . M . , Kennedy, N . , B lack, D . , and Van Dam, T. 1984. " I mage Stru c t u re
,.
and Deterioration in Albumen Prints. Pliotog. Sci. Eng. , 28 (4), 166- 1 7 1 .
8 Feldman, L . H . 198 1 . " Discoloration o f B lack-and-White Photographic Prints."
]. Appl. Pliotog. Eng. , 7 ( 1 ) , 1 -9.
9 Weyde, E. 1 969. "Stab i l i Uit von S i l berb i l dern [Stabi l i ty of si lver photographs]."
Chi-in.ia, 23 ( 1 ), 42-43.
10 Weyde, E. 1 972. "A Simple Test to I dentify Gases Which Destroy S i l ver
I mages . ., Pliotog. S c i . E ng. , 1 6 (4), 283-286.
11 Hendriks, K . B . 1989. "Sta b i l i ty and Preservation of Recorded I mages." I n :
S t u rge, J . , Walworth , V . , and Shepp, A . " Imaging Processes and Materials.
Neblette's Eighth Edition." Van Nostrand Reinhold. New York: 1 989.
12 Carro l l , J . F., and Calhoun, J . M . 1955. " Effect of N itrogen Oxide Gases on
Processed Acetate F i l m . " } . SM PTE, 64, 501-507.
13 H u n t , R. 1 855. "On the Fading of Photographic Pictures." 1-ltnnphrey's j . , 7
( 1 6), 25 1-2)5.
14 Eaton, G.T. 1 970. " P reservation, Deteriorati o n , Restoration of Photographic
I mages . ., Library Q. , 40 ( 1 ) , 8599.
15 Kopper!, D . F . , and H uttemann, T.J. 1 986. "Effect of Residual Thiosulfate I o n
..
on the I mage Stabi l i ty o f M icro f il m s . " }. Imaging Teclinol , 12 (4), 1 73-1 80.
16 Torigoe, M . , O h mura, D., Yagami, S., and l wano, H. 1 984. "Kuroshi ro
shas h i n no choki hozonho [A Challenge in Preservation of B lack-and-\Vhite
Photographic I mage ] . " Sci. Pub. Fuji Photo F i l m Co., Ltd. No. 29, pp. 3 1 -36.
17 H e ndriks, K . B . 1 987-88. " O ber die chemische Restaurieru ng des S i l berb i ldes
vergilbter oder verfarbter Photographien [ O n the Restoration of Yellow or
Discolored S i lver I mages in Chemica l Solutions ] . " Wiener Bericlite iiber
Naturwissenschaft i n der Kunst., Band 4/5, 372-389.
18 H e n n , R.W., Wiest D . G . , and Mack, B . D . 1 965. " M icroscopic Spots i n
Processed M icrofi l m : The E ffect of I odide." Photog. Sci. . E ng. , 9 (3), 1 67-173.
19 Luckey, G .W., J a mes, T. H . , and Vanselow, \>V. 1 955. "The Effect of Various
Pretreatments on the React ion of Hydrogen Peroxide with a S i lver I mage."
Photog. Sci. an.cl Technique, Nov. 1955, 1 30-1 34.

235
 P A R T I I I

Silver, Mercury, and Gold:

Philosophical and Practical
Approaches in the Preservation
of Daguerreotypes

The fi nely polished s i lver-p lated daguerreotype i mage, u npara l leled i n deta il
as well as fragility, was p lagued from its i nception in the n i neteenth cen­
tury by the formation of d i sfiguring corros ion fi l m s and deterioration prod­
ucts caused by poor handli ng, ell.']JOSu re to i n adequate environments, and
i n h erent vice. The readi ngs in t h i s part doc u ment the h istory and evolu­
tion of daguerreotype treatment and care, as generations of photograph i c
custodians, scientists, practitioners, and conservators i ntroduced n ew clean­
ing techniques and preservation measures. Narratives of s uccess and fai l u re
are recou n ted i n the fol lowing pages, all of which serve as i nspi ration for
ongoing scientific efforts to preserve these u n i qu e treasures of n ineteenth­
century l ife.

Jeremiah G urney (American, 1 8 1 2-1886), Porlrai/, of a-n American Yo1ll-'11 1 8 52-56. Daguerreotype,
hand-colored, 8.7 X 7 cm (3i/1 6 X 2� i n . ) . Los Angeles, J . Paul Getty Museum 84.xT. 1 56+27
 R e a d n g 25

E U G E N E VAI LLAT

Process for Restoring Stained

and Oxidized 0 ld Prints to Their
Original C ondition ( 1 8 50 )

E ugene Vail/al was a well-respec/.ed French photograpl1er who also worlwd as

an opti.cicm. and a fou nding nw1nber of t he Societe fraru;aise cle photograph. ie.
1-l e began advertising his worlz in 1 845, and by 1 854 his advertisem.ents promoted
a prosperous photographic business wit h two locat ions. 171.is citation, one of
t he earlies/. published t echniques for cleaning daguerreotypes, describes J;he use
of a potassi111n. cyanide soli1 tion l:o reduce oxidation and staining. Despite con.­
s-iclerable health. and safety rislzs, t h.is l:ech n:ique was 11tilized by photographers
and avid collectors for nearly a cen l: u ry.

There is a type of framing that is we l l su ited to daguerreian prints, and espe­

cially to portraits. It is an oval m i n ia t ure frame with gilt circles and glass.
U se of the passe-partout mat becomes u n necessary with this type of Fram­
ing. H owever, while such frames enhance the pri nt, the latter is very subject
to oxidation after a time, espec ially aro u nd the edges.
Alt hough prints fra med in passe-partout mats are better preserved
than those placed in the fra mes of which I spoke above, they a re neverthe­
less subject to oxidation and stai ni ng-after a longer t i me, i t is true. H ow­
ever, the drawback exists with both man ners of fra m i ng. It is but a question
of time before that u ntoward result occurs.

E u G E N E V1\ I LLAT. " P rocede pour rcrnettrc dans lcur ctat prim it i i' lcs ancicn nes eprcuvcs

tachees ct oxidees " ( Process for restoring stai ned and oxi d i zed old prints to their original
condition), i n DaguerrCotype Sllr Plncf11es-Re11seigne111e11ts co11scie11cieux pour opdrer
avec s11rete. E111ploi du chloro-bro11111re de cf/(/11x et de /'iodo-bro111e ( Plate daguerreotypes.
Conscientious i n formation for working sal'cly. Use ol' chlorobromidc of' l i me and iodized
bro m i ne . ) ( PLJris: October 1 850), 52-53.
 Reading 25 V A I L L A T

All who work with daguerreotypes have n oticed the m ilky circles that
s u rro u n d prints enclosed in oval m i n iature frames and that end up foggi ng
the entire print.
I a m going to provide a quite simple means of removi ng that veil, how­
ever old it m ay be.
D isso lve a piece of white potassi u m cyanide the size of a hazel n u t in a
glass of distilled water and filter the solution .
I mmerse the pri n t that is to be restored i n ordinary water.
Without allowing it to dry, place it o n the stand that is ordinarily used
for chloridation and pour over it as much of the potass i u m cyanide solution
as the level of the plate allows to hold. H eat with a wine spi ri t lamp, but
ge ntly. When the solution is ju dged to be a bit more than tepid, the heating
should be discont i n ued.
Then take a very clean, small cotton ball and wipe it gently over the
stained or oxidized parts, always moving horizontally over the print.
The b l u ish layer that fogged the pri nt i nstantaneously d isappears.
Riel the .p late of that solution and pour on more of it a second time, but
without heating. Spread the solution over the p l ate, while holding it by one
corner with a small pair of flat-nosed tongs and shaking i t gen tly, keep i n g it
as horizon tally as possi b le in order not to i mmediately pour off the liquid.
Then rinse u nder run n i ng water, and d ry it as would be i nd icated after fixing
with gold chloride.
Using this method, I have cleaned and made use of pri nts that I had
neglected to frame and that I had left for several weeks exposed to the air and
the iodine and bromine fumes that are always c i rculating i n a Daguerreo­
typer's workshop.
I t takes four to five m i n u tes to accomplish this entire operation .
This c lean i ng may be u sed on prints, whenever oxide forms aga i n over
ti me, to endlessly retu rn them to their origin al condition.

239
 R e a d i n g 26

C H A R L E S VAN RAV E N S WAAY

An I mproved Method for the

Restoration of Daguerreotyp es ( 1 956)

Charles van Ravenswaay ( 1 9 1 1-1 990) was director of the Missouri Historical
Society from 1 946 to 1 962. His article is the first to cite the use of acidified thio­
urea to successfu lly c lean damaged daguerreotype plates, yielding "astonishing "
results and obviating the use of potentially damaging potassiuni cyanide. T7ie
discovery of this technique is attributed to Ruth Field (see Reading 27), a col­
league of van Ravenswaay's. Here, van Ravenswaay celebrates this "superior"
1nethod, which is "harmless if used with normal care. "

Du ring the course of restoring the collection of daguerreotypes at the M i s­

souri Hi storical Society, our observations have s hown that potassi u m cya­
nide, usually employed for the pu rpose, etches i nto the plate, destroyi ng
much of the original sharpness and depth of the pictu re. I n addition, if the
plate is left i n the solution too long, there i s always clanger of the i mage
bei ng destroyed; consequently, with a daguerreotype so badly discolored that
the picture can barely be seen, restoration i s often i m possible.
Real izing the need for a less destructive chemical, we have fou n d a solvent
which causes no damage to the plate and gives startling res ults. The chemi­
cals u sed were chec ked by Mr. H . E . Wiedemann, a consu lting chemist.

The following technique is employed :

1. Wash daguerreotype i n distil led water to remove surface dirt . 1

2. Drain and immerse u n t i l discoloration is removed i n a solu tion of: 2

C HAHLES VAN R,wENSWAAY, "An I m p roved M ethod for the Restora t i on of Daguerreotypes,"
l rnage�Journal of Photography and JV/01.ion Pictures of the George Eastincm House 5, no. 7
(September 1956) : 1 56-59. © 1 956 George Ea s t m a n I-louse, I nc . R ep r i n t e d by permission of
G eorge Eastman H ouse, I nternational M u seu m of Photography a n d F i l m .
 Reading 26 H A V E i\1 5 \V A A Y

D i s ti l l e d water 500 cubic cen timeters

Thiourea 70 gran1s
Phosphoric Acid (85%) So cc
Non- Ionic \Vet t i ng Agent 2 cc (PhotoAo)
Disti l l e d water to make 1 l i tre

3. Remove from bath and i mmediately hold u n der ru n n i ng water.

4. P l ace in a mild soap solution (face soap) and agitate briefly.
5. Rinse thoroughly i n running water, then was h in a second bath of

distil led water.

6. I mmerse in 95% gra-in alcohol. Drai n .
7 . Hold high over a small flame until dry.

Advantages of the Method

Stain i s completely removed without the plate being etched .

Detai ls of the picture are brought out clearly, and the mirror- l i ke qual­
i ty of the si lver p la te is retained .
Daguerreotypes can be left in the chemical solution i n de fin itely with­
out removing the i mage. In one experiment the p late was left i n the solu­
tion for one hour and twenty m i n u tes withou t visible cha nge. Conseq uently,
daguerreotypes formerly considered beyond restoration because of their
extensive discol oration can now be restored.
Plates can be cleaned over agai n as often as necessary without harm.
It should be n oted that daguerreotypes which have previously been
restored with cyanide lose their origi nal lustre. Thus, plates that have not
been c leaned before with cyanide will show far superior res u l ts.

Notes

1 Any paper on the back shou l d be soaked off and removed in this bat h . ( Eel.)
2 5 0 0 cc apparently c leans about 2 50-3 00 square inches. ( E el . )
 R e a d i n g 27

RUTH K . FIELD

C leaning of Daguerreotyp es ( 1 9 5 8 )

R u /;h /(. Field ( 1 903-1995) was c u rat;or of the P·ictorial History Gallery at the
Missou ri Histori.cal Society when she began experi-inenting with techniques
for t h.e proper clean i ng of daguerreot,y1n plates, using a variety of chem icals
fro- m Coca-Cola® to t hiourea. This an notat;ed 1 958 letter is Field 's first-hand
account of her experirnentation. R u th Field 's conimitment to preservi ng
badly discolored and blaclwned dagu erreotype plates illustrates haw staff and
ad·1ninistrators were often actively e ngaged i n and responsible for 11hotographic
preservation practice in the 1 9 50s, and how this accoimtability led to greater
e.,·cperi Tnentation .

M r. Daniel \TV . Jones

N BC "Special Projects"
30 Rockefeller Plaza

New York 20, N.Y.

Dear iVl r. Jo nes

iVl iss
Douglas has told me of you r request for fu rther i nformation on the pro­
cess I use for the clea n i n g of daguerreotypes. I u nderstand that you have the
copy of I mage cont ai n ing the article which l wrote. That covers t he subject
as far as the technique goes, and of Eastman's kind reception of it. Before I

HuT1 1 K. F1 ELD, personal correspondence to Daniel \/\/. Jones, October 25, 1 958.
 Reading 27 F I E L D

go any further on the s u bject I better tell you that I a m no chemist, nor a m
I a p hotograp her-bu t j u st curious. I n our large collection of daguerreo­
types which I was i ndexing and fi ling, there were many of them that were
badly d iscolored-some with the i mage barely visible. It was fru strating to
fi le away i n a b rand new cabinet pictures that were i n such bad shape. So
my first move was to take them from the cases a n d clean the glass that cov­
ered them. That helped some, b u t not enough to satisfy me. I read every­
thing I could get hold of on the restoration of daguerreotypes, but could
fin d only one process-that of using cyan ide. l had seen some restored by
this method, and was not i mpressed with the results . Sometimes parts of the
picture were entirely erased by this strong chemical, and i n every case the
m irror-like q uality of the p late which gave the picture its depth, had d isap­
peared. The next step was to fi nd something better. ! learned how daguerre­
otypes were made, then read i n the encyclopedia and other books about
various chemicals and their reaction on different metals. At an antique shop
I was able to p urchase about 50 daguerreotypes of u nidentified people for
about 35¢ apiece, and I took them home where I e>..lJ erimented with all kinds
of t h i ngs-even Coca-cola! That, by the way, contained a n i ngredient which
had great possibi l i ties, but the combination wasn't right-it is better as a
beverage! I did not hesitate to get all the i n formation I could on c hemicals
from the corner druggist, and from manufactu rers of chemicals. F i nally, one
day I fou n d a brew that did the work. The effects were i nstanta neous, and
close to perfect. Then I asked one of the foremost chemists i n the city to
check on the chemicals u sed, and he assu red me that they were h armless. I
processed a few plates and kept them i n the open a i r for over t hree months,
observing them every day for any reaction. \Vhen I was satisfied t here would
be none, I wrote to Eastman . . . and t hat's the s tory.
I am c u rious to know why you wanted the details and how it might
tie i n with you r work. I s i t beca use i n you r search for old pictures that you
have run across many daguerreotypes with the i mage almost i ndistinguish­
able? U nless the plate has had somethi ng spilled on it that has eaten i nto the
metal, I have yet to fin d one, no matter h ow clouded, that cannot be brought
back to its original clarity. H owever, one must bear i n mind that there were
good p hotographers and poor ones, just as there a re today. There were plates
that were not buffed or treated properly before exposure, or that were u nder
or over exposed by the photogra p her. But bad or good, the pictures wil l all
come out i n their original state after processing by this new method-whi c h
h a s two i mporta nt advantages over the u s e o f cyanide i n t h a t i t does n o t etch
the surface of the plate, and that it can be u sed as many times i n the fut u re
when clea n i ng may be necessary without ever removing the i mage. Many
museums, dealers, and i ndividuals who own b lackened daguerreotypes throw

24 3
Part III S I L V E R , M E R C U R Y , A N D G O L D

them away because they think the picture has disappeared. I am sure that
many rare and valu able pictures h ave been lost forever, when they might
have been saved by proper cleaning.
Perhaps I am prej udiced, but I think that for cla rity, depth, and deta i l ,
there is noth i ng that we have today i n photography t h a t c a n compare t o the
combination of a fin e ly polished daguerreotype plate plu s a good photogra­
pher. A good daguerreotype can be enlarged to ma m moth proportions with­
out losing any of its fine qual ities. Two years ago we had an exh i bit of them
enlarged to s izes as large as 30 11 X 40 11 • They were exci ting and effective.
I am enclosing an article from the Post Dispatch which may Fi l l in o n
any i nformation I may have left out. If I have not a nswered t h e questions
that were i n you r mind, p lease do not hesitate to let me know.

S i ncerely,
RUTH K. FIELD
Pictorial H istory G al lery.
 R e a d i n g 28

I RV I N G P o s s o RAVS KY

Daguerreotype Preservation:
The Problems of Tarnish
Removal ( 1 978)

Irving Pobboravslzy is a celebrated twentieth-centu ry dagu erreian artist who

spent 39 years as a researcher at the Rochester Institute of Technology. The fol­
lowing excerpt fmm his influential article, "Daguerreotype Preservation: T1ie
Problems of Tarnish Removal, " addresses observed negative effects of thiourea
c leaning on daguerreotype plates, s11ecifically the formation of small blaclz spots
or "1neasles " within days of acidified tliiou rea treatment. T1iis article confirmed
the enormous rislzs associated with daguerreotype cleaning and u rged further
study and investigation.

E�'Posure to the E nvironment Causes Damage

Properly sealed daguerreotypes have lasted in tact for over a centu ry and
a quarter. (The vast majority of American daguerreotypes will be fou n d i n
cases. However, l arger t h a n normal sizes m ay b e framed, while smaller than
normal sizes may be mou nted in jewel ry such as brooches, pendants, watch
cases, and even signet rings. ) H owever, if the seal is broken, or if the materials
sealed inside contain su lfur, the p late will tarnish m uch like silver tableware .
This tarnish can be removed chemica l ly. B u t questions have been raised dur­
i ng the last few years about the desirability of such treatments, and sci entific
studies of these cleaning processes are begin ning to be u ndertaken.
Although a variety of chemicals have been proposed for tarnish removal
from daguerreotypes, o n ly two basic formu l ae have had extensive use. The

From IRVlNG PollBORAVSKY, " Daguerreotype Preservation: The Proble!lls of' Tarn ish
He!lloval , " Tech n ology and Consen>alion (Su Ill Iller 1 978): 40-45 (43-44 excerpted here).

245
Part III S I L V E n , M E 11 C n Y . A N D G O L D

first of these, a weak solution of potass i u m cyani de, was used al most un iver­
sally until about 1956. The d isadva ntages of this solution are that it is highly
toxic and that it etches the metal su rface making i t matte where i t should be
m i rror- l i ke. In fact, i f the potassi u m cya n ide t reatment is prolonged , there is
a clanger that the i mage will be destroyed .
It is probable that this solution was used in the unsuccessfu l attempt
in 1 934 to clean the tarn ish from the fa mous claguerreOt)1Je portra it of Doro­
thy Catherine Draper, a daguerreotype made prior to the adoption of go ld
ton i ng. 1 The restorer stated that "the i mage had not been affected [ by clean­
i ng ] . The 'bloom ' is upon the bare si lver portion, which has the effect of
bri nging u p the parts which reAected dark nearly equal to the l ighter por­
tions which give the h ighlights."
The use of cyanide for cleaning was dropped about 1 956 when a safer
cleaning fo rmula, having the main constit uents of thiourea and phosphoric
acid, was annou nced by the M i ssouri H istorical Society. This sol u t ion is fa r
less toxic than the cyanide one. (Thiou rea/acid c leaners have been used for
many years for tarnish removal on household si lverware and both their chem­
istry and h istory are we l l documented .2) In add ition, the form ula was clai med,
at that time, not to etch the plate su rface even with prolonged i mmersion.'
S u bsequent to the i ntrod uction of t he thiourea/acicl solution, another
restorat ion attempt was made on the non-gilded Draper daguerreotype. A
modi fied ve rsion of the M issouri H istorical Society's solution i n which the
concentration of thiourea was doubled to 140 gm/l iter and the phosphoric
acid was red u ced to 1hooth of the origi nal formula was employed by J. L.
Enyeart. This reduction in phosphoric acid was said by h i m to m i n i m ize t he
chances of the acid attacking t he metal of t he daguerreotype i mage and sub­
strate.4 Atomic absorption a na lysis was applied to the solu tion after it was
used on the Draper portrait. The solution was foun d to conta i n : no silver, no
merc u ry, but lots of copper. The result ing clai med " revival " of the portra it is
thought by some to be just cleaning of the tarn i s h . 1
A s experience was gained w i t h t h i s new solution o n daguerreotypes,
some users began to notice that on some claguerreot)1Jes small brown or black
spots wou Id appea r fro m a day to weeks after treatment. These spots cou lei
be removed by ret reatment with the solution, but the spots woul d reappear.
The problem was considered sufficiently severe that a photographic antiques
catalog annou nced: (a) that they had slopped using this solution because of
this "molcl l i ke " growth on some plates after being cleaned with a thiourea/
acid solution, and (b) that the major A merican museum of photography had
s i m i larly stopped cleaning its daguerreotypes using this procecl u re . 5 Si nce
t hen, that museu m has cautiously rest arted clea n i ng some daguerreotypes.
A study was undertaken by L. Jacobson and VJ. E. Leyshon of Gen­
era l E lectric Co. on this daguerreotype " measles " problem.6 A daguerreot)1Je
 Reading 28 P 0 13 B O B J\ V S l< Y

pl ate that developed black spots after treatment with thiourea/acid solution
was examined with a scann i ng electro n microscope. Zoom i n g i n on one of
the measle spots showed the n u c leus of the spot to be a c rysta ll i ne, flower­
l i ke structure with the "petals" sta nding at right angles to the plate su rface.
Analysis of the chemical elements of this spot's nucleus fou n d silver, mer­
c u ry, and traces of chlorine, su lfur, and silicon ( non-significa nt). Jacobson
and Leyshon reasoned that the crystal l i n e petal structure could e ntrap clean­
i ng solution which, if not completely removed, would allow the sulfur i n the
t h iourea to react with the silver to produce a tarni sh spot.
To test th is hypothesis, spots were removed by treatment with a t h io­
u rea/acid solution. The p late then was given a two-m i n ute u l trasonic clean­
ing treatment and careful l y washed. The thorough cleaning proved effective.
No spots appeared even after six months. They also found that repeated
cleanings in the thiourea/acid solution did not change the c rystalline struc­
ture of the measle. Their conclusion was that the spots could be avoided by
thoroughly washing the plate after cleani ng with the thiourea/acid solution.
Their work is admi ttedly l i m ited to one daguerreotype and n eeds to be
expanded, using more samples to confirm and gen era l ize thei r conclusions.
It would be i mportant to know i f t here i s any su l fu r i n the f lower- l i ke struc­
t u res after wash ing and how mu ch washing is needed to remove all t races.
One su rpris ing resu lt that needs fu rther exami nation is the fact that gold
was not found, since presu mably a gilded plate was studied.
Recently, another c leani n g p roblem was made public-thiourea/acid
mixt ure may affect the daguerreotype i mage. At a symposi u m on the preser­
vation and restoration of p hotographic i mages, September 28, 1 977, E ugene
Ostroff, C urator of Photographic H istory at the S m ithsonian Institution,
indicated that this solution may cha nge the daguerreotype surface. That is,
i n order to show the dramatic effects of cleaning a tarnished daguerreotype ,
he had used this sol u tion to clean only half of the tarnished i mage, leavi ng
the other half u ntouched for comparison. Once sl ides of this daguerreotype
had been made, he proceeded to clean the entire daguerreotype but, when
he fi n ished, a dema rcation line between the two ha lves was still visible.
Research is presently underway at the Canadian Conservation I nsti­
tute to examine the thiourea/acid t reatment, as we ll as another method for
tarnish remova l-conservation t reatment for daguerreotypes, this procedure
being a modification of the rapid fixer reducer publ ished i n the early 1 95o's
and based on an acidic ammon i u m thiosulfate bath . Accordin g to Siegfied
Rempel, Conservation Processes Research , C. C. J . , exhausted clean ing
solutions are being supplied by Alice Swan of the I n ternational M u seum of
Photography, and the a nalysis is being conducted by the C. C. I. 's Analytical
Research Section util izing the atomic absorption techniques for determ i n i n g
gold, silver, mercury, and copper concentrations.

247
 Part III S l L V E H , M E R C U RY , A N O G O L D

Figure 1
A scanning electron m ic rograph
o f a measle-spot fou n d on the
daguerreotype plate shown on the
opposite page [ not reproduced
hcre J . Measle has a Hower-like
structure with its ;,petals'' at
right angles to the plate su rface.
( Photo courtesy ol' L. J a cobson
and W. E . Leyshon, General
Electric Company)

The present consensus of the people closest to the problem is that

too little is lrnown about tarnish removal on daguerreotypes and, because
of th is, the risks for damage may be high . U n t i l more is known, it is wise to
refrain from cleaning d aguerreotypes. The damage to the Draper daguerreo­
type and the onset of " measles" after treatment with the newer sol ution
are just two problems that have surfaced i n the literature. How many have
occu rred and remain u n reported and how many lie in waiting, incubating
with time, is u nknown. At present, the various cleaning solutions can only
be considered " recipes" which req uire further study. And also keep in mind
that if the daguerreotype had been hand colored, i mmersion i n any solu tion
will remove most of the colori ng matter. M ore research must be done before
daguerreotypes can be c leaned wit h a minimum of risk.

References

1 Wood, H. D . and E . D. Shorl an d , 'The Daguerreotype Portrait of Dorothy

Draper," The P ho tographic Journal, Dec. 1 970, pp. 478-482.
2 B re n n e r, 1-1 . , "S ilver D i ps, " Soa11 and Sanitary Chemicals, Vol. 29, No. 5, 1 953,
pp. 1 6 1- 1 67, 1 83 .
3 v a n Havenswaay, C . , "An I mproved Method For t h e Hestoration of
Daguerreotypes," hnage, Vol . 5, No. 7, Sept. 1 956, p . 1 58.
("Cleaning a B l ackened Daguerreotype," Caring for Photographs-Display,
Storage, Restoration , L i fe Li brary of Photography, 1 972, p p . 34-39 provides
a n other variation of the thiourea/acid clea n i ng form u la.)
4 E nyeart, J. L . , " He,�ving a Daguerreotype," Th e Ph.otograph. ic ]oumal, Sept.
1 970, p p . 338-344.
Photographic Antiq11es and LiteratHre, Cata log No. 4, \!\/inter 1 972-1973,
Daguerreian Era, Pawlet, Vermont, p . 1 5.
6 J acobso n , L. a n d \!\/. E. Leyshon, 'The Daguerreian M easles Mystery,"
Graphic Antiquarian, Spring 1 974, pp. 1 4- 1 5 .
 R e a d n g 2 9

A L I C E S WA N

The Preservation of
Daguerreotyp es ( 1 98 1 )

Alice Swan (see also Readings 56 and 57) was photograph conservator at; tJ'Le
George Eastman I-louse from 1 975 to r979. S he was actively involved in the
formation of the fie ld and widely acclaimed for her careful scientific approach,
acute observational sblls, and thoughtful publications. Tn this article, Swan
utilizes electron microprobe X-ray analysis to characterize the daguerreotype 's
image morphology and common degradation products, including crystalline
deposits, interference films, and accretions. In doing so, she creates a ·modern
lexicon for daguerreian deterioration and maizes recommendations for long­
term preservation practice, including an emphatic call to prohibit the use of
all chemical cleaning solutions until adequate research is completed. Swan's
worh directly influenced the construction of archival binding paclzages for
daguerreotype plates.

The daguerreotype process was the first widely used method for making p ho­
tographic i mages, extens ively practiced from the 184o's thro ugh the early
1 86o's. Many art and h istorical i nstitutions have i mportan t holdings in this
med i u m , and, with the presently i ncreasi ng interest i n photography, conser­
vators m ay ex'Pect to see daguerreotypes i n need of evaluation and treatment
more frequently.
There i s not space e no ugh here to describe the h i story of the process
and i ts use, which have been admirably presented in such books as L . ] . M .

AucE SWAN, "The Preservation o f Daguerreot)1Jes ," The A merican Institute for Conserva­
tion of 1-/istoric and Artistic \"1orhs: Preprints of papers presented at the n i n t h annual ·meet.­
ing, Philadelphia, Pennsylva nia, 27-3 1 May 1981 (vVa s h ingto n , DC: American I n stitute for
Conservation, 1 9 8 1 ) , 1 64-72. Text and i m ages reprinted by permission o f the American
I nstitute for Conservation of H istoric a n d Artistic Works. W\·Vw.conservation-us .org

249
Part III S l L V E B , M E B C U B Y , t\ N D G O L D

Daguerre by 1-1 . and A. Gernsheim 1 and The Daguerreotype in A rn.erica by

Beaumont Newhall, 2 or to fu lly explain the complex series of operations fol­
lowed by the early p hotographers i n producing dague rreotype i mages, which
has been described at length in a previous paper. 1 Rather, I would l i ke to
c haracterize brieAy the p hys ical structure and compos ition of daguerreo­
types in good condition, and then to describe more fully the appearance
and compos i tion of some commonly occurring deterioration processes and
to d iscuss my experiences i n their treatment. The description of composi­
tion and morphology which fol lows is based on a n electron m icroprobe X-ray
analysis of bot h well preserved and deteriorated daguerreotypes , clone at the
National B u reau of Standards i n Gaithersburg, Maryland, i n col laborat ion
with C.E. Fiori and K.F.J . Heinrich. The previously referenced paper pro­
vides ful l tec h nical detai l s of this analysis; here, I wo ul d l i ke to make use of
the resu lts of the analysis.

Properties of Wel l-Preserved Daguerreotypes

Daguerreotype i mages were prod uced on s ilver coated copper plates by fu m­

i ng the carefu l l y polished si lver su rface with iodine (and other ha loge n )
vapors, form ing a light sensitive si lver iodide ( o r m ixed ha li de) surface layer.
The i mage was then augmented to visible size by placing the plate in a box of
warm mercury vapor. The mercury vapor condensed preferentially at those
s ites on the plate which had bee n struck by light, form ing a visible image of
t i ny droplets of merc u ry which began to a malgamate with the silver available
at the site. Then the remai ni ng si lver iodide was d issolved from the plate
with sod i u m thiosulfate (present clay "fixer"), and the i mage was treated wi t h
a h eated gold solu t i o n w h i c h sol i d i fied t h e l i q u id s i lver-mercu ry droplets,
thereby "affixi ng" them to the plate, i ncreasing the con trast range of the
i mage and add i n g warmth to the color of the i mage.
I n our sample, the t h ickness of plates varied from 0.38 to 0-44 m m ,
a n d t h e thickness of t h e s i lve r layer (which woul d have been m u c h mocli ­
f1ecl from i t s manufactured state b y the p hotographer's pol ish i ng process),
measured from cross-sectioned samples, ranged from 2 . 3 pm to 8.5 p m , with
m uch variat ion i n a s ingle plate. Analyzed i n c ross-section, the copper layer
contai ned many small copper oxide incl usions, and the silver layer contai ned
about 0.02 (weight fraction) of copper. A very t h i n gold-contain i ng layer was
present at the i mage beari ng su rface, exte nd i ng in about 0.75 p m . Gold was
also present in the protru d i n g particles formi n g the i mage. These part icles
were composed of s ilver, mercury and gol d , and mercury was found only
wi thin particles.
Exami ned norm a l to the beam, the i mage su rface showed remarkably
smooth, u n i form polishing of the su bstrate, wi th discrete particles protrucl-
 Reading 29 S \V A N

ing from the substrate, usually varying i n size from about 2 . 5 µ m i n diam­
eter to i mmeasurably smal l . Large, widely spaced particles were present in
shadow areas, while great quantities of very small, closely spaced particles
were presen t i n highlight areas. Analysis aga i n showed the substrate to be
composed predomi nantly of si lver with srnaII quantities of gold and copper,
and the particles to be predominantly silver with varying amounts of mercury
and small amounts of go ld and copper.
The particles form i ng the i mage and the u n i form parallel polishing of
the silver s urface can be easily seen in a low power stereo microscope; a
metallographic microscope with magnification of 300 diameters or more wi l l
reveal s ome of the fine morphology of the larger particles.
The visible image is the resu l t of the difference i n l ight scattering prop­
erties between the smooth su rface of s hadow areas with their in frequent
particles, and the pebbly su rface of h ighlight areas with t heir myriad, tiny,
closely spaced particles. The depth of shadows ( the maxi m u m "black") is
contro l led by the smoothness of the polishing of the si lver su rface, while
the bri l l ia nce of the h ighl ights (the maximu m "white") depends o n the size
and spacin g of the particles. M axim iz i ng the con trast range became a major
aesthetic desideratu m for daguerreotypists; many of the fine points of the
process were designed to prod uce either a smoother plate surface for deeper
s hadows, or h ighlight particles of precisely the correct size and spacing to
give "pearly" whites. This aesthetic i deal carries i mplications for treatment
since many types of damage, and clean ing processes ge neral ly, tend to affect
the smooth ness of the plate, and, to a l esser extent, the bri l l iance of h ighl ight
a reas. Very s m a l l changes in e i t her cause large visual di fferences. For this
reason the c leaning problem is very m u ch more comp lex than simply fi n d i ng
the cleaning method and formu lation which takes away the least silver while
re movi ng corrosion products; one must also examine the final s moothness of
the cleaned p late. Obviously clea n i ng methods which deposit silver or form a
byproduct residue on the su rface, or which reduce corroded silver in situ are
inherently inappropriate.
Many daguerreotypes were colored, usually m i n i mally (cheeks and l ips
s l ightly pink) but someti mes they were tinted very elaborately; in either case
fi nely gro u n d pigments were applied in a dry state to the fin ished plate. To
aid adhesion, either the pigme n ts were ground i n d i l ute gu m a rabic, dried
and reground before use; or the plate was washed with a d i l u te gu m arabic
sol ution and dried before the colors were applied . Small touches of pow­
dered gold in gum a rabic solution were frequently applied wet to a sitter's
ri ngs and jewelry. \;\fith a l ight microscope at magnifications of 1 0 0 diame­
ters, pigment particles can usually be seen lying on a colored surface, though
h igher magnification s are req u i red to see very small amou nts. Since it is
predo m i nantly static forces which hold the p igment particles in position, wet

251
P a rt III S I LV E B , M E R C U R Y , A N D G O L D

treatments, particularly chemical cleaning with its vigorous su rface reac­

tion s , cannot be used for daguerreotypes with coloring of any i mportance.
This constra i n t req u i res that colored plates be supp lied particu larly good
housings, edge seals and storage environments (drier, cleaner and cooler) to
reduce the need for cleani ng. It is also i mportant that l ight eJqJosure for col­
ored daguerreotypes be m i n imized since fugitive pigments were commonly
used; j u dging by the frequency of recom me ndation in the l i terature, carmine
was by far the most commonly used red p igments, and indigo was sometimes
recommended as well . 4

Deteriorated Daguerreotype Su rfaces

O u r sample of plates was selected to contain m u l tiple examples of t he types

of deterioration I had encountered most frequently in the daguerreotype col­
l ection at the Eastman H o u se i n Rochester, New York. Flawed areas were
ident ified and characterized in the light m icroscope, and then exam ined and
analyzed in the electron probe. M a ny types of deterioration could not be
in cluded in the stu dy; our i nstru mentation, for i n stance, wh ile ideally suited
to the analysis of tiny areas of metal l ic corrosion products i n situ, is insen­
sitive to organic materials-the energy dispersive X-ray detector we used,
for example, could not detect elements below sod i u m on the periodic table.
Organic materials are c learly present on dagu erreotypes and may play an
i mportant role in deterioration processes a nd cleaning problems.

1. Smooth Tarnish Film,s S howing hite1ference Colors

This is by far the most common sort of deterioratio n . It is formed by exposure

to air, and therefore occurs at the very edges of p lates, at the i n terior edge
of the metal or paper window mats wit h which plates a re encased, below
cracks in a broken cover glass, adjacent to broken or loose edges of a case or
sea l i ng tape, and along edges where the plate or metal window mat is bent,
forming an air space. \!Vherever accessibility to air is increased over a period
of time, tarn ish is i ncreased . This tarnish is typified by the series of interfer­
ence colors it forms: the fi rst, most brilliant series of colors (with i ncreasing
thickness, from pale yellow to ora nge, magenta and deep blue) occ urs where
the layer is t h i n nest; a second order series, i n dicat i n g i ncreased t h ickness,
is commonly seen a lso, consisting of pastel shades of the same color series;
t hi rd order series, still paler, are less common, and if the t hickness is still
greater, the tarnish fil m appears pale neu tral gray and finally b lack (the color
of b u l k silver s u l fide) .
T h e existence o f well defined color series ind icates tarnish layers that
have formed slowly with very l im ited access to air, and such series are m ost
 Reading 29 S VV A N

frequently seen on cased p lates. \Ni t h the exception of i nstances where

damaged materials were included i n side the case, the smaller the air space
between i mage su rface and glass and the better the seal at the edge, the nar­
rower and fewer the color bands at the edges. P lates stored without cover
glasses and cases usually exhi b i t thicker tarni s h films with uneven , mottled
colors over the whole p l ate, combined with much loose d i rt, fi ngerprints,
scratches and other physical damages. The difference in the amount and
severity of tarnish between cased and u ncased p lates is dramatic and con­
s istent, and demonstrates the effectiveness and value of m a i n ta in i ng and
replacing well sealed cases as a primary treatment for daguerreotypes.
Analysis of these brightly colored tarnish films consistently s howed
them to be composed of s ilver and sulfur, present as silver sulfide. Exa m i na­
tion of the morphology of these tarnish fi l ms by secondary electron i maging
shows them to be so s mooth and structureless as to be i ndistingu ishable
from u n tarnished areas. Thicker gray layers s how the begin n i ngs of an
u neven, grai n y struc ture.
Thin, brightly colored tarnish layers are very successfu l ly removed by
thiou rea c leaning solutions, but tarnish layers that have formed extensively
enough to require treatment are usually present a long with other types of
deterioration which are not so successfu l ly treated. Addi tionally, at this t ime,
when t here are few conservation treatment records in existence for photo­
graphs, i nterference color series around the edges of a mat carry i nvaluable
i nformation: that a plate belongs with a particular mat (the edges matc h ) and
has been stored with i t for a long t i me u nder particular conditions, and that
the plate has not been cleaned rece ntly, or has never been c leaned. There is
not enough space here to delve i n to t he u nsolved p roblems of cleaning solu­
tions.' References to thiou rea cleaning solutions throughout this paper wi ll
i ndicate the h istorically "standard" formulation, contai ning 70 g thiourea,
So cc p hosphoric acid per l i ter of solution, with which there h as been the
largest cumulative eiqJerience. I would l i ke to state emphatically that this
and a l l other chemical cleaning solutions for daguerreotypes must currently
be considered e,\1Jeri mental, and except for u nusual c i rcumstances their
use should be delayed until adeq uate research h as been completed on their
formula tion and long-term effects. My own u navoidable response to plates
which s how no sign of tarni sh along i nterior mat edges is one of worry, not
u n l i ke the worry a paper conservator feels when confronted with an older
print or drawin g o n a heavily b leached s upport-worry that the treatment
was naively designed and the object's useful l i fe shortened. O n the other
hand, t here may be some circumstances in whi ch c lean i ng i s advisable; for
i nstance, a plate with lines of h eavy tarnish t h rough the central i mage a rea
from a cracked glass, where there is some danger that the even removal of
tarnish might become more difficult i n time.

2 53
Part III S I L VE H • �I E H C L' R \' , ,\ N D G 0 L D

Thi cker gray to b lack t a rn i s h layers are not removed very successfu lly
by t h i o u rea s o l u t ions; t h e smoot h ness o f shadow a reas i s usually lost wher­
ever the t h icker tarn i s h was located-typica l ly a heavy, " w h i te" border i s
for111ed aro u n d the 111at edge.

2. f-1 ighly Crystalline Blach Spot:s and Pa rt icles

These are fou n d very frequent ly, a n d o u r a n a l yses of 111any such spots
showed t h e 111 to be co111posed of s i lver and su l fu r, aga i n present as s i lve r s u l ­
Rde. T h e s pots are seen as c i rc u la r crystal for111at io n s w i t h i n c reas i ng c rys­
tal s ize towards the center, and they are s u rro u nded by concentric ri ngs of
brightly colored tarn i s h film. Larger ones, u s u a l l y about 0.5 111111 d iameter,
show spectac u lar crystal forms but occu r i n freq uently; s m a l l e r ones are very
com111o n . S u c h s 111all spots are so111eti 111es fou n d evenly d i stri buted over a n
e n t i re p l a t e w h i c h otherwise appears to b e i n good cond i t i o n . Eve n ly d istrib­
uted spots a re probably t h e res u l t of res i d ues fro111 t h e ori g i n a l process i n g o f
the plate: daguerreotypists were w a rn e d , for i n stance, to R i t e r t h e i r t h i o s u l ­
fate sol u ti o n s before u s e , or spots w o u l d for111. One w o u l d expect a part i c l e
deposi ted fro111 a t h i os u l fate b a t h to b e capa b l e o f formi n g s i lver su lRde on
a s i lver su rface. On moderately to severely t a rn i s hed plates, col lections of
bl ack, needle-shaped crystals are frequently seen lyi ng al ong scra tch l i nes
and other su rface i rregu l ar it i es, as we l l as along t a rn i sh boundaries. These
s i lver su l R de c rysta l s , lying a t nat u ral reaction s i tes a m i d heavy t a rn i s h , have
p robably for111ed in place b y recrysta l l i za t i on of t a rn i s h Rims, in con trast to
the sma l l , eve n l y d i s tr i b u ted spots where the t a rn i s h film p robably formed
fro111 a crysta l l i ne deposi t .
C rysta l l i ne s i lver s ulRde tarnish prod ucts d o not appear t o be success­
fu l l y removed by any clea n i ng met hod . Short baths of t h i o u rea sol u t i o n ,
so s uccessful i n re111ovi n g t h i n R l 111 s, l eave m u c h o f t h e crysta l l i ne 111ate­
rial beh i n d , and l have observed ri ngs of t h i n R i m t a rn i s h to slowly reform
around the res i d u a l parti c les. S i 111 i l a r to t h e i r effect on heavy, se111 i -crysta l l i ne
black t a rn i s h R i ms, long treat m e n ts i n c l ea n i ng solutions eve n t u a l ly d i ssolve
smaller crystal stru c t u res, b u t s m a l l p i t s and su rface i rregu lari t i es are l e ft
behind where t h e part i c l es were located, scattering l ight and p rod u c i ng non­
i mage " w h i te" areas. Long baths a l so appear to s p o i l the smooth ness o f the
s u rface o f t h e plate genera l ly, e i t her by prod u c i ng a su rface depo s i t or by
a ttacking t h e plate.

3. Accretions of G reen a nd Blue Salls

These are very common, occu rri ng where the t h i n s i lver l ayer has been p u nc­
t u red, exposi n g the u n derly i ng copper su pport . These accretions are u s u a l l y
 Reading 29 S \V A N

thick and may project from the plate considerably. They commonly occur
a l o n g the rou gh edges of the metal mats, but ar e frequently seen i n i nte­
rior portions of i mages as wel l . For i n stance, green accretions are frequently
found i n combination with glass s hards, where splinters from a broken cover
glass have punctured the s urface. S u ch accretions are indicators of surface
damage. Analysis of these salts always yielded copper peaks, sometimes
alone (e.g., basic copper carbonates), but frequently also i n combination
with sod i u m , potassium, calci u m and s ul fu r. These salts a re dissolved by
d i l u te acids and by thiou rea clea n i ng solutions; and, when removed, a small
copper colored pit i s frequently visible underneath. Spots reform readily
at such s ites.

4. Spots of Clear, Golden. Crystals

These are commonly fou n d with the t h icker, green and blue accretions, b u t
also occur alone. They frequently form along "tide l ines" a s though associ ­
ated w i t h l iq u i d drips. T h i s category i s a visual rather t h a n a structural o r
compos itional grouping; i t i n clu des several types of material w i t h a s i m ilar
appearance in the light m icroscope, which also occur together, but which
have dissimilar forms in secondary electron i m ages . Copper was always p res­
ent in these spots, along with widely varying amounts of sod i u m , potassium,
s u l fur and calcium. Some of these spots may be early stages of the blue and
green accretions; they are usually not soluble in water, but dissolve i n d i l u te
acids. They can perhaps be best thought of as combinations of copper corro­
sion with glass decomposition p roducts .

5. Thi n Orange and Iridescent Films

These orange spots typical ly occ u r i n ring forms, frequently with a small
c rack or other surface flaw at the center. They are frequently seen on plates
otherwise in good condition, and they are typical ly l a rge, brightly colored and
disfiguri ng. These spots occ u r in c i rcular and u neven forms as well as rings.
S u rface morphology appears to i n fl u ence their s hape as well as the shapes of
other types of spots-their edges frequently lie along slightly deeper polish­
i ng "furrows . " Circular and ring forms are characteristic of many types of
spots on daguerreotypes and imply a central source of one of the materia l s
of t h e product as well as its l i m ited mobil i ty-the m i n i ma l air movements
i ns ide the case, for instance, would seem to contribu te to ring or circ ul a r
forms.
Analysis of such fil m s showed i ncreased amou n ts of copper al ong
with the normal distri b ution of elements. The fil m i s extremely thin and no
morphology can u s u a l ly b e seen i n secondary electron i m ages . Th e color of
P a rt III S I L V E H , M E H C U R Y , A N D G O L D

these fi l m s disti nguishes them from si lver su lfide films: they do not show
interference color series with th ickness variation, b ut rather range from pale
to mediu m orange and then towards i ridescent p i n k as th ickness increases.
These pastel orange fi l m s are eas i ly removed in thiourea baths; water baths
and dilute acid baths do not disso lve them. They seem to reform gu ickly and
eas i ly after cleaning, and are the type of spot that typically reforms at s ites
where green salt accretions were present before cleaning.

6. Particles of Polishing Materials Embeclclecl in the Swface

One of the m ost surprising results of our analytic project was the n um ber of
plates which s howed wide distribution of small particles composed of sili­
con, carbon, or s i licon with aluminum, deeply em bedded i n the polished
su rface. The i r placement i n relation to polish i n g marks and their composi­
tion, accou nted for by commonly used daguerreotype pol i sh i ng compounds,
identifies them as particles of pol ishing m aterials. They were freguently
found associated with orange fil m rings and also with cavities i n the polished
su rface. They were also frequently found with no associated corrosion prod­
ucts. These particles are extremely difficult to see in a light m icroscope, and
the extent of their presence was unexpected: they were observed by second­
ary electron i maging on one t h i rd of the p lates in the sample.

7. Losses of the Image Swface

Exa m i nation of the su rfaces of sample plates by secondary electron i mag­

ing showed an alarm i n g n u mber of cavities i n the su rface which were not
deep enough to extend to the copper layer. Some were extremely small and
randomly located, with soft, rounded edges ( i n contrast to cavities caused
by po l ish ing particles); j udging by their size and p lacement, some appeared
to be sites where i mage particles had detached and separated-and, i ndeed,
i mage particles were observed partially u n dercut by such cavi ties. These cav­
ities were present on both corroded and uncorroded plates, though the l arg­
est and most severe were fou nd on bad ly corroded p lates. Cleaning appeared
to enlarge them somewhat. They cou ld not be seen in a metallograph ic
m icroscope at 500X magn ification. Their p resence indicates a considerable
fragil ity to the i mage su rface beyond the well known softness and vulner­
abil ity to abrasion; gentle treatment of plates i n l iguid baths, for i nstance, i s
essential if u ndercut i mage particles are not t o b e removed .
Another type of su rface loss which i s not i n freguent is a cracking and
peeling of the image surface. It usually occ urs at the edges of a p late , but
may also be fou nd in the interior. It typically occurs i n shadow areas; h igh­
l ight areas are affected o n ly i f the whole i mage exfolia tes. Without m agn i fi -
 Reading 29 S W A N

cation, separati ng fragments catch l ight and resemble pi npricks or scratches;

u nder m agn i fication, a thin surface foi l can be seen projecting up or folded
back, revea l i ng an even, pebbly silver su rface beneath, without polishing
marks and without i mage particles. The daguerreotype manuals explained
this as the result of excessive treatment with gol d . I n our preparation of
cross-sections we notice a strong tendency of the i mage su rface to separate
From the plate at approxi mately the depth containing gold. B u t many other
factors, polishing for i nstance, could also have contri buted. Once begu n,
exfol iation is worsened by wet treatment. Temperature changes should be
particularly avo ided for such plates.

Figure 1
Secondary electron m i c rograph
of particles of polishing compound
embedded in the surface
of a daguerreotype. The cavity
at the center was caused by the
loss of such a particle. This
area Formed t h e center of an
orange colored spot. The light
colored particles on the s u rface
are silver-mercury-gold amalgam
particles forming t h e image.

Figure 2
Secondary electron m icrograph of
cavities in the su rface of a cleaned
daguerreotype, in a shadow area.
The Flat structure in the foreground
is a large image particle. Note t h e
slight. d i agonal polishing marks.
Part III S I L V E H , M E H C U H Y , A i'/ D G O L D

8. Glass Deteriorat:ion

Cased p lates that have been stored at h igh or fluctuat i ng h u m iditi es al most
a lways show evidence of glass deteriorati o n . \!\/hen exa m ined in a h igh
hu mid ity environment, small droplets of clear liquid are visible on the i nterior
surface of the cover glass (weeping glass) and, frequently, smaller droplets
are visible on the p late su rface itself. Examined at low h u m idities, such glass
deterioration products are seen as groups of c lear, feathery or needle-shaped
crystals contai ned in a vaguely c i rcular outli ne. These crystalline forms
become Far more visible when examined in a polarizi ng microscope . We ana­
lyzed samples of cover glasses sho'-'lring such deterioration and found that
while the clear areas of glass contained silicon predom i na ntly, with smaller
amou n ts of sod i u m , al um inum , ch lorine, potassi u m , calc i u m and lead; the
surface deposits were predomi nantly sodi um (or potassi u m, depending on
the type of glass) , with smaller amounts of al u m i n u m , si l icon, chlorine, and
sometimes lead . These depos its a re extremely hygroscopic and qu ite alka l i ne:
measured u nder a microscope with s ma l l tufts of pH indicating papers laid
against the deposits while they were hu midified by i nverti n g the cover glass
over a beaker of water, such deposits typically showed pH values of 9 to 10.
S i m i lar crystal forms or small d roplets are frequently seen on plate s u r­
faces as wel l ; i n our sample these clear, small c rystal l ite forms were com posed
of sod i u m or potas s i u m with smaller amounts of s u l fur, lead and calci u m .
O ther types o f spots have been described above i n which sod i u m , potassi u m
o r cal c i u m were significant elements, a n d the cover glass i s the n earest major
source of these elements. Such deposits are extremely water soluble and easy
to remove ; however, they appear to be i mplicated in some of the more serious
types of deterioration, particu larly t hose i nvolving copper. C learly, a concen­
trated electro lyte solution, such as these salts form under h um i d conditions,
would activate copper corrosion wherever copper was exposed.
Whenever plates are rebo und, the glasses should be careful ly washed
and the plate su rface shou ld be thoroughly exa m i ned for the presence of
clear crystal l i te deposits. U ncolored plates should be gently washed in di s­
ti lled water i f such deposits are fou n d . M ost i mporta nt of a l l , daguerreotypes
m u st be stored in a dry environment at even temperatures, such that con­
densation of moisture o n the glass, the cond ition that causes glass deterio­
ration , will be prevented. Such a storage environment becomes even more
essential for colored daguerreotypes, which cannot be washed.

9. Mold G rowths

So many plates exh ibit mold colonies on their su rfaces that this type of dete­
rioration is probably second only to s ilver s u l fide ta rn i s h i n freque ncy of
 Reading 29 S \V A N

occu rrence. These growths a rc frequently very visible and d i sfiguri ng, and
they are practically u nremovable: water baths, solvent baths, t h iourca baths
and even physical treatment are u nsu ccessful in removing them. I n deed,
thiourea baths often render them more obvious, s u rround i ng them with
otherwise clean su rfaces. These growths are frequently found in association
with local variations in tarnishing, si lver sul fide crystal formation and cop­
per spots. They imply the presence of moistu re i n side the case and a film of
organic materia l on the plate.

Recommendations for Storage

All daguerreotypes need to be sca led within protective glassed cases that
m i n i mize exposure to air. The storage enviro n ment must maintain an even
temperature to prevent moisture condensation on p lates and glasses, and
tempera tu re inside the case must be a consideration i n i l l u m i nating plates on
d i splay. The relative h um id i ty should be low-the rate of most corrosion pro­
cesses is greatly increased in the presence of moisture. As with most photo­
graphic materials, maintenance of low, even h um i dities is probably the single
most i mportant factor i n preservation. For storage of very i mportant plates,
beautifu l ly colored plates or badly damaged plates, a desiccator cabi net might
be considered. Desiccation is, of cou rse, damaging to wood and leather cases,
and embrittles paper seal ing tapes; to some extent one simply has to choose
which constituent takes priority-here that is not very difficult. Perhaps a
reasonable compromise for the bulk of daguerreotype collections is an envi­
ronment of 30-40% R H . As for all photographic materials, fi ltering air for
removal of su l fu r gases and oxidants is i mportant. Even though they are the
very oldest photographs, where they have been kept in wel l sealed cases in d ry
environ ments, daguerreot)1Jes have retained their original contrast range and
pristine quality far better than any other variety of p hotographic i mage.

References

H. and f\ . Cernsheim. L . J . M. Dag11erre. tl1e Hist.DI)' Of t l1e /Jiora111a r11nl tlie

Dag11erreotype, 2nd ed., Dover, New York, 1 968.
2 B. N e w hall , Tlze Dc1guerreotype i11 A 111erica1 3 rd e d . , Dover, New York, 1 975.
3 A. Swa n , C . E . Fiori, I<. F. J. H e inri c h , " Daguerreot)1>es: a St udy of the Plates
and t h e Process," Sca1111i11g £/ectro11 Microscopy, Vol . I . pp. 4 1 1-42 3 . 1 9 79 .
4 A. Swan, ·· coloriage d e s E p reuvcs: French 1\ l ethods a n d 1\ l aterials f'or
Colori ng Daguerreotypes," to be p u b l ished as a chapter i n Janel E. Bu erge r,
French Daguerreotypes. awa i t i ng publ ication by Dover.
For a description oF t h e p rob l e m s sec: A. Swa n , "Conservat ion Treatments for
Photographs," Image 2 1 ( 2 ) , pp. 24-3 1 , 1 978 . For a comparison of t he actions of
several Fo rm u l a t i o n s sec: s. Hempel, " Hcccnt l n v e st i gatio n s Oil t h e C lea n i n g or
Daguerreotypes," A . l.C. Preprints, pp. 99- 1 05, 1 980.
 R e a d i n g 30

M o G E N S S . K o c 1-1 A N D A N K E R S J 0 G R E N

Treatment of Daguerreotypes
U sing Hydrogen Plasma ( 1 984)

JV /ogens I<och, a photograph consen1ator ancl photographer, teaches conserva­

Uon of photograpl1s at the School of Conservation of the Royal Dan ish Acacle111y
of Pine A rts in Copenhagen. 1- le is /mown for h is research in the exc 11n inat ion
and restora t:ion of water-dmnaged photographs. The following excerpt fro11i a
1 984 article by I<och and An.lzer Sjogren doc u.m.ents the conservat:ion t reat men.t
of daguerreotypes (and to a lesser exten.t, ferrot.ypes) ming hydrogen plas111.a.
Th.e effe ct of hydrogen plasma reduct ion. on. tarnished daguerreotype 71/ates
was an.aly=ed using scanning elect ron. 111icroscopy. The results were pro /1 1. isi n.g
(especially for h.ancl-colored plates) b11t t he co1n11lex cleaning apparat.11s t h.at
was req 11ired, the i n.abil i ty to visually 111onitor t reatment progress, an.cl t he for-
11wtio11 of a whit ish ha=e in areas of clarh famish pre11en.ted t h is techn. iq·ue fro111
beco111i11g widespread.

Hyd roge n Plasma

Red uction with hydrogen plasma is a process i nvo lving ion implacement,
chemical reaction/red uction and physical sputter cleani ng. O n account ol'
the low mass of the hydrogen ions, physical sputter clean i ng is, however,
ment ioned only in the i nterest of comple teness.
Ord i nary molecular hydrogen (t he den ned o-point i n the electrochemi­
cal series of metals) can reduce si lver out of a corrosion product (e.g. Ag2 S ) ,
but si nce t he d i ffe re nce i n pote ntial between Ag a n d 1-1 2 i s sma l l , reaction

Fro111 i\l l ocENS S . l<oc 1 1 and f\Nl(EH SJ0GHEN. " llchand l u ng von Daguerreotypien 111 it V\las­
scrstollplas111a," 1\ laltecl1 11ih -f-Rcstauro 90 ( October 1 984): 58-64 (60--64 excerpted here).
 Reading 30 l< O C l-1 A N D S J 0 G H E N

Figure 1
Plasma apparatus. Experimental
prototype. The vacuum bell
i s 30 c m i n diameter.

Figure 2
Plasma reduction mounting with
the daguerreotype forming one
electrode. The AC system prevents
any kin d of spotting (V. Daniels).

time is i nordinately long. i:� edu ci ng the treatment ti me to a reasonable le ngth

(4 to 5 days) by raising the temperature to 300-400°C was successful .
Atomic hydrogen is h ighly electropositive a n d is a very strong reduc i ng
agent (electron-donor) , able at ordinary room temperature to reduce meta l l i c
s i lver out o f silver su lfi de s o rapidly t h a t a fin e res u l t may b e obtained from a
tarnished daguerreotype in 5-1 5 m i n . , depend i ng on the degree of corrosion.
Atomic hydrogen can be produced i n a n um ber of ways (e.g. by ordi­
nary dissociation of water) . H ere i t i s formed in a so-called glow discharge
(plasma), [that is,] a h igh vol tage electric discharge between two electrodes
in a gas (here hydrogen) at low pressure.
Jf the voltage i s h igh enough, the electrons in t he discharge will be so
charged with energy as to break down the molecu l ar hydrogen into hydrogen
atoms and ions.
The hydrogen ions can, among other t h ings, knock new electrons From
the cathode. The discharge, and thus the atomic prod uct, can i n this way be
mai ntai ned permanently.

Apparatus [ Figures I , 2, 3 ]

The parameters for a treatment are typically: Gas: hydrogen; pressu re:
0.2 m B ; Fl ow: 1 8 m L/m i n . ; applied voltage: 1 000 V; current: 5 mA; h ighest
tem peratu res meas u red : 30-35° C.

Results

The metallic silver reduced out by the treatment with hydrogen plasma is
redeposited on the surface while acid-treatment and treatment with chelat-
 Part III S I L V E H , M E H C U H Y , A N D G O L D

Figure 3
A reduction in p rogress. The lighl
in l he glow discharge is c m illed by
impacted hydrogen products.

Figure 4
S u lfide-tarnished dagucrn:olype
with two pieces removed for
S E M/Edax testing.

i ng agents remove the s i lver of the tarnish (except meta l l ic si lver from the
s u rface ) . Plasma red uction replaces the si lver ( re-forms the i mage-making
aggregations) and does not, by its nature , a ffect metallic si lver. Thi s has
been demonstrated with a s i mple gravimetric analysis.
That t he i mage-forming aggregations/grains are not ion-eroded (sput­
tered ), and do not change their structure or composition i n hydrogen plasma
treatment will be demonstrated in the fol lowing:
In Figu re 4 , two test pieces have been cut from a dague rreotype with
edge-tarnishing and treated i n hydrogen plasma ( 1 5 m i n . ) .
Before a n d after treatment, t he test pieces were examined i n an electron
m icroscope ( P h il ips 505 S E M with Edax X-ray mic roprobe) ( Figures 5, 6 ) .

Materia l Analysis

An analysis of the su rface compos ition performed with Edax, using a 1 525 kV
bea m, gave the foll owi ng res ult (weight % of the di scharged amount) :

Hg 6.68
s .49
o

Cl 0.26
Ag 92.58

(Gold was not fou nd.)

The va l u es given here are means of a series of meas u rements (which

gave largely t h e same resu l t ) applied both inside and outside t he grai n aggre­
gat ions and both before and after treatment.
 Reading 30 K O C H A N D SJ 0 G R E N

.� �
.

"'·

- ..:::_ - . I" ,
i 1 0 um 2 5 0 k U 9 4 u � 5 2 65 / 0 1 2 GRAA

5a

Figure 5
Exactly the same grai n aggregation
scanned before and after treatment
wi t h hydrogen plasma. Note the
i m age enhancement i n ;b.
;c ;cl

Figure 6
Better example of the i m age­
cnhancing effect (metallic si lver
reduced from s ilver compounds).

Full Treatment Procedure

The full treatment of a s u l fide-tarnished daguerreotype is as follows:

1. The surface is cleaned of grease by being i m mersed i n a m ixture of

aceton e , xylene, and alcohol ( 1 : 1 : 1 ) .
2. \Nater-sol u ble su bstances are removed in distilled water contain i n g
a l i ttle alcohol a n d detergen t .
3. T he degreasing b at h is repeated .
4. The object is treated i n hydrogen plasma for 5- 1 5 m i n .
P a rt I I I S I L V E 11 , �I E 11 C U R Y . 1\ N D G 0 L D

5. The plate is spray-varnished with I ncra l a k (acryl ic d issolved 1 11

organic med i u m ) contai ning 1 % benzot riazole ( i n h ibitor) .

Du ring the e n t i re t reatment proced ure, the i 111age surface is not touched
with so 111uch as the llnest soft-bristle brush!

Su pplementary Remarks

The low ngu re for su lfur should not be taken too l itera l ly: the largest H g
line coi ncides w i t h the S l i n e . The graphic display of t h e Edax X-ray a nalysis
shows that the su lfu r content 111 ust be sl ightly h igher and the 111ercury con­
tent sl ightly lower.
The daguerreotype t reated and invest igated [ here] was one 111ade on
a si lvered copper plate. The h igh 111ercury content shows that the si lver has
not been deposited using a ga lvanic process or pressed on, but appl ied as an
a111alga111 . The presence of ch lori ne shows that not o n ly iodine was used to
sensitize the si lver: i t was q u ickly d iscovered that ha logenation with chlorine
and bro111 ine gave h igher sensi tivity to l ight-faster "ll lms." The faster speed
produced less stiff-looking and artillcial pictures.
The SEM exposures show clearly that the treat111ent of sul nde­
tarnished daguerreotypes with hydrogen plasma is an extre111ely gent le treat­
ment that preserves the s ilver and moreover gives some i mage enhance111ent.
A 6,ooo-times en largement is a long way fro111 a visual appraisal with the
naked eye, but there can be no doubt that some changes occ ur i n the i 111age­
for111 ing grains (at the m icro-leve l ) . This transposition of si lver n la ments and
grains, si lver s u l llcle, and red uced si lver ll laments and grains will natura lly be
more pronou nced if the su rface has been heavi ly attacked before t reatment
is attem pted.

[ Fe rrotypes]

Du ring the writing of the present paper, we t u rned our atten tion to the t reat-
111ent of ferrotypes, which "superseded" the daguerreotype. Because t hey
were 111 uch faster and far cheaper to produce, everyone could afford the111,
and they therefore contain a great deal of general culture/h istorical i n forma­
tion. U n fortu nately the i ron plate to which the picture is "attached" rusts,
and the expa n d i ng corrosion exfol iates the picture. The i n itial a ttempts to
red uce rust to i ron-and remove the a n ions fro111 the corrosion with hydro­
gen plasma-were delln i tely negative: the collodiu111 e111 u lsion yel l ows
strongly in the UV-ra diation fro111 the pl as111a.
A d i fferent tech n ique will have to be found.
 Reading 30 K 0 C 11 A N IJ S J (1) c; B E N

Conclusion

If a daguerreotype is to be optimally preserved, i t is recommended that in the

fu ture it be "c leansed" of s u l fide tarn i s hi ng with hydrogen plasma.
\,\/ith respect to the problem of m i cro-transposition of the i mage­
forming gra i ns, it is also recommended that lesser tarni shing be cleaned
before it becomes too strong, and that the s u rface be stabilized with varnish
and i n h i bitor.
More work is needed before the p roblem of ru sted fe rrotypes can be
so lved.

Acknowledgments

Last , we wou ld l ike to express special thanks to the following people: Lab­
oratory tec h n i cian I nger S0ndergard and Dr. C. VII . Langer, I nsti tutet for
Metallcere, Danmarks Tekniske H 0jskole, for help with the S E M exposures
and Edax a nalysis;
Lars Vester Jacobsen , Chief Conservator of the M u seum Den Camie
By i n Aarh us, for the loan of test materi al ;
T he Department of Modern Artifacts at the National Museu m of Den­
mark, for granting the time to u ndertake the i nvestigation;
H. P. Pedersen, D i rector, Konservatorskolen, for his support of the
project.

References

S11sa11 Barger: 'The cleaning or daguerreotypes: Physical spu ller clea n i ng, a new
technique." The American I nstitute f'or Conservation or H istoric and Art istic
'Norks. Preprints oF papers presented at the Tenth Annual Meeti ng, M i lwaukee,
v\lisconsin, 26-30 May 1 982
Susa11 /3arger: "The clea n i ng or daguerreotypes: Comparison or cleaning methods." Jounw/
ofA111erica11 lnstitutefor Conservat.ion, Vol. 22, no. 1 , Fall 1 982
\!. Daniels: " Plasma reduction oF s i lver tarnish on daguerreotypes." St udies i11
Co11se111atio11, 26 ( 1 98 1 ) , 45-49
Anher Sj0gre11: "Et plasma-apparatur [ Plasma apparatus ] . " Det Kongelige Danske
Kunstakademi, Konservatorskolen 1 980
Anlter Sjr�gre11: " l on-implantering og plasmareduktion [ Ion i m p lantation and plasma
red uction ] ." Del Kongelige Danske Kunstakade m i , Konservatorskolcn 1 982
Moge11s S. J<och: "FOTOG HAFI EN- Teeh n i k, ZerFal l u n d Konservierung" f Photographs­
Tech niquc, Deteriora t ion and Conservation ] . 5 . l nternat ionaler C raph ischer
Hestau ratorentag. Den Haag, 1 2- 1 6 September 1 983
 R e a d n g 3 1

G RANT B . ROMER

Guidelines for the Administration

and C are of Daguerreotype
C ollections ( 1 989)

G rant Romer (see also Readings 1 4 and 69) is a n expert i n the history and
practice of the daguermot)'J?e and c u rated the exhibition "Young America: 'Die
Daguerreotypes of Southwort h & /-!awes " ( 2005hoo6, niu ltiple venues in New
Yorlz and Massacliusett;s). In h is "G uidelines, " Romer effectively conveys the
history, materials, vulnerabilities, and proper care of daguerreotypes in only
t·wo pages. This concise yet thoro ug h introduction to caring for daguerreotypes
is a val uable reference for /;hose interested i n t he preservation of daguerreo­
types, including students, c-ura/;ors, collectors, and conservation professionals.

Thi s year, 1 989, marks the one-h undred fiftieth anniversary of the introduc­
tion of the daguerreotype. This process began the era of world-wide photo­
graphic production. From 1 839 un t i l the mid- 1 85os, the daguerreotype was
the dominant method of practical commercial photography. M illions of
i m ages were made by t h i s p rocess i n Europe and North America. Although
the vast m ajori ty of this prod uction has been lost through neglect and igno­
rance, great numbers still exist, many s t i l l held as treasured family docu­
ments. Many public and private i nstitu tions, which gather i mportant social
documents, have amassed daguerreotype collections as part of their normal
general m ission. Collecting interest i n daguerreotypes as i mportant artifacts
of the h i story of photography has existed for over fifty years. M any such pri­
vate col!ections have come to reside in i nstitutions. Recently, a vigorous mar-

G HANT B. ROMER, "Guideli nes For the Adlll in istration and Care oF Daguerreotype Col lec­
tions," Co11serval ion Ad111inislralion News, no. 38 ( 1 98 9 ) : 4-5. © I nternational IV l u sculll oF
Photography. Repri n ted by perlllission of' G ra n t B. Holller and George Eastman House,
I nternational M useum of Photography.
 Reading 31 R O M E R

ket i n daguerreotypes has developed, replete with special izi ng profession a l

dealers and a corresponding dra m atic rise i n monetary value. Certain rare,
u n usual, and aesthetically strong examples have real ized very consi derable
sale prices. Notable fine art collecti n g institutions have begu n to acquire
such choice examples i n n u mber.
The exh ibition and p u b lication activities of the sesquicentennial wi ll
su rely br ing increased i nterest, demand, and va luation. At this t i me , i t i s
h ighly i mportan t for i nstitutions to give careful cons ideration t o the special
problems presented by daguerreotype collections. I ncreased i nterest may
resu lt in serious conservation problems and adm i n istration d i fficu l ties.
The daguerreotype d i ffers sign i fi cantly from conventional forms of
p hotography. I ts m ost d i stingu ishing feature is its totally metallic compo­
sition. The image support is a t h i n copper plate, su rfaced with a layer of
highly polished si lver. The i magin g su bsta nce is a mic roscopic deposi t of
metallic mercury globules, which form the l ights of the picture. The darks
a re formed by the reflecti ve s urface of the si lver. The vul nerability of these
materials to i mage marrin g and effa c i ng abrasion, tarn ish, and corrosion is
very great. Thus, it was necessary to provide protective packagi ng to i n s ulate
the plate from direct contact i n handling and the attack of ai rborne pol­
l u tants. Tradition protective housing varied in materials, but followed the
essen tial con struction features of a frame. Each p late was given a t h i n sepa­
rator mat, placed behi n d glass a n d boun d at the edges with tapes to secure
the elements from s h i fti ng and to create a barrier to the ingress of air. Thi s
package was often further protected b y encasement o r frami ng, creating a
considerably three-dimensional object. These protective housi ngs a lso had a
decorative fu nction, often elaborately wro ught and formi ng elements of con­
s iderable aesthetic and h istoric value, i ntegral to the entire artifact.
The preservation of the daguerreotype depends upon the i ntegrity of
the housi ng. l f the housing fails or i s damaged, the daguerreotype becomes
directly vulnerable. Fail u re to appreciate this pri nci ple has resu lted i n the
degradation and destruction of most daguerreotypes. Either out of igno­
ran ce or curiosity, caretakers regularly disturb or remove fu nctional hous­
i ngs . Those few who attempt reassembly or restoration of the housing do
so i nadequately. Like ancient Egyp ti a n tombs, few dagu erreotype hou sings
have gon e undistu rbed .
Hesponsible caretakership of daguerreotypes demands attention to the
provision of fu ncti onal pri m a ry housing as a first priority. U nfortunately, past
conservation efforts have focused upon the "clean i ng" of tarnished plates.
Although someti mes producing dramatic cosmetic i mprovement, these "res­
toration" treatments have created serious long-term complications and often
i rreversible damage. Despite recent efforts to evolve better and safer clean­
i ng methods, no techn ique currently available meets the c ri teria of ethical
 P a rt I I I S I L \I E R . 1\ I E R C U R Y , t\ N D C 0 L D

Figure 1
Parts of a daguerreotype.
Photo © 2:>09 George Eastman
H ouse, I nternational
1V l u sc u 111 o f Photography and
Film. Hcprintcd by permission.

conservation. I t is h ighly u n l i kely that one will ever be evolved . Those few
individuals who have devoted themselves to c reating protective housing sys­
tems have clone little more than repl icate the n i neteenth century methods
u s i ng modern materials . Hegrettably, few i n d ividuals have the knowledge
and skills necessary to renew or c reate effective primary protective hous­
i ngs. Th us, most daguerreotypes are presently-an d will continue to be- i n
a threatened s tate.
Although such a real i ty i s d istressi ng, m u c h can be clone to d i m i n ­
i s h t h e threat t h rough carefu l handli ng, a rrangement, a n d storage. The fol­
lowi ng guidel ines are believed to provide a sound administrat ive policy for
daguerreotype collections. They are based upon long experience and obser­
vat ion gai ned in cari ng for the more than three thousand daguerreotypes i n
the George Eastman House.

Tota l ly unprotected plates (or plates i n grossly d i s t u rbed or dam­

aged housings in which the plate i s directly threatened with abrasi on ,
physical stress, or atmospheric attack) must be i m mediately secu red
and given temporary housing (see bibliography below) . Such items
should be segregated and protected from casual hand l i ng by staff or
researchers .
I n tact, original housing should not be disturbed without preparati on
to i m medi ately restore or replace t he protective seal ing. M uc h damage
has res u lted i n i nept opening of protective pac kages to remove or clean
a deteriorated glass i n order to view or photograph the plate. Amateur
 Reading 31 B 0 M E ll

tampering with original housings is invariably dangerous, no matter

how wel l intentioned.
• C areful records of any altering of a housing m u st be kept. I f, for
any reason, origi nal housing elements are removed, they should be
labeled and retai ned. New seals should be elated and identified as to
material.
• The daguerreotype and its housing must be considered as a total
art i fact, requiring and deserving protection from handling stresses,
abras ion, impact, and atmospheric attack. Affixing labels, accession
n u m bers, or other identifying marks must be carefu lly considered.
M uc h irreparable damage to cases and images has res u l ted from this
need to identify.
• Each claguerrean artifact should have individual housing protection in
the form of a wrapper or container that conforms to its Format. Phase
boxes have proved very applicable.
• Whenever feasible, daguerreotypes should be arranged and stored by
size (sixt h-plates with sixth-plates, quarter-plates with quarter-p la tes ) .
T n secondary "group" housing containers, s uc h a s boxes, drawers, etc .,
each packaged daguerreotype sh o u l d b e sec ured from s hifting when
the container i s handled. I n dividual partitioned slots may be eas i ly
fashioned wi thin a box or tray. Flat storage is p referable. Vertical stor­
age is often necessary for large collections.
• The storage environment should be cool, dry, and constant. I nstitu­
tions with controlled envi ro nments designed for mixed photograph i c
collections m a y safely hold daguerreotypes with other collection
materials.
• Each daguerreotype available for researcher access should be pho­
tographed. Access to the originals should be carefu l ly restricted.
H a n d ling degrades the cases and protective housings. The average
researcher can be adequately served with photographic copy prints.
R esearcher handling of origin a l daguerreotypes should be supervised
at a l l times. The rising monetary value of daguerreotypes has created
serious sec urity problems, particu larly for small institutions.
N o daguerreotype should be made available for travel or disp lay with­
out a sound and fu nctional housing.
Conservation treatments should be conducted by experienced and rep­
u table ph otograph i c conservators, alone. C le a n i ng of daguerreotypes is
to be resorted to only after careful assessment of need .
Genera l collection pol icy should designate daguerreotypes as highly
val uable and vulnerable, no matter how ano nymous they may be as to
maker or subject.
Part III S I L V E R , M E B C U H Y , A N D G O L D

Daguerreotype collections present very complex problems for care­

takers. Even the most soph i sticated and equipped i nsti tutions fai l to pro­
vide comprehens ive and effective care. Those collections that have received
adva nced attention still lack the basic abi l i ty to monitor the progress of dete­
rioration by a rel iable and effective syste m . Thi s is cl ue to a general lack of
sophisticated u n derstanding of the deterioration mechanisms of daguerreo­
types a n d the function of protective housings. As with the e nti re field of
photographic con servation, the ability to respond effectively to the preser­
vation problems of daguerreotypes is h ighly l im i ted by lack of knowledge
and research support. Hence the i mportance of provid i ng, at the very least,
the basic protective system and care originally designed in the n ineteenth
century to preserve t hese most beautiful and provoki ng early photographic
i m ages. This effort m ust be a ugmented by a gen eral u n derstan di ng that these
i m ages constitute the earli est photographic record of our society, which time
will make ever more precious.

Bibliography

The following p u b lications give detailed i n structions o n sealing and re-housing

daguerreotypes:
Romer, Grant B. "A Stabil ization Packaging Technique for Photographs," R CHA
Tec h nical hifonnal;ion Sheet, No. 77, J u ne 1 985.
Rempel, S iegfried. T11.e Care of Photographs, Nick Lyons Books, 1 987, 100-102.
Ritzenthaler, iVI u n off and Long. A rchives and Manuscripts : Acl.n1.inist.rati.on of Photographic
CollecUons, SM Basic Manual, 1 98 4 , 1 0 3- 1 06.
 R e a d n g 32

M . S U SAN BAR G E R A N D WI L LIAM B . WH ITE

Corrosion Removal:
Electrocleaning ( 1 99 1 )

Susan Barger (see also Reading 33 ) is a n adjunct professor i n the de11artnient of

Earth and Planetary Sciences at the University of New Mexico, Albuquerque.
I n the 1 980s she studied the dagu erreotype and its conservation at the Materi­
als Research Laboratory of Pennsylvania State University and authored a series
of papers recounting her findings. The following reading is an excerpt from
The Daguerreotype, N ineteenth-century Tec h nology a n d M odern Science,
Barger's comprehensive volume on the history, practice, materials, deteriora­
tion, and cleaning of daguerreotypes, coau t hored with William B. White. This
excerpt prov-ides an exhaustive introduction to daguerreotype electrocleaning
systems and methodology and establishes this approach as superior to spu tter
c lean i ng and chemical dip methods. Using scanning electron micrographs,
Barger and \!Vliite document that electrocleaning does not affect daguerre­
ian image particle microstructure. This reading reaffirms the del-icacy of these
images and the danger of cleaning hand-colored and u ngilded plates.

I n spi te of the i nteresting results from the experi ments with sputter clean­
i ng, it was obvious that the problem of daguerreotype cleaning had yet to be
solved. Of the various methods that h a d been exa m i ned, electrolytic clean­
ing had the m ost advantages. Maldng the daguerreotype i n to the anode of a
battery was at least a b e nign procedu re so far as a ttack o n the metallic s ilver
was concerned. Most of the other objections to electrolytic cleaning could

From M . SuSAN BARGER a n d WILLIAM B . WHITE, "Corrosion Removal: E lectrocleaning,"

in T71e Daguerreotype, Nineteenth-century Technology and Modern Science (Balti more:
Johns Hopkin s U niversity Press, 2000), 1 92-200. Origi nally published by S m i t hsonian
I nstitution Press, Was h i ngton , DC, 1 99 1 . Text and i mages reprinted b y permission.
Part III S I L V E H , M E H C U R Y , /\ N D G O L D

be removed by a new method that made direct use of the electrochemical

reaction between silver and the si lver corrosion prod ucts. The daguerreotype
was made part of an electrochemical cell but not part of a battery.
The basic e>qJeri ment was to aga in place the daguerreotype in an elec­
trolyte solution. 1 However, this time the driving energy was su ppl ied by a n
electrical current from an external power supply. O ne lead of t he power supply
was connected directly to the daguerreotype, the other to a movable si lver elec­
trode. The movable electrode was used to direct the current and thus allow for
concentrated cleaning on specific areas of the si lver object. By using a d irect
current, the polarity of the si lver object and that of the movable electrode can
be reversed so as to make use of both anodic (i .e., reverse) cleaning in addi­
tion to cathodic ( i .e., direct) c leani ng. This process is called electrocleaning
to d i fferenti ate it from the electrolytic cleaning of the simple galvanic cell.
Each form of electrocleaning, cathodic and anodic, has advantages, especially
for objects with heavy corrosion; switching back and forth from anodic clean­
i ng to cathodi c cleaning can break up corrosion layers, making them easier to
remove. The key d ifferences between electroclea n i ng with a movable electrode
and electrolyti c cleaning with the galva n ic cell is that i n electroc lea ning the
overdriving potential provided by the applied cu rrent i mproves the kinetics of
the clea n i ng reaction, al lows control over the type of cleaning that can occur,
and al lows control over the extent and location of cleaning.
The oxidation of si lver to form its various oxides or the reaction of
si lver with su lfur or hydrogen sul fide to form its various s u l fides each have
a characteristic electrochemical potent ia l that is a fu nction of pH when the
metal and oxides are in equi libri u m with an aqueous solution. These poten­
tial p l-I relations can be plotted to give a map, called a Pou rba ix diagram
( Figu re 1 ) , which shows the stabi l i ty ra nges of the various compo u nds. Si lver
resides h igh on the electromotive series; thus, si lver metal occupied m uch of
the stability region in the Pourbaix d iagra m . l n acid solutions si lver dissolves
d irectly to form monovalent si lver ions i n sol u t i o n . The oxides are the only
stable sol ids in contact with aqueous solu tions at h igh p l-I . The wide stabili ty
field for si lver sesqu ioxide l ies above the stability l i m it for water. The stabil­
ity boundaries i n t u rn determine whether the metal wil l be stable, corrode,
or form a passivation fi l m on i ts su rface ( Figure 2 ) .
The stab i l i ty field for si lver oxide (Ag2 0 ) at p l-I 1 2 lies just within the
corrosion bou n daries. The other si lver oxides-Ag2 02 and Ag2 0 3 -exist i n
the passivation region o f the diagra m , b u t these are a l l relatively unstable
at room temperature and standard pressure. These oxides can be formed at
p H 1 2 by applying a relatively small overpotential. At this poin t it is useful to
design an e lectroc lean i ng system t hat can take advan tage of both the i nsta­
bil ity of the variou s si lver oxi des and the low potentials needed to form these
oxides at p I--1 1 2 .
 Reading 32 B A H G E R AN D W 1-1 I "I' E

-2 0 2 4 6 8 10 12 14 16
2 2

+1.5 1 .6 passivation 1.6

-s� Ag 2 03
Bll.J ; y 1.2 12. 1.2
-- L ffo'1/ ;
__

+1.0
-- -
--
--

Ag+
-- -
0.8
-..:: -!}F W -
,q; -- -
- --
-- €!!..
4
[Ao +]= 10-
corrosion ----

+0.5
- -

(j)
0.4
....
>
0
..J
0
Ag - Metal w
>
0 --0.._ __ --
--
--
immunity
.c
-0.4
--
S iA Bf
w -- -- -
:-- - --
G fy - --
L 1-
-- --
-0.5 1,,l i - ----
O F W;;,';fi/ -0.8 --
-0.8

- 1 .0 -1 . 2 -1.2

- 1 .4 -1 4
2 4 6 8 10 12 14 -2 0 2 4 6 8 10 12 14 16
pH
pH

Figure 1 Figure 2
Pourbaix ( p l -I- E h ) diagrnm for t h e system si lver-oxygen-hydrogen Corrosion diagram for silver based o n Pourbaix diagram showing
(Ag-0- 1-1 ) . Phase boundaries showing t h e regions of stability or t h e chemical reactions between metallic silver and L h e aqueous soluLion.
solid si lver oxides are drawn as heavy lines. T h e solubility of silver
is c:.ilculated for a concentration in solution of 10--.-4 molal ( 1 0.8 parts
per million). These solubility bou ndaries are shown as light l i nes.
The two parallel dashed lines show t h e upper and lower stability
li mits for liquid water a t 25 degrees centigrade. The equations used
for calculating this diagram were taken from Pourbaix, At. las of
Electmche111ical Ec111ilibria in Aq11eOllS Sol111.io11s, chap. 4. sec. 1 4 . 2 .

To set u p a n electrocleaning system it is n ecessary to fi n d an e lectro­

lyte solution that can be maintained near p H 1 2. However, i f the electrolyte
was also a solvent for si lver oxide, another method to control the clea n i ng
process wou l d be added . Ammoni u m hydroxide does have these character­
istics; i ts reactions with si lver are s hown in Figure 3 . The solu tion used for
daguerreotype cleanin g is two parts water to one part concen trated ammo­
n i u m hydroxide (28 percent) by vol u me. S ilver oxide is very soluble in this
solution. The solution w i l l act o n ly o n the s ilver oxide present a n d not on any
other corrosion product or the silver of the daguerreotype plate. Ammon i u m
hydroxide w ill complex ava i lable s ilver i o n s t o form water-soluble ammon i u m
complexes that are easily washed away leaving n o su rface resi d ues behin d .
The p hase d iagram also i n d icates a region where explosive s ilver azides a n d
related compounds c a n form. These presen t n o safety hazard; t here is never
enough silver oxide present to worry about the formation of these explosive
si lver compounds.

2 73
 Part III S I LV E R , M E R C U R Y , A N D C O L O

DC POWER S U P PLY

DPDT SW I TC H

A 9 WA N D
Amrronia
Pressure
Region

T R AY WITH A M M O N I A SOLUT ION

Figure 3 Figure 4
Some regions of compound Formation in Ll1e syst<.:m Elcclrical connections for Lhc clcclroclea ning experi ment.
si lver oxide-a mmonia-waler (Ag.!0- N l -I 1-1-1 .!0).

For the application of electrocleaning to the daguerreotype prob­

lem, two electrodes-the daguerreotype itself and a wand electrode-were
attached to a de (direct cu rrent) power su pply through a double-pole, dou­
ble-throw switch ( Figure 4). In the first switch position the daguerreotype is
the anode, and the wand electrode is the cathode. In the second switch posi­
tion the poles are reversed. The de power supply provided various vo ltages
up to 1 00 volts. The bath was operated at room temperature.
The daguerreotypes used for all these experi ments covered a broad
range of quality and ages-from very early daguerreotypes ( made in 1840) to
one made in the late 1 97os-and came from 111any sou rces. The b u l k of the
samples came fro111 the M aterials Researc h Laboratory working collection
of daguerreotypes that had been specifically gathered for e>tperimentation.
The daguerreotypes were photographed before treatment to doc ument their
i nitial state. H owever, photographs of daguerreotypes can be 111 isleading
because this mode of copying auto111atically en hances their contrast ra nge.
For experi mental purposes i t is i111 portan t to maintain a record i n the for111 of
cleaned and u ncleaned portions of the same daguerreotype i n addition to the
 Reading 32 B A H G E H A N D W H I T E

To Power S u pp l y

Figure 5
Plate holder for daguerreotypes
in electrocleaning s ol utions.

p hotographic records. Thus, a few of the experimental daguerreotypes were

c u t i nto pieces before treatment so that d irect comparisons could be m ade
between treated and u ntreated portions. Daguerreotypes from several private
and public collections were also provided for field testi ng of this clea n i ng
method. These daguerreotypes were loan ed by their owners for this use with
the fu l l u n dersta ndin g of the experimental nature of the work. None of the
loaned daguerreotypes or others of last i ng valu e was cut or otherwise dam­
aged. Further, there was an additional agreement with the owners that the
daguerreotypes would be retu rned for monitorin g a n d testin g to follow the
lo ng-term resu lts of the cleaning proced ure.
A special holder of nylon and si lver ( Figure 5) was ma de so that a
daguerreotype could be securely held i n a flat positi o n and conn ected to the
c i rcuit without bei ng scratched. Each daguerreotype cleaned i n the labora­
tory and du ri ng the field testing period was exam i n ed using sca n n i ng electron
m icroscopy and energy-dispersive X-ray analysis before and after treatment.
In add ition, some daguerreotypes were exam ined using Fourier transform
i n frared spectroscopy to check for the presence of thin s urface films subse­
quent to cleani ng. Daguerreotypes were photographed fol lowin g treatment.
Overa l l , some one h u n dred daguerreotypes were cleaned.
I n some of the early ex-periments the wand electrode was made of a lu­
m i n u m . T he a l u m i n u m e lectrode worked erratically with wi ld fluctuations
and spikes in the voltage over a 20-to-60 de volt range. This erratic behav­
ior continued u nt i l the a l u m i n u m was seasoned, that is, u n ti l it grew a thick
porous coating of a l u m i n u m oxide. Once the oxide layer h a d b u i l t up, the alu­
m i n u m wan d could be used i n definitely. Often a b l ack tarnish wou ld form on
the edge of the daguerreotype p late when the a l u m i n u m electrode was used.
I f the electrode accidentally touched the daguerreotype surface d uri ng clean­
ing, an ex-plosive conn ection would be made, forming a molten pit composed
primarily of silver and a l u m i n u m , along with some copper if the s ilver layer of
the plate was pierced. F igure 6 shows a micrograph of one of these pits.

275
 Part III S I L V E H • !\I E H C C R \' , :\ N I J G 0 L IJ

Figure 6
Sca n n i ng electron micrograph
showing pit resu l t i ng from the use
of an a l u m i n u m wand electrode
that touched the cbgucrn.:olypc
su rf'acc during cleaning. Sc<Jle
bar is equal lO 50 micrometers.

Figure 7
Daguc1-rcotypc showing areas
of peeling and dclamination
of the silver layer or t he
daguerreotype plate caused by
t he use of' an a l u m i n u m clccLrode
during clcctr1H.:lcaning.
 Read i n g 32 B A R G E H A N 0 \V 1-1 I T E

More disturbin g than the pitting is that the silver layer on a daguerre­
otype could be en tirely separated and peeled away from the copper sub­
strate du ring clea n i n g ( Figure 7 ) . At first i t was thought that this peeling
was associated wit h daguerreotypes made on American process plates-that
is, cold-roll clad daguerreotype plates that have an electroplated si lver layer
added by the user. The pee l i ng was attributed to poor adhesion between the
si lver electroplated layer and the silver-clad layer of the plate. H owever, it
became apparent that i f an a l u m i n u m electrode was used for cleaning, peel­
i ng occu rred regardless of the method of p late manufacture . An i nvestiga­
tion of this phenomenon using si lver blanks showed that pee l i ng occurred at
power levels as low as 29 de volts and 10 to 1 5 m i l l iamps.
The a l u m i n u m electrode is c lea rly not an appropriate material for u se
in this application of electroclean i n g. The natural a l u m i n um-si lver galvan ic
cell i nterferes with the driving potential of the appl ied vol tages. Further, the
a l u m i n u m tends to act l i ke a capac itor and store c harge, thus accounting for
the wild vol tage fl uctuations.
To avoid the p roblems associated with the a l u m i n u m electrode, elec­
trodes oF more noble metals-copper, brass, platin u m , and si lver-were
tested . The cleaning results and control i mproved marked ly with electrodes
of increasi ng nobility. \i\/hen the silver e lectrode is u sed, the natural gal va n i c
cell is e l i m i nated, but electrolysis from t h e app lied potential is maintained .
Thus, when a s ilver electrode is used , there is n o seasoning period, no fl uc­
tuations in voltage, no peeling or pitti ng, and no blacke n i ng of the edges,
and clea n i n g is more rapid and com plete. I n addition, if the si lver electrode
is used , the voltage remains constant at 2 to 5 de volts. The current of the cell
varied between 8 and 25 m i lliamps accord i n g to the d istance from the e lec­
trode to the plate surface. The variation i n c u rren t appears to have no effect
on either the rate or the effectiveness of clea n i ng. I n a few i nstances s lightly
h igher voltage was n ecessary to remove u n usually resistant corrosion. H ow­
ever, lower voltages are recommended. As in all conservation treatments,
use only the amoun t of energy that will accomplish clea n ing. Some experi­
menters have used pl a tin u 111 electrodes for e lectroc leaning daguerreotypes;
however, these offer no real advantage over silver electrodes, and the cost
per electrode is cons iderably h igher.
Essentially, electroc l ea n i ng uses the applied voltage to form si lver oxide
t h i n films several atomic layers thick at the corrosion-plate i n terface when
the dagu erreotype is i n the cathode posi tion. The si lver oxide fi l m is extremely
u nstable because of its t h i n ness, its sol ubility i n the a mmo n i u m hydroxide
solution, and the h igh p . H (pH = 12) of the electrolyte sol ution. The i nsta­
b i l ity of the oxide layer helps loosen and break u p the thicker tarnish layer.
\i\/hen the polarity of the cell is reversed, silver ions at the plate surface are
reduced to si lver, and the tarnish layer is l i fted from the plate. The tarn ish

277
 Part III S I L V E H , M E R C U H Y , A N D G O L D

Figure 8
Sca n n i ng eleclron m icrograph oF
daguerreotnJe surface before and
after electrocleani ng. Scale bars
are equal to 10 micrometers.

layers come off i n sheets or disappear i n to the solution depending upon the
daguerreotype treated and the extent of its corrosion. Cleaning i s contin ued
by switching back and forth from anodic to cathodic p hases u n t i l there is no
longer any visible removal of tarnish or i mprovement i n i mage appearance.
A certain amount of microscopi c improvement in the daguerreotype
p late surface occ urs as a resu lt of slight electropoli sh i ng caused by the elec­
trocleaning ( Figu re 8 ) . E lectropolishing is related to a nodic p hase c lean ing
and is u sed to p roduce bright metal su rfaces without mechani cally work­
i ng the su rface. B righte n i n g observed on daguerreotype plates is due to very
sl ight e l i m ination of surface m icroroughness and microirregularities on the
order of o . 1 to 0 . 0 1 micrometers. Anodic fi lm formation on a metal surface
helps promote the u niform removal of unwanted material by the electrolyte;
 Reading 32 B A H G E B A N D \-V l- l l T E

Figure 9
Scanning cleclron m icrograph of'
daguerreotype su rface severely
cleaned by cyanide and l h c n
electrocleaned. T h e cyanide
solutions etched away the s i l ver
i n grain boundary regions, leaving
the grains standing i n relief. The
grain boundaries were covered
w i t h laLer corrosion products
that were duly removed by t h e
clectrocleaning procedure, thus
revealing the damaged surface
in fine detail. The scale bar
i s equal to 1 0 m i c rometers.

thus, the su rface i s evenly "pol ished . " Electropolished su rfaces have u n ique
properties in that they are very smooth and have few voids. As a result, they
also are more corrosion resistant than mechanical ly polished or etched sur­
faces. The brigh teni ng effect i s seen visually as an increase in the specu­
lar reA ectance of the metal su rface. 2 This i ncrease in specular reAectance
improves the appeara nce of the electrocleanecl daguerreotypes by i ncreasing
t heir contrast range since the maxi m u m amou n t of blackness observed on
daguerreotypes i s d irectly rel ated to the spec ularity of their su rfaces.
Electrocleani ng does not affect the i mage particle microstructure in
any way. I ndeed, there is some evidence that an electrocleanecl dagu erre­
otype may closely resemble what a daguerreotype looked like when it was
first made, before it had any corrosion films or had been subjected to any
kind of solvent clean i ng treatment. The brighten i ng seen visually after e lec­
trocleaning is a combination of two effects: primari ly, the removal of tar­
n ish films and, secondari ly, a slight amount of electropolishi ng. Si nce the
original m icrostructure is usually u n known, the relative proportions of these
two effects cannot be q uantified. H owever, the electropolishing takes the
daguerreotype plate a bit closer to its origin a l freshly polished condition.
M odern daguerreotypes cleaned by t h is method show no recogn izable a ltera­
tions i n either the i m age structure or the p late surface at the level of scann i n g
el ectron microscopic exami nation. 'vVith conventional silver clip c leaners, the
effects are quite marked when exam inations are carried out in the same way.
U nfortu nately, electrocleaning can never restore a daguerreotype to its origi­
nal pri.stine condi tion. The etch patterns characteristic of silver dip cleaners
can never be removed. F igure 9 shows a section of plate that had at some

279
 P a rt III S I L \I E B , 1\ I E B C U B Y , 1\ N D G 0 L D

Figure 1 0
Parlially cleaned daguerreotype.
The right side has been
ckclroclcancd. Tht' left
side is undcancd.

time in the past been heavily etc hed by cyan ide t reatment. E lectroc lean i ng
bri ngs out the etch pattern i n exquisi te deta il but docs not help the deeply
corroded grai n boundaries heal. At best only a s l ight healing of the plate sur­
face occ u rs, and it is not s u fficient to alter the overri d i ng optical behavior of
the damaged plate and i mage particle m icrostruct u rc .
On a more cheerfu l note, Figu res 1 0 and 1 1 give comparisons between
u ncleaned and cleaned dague rreotypes. I n Figure 10 only the right half of the
daguerreotype was electrocleanecl, with i m mense i mprovement i n detail i n
t he woman 's portra i t .
H aving establ i s hed t h a t electroclea n i ng was defin itely superior t o sput­
ter clean i ng and any of· the chem ical cl ip methods previously used, there
remained the question of whether the au thors could effect a technology
tra nsfer and recommend electroclea n i ng for general u se. \11/e cleciclecl that
out -of-laboratory testing by a working conservator was vital to the develop­
ment of electrocleaning as a useful methodology. Thus, daguerreotypes were
given the usual preparatory exa m i nations and sent to a private conserva­
tion shop for an application of the electroclea ning treatment.·' The conser­
vator had seen the method in the laboratory setting and was given written
 Figure 11
Comparison of-' electrocleaned
daguerreotype with its pretreatment
condition. Cleaning by Tom
Edmondson. summer 1988.
Cou rLcsy of Paul Katz.
 Part III S I L V E H , M E B C U H Y . 1\ N D G O L D

Figure 12
Daguerreotype wiLh f i l iform
dclamination <.1cross the central
portion of t he image caused
by treatment in a n u l t rasonic
cleaner wid1 water. This
dagucrrcOlypc was previously
heavily corroded. and most of the
im<-1gc was occluded by tarn ish. The
tarnish was cleaned away
using 11 silver wand electrode
and the clcctrocleaning regime
described in the Lcxl.

guidelines and the daguerreotype holder for use i n field testing. All other
equ ipment necessary for the field testing was put together on site. Close to
40 daguerreotypes were c leaned in the first group of tests. 'vVhen the work
was completed, the daguerreotypes were brought back to the laboratory and
given postclea n i n g analyses. Usi ng the observations and e>..' Perience ga i ned
in field testi ng, more daguerreotypes were treated, and the process took on
the shape in which it has n ow been presen ted. The field testing was deemed
a success. O f about 1 20 daguerreotypes cl eaned and eval uated, the tarnish
could be removed from most with su bstantial i mprovement in the appear­
ance of the object.
All the experimenting with clea n i ng methodology re i nforced a long­
known fac t : daguerreotypes were and are extremely deli cate objects.
l mmers i ng them in solutions of any kind must be clone with care, and cer­
tai n procedures m ust be avoided . I n the water-washing stage of the electro­
cleaning process, the daguerreotype should only be soaked and rocked gen tly
from time to time so that fresh water reaches the pl ate su rface to carry away
water-soluble tarnish products. Warm water, not hot water, may be used for
this step. U n der no c i rcu mstances should u ltrasoni c agitation be used for
this portion oF the clea n i ng or for any other treatment of daguerreotypes.
 Reading 32 B A R G E H A N D \V l l l T E

l t was fou nd that daguerreotypes s u bjected to u ltrason ic t reatment can

develop unpredictable fi l i form delam i nation of the plate su rface, an example
of which i s s hown in Figu re 1 2 . The filamentary l ines moving across the face
of the daguerreotype were formed d u ring ultrasonic cleaning in water and
a re the res ult of delam i nation of the s i lver layers of the plate. No remedy has
been found for this prob l em .
U ngilded daguerreotypes cannot b e e lectrocleaned . Without the
strengthening of the i mage part icles i n the gilding step, the mic rost ructure
will not withstand electrocleani ng.
Dague rreotypes with excessive hand-applied color shou Id not be placed
in so l utions because of the risk of losing t he pigments. Daguerreotypes of
this type that need clean i ng should probably be sputter cleaned , as there is
less risk that color will be removed by sputtering. A colored daguerreotype
should be checked using an optical m icroscope for the presence of pigment .
Often daguerreotypes that appear s l ightly colored (e.g., natural skin tones i n
portraits or blue skies i n la ndscapes) are colored because of optical effects
of the i mage m icrostructure and not beca use of appl ied color.4 \Vhen this is
the case, electrocleaning will not harm or remove the color. I n herent color­
at ion of t h i s type is caused by i mage particle spacing and size and will not be
al tered i n the cleaning process.

Notes

1 M. Susan Barger. A. P . C iri, W i l l iam B. W h i te, and Thomas i\1 1 . Edmonson,

.
Clean i ng Daguerreotypes, . St11clies i11 Co11servatio11 3 1 ( 1 986): 1 5-28.
..

2 W i l liam John J\ l cC regor Tegarl. The Electrolytic a11cl Che111ical Polishi11g uf

Metals ( New York: Pergamon Press, 1 958).
3 The Eeld trials were carried out i n t h e conservation shop or Thomas i\1 1 .
Edmonson, Connec t i c u t .
4 i\11 . S u san Barger, Pau l Messier, a n d W i l l i a m B . White, " A Physical Model fo r
t h e Daguerreotype," P/10tograp'1ic Science a n d Engineering, 2 6 ( 1 982): 285-9 1 .
 R e a d i n g 33

THOMAS M. E D M O N D S O N AND
M . S U SAN BARG E R

The Examination, Surface

Analysis , and Retreatment of Eight
Daguerreotypes Which Were
Thiourea Cleaned in 1 977 ( 1 993)

To·m Edmondson is a photograph conservalor i n private practice a t; 1 -leugh.­

Edmondson Conservation Servi.ces in Kansas City, Missou ri. ( For S usan
Barger, see Reading 32. ) Th is readi ng si1 m mari=es t h.e effec t of thioi1rea clea n­
ing on eight da maged daguerreolypes. Usi ng Fourier t ra nsform. infra red spec­
t roscopy, Edmondson. and Barger conclude lhat high.Ly reactive thiou rea-si.lver
cO' lnplexes re 1nain on a daguerreotype plate following standard thi.ou rea clean­
ing protocols. Their collaborative research. cle·1n.onst rates the pol;ential clan­
gers of t h. i.ou rea clea ning an.cl n1.0re broadly i i nclerscores the need to rnut inely
reevali1at:e an.cl reassess conservation t reat 1n.en/; 11ract ice.

1. Background and I n trod uction

Thiourea and minera l acid s i lver-dip sol ut ions were first described by H ow­
ard Bren ner in 1 953 for the cleaning of Fragi le silver object u nable to with­
stand abrasive cleaners. 1 The origi nal formulas recommended by Brenner
were modified and adapted for cleaning daguerreotypes by M rs. Ruth K .
Field, ass istant curator of the M i ssouri H istorical Society, and her formula
was first published by C harles van Ravenswaay i n 1 956.2 The M issouri H is­
torical Soc iety formula and its variations were widely used and were thought
to be perfectly safe and fool -proof t reatments for daguerreotype cleani ng.
H owever, by the early 1 970s some reports about problems associated with

T1 10�li\S \i I . E o � 1 0NDSON and M . Sus,\N BARG E H , "The Examination, Su rface Ana lysis, and
Het rcatment of E ight Daguerreotypes Which \Mere Th iourca Cleaned i n 1 977," Topics
i11 Pl10togrnpliic Preservatio11 5 (v\lashi ngton, DC: American I nstitute for Conservat ion,
Photographic Materials G roup, 1 993), q-26. Hepri nted by permission.
 R e a d i n g 33 E D J\' I O N D S O N A N D BA H G E H

thiourea cleaners began to appear. These problems i ncl uded i ndications

that daguerreotypes could not be repeatedly cleaned in thiourea solutions
as had been previously thought, that some thiourea-cleaned daguerreotypes
developed m i l ky-white coatings over time, and that some daguerreotypes de­
veloped "measles."3 The i ncreasing alarm over the possible adverse effects
of thiourea c leaners was addressed by the Aedgling Photographic Materi­
a ls Group ( PM G ) of the American I nstitute for Conservation and i n 1 979,
the membership of the P M G agreed to a moratori u m on the cleaning of the
daguerreotypes until more research could be done.
A few papers were published describing research to improve thiourea
daguerreotype cleaning solutions, 4 however, very l i ttle research was done i n
looki ng for alternatives t o thiourea for cleaning daguerreotypes.; A method
for electroc leani ng daguerreotypes was published i n 1 986.6 ln the latter
paper, it was reported that su rface characterization of dague rreotypes showed
that thiourea-silver complexes remai n on the surface of thiourea-c leaned
daguerreotypes and that these byproducts are not removed by washing.

2. Treatment and Retreatment of Daguerreot·yp es

I n 1 977, Thomas M. E dmondson treated a set of eight daguerreotypes from

the col lection of the Torrington (Con necticut) H istorical Society using the
standard Missouri H istorical Society form u lation thiourea cleaner. The
photo-docu mentation and reports on the treatment have been misplaced in
the H istorical Society's files and only Edmondson's personal notes written
on the seals of the daguerreotypes are cu rrently ava ilable. After cleani ng,
the daguerreotypes were resealed using Permalife paper with an adhesive
made of starch paste, and sealed with a coati ng of B-72. The daguerreotypes
were recased and s ubsequently stored in acid-free storage boxes in the base­
ment of the Hotchkiss-Fyler House which is the main location of the Tor­
rington H istorical Society's collections. The house m u seu m does not have a
heati ng-ventilati ng-air con ditioning ( l -J VAC) system, however the basement
storage area is a fai rly stable enviro n ment with only occasional excursions
of temperature or h u mi dity duri ng extreme conditions in the s u m mer and
wi nter seasons.
In December 1 990, Ed monson re-exam i ned the Torrington daguerreo­
types and fou nd that seve n of the eight were showing signs of deteriora­
tion related to their previous thiourea treatment: the i mages were cloud i ng
over and some daguerreotypes had developed "measles. " Recognizing that
the opport u n i ty to study this set of daguerreotypes offered the possibi lity of
verifyi ng pre\riou sly reported results on the effects of thiourea cleaner, he
obtained permission to have the daguerreotypes submitted for su rface analy­
sis, re-treatment using electrocleani ng, and follow- u p surface analysis.
Part III S I L V E H , M E H C U H Y , A N D G O L D

2c1. S u . 1face Analys·is

All eight daguerreotypes were submitted for su rface analysis to Dr. i\11 . S u san
Barger ( U niversi ty of New i\ll exico7). The daguerreotypes were analyzed with
the assistance of Dirk Kurth ( U n iversi ty of New i\l l exico8) using a n itrogen
pu rged M attson Polaris Fourier transform i n frared spectrometer with a nar­
row band l i q u id-nitrogen-cooled mercury-cad mi u m-te l l u ride ( M CT) detec­
tor. The polarized light from the spectrometer was i nc ident on the sample
at an a ngle of 75° from normal to the s urface. After triangu lar apodization
the spectral resolution was equal to 4 c m- 1 or 4 wavenum bers. The moving
m i rror ve locity was 1 . 264 centimeters per second and 250 to 1 ,000 scans were
recorded for each spectru m . All spectra were reported in log( R/R0 ) , where
R is the reflectivity of the sample and R 0 is the reflectivity of the reference
su rface. Evaporated gold-on-glass sl i des were used as refe rence surfaces. I n
some cases, the spectra were electronica l ly corrected i n the basel i ne using
two points at the outer edges of the bands of i n terest.
This experimental set-up gives spectra cal led reflection-absorption
i n frared ( RAI R ) spectra beca use the i n frared bea m reflected from the sam­
ple su rface makes a double pass (in and out) through any absorbing su rface
films. The RAJ R technique i s used primarily to obtain spectra of thin s u r­
face films l i ke the corros ion films foun d on daguerreotype surfaces. In the
daguerreotype case, i n frared spectroscopy i s a particu larly good technique
for analyzi ng corrosion films beca use s ilver is a perfect refl ector i n the i n fra­
red ; it therefore co ntributes not h i ng to the i n frared spectra obtai ned from
the plate s u rface. H owever, previous infrared exa mi nations of daguerreotype
su rfaces merely ind icated that thiourea is present on the s u rface of thiourea­
c leaned daguerreotypes, but no other i nformation could be derived from the
earlier spectra.9 In those cases, the daguerreotype plate could only be posi­
t ioned perpendicular to the i n frared beam and so the pathway of the bea m in
the corrosion fil m was very short. The i nstrumentation avai lable for the cur­
rent exam i nation allowed the daguerreotype to be pos i t ioned at an oblique
angle to the infrared beam, and thus the bea m had a longer pathway i n and
out of the corrosion fi l m s resulting i n a n effect ively th icker sample.
The spectru m obtained from a ll eight of the u ntreated daguerreotypes
was that of the thiourea breakdown product, d icyandiamidinsulfate. The
i n tensity (peak height) of the spectra is i n d icative of the amount of d icyandi­
am idinsul fate p resent on the daguerreotype su rface and this amount varied
fro m daguerreotype to daguerreotype; h owever, it was not possible to deter­
mine the exact amount of breakdown prod uct present on each daguerreo­
type. This is because the i n tensity of the spectru m for very thin fi l ms is
highly dependent on both the flat ness and the pos ition of the sample. Si nce
the daguerreotypes were not absolutely flat and there was also no way to
 R e a d i n g 33 E D M O N D S O N A N D B A H C E H

assure that each daguerreotype was pos itioned i n exactly the same way as
the others, spectra l i ntensity had some variation. That notwithstandi ng, the
breakdown films appeared to be on the order of 50 to 1 00 nanometers thick.
To verify the composition of any thiourea breakdown products, pol­
ished, blank daguerreotype p lates were cl i pped in a sta ndard thiourea clean­
i ng sol ution, rinsed in water and dried i n a strong stream of n itrogen gas. The
spectra obtained from these e>qJeri mental plates after drying were the same
spectra as for a simple si lver-thiourea compl ex. Th is is the i nitial complex
formed d u ri n g thiourea cleaning and it is not water solu ble. These experi­
mental plates were placed i n a drying oven at 90°F in the ambient atmo­
sphere for 4 to 5 days. RAI R spectra were taken period ically. After the agi ng
period, the spectra obtained the su rface fi l ms on the experi mental plates
could be s uperi mposed with the RAJ R spectra obta ined from the daguerreo­
types. Add itionally, the i n frared spectru m of a p u re sample of clicyandiami­
dinsu lfate was also compared with spectra taken from the daguerreotypes
and these spectra cou ld also be superimposed. We "recleaned" some of the
experimental p lates i n thiourea solution and found that the second "clean­
ing" does not remove all of the dicyand iamidinsulfate breakdown prod uct
and that this breakdown product actually acts as a catalyst for the break­
down of any new surface fi l m s.

2 b . Electrocleaning a n d Re-Analysis

Following RAI R analysis, the daguerreotypes were sent back to Edmondson

who electrocleaned three of the daguerreotypes and returned them for a
fol low- up ana lysis i n order to see if electrocleaning removes thiourea break­
down products. These daguerreotypes were n u m bers 1 , 5, and 8. After elec­
troclea n ing, only nu mber 5 was " clean" and free of s u rface films. This was
surprising because while the silver-thiourea complex is insoluble i n water,
the in termediates and the fi n al breakdown product are moderate to very sol­
uble i n water. The sol u bi li ty of the i ntermediates and the fin a l product, clicy­
andiamidinsulfate, woul d be altered if the corrosion fi l m formed is a polymer
i nstead of a monomer or if a metal salt is formed.
In an effort to determine if hot water wou l d remove the clicyancl iamicl i n­
sulfate, daguerreotypes 1 and 8 were cl ipped five and one minutes respectively
i n hot (200°F) deionized water and dried. These two dagu erreotypes were
then re-exam ined and i n both cases the su rfaces were found to be clea n .

2c. Experimental Conclusions

A great deal is known abou t the chem istry and reactivity of thiourea with
si lver. H owever, much of this information was not considered in the applica-
Part III S I L V E H . M E H C U H Y , 1\ N D G O L D

tion of thiourea cleaning sol ut ions for daguerreotypes. I n the development of

a su rface characterization tool cal led "Su rface Enhanced Raman Spectros­
copy" or S E RS, silver p lates cl ipped in thiourea solu tions were used to cali­
brate i nstruments because thiourea forms a characteristic comp lex that can
be easi ly detected and that cannot be removed from a s ilver su rface by sim­
ple was h i ng. 1 0 Thiourea-silver complexes have been used as a p hoto-oxidant
for one type of actin ometer. 1 1 In a nother context, thiourea has long been
u sed as a stabi l izing agen t i n photographic chemistry . 1 2 I t has been used i n
some monobath formu l ations in l ieu o f a fixative such a s sod i u m t h iosulfate
( hypo). The pri mary drawback to the use of thiourea as a stab i l izer is that
the silver-thiourea complexes formed in these treatments degrade to si lver
su lfide. Add itionally, in the presence of oxygen, thiourea is strongly corro­
sive to si lver. Th us, when thiourea is used as a stabilizer for monobath pro­
cessi ng, the resulting i mage eventually d i sappears because of the corrosive
action of thiourea on s ilver, the formation of si lver sulfide on the su rface of
i m age particles as result of the thiourea breakdown cycle, and the u l ti mate
conservation of the i mage to si lver su lfide. 1 3 Th iourea has also been used on
silver bromide crystals to form a s ilver sul fide su rface layer than can then be
used to fu rt her adsorb certai n kinds of sensi tizi ng dyes used in making pho­
tographic emu lsions . 1 4
Thiourea is known to u ndergo a photochemical degradation i n the
p resence of oxygen to form cyanamid and su lfuric acid. 1 1 • 1 5 Th iourea-si lver
com plexes u ndergo a si mi lar reaction upon treat ment with a base, such as
ammonia. 1 4· 1 6 The formed cyanamid is not stable but u ndergoes cl imerization
to dicyanamicl . 1 7 I n the presence of s u l fu ric acid, the cl icyanamicl undergoes
hydrolysis form i ng clicyandiamicli nsul fate. [ . . . ]
We concluded from the RAIH spectra that the decomposition of the
thiourea-si lver complex left on dagu erreotype su rfaces after clean i ng is
as out l i ned above [ n ot reproduced here ] . Basical ly, the chemistry of the
thiourea-si lver system i s well known and the chemistry of the corrosion cycle
of the thiourea-cleaned daguerreotype is no different from that already pub­
l ished i n the l i terature. F u rther, re-clea n ing a thiourea-cleaned daguerreo­
type in thiourea does not remove the corrosion breakdown prod ucts from
the previous cleani ng. These residual products act as catalysts to speed the
degradation of new s i lver-thiourea complexes on the daguerreotype su rface.
Lastly, when a daguerreotype is c leaned in thiourea, the thiourea cor­
rosion cyc le is i nitiated and it wi l l cont i n ue u n t i l the surface is covered with
dicyancliamicl i nsu l fate. The rate of the corrosion cycle i s dependent upon
many factors i ncluding storage conditions, the effectiveness of the daguerre­
otype seal , and whether or not the daguerreotype is displayed . The corrosion
prod ucts fou n d on a thiou rea-c leaned daguerreotype are not l i m i ted to the
thiourea breakdown produ cts, but they also i nc l u de s i lver phosphate, si lver
 Reading 33 E D V
i I O N D S O N A N D BA H G E H

oxides, and su lfuric acid . Th us, attempting to remove the thiourea breakdown
products using a hot water wash will have l i m i ted effect. A daguerreotype
needs to be treated i n a way that will remove all of the corrosion products n o
matter what t h e source.

3. I mplications for Conservation

This project u nderscores how i m portan t it is for conservators to reval uate

t reatments and their application. It is i m perative that conservators keep a n
open m i n d a n d that they be willing to examine n o t o nly the i r procedures a n d
materials, b u t also their p h i losop hical perspective towards their work. Thus,
i t is i mportant that conservators be certain that treat ments are as appropri­
ate and safe for objects as is possible to determi n e , and it is equaJJy as i mpor­
tant that the conservator be clear abou t their objectives in treatment.
The object of this particu Jar project was to establ i s h that the use of
thiourea cleaners for daguerreotypes p resents real clangers to these objects.
It was also hoped that electroclea n i n g would be shown to be a s ingle, effec­
tive method to remove t h i o u rea corrosion films from daguerreotype su rfaces.
The resu l ts show that the thiourea corrosion cycle is c learly a factor i n the
degradation of dagu erreotypes previously cleaned i n thiourea silver d ips.
O n the other hand, electroc lea n i ng was effective i n removing almost a ll of
the thiou rea corros ion products. In some cases, a barely detectable amount
of thiourea breakdown products was left on the daguerreotype plates a fter
electroclean i ng. In all cases, a hot water rinse removed any trace amounts of
thiourea breakdown p roducts following electroclea n i ng. The dagu erreotype
cleaning problem is very complex and m ust be considered careful ly. A con­
servator must decide on a cou rse of action that is appropriate for each case.
This means that it might not be appropriate to rely on a standard method that
will be good in the general case and not be applicable i n a speci fic situation.
Th iourea cleaning treatments were o n ce considered safe, effective,
and accepted procedures for the care of daguerreotypes. No finger of blame
can be poin ted at those who used this p rocedure before the P hotographic
M aterials G roup's moratori u m on its use. Any u n i n formed dealer or collector
today may be excused for i ts u se, but they do n eed to be educated about the
damage that this treatment i n A icts on daguerreotypes. However, for any per­
son who has been aware of both the concern s about this treatment that have
been raised in many articles and presentations over the l ast ten years, t he re
can be no excuse for the conti nued u se of thiourea cleaners. Any doubts
as to the damage caused by these treatments shou Id now be erased, a n d i t
should b e clear that it i s no longer acceptable u nder a ny circu m stances to
cont i n u e to u se thiourea treatments or to suggest their use. The informa­
tion presen ted here c learly shows t hat t hi ou rea t reatments cause irreparable
P a rt III S J L V E H , M E R C U H Y , A N D G O L D

damage to [ . . . J daguerreotypes and t hat there are no circumstances when

this treat ment can be considered ethical.

Acknowledgments

We wish to thank M ark M c Eachern and the Torrington (Connecticut) H is­

torical Society for giving perm ission for the analysis and retreatment of their
daguerreotypes as described here. We also wish to thank Di rk Kurth for his
role in carrying out the analyses and Or. Thomas Bein ( now, Department of
C hemistry, P u rdue U niversity) for making it possible to use one of the spec­
trometers i n h is group.

Endnotes

H oward Brenner, " S i lver D ips,'· Soap and Sanita,.y C/1e111icals 29 ( 1 953): 1 6 1 -
1 67, 1 83.
2 Charles van Ravenswaay, "An I m p roved M et hod For the Restoration or
Daguerreotypes," hnage 5 ( 1 956): 1 56- 1 59.
The M issou r i H i storical Society formula is as Follows:

Distil led water 500 cubic cen t i meters

Thiourea 70 grams
Phosphoric acid (85%) So cc
Non-ionic wetti n g agent
(e.g., Kodak " Photo-Flo" sol ution) 2 cc
D i st i l led water to make 1 ,000 cc

The daguerreot)1>e is uncased and washed in disti l led water to remove

any su rface d i rt. It is then i m mersed in the t h i o u rea sol u t io n u n t i l any
d i scoloration is washed away. Final ly, the plate is rinsed i n tap water, possibly
washed i n d i s t i l led or soapy water, rinsed again in water. A final alcohol d i p is
someti mes used to fac il itate drying oF the plate.
3 Leon Jacobson and \N. E. Leyshon, "The Daguerreian Measles Mystery,"
Grap/1ic A n.1-icr11a,.ian (Spring 1 974 ) : 14- 1 5.
4 For example see: T.J. Col li ngs and F.J . Young, " I mprovements in Some Tests
and Techn iques in Photograph Conservation," St11dies in Conse,.vation 21
( 1 976): 79-84; Siegfried Rempel, " Recent I nvestigations on the Cleaning
oF Daguerreot)1Jes," i n !\I C P1·ep,.ints (\•\/ashi ngto n , DC: American
I nstitute for Conservation, 1 980): 99-105; Alice Swan, "The Preserva t ion of
DaguerreOt)1>es," i n !\ IC p,.epri11ts (\i\/as h i ngton, DC: American I nstitute for
Conservation, 1 98 1 ) : 1 64- 1 72.
V i ncent Daniels, " Plasma Red uction or Si lver Tarn ish on Daguerreotypes,"
Studies in Conse,.11atio11 26 ( 1 98 1 ) : 45-49; M. S usan Barger, S.V.
Krish naswamy, and R. Messier, "The Clea n i ng of Daguerreotypes: I . Physical
Sputter Cleani ng. A New Tec h n ique," in !\I C Preprints (\Nashi ngton,
DC, 198 2 ) : 9-20; Barger. Krish naswamy, and M essier, "The Clean i n g or
Daguerreot)1>es: Comparison of" Cleaning Methods," Jo11 rnal of t.he American
 R e a d i n g 33 E D M O N DS O N A N D B A R G E B

Institute for Conservation 22 ( 1982): 1 3-24; Mogens S . Koch and A n ker Sj0gren ,
" Behancl l u ng van Dagucrreotypien m i t WasserstoffiJlasma," Maltechn.ih
Restauro 90 ( 1 984 ) : 58-6 4 .
6 M. S usan Barger, A . P . C i ri, W i l l ia m B. White, a nd Thomas M . Ed mondson,
"The C l ea n i ng oF Daguerreotypes," Studies i n Conservation. 31 ( 1 986): 1 5-28.
7 Associate Adj u n c t Professor, Department of Geology; on leave: Associate
Hesearch Professor, Department of Materials Science and Engineering, J o h n
1 -lopki ns U n iversity, Baltimore, M D .
8 G raduate Student, Departm e n t o f C hemistry; now Doctoral Candidate,
Department of Chem istry, P u rd ue U n iversity, \!Vest Lafayette, I N .
9 See F i gu re 1 0 . 5 i n M . Susan Ba rger and \Vil l i a m B . \Vhite, Tiie Daguerreotype:
Nineteen.t.1·1 Century Technology and American Science (Washi ngton, DC:
S m i thsonian l nstitu tion Press, 1 99 1 ) : 1 68.
10 B . l-1 . Loo, " Molecu l a r Orientation of Thiourea C h e m isorbed o n Copper a n d
S ilver Su rfaces, " Chentical Physics Letters 89 (i982 ) : 346-350.
11 Otto \Varbu rg a n d Victor Schoken, "A Monometric Act i nometer For the Visible
Spectru m , " Archive of Biochernistry 21 ( 1 949 ) : 363-369.
12 Half S . B ru e n ner, "Thi o u rea and Its Derivatives in Photographic Stabilization
Processing," Photographic Science and E ngineering 4 ( 1 960): 186-195.
13 See: C . 1 . P . Levenson and K . H . Stephen i n The Tlieo1y of t h e Photographic
Process, 4th e d i t io n (eel. T. 1-J . James, J . F. H a m i lton, G.C. H iggin s , and J.E.
Starr), New York: M ac m i l la n P u b l i s h i ng Co., I nc., 1 977, C h apter 1 5.
14 T. H . James a n d W. Vaneslow, " Kinetics of the Heaction Between S i lver
B romide and an Adsorbed Layer of Allylt h i o u rea," Journal of P hysical
Clie1nistry 5 7
( 1 953): 725-729.
1 5 G.O. Schenck a n d H . Wirth, Naturwissen.schaften., Tei.I B 40 ( 1953): 1 4 1 .
1 6 \!\/ . ! . Stephen a n d A . Townshend, 'The Heact i o n o f S i lver ( I ) I o n s with
Organic Compounds Conta i ni ng H N-C=S Groupi ng. Part I I . Some Th iourea
Derivatives," journal of t.he American. Che·m ical Society (A) ( i 966): 1 66-1 68.
1 7 J . Soll and A. S t u tzer, " M itte i l u ngen i.i ber e i n i ge neue \lerbincluge n , d ie aus
G uanylharnstoff u n d aus Digu a n i d erhalten wurclen," Ber. dt. Chent. Ges. 4 2
( 19 1 0 ) : 4532-4 54 1 .
 P A R T I V

Albumen Print Materials :

Manufacture, Structure,
and Treatment

I ntroduced in 1 8 50, the albu men process was the dominant p hotographic
print medium of the n ineteenth century. The popularity of albumen paper
was due to its ease of use and its suitability for p ri nting from wet-collodion
n egatives, the negative process with whi c h it was most often paired. Albumen
prints were able to capture the ful l tonal range and fine detail of the wet­
collodion negative. The freq ue ncy with which albumen photographs appear
in collections world"'tide as well as their acute vul nerability to i mage fad i ng
and b i nder degradati o n h ave led to considerable research and writing about
this process. In 1 997 two American conservators, Tim Vitale and Paul Mess­
ier, deve loped a Web s i te called "The Science, Technology and Treatment
of Albumen P hotographs: A Comprehensive Resource on the World Wide
Web." I t made accessible fu ndamental h i storical and contemporary resources
on the chemical properties and preservation of albumen photographs. Part IV
consists of fi v e i n fluen tial writings t ha t spa n 130 years. These ci tations, pre­
sented c h ronologically, doc u ment our u nderstanding of the structure, degra­
dation, and conservation treatment practice of albumen photographs.

Carleton Watkins (American, 1 829-191 6), Thom pson's Seedless Gra 11es (deta i l ) , 1880. Albumen silver
print, 37.6 X 55.7 cm ( 1 4 1 3/1 6 X 2 1 1 5/1 6 i n . ) . Los Angeles, ]. Paul Getty M useum 98.Xi\J .21 . 1
 R e a d i n g 34

M AT H EW C A R EY L E A

An Examination I nto the

C ircumstances Under Which
Silver Is Found in the Whites of
Albumen Prints ( 1 866)

Mathew Ca rey Lea ( 1 823-1 897) of Philadel11hia was a vl10togra11hic cheniist,

vhotogra11her, and distinguished a u thor. Jn 1868 Lea vublished the vov u la r
A M a nual of P hotography: I n te nded as a Text B ook for Begi n ners and a
Book of Heferen ce for Advanced Photographers, and i n 1877 he was elected
to several vrestigious academic societies, including the National Academy of
Sciences and the American Academy of Boston. Lea's early scientific investi­
gations contributed largely to the u nderstanding of silver image degradation.
Whi le strongly advocating for the extraordinary beauty and 1?ermanence of car­
bon vrinting, this reading foc uses on Lea 's efforts to address the vexing "fatal
yellowness " of albumen ·p rints and to cletennine how and when silver is formed
in. the unexvosed white areas.

The last two years have witn essed the most serious assau Its that have ever
been made upon si lver printing, and for a ti me with every prospect of i mme­
d iate s uccess. Nevertheless, the old process i s j ust as fixed as ever, and there
seems as yet l i ttle prospect that any of the novelties so vau nted will secure
even a h umble share of the work. Not that l have the least d isposition to
u n dervalu e carbon printing. I earnestly hope to see the day come when i t w i l l
entirely replace chloride printing. M r. Swan and Mr. Pou ncy have produced
some specimens of work of beau ty so extraordi nary, as, i n my opinion, to
have surpassed the best silver printing. And some specimens of M r. Wood­
b u ry's rel i evo pri nting are extremely good. B u t something easier, simpler,
and more certa i n will have to be thought out before the old method becomes

M ATHEW CABEY LEA, "An Exa m i n a tion I nto the C i rc u mstances Under Which S i lver Is
Found in the vVh ites of Albumen Prints," http://albumen.stanford.edu/l i b rary/c 1 9/le a 1 .
h t m l . Origin a l l y p u bl ished i n The Pliotogmphic News 1 0 , n o . 4 1 5 (August 1 866): 394.

294
 Reading 34 L E "

a n tiquated . So long as it does not, it will be a matter of u nceasing regret that

any doubt should exist as to the perfect permanency. To p u rchase an exqu i ­
s i tely beautifu l p hotograph , an d , after a ti me, to see t h a t fatal yellowness
s tealing over the h igh l ights, and to know that i ts final destruction is only
a question of time, is a real vexation. Fifteen years ago I p urchased, when
abroad, a n u m ber of Roman photographs, not one of which is now worth the
paper on which it is printed; and everyo ne has had [a] similar ex'Perience.
It, therefore, is clear that the two directions i n which study can be
most profitably directed for the advancement of p hotography, are, in the
s i m pl i fication of carbon printing, and i n the determination of all the causes
of deterioration to the silver pri nts.
I t is a well-known fact, though only lately ascertained, that si lver exists
in the whites of a l b u men p ictures. I have careful l y studied the conditions
of its presence, and, without being able to make so satisfactory a report of
res u lts as I cou ld wish, I hope to have clone something towards extending
o u r knowledge in this direction.
Before proceeding to detail the resu l ts of individual ex'Periments, I may
mention one general fact. It has been asserted that the existence of si lver i n
the wh i tes was clue t o the action o f faint light, passing through the darkest
parts of the negative-light too fai n t to visibly darken the ch loride of si lver,
and t hus impa i r the whiteness of the h igh l ights. I have disproved this i n
t h e fo llowi ng manner: A piece of a l b u men izecl paper was sensitized a t night,
d ried, washed, and fixed, without any expos ure, u n der a negative. It was, of
course, snow-white. Tested with s u l phydrate of am monia, i t gave i ndications
of silver, j ust as well - marked as other pieces ex'Posed u n der a negative, and
fixed and toned i n the usual way. There can exist, therefore, no doubt that
the presence of s ilver i n the whites is owi ng to a combination formed at the
time of sensitising, and that it has nothing to do with the ex'Posu re.
I have a lso remarked another fact which has its importa nce, and which,
if not d u ly borne in mind, may lead to erroneous conclusions. It is, that even
d i l u te sul phydrate of ammonia will make a very evident mark upon albu me­
nisecl paper which has never been sensitised, and which conseq uently does
n ot conta i n a trace of silver. \!\!h i le wet, this mark is yel lowish, and so exactly
s i m u lates the appearan ce prod uced when a fai n t trace of si lver is present,
that even a careful observer m ight be deceived. Even after drying, the mark
does not disappear. The yellowish colour of course is gone, b u t t here re mains
a dead mark that contrasts with the brilliance of the general albu men su r­
face, and this a l l the more strongly, as the dead mark is su rrou nded by a
bright border, brighter even than the rest of the albumen s u rface.
\!\!hen testing, t herefore, in this manner, it is necessary to let the mark
made by s u l phyclrate of ammonia become completely dry before ju dging of
i t ; and also to bear i n m i n d , in the case of very fai n t marks, that their in ten-
P a rt I V A L B U t\I E N P H I N T t\ l t\ T E H I A L S

si ty is i ncreased i n appearance by the great alteration of su rface caused by

the reage nt.
I shall next proceed to give the comparative res u l ts i n the examination
of the condition of the whites in a great many d i fferent toni ngs. To make
the res ults fai rly comparative, the fol lowing method was resorted to. A large
negative, h ighly intensified, so that the high l ights were perfectly protected,
was pri nted . A n u mber of d i fferent toning baths were prepared, a nd got into
worki ng order together. The pri nt was washed, then cut up, and different
pieces were toned i n the respect ive d i fferent baths, were fixed with hyposu l ­
phite of soda, a n d , after d ryi ng, were tested with hyclrosulphate of ammonia.
The speci mens thus obtained-some as far back as last wi nter, and others at
various ti mes-were carefu lly i nclorsecl and noted, and are now before me as
I write. I n all cases when the contra ry is not stated, the pri nts were made on
ammon io-n itrate paper.

1. Toned in the c i t rate of gold bath. Fixed in hypo.-A camel's hair pencil
or clean pen cl ipped i n di lute s u l phyclrate of ammonia, and d rawn over
the whites of this spec imen, left a c lear buff mark of sulphide of silver.
2 . Toned with benzoate of gold as descri bed by me.-Result the same as

the last.
3 . S u l p h u r toning (trithionate toni ng), obta i ned by add ing ch loride of lead

to hyposu lph ite of socla.-Th is toni ng, with or without the add ition of
gold, is sometimes u sed still for obtain i ng i n tense blacks upon plain
paper. It is, of course, not to be recommended, and is included here
for greater completeness. H e re a larger amount of si lver seems to be
left in the albumen, for the application of the sulphyclrate caused a
much deeper mark than i n the precedi ng.
4 . The next trial was made with the well-known old toni ng and fixing bath
of hyposu lph ite of soda, to which gol d has been added . On treating
the white with su lphyclrate of ammonia, ind ications of si lver were
obtained, but much l ess than in any of the precedi ng. The streak, i n
fact, was pale yel l ow .
5 . Th e l i me toni ng.-The i nd ications of si lver i n this case were b ut

m ocl era te.

6. Alka l i ne chloride ton i ng gave results not varying materially from
the last.

The trials in three of the above tonings were repeated su bsequently.

The citrate and benzoate of gold gave the same resu Its as above stated. The
third was the fixi ng and toni ng bath of hypo and go ld. Jn the trial above given ,
i t i s mentioned that the mark, i n its case, was much paler than i n the others.
I n the repetition, a prin t was obtai ned of which the whites were 1n1fectly free
from, silver. After the mark of sulphyclrate was d ry, it could not be found.
 R e a d i n g 35

GARY E . A L B R I G H T

The C onservation of
Albumen Prints ( 1 980)

Gary Albright, a photograph conservator i n 1nivate practice in. 1 -/ oneoye Falls,

eiv Yorh, has worhed for nearly t wenty years at t he Northeast Doc u ment Con­
servat;ion Center i n Andover, Massach usetts, where he developed 71rocedu res
for the mass t reatment of large ni.net;eenth- and twe ntieth -century 71hotographic
pri nts. The following reading, i nt:ended to bui.ld a base for fut u re research a nd
develop·m ent , is one of t h.e earli.est writ:- i ngs to detail t he conserva t ion t reat­
ment: of albumen prints. Though some of t:h.e tech niques discussed are infre­
quently practiced today, many form t h.e core of accepted treat ment: protocols
for clegraclecl album.en. p rint materials.

I n troduction

On May 27, 1 850, B lanq uart Evrard described a n ew process, a l bu men print­
i ng, to t he French Academy of Sciences. Within a few years its practice had
spread throughout the world, bringing an end to the daguerrean era . In Feb­
ruary of 1 862, Hmn.phrey's )ourn.al annou nced that albumen paper " is now
the rage, and our country ( U n i ted S tates) operators m u st learn the process
very thoroughly if they wish to keep up with times . " ' Between 1 855 and 1 890,
albu men prints dominated the photographic market, being used for stereo­
views, carte-de-vis ites, cabinet photographs, and various other formats. The
quantity of prin ts produced was phenomenal. In October, 1 866, it was esti­
mated by the B ritish Qu.a1i:erlJ Review that E ngland consumed some six mil-

GABY E . Aum1G1 1T, "The Conserva t ion of' Albume n Pri n ts," American I ns t i t u te for Con­
servation, A n n u a l Meeting, San Francisco, Preprints, 1 980. Reprinted by permission of ' the
a u l hor.

2 97
Part IV A L B U 1\ I E N P B I N T 1\ l A T E B I A L S

lion egg whites an n u ally i n the production o F albumen paper. For t h e period
prior to 1 8 73 , G reat / 11di1stries of the United Sl;ates calcu lated that 55,400,000
albu men i m ages were pri n ted yearly with in the cou ntry. 2 It is no won der
that albumen p hotographs are the largest category of p hotographic materials
to survive from the n i neteenth century. Due to their quantity and h istori­
cal im portance, interest has been stead ily growing in their preservation and
conservation. The fo llowing is a d i scussion of the deterioration of a l bumen
photographs and of methods curren tly util ized to conserve them.

T h e Process a n d its Deterioration

Albumen paper was prod uced by the photographer or a m a n u facturer by

floating a sheet of paper on a bath of egg white mixed with a mmoni um or
sod i u m c hloride. J ust prior to use, the coated paper was sensitized by float i ng
on a solution of si lver n itrate, forming the light sens itive silver chloride. I t
was then h u n g u p t o d ry. To make a pri nt, the se nsitized paper was placed i n
con tact with a negative exposed i n sunlight. After obtain i n g a visible i mage ,
the pri nt was washed i n water, toned i n a solu tion of gold ch loride, fixed i n
hypo (sodi u m th ios u l fate) t o remove unexposed silver salts, washed aga i n ,
a n d dried. D u e to t h e t h i n ness o f t h e paper, most prints were subseq uently
mounted o n cardboard .
The causes of alb u men print deterioration have been known since
1 855. In that year, the London Photographic Soci ety established the Fading
Committee to investigate the stability of pri nts. Their resu lts, published i n
the Photographic Journal o f 1 855, stated that Fading was clue t o 1 ) the i mper­
fect washing of pri nts, 2) the use oF old or insufficiently acid hypo baths,
3) the acidity of mou n t i ng materials, and 4 ) excessive moisture and su lfur i n
the at mosphere. They stressed that thorough washing of pri nts after fixjng
was essential, an d recom mended the gold toning of p hotographs for pro­
tection from atmospheric deterioration. Later, it was d iscovered that sulfu r
in herent i n egg white was an additional reason for fad i ng. S u l fur, a lso, was
the cause for an effect called " measles,'' small areas of d iscoloration wh i c h
appear as clo ts.
Along with fading of the i mage, there is a concurren t problem of h igh­
light yellowin·g . Th is, too, can be ca used by i mproper wash ing and fixing.
H owever, there is evidence to i nd icate that the yellowing i s related to silver
in the e m ulsion, which has reacted with the a l bumen and is, t herefore, not
washed out with su bsequent fixi ng.3
In addition to Fad i ng and h igh l ight yel lowi ng, albumen pri nts face a
t h i rd serious form of deterioration. As mentioned previ ou sly, most albu­
men pri n ts were mou n ted to a rigid board . The q uality of these boards is
often questionable. M a ny are com posed of t h i n top and bottom layers of
 Reading 35 /\ L B B I G l l T

good qua l i ty paper, ad hered to a thick core consisting of poor qual ity pulp.
The acid ity of the core material will eventually m igrate i n to the photograph,
causing stai n i ng, bleach i ng, or yel l ow i ng of the s ilver i m age. S ta i n i ng and
b leac hing may also resu l t from the use of a n i mp roper moun t i ng ad hesive,
such as a n i ma l glue, or moldy starch or gelatin. Often this form of sta i n i ng
wi l l fo l low the strokes of ad hesive application and w i l l vary i n d i rect propor­
tion to the amount of adhesive present .
Mou n ti ng of albu men prin ts on cardboard h as le a d to physical as we l l
as chemical problems i n the photographs. Often, t h e photograph-cardboard
is d i mensionally u nstable, and will exhi bi t a ripp l i n g aroun d the edges or
a general wavi ness. This i s a resu l t of the mounting proced ure where the
p hotograph is adhered wet to a dry board and placed i n to a press . U pon
removal , the unit is flat, but u nder great tension. With changes i n the envi­
ronment, this tension often res u lts i n the board warping. Little can be done
to remedy this situation o nce it has occurred. Thi s tension may also contrib­
ute to the fine crackle pattern which many albumen pri n ts exh ibit. Si nce
the photograph woul d be u nable to e;-qJand or contract, the albumen emul­
sion wou l d be placed u nder strong stresses. These stresses, coupled with the
brittleness of the albumen, could lead to the crackle network. Th is crackle
can a lso be a d i rect resu l t of mishandli ng, such as h arsh remova l of the pho­
tograph from its mount or severe bending of the photographic i mage. Usu­
ally these cracks present no conservation problem except as a site for dirt
accu m u lation.
Albumen pri nts also face the problems common to paper objects. These
include foxi ng; stains fro m mold, water or pressu re sensitive tapes; and the
results of i m proper handling or storage, s uc h as d i rt, tears, creases and losses.

Considerations B efore Treatm e n t

Before treatment can proceed several factors h ave to be consi dered.

-ls the print colored? Often album e n pri n ts will have been hand colored
with watercolors. This coloring is usual ly water soluble and thus woul d
precl ude aqueous treatment. Coating the pigment with B-72 t o protect
the color may al low water treatment. H owever, since these pigmen ts
do not penetrate i n to the albumen and are often dehydrated, t here is
the danger that removal of the B -72 wil l remove the pigme nt as wel l .
-Is there any writi ng, such a s a sign ature, o n the p hotograph o r mount?
I f so, the treatment may h ave to be modified depending on the sol u b i l i ­
ties of t h e med i u m used.
-Is the mount original, and therefore h istorically or artistically i m por­
tant? All attempts should be m ade to preserve an original mount, as
it is an i n tegral part in the p hotograph's presen tati on . Usually this
Part IV A L B U M E N P B. I N T l\ I A T E B I A L S

will resu lt i n the pri n t being removed from the moun t, a n d t h e mount
bei n g t reated as a separate entity. After treatment, the two wou ld be
reattached.

Treatment of Albu m e n Prints

Once the exa m ination of the photograph has been completed and any spe­
cial problems noted, the treatment of the print begi ns. Usually, the sequence
followed in treatment is as follows: 1) su rface cleaning, 2 ) removal from the
mou nt, 3) aqueous and nonaqueous treatments, 4) mending and l i n i ng,
5) retou ch ing, and 6) remou nti ng. The sequence of steps and the procedures
employed can vary, depending on the nature of the problems.
The surface clea n i n g of albumen prints may proceed in one of sev­
eral directions. The most obvious procedu re is the use of erasers. H owever,
there is the danger that an eraser may abrade the albumen, causing separa­
tion from the paper support, especially if the crackle pattern is pronou nced.
Also, the dirt and small bits of eraser which can collect in the cracks d u ri ng
clea n i ng are very d i fficult to remove. I nstead of erasers, cotton swabs can be
u sed . These are less harsh and may be used with either a rol l i n g or a light
ru bbing action. Care must be taken not to catch the cotton fi ber on the
crackle edges. Another procedure is to use a t h ic k wheat starch paste as a
poultice over the image. Once app lied, t he paste is a llowed to dry for twen ty
m i n u tes. Upon removal with cotton swabs and moisture, the paste will have
l i fted the d irt from the su rface and cracks. This procedure should only be
u sed with prints in good cond ition. Otherwise there is a risk of losing frag­
ments of the a l bumen layer. One can also clean the s u rface with Kodak Film
C leaner appl ied with cotton swabs. It may be necessary to follow the fi lm
cleaner by swabbing wi t h denatured alcohol to remove any streaking caused
by the cleaner. 4 One last method i nvolves clean i ng the surface with cotton
swabs and a weak ammonia solution ( 1 -5% of liquid ammoni u m hydroxide
concentrate). Care must be taken as the h igh p H of ammonia can affect the
albumen and swell it to varying exten ts depending on its degree of deteriora­
tion. ( I f ammonia affects the albumen adversely, water can be used i nstead. )
O n e should not apply ammonia solution t o a n area more than once a s this
cou ld remove some of the emulsion. I nstead, the solution should be al lowed
to dry and the process repeated. The amount of d i rt which can be removed
by this method is surpri s in g. Even apparently clean photographs will usually
yield some gri m e.
Before tears can be mended or stains removed, i t is necessary to
remove the photograph from its mount. Luckily, the adhes ives commonly
used were starch or gelati n based. As a result, most albumen prints are read­
i ly separated from their mou nts by im mersion in water for long periods of
 Reading 35 A L IJ 11 I G 1-1 T

time. Once the adhesive softens, the print is easily l i fted from its bac king.
To speed up the p rocess one can brush Kodak Photo-Flo (a wet ti ng agent)
on the su rface of the i mage, or one can use warm water. Often, however, it
is des irable to remove the print from its mount d ry. A d ry removal may be
necessary if t here is water soluble coloring o n the photograph, or a concern
for the safety of the object when subjected to long periods of aqueous t reat­
ment. Long exposu res to water tend to i n tensify the p roblems of deteriorated
albumen, ren dering i t water sensitive, or i n itiating a local separat ion of the
albumen from the su pport. A d ry removal is performed with a very t h i n Rat
spatu la. The spatula is slipped between the pri n t and the mount, and care­
fu lly slid around the edges of the photograph. For this operation, it is crucial
that the spatula be held as Rat as possible, parallel with the su rface of the
mount. There is a slight t i lt i ng of the spatula i n to the mount, which pro­
vides a downward pressure to prevent slitting of the i mage. A c i rc ular motion
with the spatula is u sed t h roughout the process, with the cutting occu rring
when the spatula i s movi ng towards the operator. This procedure is tricky
and can be dangerous, but once mastered is very quick. I f not performed
properly i t is easy to create a crackle pattern i n the photograph which is
i mpossible to remove. Also, care must be taken not to a llow balls of paper to
form u nder the photograph as these can cause ridges i n the e m u lsion. Once
off the mount, the residue paper and adhesive on the reverse are removed
with locally applied moisture or by i mmersion.
Occasionally, one will fi nd an albumen pri n t mounted with a case i n
adhesive. Often this adhesive w i l l loosen i n warm water o r a weak ammonia
bath. However, there are ti mes when the adhesion i s so strong that part or
all of the mount m ust be destroyed i n order to save the p hotograph. Some­
ti mes only the top layer of the mount d i rectly u nder the p hotograph needs to
be disturbed, leaving the remainder of the mou n t i ntact.
After removal from the mount, the pri n ts are bathed in water, photo­
graphs having solu ble media being excluded . Bathi n g removes the res idual
adhes ives on the reverse, lessens the acidity of the support, helps reduce cer­
tain stains, and occasionally lighten s some of the yel lowed highl ights. One
problem encountered is the formation of air pockets between the emulsion
layer and the paper su pport. M ost of the time these will Flatten out upon
d ryi ng. H owever, i f they become too large, the e m ulsion ma y stretch i rre­
versi bly. Before excessive stretc h i ng occurs, the pockets m u st be punctured
with a needle and pressed down , otherwise the e m u lsion will dry with over­
lapping creases.
After wash ing, p r i n ts are often neu tral ized. U n l i ke many paper objects,
albumen photographs should not be buffered si nce albumen is u nstable at
a p l- I above ten . One solution commonly used is 1 % Kodak Balanced Alka l i
(sod i u m metaborate) . This compound is used i n p h otographic developers to
Part IV A L I3 U iVI E N P R I NT MATE RIALS

mainta i n the alkali n i ty o f the sol ution between a p l-I of 9 . 8 and 1 0 . After
i mmersing an albumen prin t i n the solution, it should be thoroughly washed
in water to rem ove any traces of the borate. This treatment will often reduce
the intensity of acid stains and can lighten the highlights.
Another bath which is occasionally used is a 5% sol u tion of sod i u m
bisulfite. I n p hotographic applications t h i s compound is employed as a weak
acid or preservative, where it acts as a reducing agent. How it reacts with the
albumen e m u lsion i s u n kn own , but the solution can d i m inish the yellowing
i n the h ighl ights and help wash out processing stains. S uccess, however, has
been very l i mi ted .
Fading of albu men prin ts can be caused by i mp roper fbd ng and wash­
i ng. For this reason some conservators advocate the archival processi ng of
albumen p hotograph s. The process consists of bathi ng the wetted prin t i n
two successive solutions of fixer for two m inutes each, wash ing t h e prints i n
water for thirty seconds bat h i ng i n hypo clearing solution for th ree m i nutes
(this greatly e n h ances the removal of fixer from paper), a n d finally, was h­
i ng i n ru n n i ng water for thirty m i n u tes. However, recently there has been
some q uestion regardi ng the safety of the procedu re . By refixi ng, one is rei n ­
trodu c i ng sulfur t o the e m ulsion . This su lfur may b e i mpossible t o remove
completely, a n d cou ld eventua lly lead to further fading of the image. Also,
refixing often i ncreases the contrast of the pri n t by bleac h i ng out some of the
si lver in the h igh l ights. If there is concern for res idual processing chemicals
i n the print, the photograph can be treated i n hypo c lear, followed by hypo
e l i m i nator and water baths. This woul d remove excess fixer previously left i n
the support, w h i l e avoiding the i n troduction o f new fixer t o the e m u lsion.
Stains o n albumen prin ts pose a major problem . The standard paper
bleaches generally are not effective and if they do remove the sta in, the
i mage is bleached as we ll. H owever, UV b leac h i ng is one technique which
has proven to be fai rly successfu l . ' H ow it works, and the dangers it presents
are u n known at this time. The procedure involves i mmersing the photograph
in a tray filled with three-quarter i n c h of water, which has been m ade sl ightly
basic (pH 7-8) with am m o n i um hydroxide. Placed over the prin t, as close to
the water as possible, are several s u n lamps ( UV light source ) . After an eJ( pO­
sure of one hour, the lamps are shifted and the process repeated u n t i l the
entire photograph has been exposed. The process can be repeated, locally or
gen erally, as n eeded. This procedu re will bleach many of the stains caused
by mold, water, or by contact with wooden backi ngs. I t i s much less effective
with rubber cement or pressure sensitive tape stains.
As in paper conservat ion, organic solvents are used on albumen pri nts
to remove greasy dirt, and tape stains. The one concern with solven ts is the
clanger of dehydrating the albumen and causing c racking of the emulsion.
 Reading 35 A L B B I G H T

By was h i ng i n water afterwards, moisture w i l l be replaced i n the emu lsion,

hopefu l ly preventing any damage to the print.
H istorically, albumen prints were wet mounted to a dry, rigid board.
Th is i n s ured their flatness and i m parted a sheen to the s urface. Today, con­
servators usually fol l ow the n i neteenth century example and either remount
or line the p hotograph using a water-based adhesive and some method of
stretch d ryi ng. ( Dry mounting of an albu men prin t to a board i s very difficult.
The pri nt tends to cockle from the heat, will not lie flat, and does not yield
the same su rface q uality as wet mounti ng. ) Before lining occ urs, any tears
or losses should be repaired. This is clone in the usual way with Japanese tis­
sue, matching papers, and wheat starch paste. One l i ni ng p roced u re involves
backi ng the p hotograph with J apanese paper and wheat starch-methyl cellu­
lose paste, 6 a n d stretch drying i t on glass by adherin g the edges of the l i n i ng
tissue to the glass. I f p u re wheat starch paste is u sed i n stead, the p hotograph
tends to pull away from the lin i ng. D u ri ng d rying, tears m u st be carefu lly
watched as they can b e p ulled open. After drying, the print i s i npa i ntecl, c u t
from t h e glass a n d mou nted, if desired.
Another l i n i ng m ethod i s s i m i lar to a procedure u sed in E ngland.
On top of a roughened s heet of plexiglass is pasted (wheat starch paste7) a
moist dacro n cloth. To the cloth is applied another l ayer of paste, permal ife
(So pou n d ) or Japanese paper, more paste, and finally the photograph, which
has been previ ously relaxed with moisture. After d rying and i npa inti ng, the
Dacron is p u lled from the plexiglass and then stripped from the l i n i n g paper.
During treatment of the p hotograph , conservation of the mount could
be proceedi ng as well. These mounts are treated as paper objects, one com­
pl ication being their t hickness. Often the mount consists of a thin top and
bottom layer with a wood pulp core. By i mmersion i n water or carefu l manip­
u lation with a spat u l a, one or both of the t h i n layers may b e separated from
the board . They can then be attached to an acid-free moun t. One alternative
is to l i ne by the Engl i s h method, the top l ayer could then be applied between
the lining paper and the photograph.
The final step b e fore remounting the photograph i s i npa i nting the
losses, tears and abrasions i n the image . Some s uccess can be ach ieved by
using watercolors or acrylics with occas ional l ayers of gel a t i n or methyl cel­
l ulose. Another method i s to use albu men8 as a mediu m in which to m ix
the coloring agents. Thi s i npainting is readily removed before the final step
when the albumen is h ardened by applying isopropyl alcoho l . For i np a i n t i ng,
three co lors are fou n d to be very usefu l when matc h i ng original tones: b lack,
warm sepia, and scarlet l ake.
Trad itionally, albumen prints were presented mou n ted on a rigid sup­
port. To mai ntain this tradition, the prints should be remou nted after treat-
Part IV A L B U 1\ I E N P H I N T M A T E H I A L S

ment, h opefu l ly onto their origin a l mou n ts. Wet mou nting the i mages onto
a thick board poses tremendous problems with cockl i ng. Some success can
be achieved by cou n terl i n i ng or drying in a press for long periods of time,
but often cockl ing will remain. One sol ut ion is to use a d ry mount tissue.
The photograph and mount wil l rem a i n Aat and the operation is very fast,
however, there is some q uestion concern ing the d ry mount and its i nAuence
o n the si lver i mage over long periods of time. Another consideration i s that
the heat to which the p hotographs are subjected (2oo°F) d u ri ng moun t i n g
c o u l d conceivably cause changes i n t h e a l b u m e n su rface. Yet, by carefully
choosin g a good q u a l i ty d ry moun t tissue, and by having a n i nterleaving l i n ­
i n g between t h e photograph a n d t h e adhesive, t h e tec h n ique is a viable a lter­
n ative. Besides wet or dry mounti ng, one can use hi nges or photo corners
or simply leave the image u n moun ted . When reattach i ng the photograph to
i ts original mount, one may fi nd that the two no longer flt together cl ue to
shrinkage of the photograph during treatment. Little can be done to remedy
the situation, except to inpaint any exposed areas to the tone of the board .

Conclusion

The treatment of albumen photographs has only recently begun to be seri­

ously u ndertake n . New methods and tec h n iques are constantly being devel­
oped and old ones discarded. The treatments I d iscussed are all currently
being used . Often there has been l i ttle, i f any, experimentation to test the
methods or investigate their long-range i n A uence on the albumen i m age .
By presenting these tec hniques, 1 h ave a ttempted to build a base for fu ture
research and development.

Acknowledgments

I wish to thank David Kolocly for his wil lingness to share his treatment tech­
n i q ues. Of course, a special thanks m ust be given to my mentor, Jose Orraca.

References

1\�l i l l i a m \�1e l l i ng, Photography in A inerica: The FonnaUve Years, New York
( 1 978), p . ' 57·
2 G reat. lndmt.ries of the United States, Hartford ( 1 873), pp . 880-88 1 .
3 Haddon and Grundy, The British Journal of Photography, 40 ( 1 893), pp. 5 1 1-
5 1 2 : 4 1 ( 1 894), pp. 788-789; 43 ( 1 896), p p . 468-469.
4 Hobert \�lcinstcin and Larry Booth , Col/ect io11, Use and Care of 1-/istorical
Pl10togmplis, Nashville ( 1977), pp. 1 82, 1 84.
\�/i l l iarn Crawford, The Keepers of Light., Dobbs Ferry, New York ( 1 979),
pp. 300-3c r .
 Reading 35 A L l3 R I G H T

6 M i x 1 00 grams of wheat starch with 750 m l . water a n d cook for 30 m i n u tes

(the paste becomes translucent and ribbony). Meanwhile soak 25 ml. volu m e
of TALAS methyl c e l l ulose i n 100 m l . water. Once the paste h a s cooled, i n
a blender m i x the wheat starch a n d methyl c e l l ulose, add i ng water to obtai n
t h e proper consistency. For a preservative, add 2 grams ol" ortho-phenyl phenol
dissolved i n 25 m l . ethanol.
7 M ix 200 m l . vo l u me wheat starch lo 1 4 00 ml. of water and soak for 30 m i n u tes.
Divide i n to t h ree equal portions a n d refrigerate. \Vhen needed for use,
combine one portion with 300 ml. of water a n d mix in a blen der.
8 Albumen is made by mixing six fresh egg wh ites in a blender with o-4 to
0.5 ml. glacial acetic acid. Beat for one to two m i n u tes, u n t i l comp letely
foamed. Allow to settle ove r n ight before usi ng. Keep refrigerated.
 R e a d i n g 36

] A M E S M . R E I L LY , N O RA K E N N E D Y ,
D O NA L D B LA C K , A N D T H E O D O R E VAN D A M

Image Structure and Deterioration

in Albumen Prints ( 1 984)

Jam.es Reilly (see also Readings 7, 19, and 60) has p ublished widely o n the
technology, c ha racterization, and preservation of ni neteenth-cent u ry photo­
g raphic print materials, He is the author of two boohs on n ineteen t:h-century
photography; The Albumen and Salted Paper B oole The H istory and Practice
of P hotographic Pri nting 1 840-1 895 and The Care and Ide nti fication of 1 9th­
Century P hotographic Prints. His gro u ndbreahing research-in collaboration
with Donald B lach and Theodore Van Dam of the Research Laboratories of
Eastman Kodah Conipany and Nora Kennedy (see Reading 1 2 )-advanced
u nderstanding of the image microstructure and degradation of a lb um.en prints,
clea rly demonstrating the vulnerability of a lbumen p rints to oxidative-reductive
deterioration ( resulting in fading and loss of highlight detail) and the need for
controlled-humidity storage environments. Equally important is Reilly's worh
from 1 978, "Die Manufacture and Use of Albumen Paper, " Journal of Photo­
graphic Science 26, no.4 (July/A ugust 1 978 ) : 1 56-6 1 ,

I n troduction

Because of the domi nance of the albumen print materia l in p hotographic

practice from � 1 855 to 1 895, a s ubstantial portion of the legacy of 1 9t h-cen tu ry
p hotography exists i n this form. The nature and structure of these prints, a n d

] AiV I ES t\1 1 . REI LLY, NOHt\ KENNEDY, DONALD B LACK, a n d T1-1 EODOHE VAN DAM, " l n1age
Structure and Deterioration in Albumen Prints," Phot.ogrnphic Science and Engineering
28, no. 4 ( 1 984): 1 66-7 1 , © 1 984, Society oF Photographic Scientists and E ngineers, Text
and i mages repri nted by permission of I S&T: The Society for I maging Science and Tech­
nology, sole copyright owners of Pliot.ogrnpliic Science and Engineering,
 Reading 36 H E I LLY ET AL.

particu larly their i mage stability, are a concern to arc hives, l ibraries, and muse­
u ms. Most albumen prints have deteriorated, showing overall density loss,
severe highl ight density loss, and a marked sh ift i n i mage h u e . A recent i nves­
tigation 1 fou nd thiosulfate retention from i m proper processing u nl ikely to be
the explanation for such vvidespread deterioration; t hiosulfate was adeq u ately
removed fairly rapidly, and even well-processed i mages were u nstable i n moist
air at moderate temperatures. These res ults, together with the evidence from
> 1 00 years of natura l aging, suggested that more fu ndamental fac tors, perhaps
related to i mage structure, were responsible for the deterioration.
A relationship between si lver i mage structure and resistance to s u l fiding
and oxidate-red uction deterioration has long been known. Baekeland i n 1 8972
related the poor image stabil ity of pri n t i ng-out to a m u c h smaller particle size,
though he sti ll had dou bts about whether the i mage was composed entirely of
metallic si lver. He a lso noted that among developed i mages, coa rse-grai ned
pri nts were more resistant to attack than fi ne-grai ned ones. Considerable prog­
ress has been made in o u r u ndersta nding of the mechanisms of si lver i mage
deterioration and the relationsh i p between i mage struct u re and resistance
to attack. The relevan t structural features are m u c h too small to be observed
with an optical m icroscope and can be studied only by use of electron micros­
copy. Our study of albumen-pri nt i mage stru ct ure has the dual objective of
i nvestigating image formation in albu men prints and relating characteristic
structural features to deteriorat ion patterns observed in both nat u ral aging of
h istorical pri nts and the i n c u bation of prin ts made i n the laboratory.

The A l b u me n Pri nt

The albumen print material3·4·5 consisted of a relatively thin paper support

coated on one side with an i mage-bearing layer of hen's egg white. Overall
sheet thickness was typically �0. 1 m m , and the albumen layer varied i n t h ick­
ness up to ca . 12 µm. The albu men coating (containing 1-2% ammoni u m or
sod i u m c h loride) was applied by Aoating individual sheets on a tray of albu­
men sol ution; they were then h u ng vertically to d ry. Thi s caused the albu­
men layer thickness to vary from top to bottom. A second layer was often
applied and the sheet h ung upside down d u ring the drying to compensate
for the u neven first coating. To achieve a net gain i n coati n g thickness, some
met hod for loweri ng the solubility of the fi rst coating was req u i red. Bathing
the coating in low- molec u lar-weight alcohol solutions was freq uently men­
tioned in the l iterature but apparently not widely used commercial ly. Si nce
the sol ubil ity of dried al b u men declines naturally over a few months, most
manufacturers simply "cured" the product between coati ngs. In our study,
when the first coating of laboratory- made prints was coagu lated in a 70%
solution of 2-propanol, a definite i nterface between the layers was visible i n
Part IV A L B U 1\ I E N P H I N T J\ I A T E B I A L S

Albumen
Layer

A l bu m en
Layer

Paper
Support

Figure l Figure 2
Cross-sect ion electron 111 icrograph I mage deposit From Figure r at
ol' a 1 9 t h-ce n t u ry albumen print, higher magnification (80,ooo X ) .
showing a l bu men layer. image deposit
(conccnt ralL'd in top haJI' ol' albumen
layer). and uppermost paper fibers
(spongy area at bottom) {20,ooo X ) .

the electron m icrogra ph cross-sections. Only one 1 9th-century pri nt among

the eleven exam i ned had such an i n terface.
For use, the albumen paper was sensitized by floati ng it on a 6- 1 0%
s i lver n it rate sol u t io n . A more sensi t ive paper with better keepi ng proper­
t ies was obtai ned when up to 5% c i t ric acid was added to the si lver solut i on .
Th e al b u m e n p r in t image was prod uced b y printi ng-out, i .e ., ent i rely b y pho­
tolysis. Processing i n c lu ded an i n itial wash to remove all soluble si lver com­
pounds, go ld toning, fixation in sod i u m t h iosu l fate, and a final was h .

Overview of I mage Structure i n Albumen Prints

For stud ies of i mage structu re and the various i n f l uences on i mage forma­
t ion and deteriorat ion, cross-section electron mi c rographs c u t normal to the
pri nt su rface were prepared . In all, 1 1 d i fferent 1 9th-century prints and ca.
40 laboratory-made pri nts were exa m i ned, usually at several density levels.
Typical electron m icrographs at low and high magn i fication of a 19th-cen­
t u ry albumen print (ca. 1 890) arc shown in Figures 1 and 2.

.108
)
 Reading 36 R E I L L Y ET A L .

Two features are noteworthy: The i m age material is largely confi ned to
the u pper half of the a l b u men layer, and the particle size and n u m ber of par­
t ic les progressively decrease at greater depth i n the coating. All pri nti ng-out
papers share these features, and the presence of a vertical gradient of den­
sity (which can be c learly seen at the lower magn i fications possible with the
optical m icroscope6) is a u seful characteristic in d ifferentiating printi ng-ou t
papers from developing-out papers. The progressive decrease i n particle size
and n u mber is due i n part to the shielding effect of photolyzed s ilver, which
forms i n i ti a l ly i n the uppermost parts of the coating and gradually attenuates
the amount of exposing radiation reach i ng the lower parts of the coati ng.
I n albumen prin ts (and other early types of printing-ou t papers) there
may be other reasons for the vertical gradient of i mage materia l. vVhen a n
albume n pri n t i s sensitized, it is floated albumen-side clown on a strong s i lver
n itrate solution ; the si lver ions d i ffuse i n to the albumen layer, which already
conta in s chloride ions. Silver chloride crystals are n uc leated a n d grow u n der
c i rcu mstances governed by diffusion, and the net result i s that the most
favorable conditions for i mage formation occur n ear the u pper su rface. Thi s
i s n o t t h e case in more modern "emulsion"-type prin t i ng-ou t papers, where
the si lver ch loride suspension is mixed i n a kettle and is a h omogeneous d i s­
persion when coated o n the support.
At h igh m agni fication ( Figu re 2) the i m age material of albumen prints
is seen as discrete, roughly spherical particles rangi ng i n d iameter from <3
to 50 n m , with most between 5 and 20 nm. Larger than average particles
form at discontin u ities such as air bubbles. I n e>qJosecl areas, i m age material
is a lways fou n d i n the paper fibers i m mediately below the albumen layer.
Here the particles are typ ically as large as or larger than a ny fou nd i n the
albumen matrix above.

Photolytic I mage Formations

The i m age material of albumen pri n ts is formed by photolytic reduction of sil­

ver on the su rface of silver ch loride crystals embedded i n the albumen matrix.
For the paper to have adequ ate sensitivi ty, the silver ch loride crystals m ust be
s urro unded by an excess of free si lver ions or soluble silver complexes which
will make s ilver ion avai lable for photo lytic reductio n . A detai led i nvestigation
by Fergg on the formation of pri n ted-ou t i mages in collod i on is recommended
for further study on this poi nt.i Fergg showed that little of the s ilver which
i n i tially existed i n the coating as si lver chloride actually e nded up as part of
the i mage. H e found the i m age to be primarily composed of s ilver which had
been reduced at the crystal su rface but which previously existed in soluble
form i n the collodion matrix and had d i ffused to the crystal surface prior to
reduction . A sim i lar mechanism appears to operate i n albumen prints.
 Part IV ALBUMEN P H I NT M A T E B l t\ L S

Other i m age si lver may be fo rmed by p hotolytic reduction o f s ilver

complexed to the albumen i tself. A much less sensi tive paper, but one with
many qualities i n common with standard albumen paper, may be obtai ned
by omitting the c hloride al together. Probably this secondary mechanism

;f�>
accou n ts for o n ly a small amount of the i mage material i n albumen pri nts.

t.� .:'.:- . Effect of th.e Composition. of the Sensitizing Solution.

·:/". >
.. :
..-.·... ..
•
.·
. . Since the i mage material originates mostly on the surface of the s i lver chlo­
. . . �· ..
·
ride crystals, the gra i n s ize and spatial d istribution of the s ilver halide are
.

• . .. . .. :.'. '
. . .. i mportan t i nfl uences on the fi nal i mage structure. Factors which tend to

;.
a lter the grai n-size d istribution of the h a li de will lead to d i fferent configura­
.
� :: ··.
tions i n the final s ilver i mage. Two very d i fferent general configurations of
i mage si lver were encountered i n this study. One was characteristic of sensi­
tization with a plain silver n itrate solution, and the other was characteri stic
of the use of citric acid and si lver n i trate.
The configuration assoc iated with plain si lver solutions is shown i n
the micrographs of Figures 1 and 2 and i s schematized i n F igu re 3 . One of
the structural elements typically presen t is a "crust" or deposit of particles
Figure 3
Schcmat ized cross-section of image at the extreme uppermost su rface. Thi s forms during eiqJos ure, becom i n g
deposit of a l b u m e n print sensit ized a n early contin uous l ayer a t h igh densities. Below t h e crust i s a n a rea rela­
with p l a in silver ni trate solution.
tive ly sparsely populated with particles. Still lower i n the coating is the m a i n
i mage deposit. H ere t h e i mage material is evenly d ispersed spatially, w i t h
t h e particle size a n d n um ber gradually decreasi n g from top t o bottom. Thi s
general con figuration i s t h e o n e most frequently encountered i n t h e 1 9th­
. .. � ·"'· - :
.. cen tury prints we exa m i ned .
. �... The use of citric acid i n the sensitizing solution (a practice extensi vely
. - ·. · .... ,,.
.. ... .
. .· employed for producing albumen paper for amateur use during the 1 88o's
""' ·. ·

;,.. and 1 89o's) leads to the general configuration sche matized in Figure 4 . No
:;.; �·
,
.
,
.
crust is i n itially present, though one may su bsequently form during deterio­
ration. There is a relatively em pty area just below the prin t surface. Beneath
it, the main i m age deposit is divided i n to two d istinct layers, one with rela­
..
�· tively large particles packed loosely together in colonies, and below this, an
area of smaller particles even ly d i stribu ted spatial ly. \Vit h in each of these
two layers the particle s ize and nu mber decrease at progressively greater
depth in the coating. The ent ire i mage depos it, however, is s t i l l concen trated
in the upper half of the albumen l ayer. O n ly two of the eleven 1 9th-century
prints exam i n ed had this configuration.
F igu res 5 and 6 are electron m ic rographs of contemporary laboratory­
made albumen prints which show the i mage structure typica l ly assoc iated
with the use of citric acid. F igu re 5 s hows an area near the top of a n unpro­
Figure 4 cessed pri n t . The dark partic les are the AgC I crystals, and the gray clouds
Schcmatized cross-section or
image deposit of albumen print
sensit ized with s i lver n i t rate/c i t ric
acid solution.
 Read ing 36 ll E I L L Y ET AL.

Figure 5
Cross-section, electro n m icrograph
of u n p rocessed experimental
albumen print sensitized with a
silver n i t rate/citric acid solution .

Figure 6
Coating s i milar to that of-'
Figure 5 <.1Fter normal exposure
and processing.

s u rrou n din g them resu lt from an i n teraction between the crystals and the
electron beam. F igure 6 is a s i m i lar coati ng after n ormal exposu re and pro­
cessing. It m ay be seen from this comparison that the general spatial con­
figuration of i m age material in the processed pri n t is determined by that of
the s i lver hal ide prior to exposu re.

Structural Features Arising from Photolytic Reduct-ion.

An i mportant aspect of i mage formation in all pri nti ng-ou t papers is the
increase in both particle s ize and n um ber with i nc reasing e)qJosure. At low
densities, the s ize of the i m age particles i s at a m i n i m u m and their degree of
d ispersity i s at a maxi m u m . Because of their extreme small ness, a t low densi­
ties the i mage particles are d ifficult to resolve in the electron m icrographs.
H owever, the typical appearance of albumen prin t i mages at various densi­
ties is shown schematically i n Figure 7 . These schematic representations of
the i mage deposit approximately correlate to the three density levels i nd i ­
cated o n the D log E cu rve above.

Comparison with Deve lo p i ng-Out Print M aterial s

It is useful to compare the albumen print i mage stru cture shown i n Figure 7
with a schematized version (at the same scale) of the i mage structure of a

311
 Part IV A L B U M E N P B I NT MATE R I A L S

2.0 2.0

>­ >­
f- f-
I/)
z
1.0 � 1.0
w w
0 0

RELAT I VE LOG E X POSURE RELAT I VE LOG E X POSURE

DD low mid high

u�•l ow mid high

I /A- m 1 14 m

Figure 7 Figure 8
D log E cu rve of a l bumen paper showing schcmatized IJ log E c u rve of t�1Jical developing-out paper showing
representations of the image deposit in low-. med i u m-. sc hematized representations of die image deposit
and high-density areas. i n low-. mediu m-, and high-density areas.

typical developi ng-out paper, shown in Figu re 8. There is a large size differ­
en tial between i ndividual i mage particles in the two types of paper. Devel­
opi ng-out papers typically conta i n much larger si l ver hal ide crystals than
do albumen prints. I n images produced by direct development, the action
of the developer converts the entire s ilver halide crystal to metallic silver
in the form of a filament b u ndle. This i mparts a relatively large m i n i m u m
size t o t h e basic structural u n i t of developed i mages, even at very low densi­
ties. The development mechanism also ensures that the filaments are c losely
packed spatially. These features give developed images distinct advantages
over pri n ted-out i mages in resisting attack by oxidants, espec ially i n low­
density areas.
The relatively greater resistance to deterioration of h ighlight areas of
developed-out prin t (compared to printed-out i mages) may be seen in the
data from an i ncu bation experi ment comparing both types . The data i n
Table 1 are from a typical experiment of this kind, i n which laboratory­
made albumen prints a n d pri nts made on a contact-speed develop-out paper
( Kodak Azo paper, grade 2 ) were i ncu bated together at 50°C, 86% RH, for
 Reading 36 H E I L L Y ET A L .

Table 1
Relat ive density changes i n albumen prints a n d Kodak Azo paper during i ncu bation tests.

Percent Change from Starting Density

Starting Density of Both P r i n t Types after 60 Days at 5 0°C , 86% R H
Before Incubation Albumen Azo
B l u e fi l ter 0 . 30 - 32.0 - 7.5
0.50 - 24.7 -6.o
1 .00 - 17.2 - 3.3
1 . 50 - r 3.9 - 9.2
Red fil ter 0.30 - 37.7 + 1 .5
0.50 - 25.8 +o-4
J .00 - 20.5 +0.7
1 . 50 - 23.6 - 9.3

60 clays. S hown in Table 1 are percent density changes from starting densi­
ties of 0.30, 0. 50, 1 .00, and 1 . 50 for each materi a l . The fi l ters used for the
reel and blue reflection density measurements were Kodak Wratten fil­
ters 25 and 47B, respectively. The albumen prin ts were made by using two
coati ngs of a lbume n (con ta i n i ng 1 .25% N H 4 C l by weight), sensitized with
a 1 0% AgN 0/1 % citric acid solution, exposed to a 1 000 \,Y mercu ry vapor
lamp ( N uArc G\,Y 1 14), toned with a gold c h loride/borax toner, and fixed i n
1 0% sod i u m thiosulfate. The developed-o u t prints were made o n Kodak Azo
paper, grade 2, developed i n Kodak developer D-72 1 : 1 , and fixed in Kodak
rap i d fixer. Before the density changes in Table 1 were calcu lated, sta i n den­
sity ( meas u red in n o n image areas) was subtracted from the i mage densities
to correct for differing stain s. The albumen prin ts were obtai ned when other
types of printing-ou t papers were compared with a bromide e n largi ng paper.
The small particle size and h igh degree of dispersity characteristic of h igh­
light areas of printing-out papers are the structural features responsible for
their i n ferior im age stability.

Effects of Gold Toning on Image Structure

I-I istorically, nearly a l l albu men prints were gold toned prior to fixation.
N u merous tone for m ulae were used, with various conseque nces for i mage
color and stabil i ty. I n our incubation experiments, gold thiocyanate toners
provided more i mage stability in albumen prints than did a l kaline gold ton­
ers conta i n i ng sod i u m carbonate or sod i u m acetate. O n the m icrostru ctural
leve l , gold toning causes va rious degrees of distortion of the origin a l particle
morphology. Depending o n the form ula used, after to ning such general fea­
tures as the presence or absence of a crust, the group i n g of particles into col­
onies, and the depth of i m age material i n the coating are the same, but the
 Part IV A LB U M E N P H I NT M ATE H I A L S

Figure 9
Cross-section electron micrograph
from high-density area of'
experimental albumen print
toned in a gold chloride/sodium
carbonate toner.

t--1
0.1 µ.m

particle size decreases and individual particles are more irregu lar and elon­
gated. A few become almost c ircu lar, with one or two thickened areas. Some
gold toners tried i n this st udy produced large ch anges in particle morphol­
ogy i n albumen prints, whereas others produced more subtle changes. F ig­
ure g shows an albumen pri n t i mage showing consi derable distortion of the
original spherical particle shape due to ton i ng with a gold chloride/sodium
carbonate toner. The elo ngated, c i rcular shape seen in some particles here
is even m ore promi nent i n pri n ted-out images which have been toned with
platin u m , a technique used mai n ly with matte collodion p rinti ng-out paper.
The ton i ng process substitutes gold for some of the s i lver in the
i mage.8·9 The final a l b u men prin t i mage conta ins 20-25% gold . 1 0 Gold(!) ions
will oxidize silver atoms o n a one-for-one basis a nd take their place i n the
si lver lattice. This is the l i kely cause for the observed distortion of particle
shape d u ring toning, and i t provides evidence against the view of gold ton­
ing as merely a superficial deposition of gold. Gold( I I I ) ions, if present, w i l l
oxidize three silver atoms for each gold atom reduced. T h e tendency for gol d
toning t o diminish t h e particle size m a y b e rationalized through t h e oxidative
nature of the toning process and the presence of some trivalent gold. The
starting point for all the common toner formu lae was gold c h loride (chlorau­
ric acid, H Au C l d l-1 2 0), a Gold( I I I) complex.

M icrostructural C h a nges During D eterioration

For the studies of i mage deterioration i n albumen prin ts, both 1 9th-century
and laboratory-made prin ts were used. The view of the deterioration pro­
cess that emerged is one in which the image is wholly re-formed through a
conti n ui ng cycle of oxidation and reduction. The extreme small size of the
i nd ividual i m age particles (with their consequent enormous su rface area
relative to their mass) ren ders them thermodynamically u nstable. Gold ton­
i ng may retard but does not fundamentally change this behavior. Albu­
men prin ts displayed rapid and dramatic changes in image m icrostructure

314
 Read ing 36 H E I L L Y E T A L .

u n der attack by moist air at moderate temperature. These microstructural

changes are so extens ive that they cannot be rational ized except through a n
oxidative-reductive mechanism. Structural features such a s particle size, num­
ber, a nd spatial distri bution h elp determi n e t h e degree of resistance of a given
i mage toward oxidative attack. These features are i m porta nt not only because
they affect the oxidation step of the cycle, but also for thei r i n fluence on the
re-reduction of the silver ions formed when the original image was oxidized.

Tnitial Stages of lmage Deterioration

The microstructural changes which occ u r rn albumen pri nts i n cubated at

50°C , 9 5% R H illu strate how the structural factors of particle size, size fre­
q ue ncy distribution, and spatial distribution are related. Figure 9 shows a
m icrograph of a high-density area n ear the upper su rface of a newly made
albumen pri nt. A comparable area after 48 clays of incubation i s shown i n
Figure 1 0 . The particles i nside the marked boxes were cou n ted and measured
with a ret icle magn i fier. F igure 1 1 shows the particle s ize frequency d istribu­
tion before and after incubation; the mean particle d i ameters (measured on
longest axis) and the total particle coun ts before and after incubation are
given in the caption.
The image structure before i n c u bation ( Figure 9) is characterized by
a small mean particle diameter (5 · 5 n m ) , a wide range of particle diameters,
a nd an even , relatively close spatial distribution. After only four clays of i ncu­
bation ( not s hown) , many of the smallest particles had disappeared, and the
m ean particle diameter had i ncreased; Weycle 1 1 reported s i m ilar changes for

200

�
0. 1 µ.m
20 25
Particle Size. nm

Figure 1 0
Arca comparable Lo that of Figure 9 after 48 days
of incubation al 50°C, 95% R H .
Figure 11
Size frequency dislribution of i m age particles inside marked areas
or Figures 9 and 10; experimental albu men print. (-) Before
incubalion. 5.5-11111 particles, 649 total particles. (- - -) After
incubation. 7.5-11 111 particles, 195 total particles.
 Part IV ALBUMEN P H I NT MAT E H I A L S

small s ilver particles i n gelat i n . The particles were much rounder, los i ng the
elongated and irregu lar outline i n duced by go ld ton ing. These i n itial changes
in m icrostructure have probably occu rred to some degree i n all surviving
1 9th-century albumen prints.
After 48 clays of i ncubation (Figure ro), complete re-formation of the
i mage is evident. The mean parti cle size has increased consi derably, and
. ·. .
. .
the total n um ber of particles has sharply decreased. These changes are typ­
ical of h igh-density areas of albumen prints d u ri ng i n i ti a l phases of dete­

j
rioration. Figu re 12 shows this i n itial re-formation in schematic form. At
this point in the deterioration, the visual appearance of the a lb umen print
i mage has changed cons iderably; low-density areas have faded to i nvis i b i l i ty,
w h i le m iclclletone and h igh-density areas have both lost densi ty and become
·� . . . more reddish.
·, .
.. . . .. . .. �'·
When a silver n itrate/citric acid sensitizing solution is used and the
.. . .. � . ..
. .
i mage particles are grouped together in colonies, as in F igure 4, the process of
re-formation i s similar, but the colonies tend to retai n their general shape and
.•. .
. .
..
location in the coating. The grouping of particles in this way is advantageous
'
. ,
i n resisting oxidative attack, and in i n c u bation studies coatings like those of
Figure 4 proved to be more stable than ones with a more even spatial distribu­
Figure 12
Schcmat ized representation of'
tion. The i ncreased stab i l i ty was partic ula rly evident i n highl ight areas.
i n i tial stages of-' deterioration
i n albumen prints, showing
a decrease i n the n u mber of Predicti n g M icrostructural C hanges
p�1rticles and a n increase in
average particle diameter.
What m icrostructu ral changes are l i kely to occur depends on the i n itial con­
figu ration of the image. Assu m i n g a constant level of oxidant concentration
and restricting the d iscussion to i mages with particle dia meters of 50 nm
or less, there are three operative factors: particle size, size frequency dis­
tri bution, and spatial d istri bution. Size is i mportant because smal ler parti­
cles have a faster effective rate of attack. l f a range of sizes is present, then
smaller particles will d isappear before larger ones. I mage deterioration is a
process which includes both oxidation and reducti on ; wh i le small size favors
oxidation, larger particles appear to act as favorable sites for the reduction
of mobile silver ions formed during the oxidation step. Th is is why the i n i ­
t i a l stages of deterioration are characterized b y a narrowing o f t h e range o f
particle diam eters and a decrease i n t h e total nu mber o f particles. Although
new particles are constantly being nucleated, t hey have l i ttle chance to grow
at this stage because they cannot compete effectively with existing large par­
t icles for the s ilver ions necessary for growth .
Spatial d istrib u t ion is i mportant i n two ways . \!Vhen an i nd ividual par­
ticle is attacked by an oxidant, the si lver ions and soluble silver compoun ds
formed tend to d iffuse and migrate away from i t i n a ll d irections. Close pack­
ing of particles favors red uction of the si lver ions beca use it tends to keep
 Reading 36 H E I L L Y E T i\ L .

the silver i o n concentration high. Close packing also i ncreases the l i ke l ihood
of reduction by provid i ng other partic les nearby which could serve as pref­
erential s ites for reduction. The s i lver ions from an isolated single particle
are not as l i kely to encoun ter circumstances favorable for red uction back to
metallic s ilver.
From the above discussion and the schematized i mage structure shown
in Figure 3, the extremely poor i mage stability of h ighlight areas of pri nti ng­
out papers can be readily u nderstood . In low-density areas the conditions a re
most favorable for the oxidative step and least favorable for reduction of the
resu lting s ilver ions. The m ic rographs of low-density areas showed a gradual
withering away of image material rather than the re-formation which takes
place i n high-density areas.

Later S tages of Image Deterioration

The microstructu ra l changes typ ical of later stages of i mage deterioration

i n albumen pri n ts are notably differen t from earlier stages. They can be
observed when a 1 9th-cen tu ry albumen prin t ( i n which some deterioration
has already taken place) is subjected to h igh- h u m i d i ty i ncubation. The visual
consequences of these m icrostructura l changes are conti n u i n g density loss
and a shift to even yel lower and redder i m age h ues. Figure 13 is a micrograph
from a h igh-density area of [a] 1 9th-cen t u ry albumen pri nt i n average condi­
tion . The changes produ ced in a comparable area of the coati ng after 90 days
of i nc ubation at 50°C, 95% RH are shown in Figu re 1 4 . Figure 15 shows the
size frequency distribution before and after i nc u bation ; the particle cou nts
and mean particle diameters are given i n the caption. These m icrographs
i llustrate the second characteristic type of microstructura l c hange observed

..•

. ..

:
. . .. J .
. .. ·: . .

•
.. .
.

1--1 1---t
0. 1 µ.m 0. 1 µ.m

Figure 13 Figure 14
Cross-section electron micrograph from high-density area Area comparable to that of Figure 1 3 after 90 days
of a 1 9th-cc n LU ry albumen print in average condition. incu bation at 50::.C, 95% R H .

317
 Part IV A L B U fvl E N P B I NT !VI A T E H I A L S

200

150

100
: \ ·,
•
.... .

· '

'
.
/ f -� . • :. ..
,. .
Particle Size, nm .

Figure 15
Size frequency distribution of image particles inside marked areas
oF Figures 13 and 14, 1 9 t h-cenlllry albumen print. (-) Before
incubation, 8 . 1 -n m particles, 202 total particles. (- - -) After
incubation, 6.8-11111 parLiclcs, 343 total particles.
Figure 16
Schematized representation of later stages of deterioration in
albumen prints showing a tendency for the imHgc t o re-form i n to
smaller, more nu merous, and more evenly spaced particles.

in this study: a tendency for the i mage to re-form i n to smal ler, more n u mer­
ous, and evenly spaced particles. This is shown schematically in Figu re 1 6 .
The fact t hat smaller a n d more n u merous particles are formed a t this
stage seems al most contradictory to what occurred i n the early stages of
deterioration. Actually the same forces are a t work, b u t the dominant factor
is no longer [given by] the competitive advantages of existing larger particles
because all the particles are close to the same size. From this poi n t on, the
range of particle diameters wil l cont i n ue to be n arrow, and spatial distri b u­
t i o n wil l be t h e key factor. The changes which occur i n the later stages of
deterioration can best be u nderstood as moving toward a n equ i l ibri u m con­
dition where al l the particles are of u n i form size and are u n i formly spaced.
New particles will n ucleate and grow i n any empty area far enough removed
from an existing particle to negate its advan tage as a preferential site for
reductio n . Feldman 12 reported the nuc leat ion a nd growth of colloidal sil­
ver particles in the e mpty gelatin surro u nding bundles of filamen tary si lver
u ndergoing oxidative attack.
The particle size at equilibriu m w i l l depen d on the total amount of sil­
ver and silver ion avai lable to take part i n the contin u i ng cycle of oxidation
and reductio n . F i l li n g the empty areas decreases the mean particle s ize, but as
deteriorati o n progresses the particle size will further decrease because of the
m igration of si lver ions away from the area of the main i mage deposit. Some
silver ions are drai ned away to form a crust of closely spaced particles at the
uppermost su rface, while others migrate i n to lower areas of the coating.
 Reading 36 H E I L L Y ET A L .

Conclusions

The image structure of albume n prin ts is determined by the photolytic

mec hanism of i mage formation. Structural features typical of photolytic i m­
ages are responsible for the i n ferior i mage stability of albumen prints, i n par­
ticu lar the rapid loss of highlight deta i l . The fact that in i n cu bation experi­
ments moist air produced d ramatic transformations in albumen pri nt image
microstructure demonstrates the vu l nerability of albumen prints to oxida­
t ive-reductive deterioration and u nderscores the need to control the relative
h u midity of the storage environment for these objects.

Acknowledgments

We acknowledge the support of the National E n dowment for the H u mani­

ties Research Resou rces Program and the 1ational M useum Act (adm i nis­
tered by the S m ithsonian I nstitution) for making this research possible. I n
addition , the assistance o f Dr. Wesley T. H anson and Eastman Kodak Com­
pany are gratefully acknowledged.

References

1 J . M . R e il ly, D. Severson , and C. McCabe, image Det.eriorat.ion. i n Alb11111e11

Print.s; In Preprints of Cont.ribat.ions, 9th I n ternational Congress of t he
I n ternational I ns t i t u te For Conservation of Artistic and H istoric \"forks,
Wash ington, DC, September 1 982, pp. 16-65.
2 Leo Baekeland, in The Phot. ogra m , H. Snowden vVard, E d . , Dawbarn and
Ward, Londo n , 1 897, Vol . I V, pp. 269-271 .
3 ] . M . Eder and F. vVen tzcl , Die photographisclien Kopi rve1fa h re1t 111it
Silbersalzen ( Positiv- Prozess), \"lilhelm Knapp, H a l le, 1 928, Ch. 10.
4 A. M iethe, Lelirbucli d e r prahtischen Photographie, Wilhelm Knapp, Halle,
1 902, Ch. 5.
H . Stiefe l , Sensitized Papers, /-low Made an.cl. Used, The Adams Press,
New York, 1 894, Ch. 10.
6 K. B . Hendriks, T/1e Archivist. 1 0 : 6 ( 1 983).
7 B . Fergg, Z. Wiss. P/1otogr. Photophys. Plwtochem. 52: 224 ( 1 957).
8 F. Formstecher, Camera (L-i1=ern) 3 : 193 { 1 924).
9 R . W. Henn and B . D . Mack, Pliotogr. Sci . Eng. 9: 378 { 1 965).
10 F. Novak, in ]alirb11ch fii r Plwtograpliie 1111d Reproduct. ionsteclm ih 1902.
J. M. Eder, Ed., Wil he l m Knapp, H a l le, 1 902, pp. 1 83-1 85.
11 E. Weyde, Pliotogr. S c i . Eng. 1 6 : 283 ( 1 972).
12 L. Feldman,]. Appl. Pl1otogr. Eng. 7: 1 ( 198 1 ).

319
 R e a d n g 37

PAU L M E S S I E R A N D T I M OT H Y V I TA L E

Effects of A q ueous Treatment on

Albumen Photographs ( 1 994)

Ti mothy Vitale is currently a paper conservator in private practice in

£1neryville, Californ:ia. \A/hile at the Smithsonian. fn.sti.tution, he initiated the
Advanced Training Seminars for 1nofessional developnient at the Conservation.
Analytical Laborat:ory (CAL). Pau l Messier (see also Reading 13 ) was awarded
a fellowship at CAL to worh with Vitale to research the fundam.ental chemi­
cal and physical properties of a.lbmnen. prints. Their collaboration. resulted in
six Cll'ticles, pu blished betiveen 1 9 9 1 and 1 994. They studied the effects of how
aqueous su 1face cleaning and bat h ing techniques adapted from. paper con­
sen1ation affected the wetting a nd drying of albumen prints. The results were
t roubling-an. in.crease in s-inface cracking and decrease in su.1face gloss was
det:e ct:ed. This study established t:hat the aqueous treatment of albumen pho­
togravhs may have serious consequences and resulted in a reevaluation of t he
rish an.cl benefits associated wi.th the conserva t ion treatments of these often
fragile materials. -n1e folloi11i. ng excerpt highlights the exveri men.tal design and
conclusions of this study; for a detailed understanding of the results readers are
encouraged l:o re11i.ew t:he enti re dtat: ion.

From PAU L M ES S I E H and TJMOTllY \IJTA LE, " E ffects or Aqueous Treatment on Albumen
Photographs," Jou rnal of I.lie A merican I nstit.ute for Co11ser11at.ion 33 , no. 3 ( 1 994) : 257-78
( 1-2, 5 , 1 8-20 excerpted here). Reprinted by perm ission oF Paul Messier, Conservator oF
Photographs, Boston, MA, U SA, and Timothy Vitale, Conservator of \>Vorks or Art o n
Paper, Photographs a n d Electronic M edia, E meryville, C A , U SA.

32 0
 Reading 37 M E S S I E H A N D V I T A L E

1 I n trod uction

The aq ueous su rface cleaning, u n mounting, and i mmersion of albu men

prints are among treatment options u sed in the craft practice of photographic
conservation . The association of al b u men photographs with water is a natu­
ral one. Albumen p hotographs are born of water. P hotographic processing
has always i nvolved the use of aqueous solutions that are followed by pro­
longed water baths. J n particular, the wash i ng of albumen photographs has
traditionally been associated with preservation. N i n eteenth-century albu men
printers were very aware of the link between i m age permanence and extensive
postprocessi ng washing i n c lean water. During manufactu re, albumen pho­
tographs often go through several cyc les of wetti ng and drying. Not only a re
they thoroughly was hed, b u t prints are fixed and toned in aqueous solutions.
In the 20th century, paper conservation practice has often i nvolved the
washing of degraded or discolored paper artifacts. After bath i ng, paper arti­
facts are often perceived to be whiter, stronger, and healthier (Vitale 1 992a ) . As
the field of photographic conservation evolved, i t natura l ly adapted tech niques
and approaches from both paper conservation and p hotographic processing.
Eva luation of aqueous treatment of albumen photographs is not new.
Al ice Swan ( 1 98 1 ) made several observations on the detrimental effects of
water on albu men photographs. Swan asserted that albu men pri nts t reated
with water exhibited an i ncrease in al bu men layer cracki ng, but she did not
quantify the phenomenon . She also expressed concern that aqueous treat­
ment seemed to cause an overal l "contraction" of the albumen ( 1 98 1 , 276) .
Although alarmi ng, the aqueous t reatment of albumen pri n ts is still ( M oor
and Moor 1 99 1 ) , with some exceptions ( H il l 1 99 1 ) , a traditional technique
that remains an accepted practice i n photograph i c conservation.
The perceived benefits of aqueous treatment a re: ( 1 ) aqueous su rface
cleaning is a q u ick and effective means for removing dirt and accretions;
(2) aqueous i m mersion is often a rel iable method for re moving albumen pho­
tographs from degraded, damaged mou nts; and (3) the was h i ng of albume n
pri nts m a y reduce the presence of degradation products in t h e paper su pport
and may decrease the yellow-brown discoloration i n the a l b ume n layer.
The pu rpose of this research was to assess the aqueous treatment
regime and determ ine its benefits and risks. Prior to treatment, print color,
gloss, and c rack width and popu lation were q uantified for 20 albumen pho­
tographs. The photographs were then treated by aqueous su rface cleani ng.
Color, gloss, and crack width and population were remeasured. The pho­
tographs were im mersed in water and dried. Agai n measurements of color,
gloss, and a lbu men layer crack width and pop ulation were made. It should
be noted that the treatment protocol outlined in this paper is not necessarily
standard; several a lternative tech n iques exist.

32 1
Part IV ALBU M E N P R I NT M ;\ T E R I A L S

2. 1 Materials and M ethods

2. 1 . 1 Ex'Perimental G roup

The 20 1 9th-cent ury albumen photographs selected for this study typify the
mature albumen printing process used between the m i d - 186os and the 1 890s.
They have a moderate to h igh sheen. Ten of the photographs were moun ted
to heavy paperboard; I O had never been mou nted. All appear to have been
coated with albumen by large-scale, commercial m a nufacturers. Prints were
selected to avoi d additional variables, such as tinting with a n i l i n e dyes or s i l ­
ver mirroring. An attempt w a s made t o secu re photographs w i t h diverse ori­
gins. Of the 10 never-mounted prints, 7 are by various photographers active
i n the American \Vest, a n d three originate from the same p hotographic pub­
l is h i ng house i n Paris. The seven American photographs came from the same
i nstitutional collection. Of the 10 mounted photographs, 3 are German, 2 are
American, 2 are English, and 1 is of French, 1 of I talian, and 1 of Span ish
origi n . All mou nted prin ts are from two private collections.

2.2 Experi mental Design

Once fu l ly characterized , the 20 photographs were treated. The treatments

were designed to best approximate common conservation practice. The
experi mental phi losophy was to follow the effects of a common treatment
protocol rather than the i n dependent effects of surface cleani ng or i mmer­
sion. The latter experimental design would have requi red twice the number
of prints i f performed at the same level of accuracy.
Note that the data used in a previous report on this work ( M essier and
Vitale 1 993a) have been recalculated. The previous report concentrated only
on gauging the width gai n of pre-exist i ng cracks. Following that report, it
became apparent that means existed to gauge the formation of new cracks.
This assessment of new crack formation required a repetition of crack mea­
surements for the never-mounted photographs. Measurements were also
collected for the moun ted p hotographs (these measurements were not pre­
viou sly reported) . The c urrent data for crack width i n crease for the never­
mou nted photographs are lower by approximately 1 0- 1 2%, a range within the
95% confidence intervals previously reported.
The photographs were f irst su rface cleaned with deion ized water applied
with cotton swabs. After surface cleani ng, the mou nted p hotographs were air­
d ried, while the u n mo u n ted photographs were dried between smooth pho­
togra phic blotters and u nder weight (0. 1 psi) to m i n i mize planar d istortion .
Once dry, color, gloss, and crack width and popu lation data were collected
aga i n .

322
 Reading 37 M E S S I E H 1\ N O V I TA L E

The p hotographs were immersed i n baths of deion ized water. The

never-mounted p hotographs were im mersed for r hour, then transferred to a
final bath of fresh deionized water for 1 5 mi nutes. P hotographs with mounts
were immersed u n ti l they could be safely separated from their mounts with
gen t le manipu lations of a Teflon spatula. Length of i mmersion time varied
from approximately 1 hour to up to 4 hours. I mmersion times were noted,
though it became clear that the amount of time spent in water had no corre­
lation to the amou n t of change measu red after treatment. Once u n mounted,
each photograph was p laced i n a fres h bath of deion ized water for 1 5 min­
utes. Following immersion both sets of mou n ted and never-mounted pho­
tographs were a llowed to air-dry face u p u n til the surface gloss was gon e
(approxi mately 10-15 minu tes). They were t h e n p laced between smooth pho­
tographic blotters and u nder l ight pressure (0. 1 psi) u n til d ry. The b lotters
were cha nged once after 15 min utes. The p hotographs remained between
b lotters for approximately 48 hours before the effect of treatment was
assessed. There was no evidence of a l b u men adhering to the blotters.

5 Concl usions

Th is research quantitatively establishes that the aqueous treat ment of albu­

men photographs has serious consequences. Pre-existing cracks i n albume n
photographs are measurably wider after treatment, a n d there are additional
cracks after treatment. Print gloss is red uced after treatment. Print color,
partic u larly highlight yel lowing, is not improved by aqueous treatment.
Removal from a mount by aqueous immersion appears to res u l t in some
transfer of soluble colored material from the mo u n t to the pri n t .
A practicing conservator mu st j udge the potential merits of t he aque­
ous treatment of a l b u men prints agai nst the drawbacks. It is c lear that
appl ication of water to the su rface of a l bumen p hotographs causes damage.
Although this damage is large ly on a microscopic level, it is visual ly percepti­
ble in terms of redu ced gloss. In many cases this da mage may be acceptable,
i f a greater preservation aim is served. The aqueous su rface cleaning of a n
extremely soiled print, for example, may achieve a greater i mage c larity that
outweighs the damage created by i ncreased overal l cracki ng.
Aq ueous treatment of albume n prints should not be considered rou­
t i n e or noninvasive. Th e benefits and risks of aqueous treatment need t o
b e assessed for each individual a l b u men p hotograph prior to t reatment.
Alternatives to aqueous treatment, such as surface clea n i ng with solven ts
or cru mbled eraser particles, warrant i nvestigation . These a l ternatives may
also have potential h azards. The u se of polar solvents may cause excessive
swelling, a n d rapid evaporating solvents may result in dramatic d imensional
Part IV 1\ L B U M E N P R I N T M A T E H I A L S

cha nges. The use o f eraser particles may cause abrasion , and there is the risk
of leavi ng particles in existing albumen cracks. Furt her work is needed to
develop and assess nonagueous treatment alternatives for al b u men prints.

References

H il l , G. 1 99 1 . " The conservation of a photograph album at the National Archives ol'

Canada." Journal of t he A ll'lerican lnstit. ute for Conservat.ion 30:75-88.
Messier, P. A., and T. J. Vitale. 1 993a. ''Albume n photographs: Effects of aqueous
treatment and Fu ndamental physical properties." In The lnipe1fec1. Image:
Photogmpliy, Past, Presen t and Future. London: Centre For Photographic
Conservation. 209-35.
Moor, I . L., and H . 1-1 . Moor. 1 99 1 . "The effect oJ' aqueous treatment on photographs." I n
SauvegMcle e t conservation. Paris: Association pour l a Recherche Scienti flque s u r
l e s Art G raphiqucs. 62-66.
Swa n , A. 198 1 . "Conservation of photographic print collections." LibrCll)' Trends 30:
267-96.
Vitale, T. J. 1992a. ''Comparison between practit ioner observed and measured changes
i n mechanical and physical properties of paper before and after washi ng." AIC
abstracts. American I nstitute for Conservation 20th annual meeting, Buffalo, N .Y.
Wash i ngton, 0 . C . : AIC, 1 5-16.
 R e a d n g 38

VA L E R I E B A A S , C H R I S T O P H E R F O S T E R ,
A N D KAR E N TR E NT E L M A N

The Effects of Four Different

Wet Treatments on Albumen
Photograph s ( 1 999)

The following reading summarizes one of many important collaborative

research projects between Valerie Baas, former head of the Paper and Pho­
tographs section; Christopher Foster, associate conservator of Art on Paper
and Photographs; and Karen Trentelnian, associate research scientist, at the
Conservation Services Laboratory, Detroit Institute of Arts. This investigation
was an expansion of the albumen research conducted by Messier and Vitale
addressed in the previous reading in this part. 17ie goal of the authors was to
conduct a practical evaluation offour traditional wet treatment techniques on
the srnface deterioration of albumen photographs. Tiiis research affirmed the
relationship between moisture exposure and gloss reduction (caused by per­
nianent dimensional change and increased swface cracldng) to the albumen
binder layer. Limiting the expansion of albumen prints during aqueous treat­
ments through the use of water and ethanol mixtures and the use of slow dry­
ing techniques appeared to be beneficial. 17ie treatment techniques described
in this article are used with increased caution by practicing 11hotograph con­
servators today.

1 I n trod uc t i o n

I t has long been thought that moisture may be detrimental to albumen

photograph s . Cracking and roughness (Messier and Vitale 1 994; Vitale and

VALE H I E BAAS, C 1 -1111sTOPHEH FosTEH, and KAHEN TRENTELMAN, "The Effects of Fou r Dif­
fe rent '"'et Treatments on Albu men P hotographs," Journal of the A1nerican fnstitute for
Conset·vation 3 8, no. 2 ( S u mmer 1 999): 1 76-8 5 . Heprin ted by permission.
Part IV A L B U M E N P R I N T M AT E H I A L S

Messier 1 994) a n d fading (Reilly 1 980) are a l l bel ieved to increase due t o the
changes that occur in the a l bumen layer and paper substrate when subjected
to cycles of wetting and drying. The dissimilar responses of gelatin emulsions
an d their paper substrates when exposed to varying moisture levels have
been demonstrated to promote significant stress levels and crack formation
in photographic prin ts (McCormick-Goodhart and Mecklenburg 1 992). The
deterioration of albumen prints m ay be produced by a similar mechanism.
The study presented here is a n expansion of the work by Paul Messier
and Tim Vitale ( 1 994; Vitale and Messier 1 994 ) , in which they foun d increased
cracking in albumen prints subjected to aqueous treatment. Messier and
Vitale fou n d that both the number and the dimensions of minute cracks in
vintage albumen prints i ncreased significantly after treatment with water,
whether by immersion or damp surface cleaning. This effect is cause for
concern, since it is sometimes necessary to use moisture i n the treatment
of albumen p hotographs. Wettings over the cou rse of a typical photograph
treatment might include damp surface c leaning, aqueous backing remova l ,
aqueous adhesive removal , aqueous stain reduction, hu midification a n d flat­
tening, and lining or mounting with aqueous adhesives .
This project was designed to i ndicate which aqueous immersion media
might be the least harmful to albumen prints. The fou r bath c hosen were:

r. deionized water
2. ammoniated deionized water (pH 9)
3 . a deion ized water:ethanol mixture ( 1 : 1 v:v)

4 . deionized water fol l owed by i mmersion i n ethanol.

An exaggerated treatment program was designed to more easily relate the

degree of deterioration of the albumen l ayer to the different baths. Groups
of newly manufactured albumen prints were repeatedly bathed in one of the
four aqueous solutions, and changes in gloss were measured and compared.
New print materials were produced for this study to provide some consis­
tency in terms of fabrication and environmental history.

2 Experimenta l

2 . 1 Sample Preparation

Samples of unsensitized a lbumen-coated papers were obtained from the

Image Permanence I nstitute ( ! PI) and the Chicago Albumen Works (CAW) .
Both fabricators coated the sheets by hand, using the same general proce­
dures (Reilly 1980) and the same p aper base (Munson 1 996). The papers were
coated in the late 1 970s to early 1 980s. Descriptions of their procedures are
presented in appendix A.
 Reading 38 B A A S , F O S T E R , A N D T H E N T E L M A N

Thirty-two samples of the albu menized paper, each approximately 5 by

8 in. ( 1 2.7 X 20.3 cm), were sensiti zed with s i lver n i trate, eiqJosed, and pro­
cessed in our laboratory (Reilly 1 980; Munson 1 996). The sensitized papers
were pri n ted out to maxi m u m density without using negatives, as a dark sur­
face was expected to make any cracks that formed easier to observe.
Processing i nvolved the fol lowing steps: wash , gol d tone, wash, fix,
wash, hypo clearing treatment, final wash , and d rying. Details of the sensi­
tizing, eJqJOsure , a nd processing p roced u res are described in appendix B.
After processing, it became apparent that there were th ree types of
prints, distinguished b y their average gloss and thic kness. The prints from
I P I tended to be thinner and less glossy than the ones from CAW.
• Type 1 ( 1 6 prints): thin (�0.09 m m ) , low gloss ( 1 2 G U )
• Type 2 (8 prin ts ) : thick (�0. 1 0 m m ) , low gloss ( 1 2 G U )
• Type 3 (8 pri nts): thick (�0. 1 0 m m ) , high gloss (24 G U )

Because t h e two manufacturers used the same papers base a n d t h e same

procedu res to coat the s heets, the observed variations in initial gloss and
thickness can be attributed to differe nces i n the albumen viscosity and flow
d u ring application of the coati ng. Both manufacturers fel t that va riables
i n here n t in the process such as temperature, relati ve h u midity, age of egg,
breed of chicke n, and quality of t h e chicken l i fe (free range or not) affected
the fi n a l product. Both also stated that dryin g was i mportant and that h i gher
d rying temperatures produced glossier e mu lsions. Aging of the solution can
also be a factor. A 19th-century photographer working i n Paris observed:
"The older the albumen becomes, the more bri l l iant the coating will be, but
t here is some clanger of yellowing of the proofs after the hypos u l fite bath"
(Ogonowshi 189 1 , 1 7 ) .
The focus o f t h i s study was t o observe t h e relative effects of t h e treat­
ment baths on a given set of avai lable materials. As will be shown below, the
relative effects of the baths were the same for al l prin ts types, so t hese varia­
tions i n i n i tial gloss a n d thickness, al though in teresti ng, did not affect the
overa l l res u l ts of this study.

2.2 Wet Treatnwn,t;s

The 32 prints were divided i nto 4 treatmen t groups (A, B , C, D ) of 8 samples

each. Each group contained 4 pri n ts from each fabricator. The print types
based on i nitial gloss and t h ickness were also distri b uted equally among
the treatme nt groups: each treatmen t group contained 4 prints with a t h i n
albu men coating a nd a l o w i n itial gloss, 2 pri n ts w i t h a thick coating and a
low initial gloss, and 2 p ri n ts with a thick coating and a h igh i n i t ial gloss.
An identification mark was applied to each sample i n pencil on the reverse.
P a rt I V ALBU M E N P H I NT f\' l /\ T E H I A L S

The sa111ples were repeated ly subjected t o the four wet treat111ents l isted i n
Table 1 [ not reprodu ced here ] .
Bath A , B , a n d C were chosen a s exa111ples o f baths that may be used
i n the treat111ent of p h otographs. Bath D was chosen because i t was thought
there 111 ight be some benefit to replacing the water i n the saturated prints
with ethanol, causing the sa111ple to d ry more quicl<ly wh i le sti ll retai ning
its enlarged d i111ension. A si111ilar procedure i s used in the preparation of
bio logical sa111ples for scan ni ng electro n microscopy/trans111 ission electron
111 icroscopy ( S EM/TEM ) analysis ( 1-/arhins 1 996). All solutions were used at
roo111 te111 perature.

2.3 Drying Technique

After each bath treat111ent, the sa 111 ples were drain ed and blotted to re111ove
standing water. The d rying then proceeded u nder restraint, usually for five
to seven clays. The prints, with lens tissue against the recto and verso, were
placed face clown between layers of four-ply 111at board, % i n . ( 9 5 cm) wool
.

felt, and Y2 in. ( 1 .3 c111) Plexiglas. Once dry, the prints showed a strong
tendency to curl, and so were kept Aat in Mylar envelopes un t i l the next
treatment cycle. For the p u rposes of this study, it is only i mporta nt that the
d rying tec h nique was consistent throughout the project, as our objective was
to study the effect of the treat111ent baths. The effects of different dryin g
tec hniques wil l be the subject of a fu t ure study.
The wet-to-dry treat111ent cycles were repeated until obvious differ­
ences were seen when comparing the treatment groups. Messier and Vitale
( 1 994; Vi.tale and Messier 1 994), working with 111ore fragi le vintage album e n
prints, observed significant cha nges after a single we t treat111ent, but this
was not the case with the newly manufactu red prints i n this study. After 1 0
cycles, there were only slight differe nces among the groups. After 20 treat-
111ent cycles, c l ear d i fferences among the groups had emerged, making i t
poss ible t o compare the data and draw conclusions.

2.4 Measurenient and Observat;ions

Changes in the surface of the prints were 111onitorecl by 111easuring the reduc­
tion i n gloss. As rou gh n ess and cracki ng develop, the a111ount of scattered
light increases and the gloss is reduced. The samples were measu red with a
M acbeth Novo-Gloss 20/60/85 Statistical glossmeter. This device 111easures
gloss in incremental u n i ts of 0. 1 G U (gloss u n i ts) and has a specified accu­
racy of 0 . 5 GU. The Novo-Gloss meter is capable of 111easuring gloss at 20°,
60°, and 85° with respect to t he su rface nor111 a l (perpendi cu lar to the plane
of the sheet), and the selection of angle is determi ned by the smoothness
 R e a d i n g 38 B A A S , F O STE B , A N D T H E N T E L M A N

of the surface being measured. For surfaces of low gloss, measurement at a

larger angle will maximize the collection of the reflected l ight, thereby pro­
ducing a more rel iable resu lt. The average th ickness of the prints was mea­
sured with a iVIitutoyo d igital micrometer.
The gloss of the samples was recorded before the i nitial treatment
bath a nd after every second treatment cycle. To reduce planar distortion,
the samples were held flat on a paper suction table during m easurement.
The i n i t ial gloss of a l l the prints was relatively low, a n d t herefore the surface
was meas u red at both 60° and 85°. At 60°, the glossmeter measures an area
approximately 2 cm 2 in size, and this area i nc reases to approximately 3 c m2
for measurements taken at 85°. Five spots were measured on each sheet,
using a template as a guide to ensure that the same area was measured each
t i me. The gloss was measured parallel to and across the grai n (mach i ne
d i rection of the paper su bstrate) of the print at each spot. I n a l l , 1 0 measure­
ments were made at each angle after every second treatment cycle for each
of the 3 2 samples in this study.
The data obtained at 60° and 85° exh i bited s imilar trends, but the
data obtained at 85° appeared to be more sensitive to smaller c hanges i n
gloss. For the sake of s i mp l ic ity, only the data collected a t 85° a re presented
here. As the bath treatments were repeated, the paper substrates showed
i ncreasing distortion, especially across the grai n d i rection. As a result, gloss
measurements taken perpendicular to the gra i n direction of the sheets
exh ibited a large degree of variation, while the measurements taken parallel
to the grain showed a consistent decrease in gloss. For this reason, only the
meas u rements taken parallel to the gra i n d i rection were used to assess the
treatment res ults.
No cracks were apparent prior to the prints havin g been subjected
to the treatment baths. During the course of the stu dy, visual examination
i n normal, raking, and reflected l ight revealed that the prints appeared to
become rougher and more matte. At the encl of the study, cracks were clearly
visible to the u naided eye, although not all prints exhi bited the same degree
of cracking. Stereo-microscopic exa m ination ( 1 0 to 40 X ) and p hotomicrog­
raphy were u sed to observe and record the relative quantities and size of the
cracks that had developed as well as their preferred orientation, if any. At
several locations on each pri nt, the n u m ber of c racks i n the field of view (at
4ox) was estimated, and the results were averaged for the p rint. S i m ilarly,
the average length of the c racks was estimated.

3 Resu l ts

G loss was d i m i n ished i n al l of the samples i n the study as a resu l t of the

aqueous treatments, and the amou n t of change in gloss was found to be
P a rt I V ALBUMEN P R I NT i\ll A T E H I A L S

related t o the type o f bath treatment. The average gloss change for a l l the
samples i n the study as a fu nction of the n u mber of i mmersions i n each
of the fou r treatment baths is presented in Figure 1 [ not reproduced here] .
The least reduction i n gloss was observed for the samples treated with the
water:ethanol (1 : 1 v:v) mixture (bath C). The water bath at pH 9 (bath B) and
the water-only bath (bath A) res u l ted in only slightly more reduction than
bath C. H owever, a sign i ficantly greater reduction i n gloss was observed i n
the samples bathed i n water followed i mmediately b y ethanol (bath D) .
Although a l l three paper types exhi b i ted the tren d discu ssed above, d i f­
ferences i n the m agn itude of gloss reduction were observed among the prin t
types. The average change i n gloss after 20 treatment cycles produced b y
each treatment bath a s a fu nction o f the i n i t ial gloss a n d t hickness of each
sheet i s presented in Figure 2 [not reproduced here] . There appears to be a
relationship between the thickness of the albumen coating and the change
i n gloss: samples with a t h icker coatin g su ffe red a greater reduction i n gloss
than samples with a th i n ner coating. The figure a lso shows that the reduc­
tion in gloss does not appear to be related to the initial gloss of the pri n t .

4 D iscussion

Of the methods used, meas uring with the glossmeter proved to be the most
quantifiable method for recordi ng changes i n the su rface of the samples.
These changes included the development of cracks, but also rough e n ing,
m i nu te d i m p li ng, and other small deformations corresponding to t he grai n
o f t h e paper. Reduction i n gloss most l i kely results from the stress i mposed
on the al b u men layer d u ring t he wetti ng and d rying cycles. The stra i n i n the
albumen layers is rel i eved by cracking and/or su rface rough e n ing, the degree
of which depends on two factors: ( 1 ) the amoun t of stress i m posed by the
specific treatment, and ( 2) the differin g response of the albumen layer and
the paper substrate.
Samples bathed in the water:ethanol mixture exhi b ited the least reduc­
tion in gloss. They were exposed to the smal lest amount of water and, as
a res u l t, probably experienced the smallest degree of wet-to-dry expansion
and con traction. Conversely, samples bathed i n water fol lowed by ethanol
showed the greatest amount of gloss reduction and roughening of the sur­
face. In this treatment, the samples expanded d u ri ng the water bath a n d
rema ined swol len as the water was displaced b y ethanol. H owever, ethanol
evaporates rapidly, causing d i mensional cha nges that may have resulted i n
the observed increased gloss reduction. Furthermore, the d isplacement of
water by ethanol may desiccate the emulsion, encouraging brittleness. The
samples bathed in water and alkaline water showed an i ntermed iate reduc ­
tion i n gloss. These samples may have expanded t o a degree simi lar t o those
 R e a d i n g 38 B A A S , F O S T E R , A N D T H E N T E L M A N

i n the bath of water fol l owed by ethanol but were n ot subjected to the rapi d
d rying caused by i mmersion in ethanol.
The thicker samples consistently exhibited a greater reduction i n gloss
than those with thinner emu lsions. Exami nation with the stereo-microscope
a t 40 X provided general information about the n u m ber, s ize, and orienta­
tion of the c racks formed during this treatment study. In general, a greater
nu mber of c racks formed in the thicker samples than the t h i n ner ones. Add i ­
tional ly, the c racks in t h e thicker samples were relatively l on g (>0 . 5 mm) a n d
tended to form across the gra i n , wh i l e those i n the t h i n n e r samples tended
to be shorter (<0.1 mm) and showed no preferential d i rection. S i m i lar obser­
vations have been reported by Alice Swan ( 1 9 81 , 275 ):

The severity o f t h e fi ssuring a n d c leavage appears most d i rectly related

to the t h i c kness of the albumen layer. The only albumen prints I have
seen completely without fiss u ri n g are prints from the 1 8 50s and 1 860s,
so t h i n ly coated that they have a l m ost no gloss and are someti mes m is­
taken for salt prints. Yet a m o re t h ickly coated spot on such a print will
show t he usual fiss u r i ng and c leavage, and the amount and severity w i l l
depend on the thickness o F the spot.

These observa tions suggest that more stress may be ass umed d u ring treat­
ment cyc l ing by thicker layers of al bu men than by thinner ones, which are
better able to fol low the expa nsion and contraction of the paper substrate.

5 Recommendations

If aqueous treatment of an albumen print is necessary, it is i mportant to

red uce stress on the al b u men-paper laminate. Limiting the expansion of
albumen prints during aqueous treatments through the use of water and eth­
anol mixtures appears to be beneficial. Along the same lines, prints should
be dried slowly, making the t ransition from wet to dry as gradual as pos­
sible to avoid abrupt d imensional cha nges. This study indicated that bath­
i ng samp les in water ammon iated to pH 9 caused slightly less c racking than
water alone. I t is known among photograph conservators that ammon iated
water causes greater swe l ling of proteinaceou s e m u l s ions than water alone.
The elevated pH may make the al b u men layer more elastic, a llowing it to
move more easily with the reactive paper substrate. Ammonia, however, may
adversely affect silver compounds (Haist 1979, 248) and therefore should be
used with caution u n t i l i ts effects are better u nderstood.
The res u lts of this study have shown that by using a mixture of water
and ethanol and careful ly controlling the wetting and d rying conditions, it
may be poss i b le to moderate the effects of aqueous treatments on albumen

33 1
Part IV A L B U t\ I E N P H I NT M 1\ T E H I A L S

prints. A comparison o f the effects o f d i fferen t d rying methods w i l l be the

subject of a fu t u re study.

Acknowledgments

The authors are indebted to the fol lowing i n d ividuals for their i nva luable
assistance and i nsights: Charles H a rkins, vVayne State U n ivers ity Biology
Department; Douglas M unson, Chicago Albumen Works; Douglas Nishi­
m u ra, I mage Permanence I nsti tute; Steve Puglia, National Archives and
Records Ad m i n i stration ; J am es Reil ly, 1 mage Permanence I nstitute; Doug
Severson , Art I nstitute of C h icago; Leon Stoclu lski, Detroit I nstitute of Arts;
and Sara \i\fagner, National Archives and Records Ad m i nistration.

N O T E S

Appendices

1 . 1 A: /\ll a n1'1fact u ring Procedures for Albu n'ten-Coated Paper

Fol lowing are descriptions of the procedures used to produce the sample
papers for the project. As stated i n the text, the manufacturers used similar
methods and the same paper base. The samples used i n our study were made
i n the late 197os/early 1 980s, and these recipes are reconstructions of what
was most l i kely clone at that time.

1 . 1 . 1 Paper (Munson 1 996)

A 60 gsm 1 00% rag photo base paper produced i n a spec ial run by the S i m p­
son-Lee Paper Co. of Kalamazoo (now defu nct). This lot was shared by
I mage Permanence I n stitute ( I P I ) and Chicago Albumen Works (CAW).

1 . 1 .2 Recipes:

1 . ! P l ( paraphrased from Reilly, 1 980, 36-40) Beat for 3 m i n u tes, or u n t i l

t h e entire m ixture h a s been converted t o a froth . Let settle f o r 2 4 hours,
strai n through muslin, and store covered i n the refrigerator for one
week. Allow to come to room temperature before usi ng. J ust prior to
coati ng, gently stir in 4 m l of Kodak Photo-Ao d i l u ted 1 : 200 with water.
If double coating is des i red, harden i ng between coats can be ach ieved
by warm aging for six months, steam , or a 70% isopropylalcohol bat h .
2. CAW (Munson 1 998) Douglas M u nson stated t h a t the methods used
varied considerably from time to time. H is comments on the proced ures

33 2
 R e a d i n g 38 B A A S , F O S T E R , A N D T B. E N T E L M A N

he used are paraphrased here: Combine: 6 gal. (approxi mately 23 l i ters)

fresh egg whites [with] 0.5 to 3% ammon i u m chloride. Whip to a soft
meri n gu e . Allow to settle, stra i n , and just before coati ng, add Kodak
Photo-flo, about 1 : 1 000. The solution was not deli berately aged or
fermented, but the coatings were done either immed iately or s hortly
after process ing the albumen. The sheets of paper were si ngle, double,
or triple coated and were sometimes hardened.

1.2 B : Photosensitizing, Exposure, and Processing Procedures

1 .2 . 1 P hotosensitizing

1. Spray s heets lightly with water on both sides to dampen them.

2. Float sheets, albumen side clown , on 1 2% silver nitrate (AgN0 3 ) solution
for 2 1h to 3 m i n u tes ( u nder reel safel ight).
3. Hang sheets by corner to d ry (safel igh t ) .

1 .2 . 2 Exposure

1 . \Nhi l e still clamp, expose prints to daylight without negatives u nder

Mylar on a Fome Cor support, for approxim ately 20 m i n u tes, producing
completely printed o u t sheets.

1 .2.3 Process ing (Reilly 1980; M u nson 1996)

1 . I ni tial wash : Wash prints in runn i ng water for 1 0 m i n u tes to remove

excess silver nitrate.
2. Gold ton i ng: Prepare toni n g solution: 1 0g borax (Na 2 B4 0 7 · 1 0 I-I2 0), and
o. 5g gold chloride as tetrach loroauric ( Il l ) acid ( HAuC1 4 ) , d i l u ted with
deionized water to m ake 1 l i ter. I mmerse prin ts i n toning sol ution for 3
m i n u tes.
3. Wash : Wash pri nts i n run ning water for 5 m i n u tes.
4 . Fixing: Prepare fixing solution: 1 5og sodi u m thiosu lfate pentahydrate

( N a2 S 2 0 3 · 5 H 2 0) and 2g sod i u m carbonate ( N a2 C0 3 ) d i luted with de­

ion ized water to make 1 l i ter. Divide i n to two baths, and i mmerse pri n ts
i n each bath for 5 m i nutes.
5. Wash : Wash prints for 2 to 4 m i n u tes in run n i n g water.
6. Hypo c learing bat h : Prepare hypo clearing agent : 1 og sod i u m s u lfite
(Na2 S0 3 ) in deionized water to make 1 liter. I mmerse prints i n bath for
3 to 5 m i nu tes to remove thiosu l fate.
7. Final wash: \Nash prints for a m i n i m u m of 30 minutes in running water.

8. Drying: Air-dry without restraint.

Part IV 1\ L B U M E N P H I N T M A T E H I A L S

References

Harkins, C . 1996. Personal com m u n i cation. Biology Department, \,Vaync State U n iversity,
Detroit, M ich. 48202.
Haist, G. 1 979. Modern Photographic Processing. New York: J o h n Wi ley and Sons.
M cCormick-Goodhart, M . , a n d i\11. Mecklenburg. 1992. "Cold storage enviro nments for
photographic materials." A/C abstracts, American I nstitute For Conservation 20th
Annual Meeting, B u ffalo, N .Y . Wash i ngton, D.C.: AIC, 55-56.
Messier, P., and T. Vitale. 1994. " Effects of aqueous treatments on albumen photogra p h s . "
Journal of /.he American lnsti/.ule .for Conservation 33:257-78.
M u nson, D. 1 996. Personal com m u n ication. C h icago Albumen \�larks, P.O. Box 805,
H ousatonic, Mass. 0 1 236.
M u nson, D. 1 998. Personal com m u n ication. Chicago Albu men \Vorks, P.O. Box 805,
Housatonic, Mass. 0 1236.
Ogonowski, E. 1 89 1 . La photocliromie: Ti rage d'epre11ves photogmpliiq11es en. co11/eur. Paris:
Gauthier-Vi liars et fils.
Rei l ly, J . 1980 The Alb1<1nen C1nd Sa/J.ed Paper Booh: The /-/ist.01)' and Prac/.ice o.f
Photograpliic Printing, 1 840- 1 895. Rochester, N.Y.: Light I mp ressions Corporation.
Swa n , A. 1 98 1 . "Conservation of photographic print collections." Li/Jrai)' Trends
30:267-96.
Vitale, T., and P. Messier. 1 99+ " P hysical and mechan ical properties of albumen
photographs." Journal o.f t he A1n.ericC1n Institute .for ConservC1t.ion 33:279-99.

Further Reading

Bergquist, D . H . 1 986. "Egg dehydration." In Egg Science and Technology. 3cl ed.
Westport, Con n . : A VI Publishing Co. 285-323.
Calhou n , J . , and A. Leister. 1 959. " E ffect of gelatin layers on the d imensional stabi l i ty of
photographic film." Photograpliic Science C1nd Enginee.-i: ng 3:8- 1 7 .
Karpowicz, A. 1 989. " I n-plane deformation of' fi lms o f size on paintings i n t h e glass
transition region. " St:udies i n Conservation 34:67-74.
Ku ntz, I . , and W. Kauzm a n n . 1974. "Hydration of proteins and polypeptides." I n AdvC1nces
in Protein Chemistry, vol . 28, eel. C. D. Anfinsen et a l . New York: Academic Press.
239-345-
Mecl<lenburg, M. F . , M . McCormick-Goodhart, and C. S. Tumosa, 1994. " I nvestigation
i n to the deterioration of p a i n t i ngs and photographs using computerized mode l i n g
of stress develop m e n t . " . Jou rnC1l o.f the A merican fnst.itute .for Co11ser11C1t io11 3 3 : 1 53-70.
Messier, P. 199 1 a . " P rote i n chemistry of a l b u me n photographs." I n Topics in Photographic
Preser11C1tion, vol. 4. vVashington D.C.: American I nstitute for Conservation
Photographic Materials Group. 1 24-35.
M essier, P. 199 1 b. "\�lork i n progress: f\n analysis of the effects oF water on t he cracki ng of
a l bu men photographs." In Topics in PhoJ.ographic Prese.-vC1t.ion., vol . 4. Washington
D . C . : American I nstitute for Conservation Photographic Materials G roup. 1 70-78.
Powrie, v\/., and S . Nakai. 1 986. "The chemistry of eggs and egg prod ucts." I n Egg Science
and Technology. 3cl ed. Westport, Conn . : AV! P u b l ishing Co. 97-139.
Reil ly, J. 1 982. " I mage deterioration in albumen photographic prints." Preprints o.f t;h e
9th I 11t.ernC1t.ional Congress o.f t.lrn I IC, \'V ashington, D.C. London: I nternational
I nstitute for Conservation. 61-65.
Romanoff, J . , and A. J . Romanoff. 1 949. The Avian Egg. New York: Academic Press.

33 4
 Reading 38 B A A S , F O S T E H. , A N D T R E N T E L M A N

Sources of M aterials

Albumenized papers (not currently comrnercially available)

C h i cago Alb umen Works, P.O. Box 805, Housatonic, Mass. 0 1236

I mage Permanence Institute, Rochester I nstitute of Tech nology, 70 Lomb

Memorial Dr., Rochester, N .Y. 1 4623

G lossmeter
M ac Best, a division of K o l lmorgen I nstruments Corporation, 405 L i ttle Britain Rd.,
New Windsor, N .Y. 1 2553-6148

Micrometer
M itutoyo Corporation, 3 1 - 19. S h i ba5-chome. M i nato-ku, Tokyo 1 08, Japan

Silver nitrate, sodium tliiosulfate, sodium carbonate

Fisher Scientific Company, 2000 Park Lane Dr., P i t tsburgh, Pa. 1 5275-9952

Gold chloride (tetrachloroauric (III) acid)

Sigma Chemica l Company, P.O. Box 14508, St. Louis, Mo. 63 1 78

Sodium sulfi te
M a l l inckrodt Laboratory Chemicals, 222 Red School Lane, P h i l l ipsburg, N .J . 08865

Borax ( 20 Mule Team. Borax)

Dial Corporation, Consumer Products Division, Phoenix, Ariz. 85077

G reen 's Lens Tissue

Rising M useum Mounting Board (four-ply, warm w h i te), Talas, 568 Broadway,
New York, N .Y. J 00 1 2

335
 P A R T V

Photographic Negatives:
Problems and Issues

William H e n ry Fox Talbot is credited as the first to make use of a negative

photographic image to c reate m u l t i ple positive images with his i nvention of
the calotype in 1 84 1 . The abil ity to create multiples of the same image, as
opposed to the u nique posi tives created by the daguerreotype process, was and
continues to be a val uable appl ication of p hotography. As the u n derstan d i n g
of photographic chemistry and t h e needs of t h e photographer evolved, nega­
tive support m aterials a n d binders c ha nged accordingly. Therefore, negative
col lections may contain materials ranging from early collodion on glass to
embrittled, channeled, and yellowed Flexible films. These materials are com­
p l ex and often i nherently u n stable, having required considerable research
over the past thirty years to advance our u nderstanding of the many factors
affecting their l ong-term preservation . A brief chronology of negative sup­
port materials, deterioration characteristics, treatment options, and the vital
importance of proper enviro nmental and i n tel lectual control of n egative col­
lections are the primary themes fou n d in this part. The readings reproduced
here are organized by s u bject matter, not chronological ly.

D r . John M u rray (British, 1 809-1 898), Nagina Mosq ue, Agra Fort, India (deta i l ) , 1 857-60. Waxed paper
negative print, 36.8 X -15·9 cm ( q Yi X 1 8 1/16 i n .) . Los Angeles, J. Paul Getty Museum, 98.x1, 1.7
 R e a d i n g 39

MART I N E G I LLET, C HANTAL G AR N I E R ,

A N D f R A N <,;; O I S E f L I E D E R

Glass Plate N egative s : Preservation

and Restoration ( 1 986)

T1iis mading was coauthored by three researchers at the Centre de Recherche

sur la Conservation des Collections (CRCC)-formerly !mown as Centre de
Recherches sur la Conservation des Docwnents G raphiques (CRCDG)-in
Paris. The CHCC is a national research laboratory dedicated to advancing the
conservation of c ultural materials including objects, photographic materials,
and natural history collections. Franc;; oise Flieder founded the CRCC in 1 963
an.cl served as its director unti.l 1 998. Jn recognition. of the considerable contri­
butions Fl-iecle r nwcle to the conservation. profess-ion., the l n.tern.ation.al Council
of M usewns ( I CO/VJ) made her an honorary 1nember at its eleventh Triennial
Meeting in. Edin.burgh. Martine G illet is a research scientist an.cl Chantal Gar­
nier is an assistant scientist, both at CRCC. 17iis excerpt serves as an appropri­
ate opening to Part: V in that it provides a detailed chronology of the use ofglass
as a negative s upport material. Glass clomin.atecl negative man:ufa cture until its
gradual re71lacement by fle:x ible film in. the late nineteenth century. Originally
published i.n French, this reading was translated into E nglish for Restau rator
in 1 986. In the fi. nal sections of this excerpt, the authors introduce the most
common forms of deterioration. associated with glass negatives, 11rovi.din.g a pre­
view of the many 11reservation challenges these CO'lnplex nwteri.als present.

From M/\HTINE G I LLET, C 1-1ANT/\L CAH N I E H , and FnANyOISE F u E D E n , "G lass Plate
Negatives: Preservation and Restoration," Resl.cn1 rat,or 7, no. 2 ( J\/lu nksgaarcl, Copenhagen,
1 986) 49-80 (49-58 excerpted here). © 1 986 K.C. Saur Verlag, M li nchen. Heprintecl by
permission.
 R e a d i n g 39 G I L L E T , G A H N I E R , A N D F L I E D E R

o. I ntroduction

O n account of i ts transparency, glass was used as a p hotographic base

shortly after the i nventions of W. H . Fox Talbot, to replace the oiled or
waxed papers the calotypes were made u p of. Du ri ng the second half of the
n i neteenth century i ts use was very widespread, especi a l ly for the produc­
tion of negatives. From the twenties onwards, the p lastic based material s
gradually replaced glass which is, however, sti l l used nowadays for a few rare
processes requiring rigidity and stability.
Various p rocesses to obtain a negative picture have been used succes­
sively: the rarely used albumen p rocess, wet and d ry collodion p rocesses, the
manufactu ri ng of which was u niversal for some 30 years before it was aban­
doned for the gelatin process.
As soon as 1 850, p hotography made great strides. The present-clay
F rench collections therefore contain several h u n d red thousand glass nega­
tives stored in m useums, archives, p u b l i c or private photographic l i braries as
wel l as private collections. M an y of the n egatives are the works of u nknown
p hotographers, but a great n u mber of renowned artists, among them G. Le
G ray, C h . Negre, F. Nadar, E. Atget . . . have left a very rich her itage.
A large part of the glass plate negatives have not been damaged though
some deteriorations can be detected which are chiefly clue to u nstable com­
ponents, fau l ty workmanship, i nappropriate use, or poor storage conditions.
I t is therefore necessary to start a research in order to eA.'P eriment with
restoration treatments. But before any attempts are made in this field, i t seems
necessary to epitomize the works carried out on the i n ternational level.

1. Man ufacturing Processes•�02

1.1. Selection and Preparation of G lass Plates

The choice of the glass is determined by the qualities required by the p ho­
tograph: transparency, no defects (bubbles, scratches, u n evenness, streaks,
striations ), a u n i form thickness and a plane su rface. The better s u i ted m irror
glass was therefore preferred to window glass as a base.
To ensure correct adhesion of the sensitive layer, the glass is cleaned
very thoroughly and then polished. New glass m ust be freed from all types
of grease, fingerprints an d other impurities. They only have to be d ipped
in a dil u ted aqueous solution of ammonium of potassiu m hydroxide for a
few min u tes. Reused glass from o l d negatives mu st be p u t t hrough a n extra
cleaning operation i n order to remove every trace of chemicals. For this p u r­
pose they are d ipped i n a rn% solution of potass i u m cyanide or i n a water
bath strongly acidified with nitric acid or in a chromic s u lphuric acid. After

339
P art V P 11 0 T 0 G H r\ P I I I C N E G A T I V E S

that they must be rinsed thoroughly, and the glass must be treated with a
solu tion of potass i u m carbonate or sod i u m carbonate to neutralize the acid­
i ty of the cleani ng.
After being cleaned, the glass has to be polished thoroughly. The glass
su rface must be rubbed vigorously in circles with a large wad of cotton after
spreadi ng a m ixt u re of alcohol and powdered chalk, or a thick paste of Span­
i sh white'" mixed with a d rop of water, or with a very fine powder of tripol it
m ixed with a l ittle water and a few drops in n i tric acid. The d rying process is
concl uded with a wad of clean cotton to remove a l l paste particles. Then the
p late is polished with a wash leather which has previously been degreased i n
a boi l i ng sod i u m carbonate solu tion and t h e n thoro ugh ly rinsed.
In order to get rid of the electrostatic properties gai ned duri ng the
ru bbi ng, which promote the acc u m u lation of d u st, i t is necessary to clean
the glass plates several hours [prior] to the appl ication of the sensitive layer.
v\fhen the negative is manufactured, the glass su rface has to be d usted with
a soft brush before the appl ication of the photo-sensitive su bstance.

1 . 2 . Tiie Albu men Process

N icephore Niepce's nephew, N iepce de Saint-Victor, was looldng for a way

of making a sensit ive layer of starch or gelatin on a glass plate. I n 1 847 he
su cceeded in obtain i ng pictures which were not perfect, but which demon­
strated the possibility of fixing them onto glass. On continuing h i s studies,
h e discovered, the fol lowing year, a type of coating-albumen from eggs­
which possessed photograph i c properties and which resulted i n the albumen
p rocess prod ucing negatives of extreme fi neness and particular gloss.
The albu men u sed i n p hotography comes from fresh hen's eggs. Each
egg contains 25 to 30 g albumen. I n order to break the large cells keeping
the albumen enclosed, the egg wh ites are beaten stiff and left to rest for
1 2 h . After being decanted, the l i qui d part constituting the albumen can be
u sed . Another effect ive p rocess is to use acetic acid. After this treatment, a
10% aqueous solut ion of ammon i u m iodide, potass i u m brom ide and iod ine is
added to the albu men . The addition of a muci laginous substance, l i ke gum
arabic, makes the albu men unctuous, increases its adhesive properties on
glass, and prevents it from c rackling d u ring d ryi ng. The p hotographic albu­
men is spread i n a t h i n , regu lar layer on the glass with a p ipette: the glass
is ti lted l ightly i n all d i rections to ensure an even d istribution. Any excess
l i q u i d is po u red away from a corner. As the d rying of the albumen has to be

'" Spanish white: crumbly chalk.

ttripoli: sil iceous stone.
 R e a d i n g 39 G I L L E T , G /\ H N I E H , A N D F L I E D E R

even, the plate should be heated sl ightly. When protected from dust, we l l ­
clriecl glass can be stored almost i ndefinitely.
The a l b u men layer is sensitized i n a solution of silver n itrate and
acetic acid.
Expos u re to light m u st take p lace within a maxim u m of three to four
clays' time. The exposure may vary from 5 to 30 min. The picture i s developed
in a 1/i ooo gallic acid solu ti o n i n to which a few d rops of pyrogal lol alcoholic
sol ution may be added. When the picture becomes visible, a 3% s ilver n i trate
aqueous solution is added. The development must be carried out very slowly;
that is the condition for obtaining the best possible albumen negatives. After
rinsi ng, the picture is fixed in a 1 2- 1 5% soluti o n of sodiu m thiosulp hate
(sodi u m hypos u lphite) . Potassi u m cyanide must not be u sed as a fixative, as
the albumen layer may then peel off. To increase the sensitivity of the albu­
men process, some p hotographers ( G . Sella and E . Bacot) have cha nged the
closes of bromide and iodide, so the exposure time has become twice as short.
The albumen process i nvolves a lot of d i fficulties; the perfect clea n i ng
of the glass, the alb u m en's attraction of dust, the slowness of the process and
the strong contrast of i ts p ictures. \Vhen the wet collodion p rocess therefore
appeared and solved these problems, a l l the photographers set about using
t h is new and fast tec h n i que.
The a l b u men was, however, sti l l u sed i n cases where the wet colloclion
was unworkable, e.g. for tourist photographers. I t was reserved for scientific
reproductions, stereoscopi c views and presentation . We only h ave knowledge
of very few a l bumen negatives.

1 .3 . The Wet; Collodion Process

We are acquainted with the first u se of col lodion -treated glass for photo­
graphic use from F. Scott Archer who published the resu l ts of h i s studies i n
1 8 5 1 , although G . Le Gray erroneously l ai d c l ai m t o an earlier publ ication.
The wet colloclion process gives pictures whose fineness of design competes
with that of the albumen p rocess without having i ts strong contrast.
Photographic colloclion spread on a scrupulously clean glass plate is
based on ord i nary collodion with ammonium, cad m i u m or potass i u m iodide
and brom ide. It must be l iq ui d , fast-working, adhesive a n d as permanent
as possible. O rdinary collodion is a complete an d concentrated guncotton
dissolution in a m ixture of ethyl ether and ethyl alcohol. G u n cotton, known
u nder the names of pyroxyli n or n itrocellu lose, consists of cellulose n i t rate
obtained through the reaction of nascent nitric acid on carded cotton. The
p hotographers usually bought the ordinary col lodion ready for use in order
to obtain reproducibility.

34 1
P art V P 1-1 0 T 0 G H A P II I C N E G A T I \! E S

The sensitizing si lver bath of the iodide-bromide colloclion layer i s a

weakly acid silver n itrate solution of varying concentration, depen d i ng on
the work to be clone.
Exposu re must take place i mmedi a tely after the sensitization whil e the
e mulsi o n i s sti l l wet, hence the name of the process, "wet collodion." The sen­
s i ti vi ty is red uced when the plate i s dry. Exposu re time is from 2 to 60 seconds.
Deve lopment of the negative has to take place very soon after exposu re
to avoid stains caused by the d rying of the colloclion. There are two m a i n
procedu res for developing t h e picture:

development with pyroga l l i c acid m an acetic solution, the use of

which is ascri bed to V. Regnau l t : the picture emerges slowly and pro­
gressi vely, and can easily be stopped at the correct moment; the tones
are strong without being harsh ;
• development with ferric ammonium sulphate i n alcoholic o r acetic­
acid solution; the picture e merges qui ckly, al most suddenly and,
con trary to the former process, the negative i s more harmonious a n d
blended n o w and then w i t h too l i ttle contrast.

Some operators have m ixed both processes to obta i n a plate combin­

i ng the special properties of the two developi n g baths. The fixing of the pic­
t u re is carried out either with a 2% aqueous solution of potass i u m cyanide,
or with a 40% solution of sod i u m thiosulphate. Then the negative must be
rinsed thoroughly and dried. In this process the picture does not penetrate
the col lodion layer; it remains in rel ief.
The development rarely gives the plate the req u i red strength ; it i s
a lmost always necessary t o intensify i t . Many p rocedu res have been used;
we will only mention a few of them: i n tensification with si lver, copper and
silver, lead, mercury, etc . Retouc h ings are performed with a penc i l , and all
parts req u i red to be u naffected by actin i c rays m u st be covered by a sol u­
tion o f fuchsine or carmine mixed wi t h rubber. Collocl ion plates a re n ot as
d u rable as albu men plates. vVhen they are to be used for many copies, they
must be p rotected against chafing and scratches by covering them with a
rather hard and transparent varni s h . Many products have been used for this
p u rpose : varn ish with gum arabic, albu men, benzole, benzoin gu m , yel low or
white shellac, a mber, yel low or reel dyed collodion-based varn ishes, etc . . . .
(Appendix A) [not reproduced here] .
The greatest i nconven ience of the wet collocl ion process is the neces­
s ity to expose it im mediately after makin g the sensitive layer; this makes out­
door photography problematic. For this reason , many attempts h ave been
made to use a d ry colloclion.

3 42
 R e a d i n g 39 G I L L E T , G A H N I E R , A N D F L I E O E H

1+ The Dry Collodion Process

This process has been u sed by professional p hotographers, but not quite as
much as the wet collodion process, on accou nt of i ts weak sensitivity. The
dry sensitive la yers can be exposed long after being made, and m ay be devel­
oped a few days later. The slowness of the development compels us to rei n­
force the adhesion of collodion to the glass p late by i n terposi ng a dry layer of
albumen or rubber varni sh d i ssolve d i n chloroform.
The principle i n this process i s the same as for wet collodion. A pro­
tective agent has to be added after the sensitization to m ake the dry later
durable, and to m ake it stay sensitive. Many substances are used for this
purpose: res in, gelatin , sugar, gum arabi c , tan n i n , gal l i c acid, albumen, mor­
p h i ne, caffeine, etc.
We s h a l l here l i m i t ourselves to describe the a l b umen-collodion pro­
cess whi c h has been named the Taupenot process after i ts i nventor, when a
layer of ordinary collodion has been spread on the glass plate. The process is
performed by adding a solution of albumen, ammonium iodide and bromide,
sugar and ammoniu m hydroxide. H. Bayard discovered that a solution of gela­
tin could replace the al bu men l ayer. Sensitization is carried out by means of
an aci d s ilver n i trate solution. The p late thus prepared is left to dry in the dark,
a n d may be exposed during the fol lowin g days. Exposure time is 5 to 6 times
longer than for a wet collodion glass p late. The p i c ture is developed i n a gal l ic
and pyroga l l i c acid aqueous solution. F ixing i s done i n a J O% sod i u m th iosul ­
p hate solution. The negative then is s o strong t h a t it is n o t necessary t o varni sh
i t . T h e pictures evi nce a p leasan t transition between the firmness of design of
the albumen process and the harmonious softness of the collodion process.
Collodion processes were u sed for approxim ately 30 years, u nt i l pho­
tography made great strides with the i nvention of the gelatin process.

1 . 5. The Gelatin Process

I n a letter to the B ritish Journal of Photography, R . L. M addox i n 1 871

described his experiments on a production of pictures from silver bromide
scattered i n gela tin . The sensitivity of these plates was very weak, however.
O n ly i n 1 878, when C . H . Bennett discovered a way of i ncreasing the sensitiv­
i ty through a ripening of the emulsion, does the d ry gelat i n process become
popular and almost u n i versal ly used. As the art of p hotography developed,
thanks to the qualities of this process, the production of these glass plates
soon became i n dustrialized.
The gel a t i n used comes from bones of animals and its quali ty is i n fl u­
enced by the extracts which have to be purified an d freed from all reduci ng

343
P art V P H O T O G R A P H I C N E G A T I V E S

substances and greases; its setting and melting points m u st be as high as

possible in consideration of the fact that its dissoluti on in water must be
complete at 40-50°C . To prevent the ge latin from peeling, the cleaned and
polished glass plate must be ru bbed with a wad of cotton i mpregnated with
sod i u m silicate. A better adhesion of the gelatin to the glass can be obtained
by dippi n g the plate in a 0.5 or 1% gelatin sol u tion to which 0 . 1 to 0.2%
chrome a l u m is added . After drying, this leaves a substratum on which the
e m u lsion l ies.
The preparation of the sensitive layer is rather tricky. There are tvvo
types of emulsions:

• S ilver bromide em u lsions: they consist of a s ilver b romide precipitate

s uspended in the gelatin. This precipitate is obtai ned through a reac­
tion between si lver n itrate and potassi u m bromide or ammonium bro­
mide dissolved i n an aqueous sol ution of ge latin. The sol ub le salts,
i.e. the nitrates, are washed out. The sensitivity of the si lver bromide
is increased, as mentioned earlier, by a special process cal led ripening
which produces a change of the gra i n . The ripening consists i n letting
the emulsion rest after addition of am moni u m hydroxide or keeping it
for a week at 40°C , or in bringing it up to 1 00°C for 30 min. The emul­
sion is now ready to be poured onto the glass p late covered with the
su bstrat u m. After drying, the p l ate may be stored for several months,
either before exposure or between exposure and development.
• S ilver c hl oride e m u lsions: they contain silver chloride instead of silver
bromide, which gives them a red uced sensitivity. The layers become
very thin , a lmost without grains, and completely transparent. They are
especially used for the production of s l ides on glass. The negatives are
exc l usively silver bromide emulsions.

During the deve lopment, the picture obtained with the gelatin process is
formed in the whole depth of the l ayer, in contrast to the wet col lodion pro­
cess where it remai n s on the surface. The developer acts as a reducer on
si lver bromide insolated d u ri ng the expos u re and transforms the Ag+ ion i nto
metal l i c s ilver. Many developers h ave been successfu l ly used for the devel­
opment of the image. There are two types:

• Metal l ic salts: fi rst developer for gelatin plates, ferrous oxalate was
mostly used.
• Organic developers: pyroga l l i c acid in a l kaline solution was used after
the ferrous oxalate. Hydroguinone, the developing qualities of which
were discovered by Abney in 1 880, distinguished itself in preference
to other developers because it gives pictures of great i n tensity, its

3 44
 R e a d i n g 39 G I L L E T , G A B N I E R , A N D F L I E D E B

u se became more and more widespread and i s still extensively used

i n modern photography. Pyrocatech i n (hydroq u inone isomer) and
" hydramine"t d iscovered by L u mi ere and Seyewetz are also developers.
Dr. Andresen (Berlin ) u sed eikonogen§ i n 1 889, although the pictures
become a l ittle too transparen t i n contrast to hydroq u i none. Even
if it is possible to see very small details i n the highlights, negatives
made with this product i nvariably have to be i n tensified to obtain good
prints. Various phenol derivatives (para m i no-phenol, d ia m i no-phenol ,
d i a m ino-resorc i n ) have good red uc i ng properties, and are therefore
u sed as developers. Finally metol (discovered i n 18 91) and glycine
should be mentioned , whi c h give pictures that are neither too hard
n or too soft. Th is i ncomplete l i st gives one a general i dea of the many
substances used to develop gelatin negatives.

It should be mentioned that the development should always be carried out

in a n alka line bu ffer and with sod i u m sulphite which enhances the effect of
the developer. Moreover, sod i u m sulphite acts as a preservative for the bath .
After being developed, t h e glass p late is i mmersed i n a 5% o f potass i u m o r
c hrome a l u m solution which hardens t h e gelat i n . T h e fixi ng is made with
sodi u m t hiosu l phate exclus ively.
It very often happens that the negative has to be intensified or reduced .
Many formu las are described in the l iterature : i ntensification with mercuric­
ammon i u m c hloride, mercuric iodide, c uprous b romide, reduction with
potass i u m cyan ide, copper sal ts, thiosulphate, potassi u m ferricyanide, per­
m anganate, etc.
The negatives are protected with a varnish as is described i n the wet
collodion process. I t should be mentioned, however, that the strength of gel­
atin p lates is i ncreased by an a l u m treatment.
In Appendix B [not reproduced here] we show some prescriptions for
the manu facture of negatives.

2. Preservation: B i b l i ographic S urvey

2. 1 . Deteriorations

Although most glass plate negatives are wel l preserved, various kinds of dete­
rioration wil l be noted, physical, chemical or b iological, whi c h are caused
e ither by the manu facturing treatment or by attacks from the surrounding
agents.

l hydram i n e : prod uct of reaction between hydroq u i none and para-diphenyl a m i n e .

l e i konogen: Sod i u m 1 -a m i no-2-naphtol-6-s u l phonate.

345
P art V P H O T O G R A P H I C N E GA T I V E S

Physical Deteriorations

The glass impl ies fragi l ity in the handling because of its properties. There­
fore one often encou nters cracked negatives and even negatives which have
been broken i nto many pieces. Old negatives are always more or less dusty
an d marked with fingerprints, either on the glass or on the e mulsion. Fre­
quently, there are scratches, more or less deep, on the i mage surface. lf the
negative is varnished, the scratches have not destroyed the e m u lsion and the
picture is u ntouched u n der the protective coating. It happens that gelatin
p lates stored next to one another without anything to separate them stick
together. Th is happens when plates are stored at h igh hum idity or when pro­
tective varn ish or the gelatin have become sticky because of decom position.
Finally, the peeling of the i mage on some negatives may have vari­
ous causes. The first p hotographers using glass negatives have stressed the
i mportance of the cleaning and polishing processes req uired to ensure adhe­
sion of the emu lsion to the glass. 2 6 ·36 In connection with the gelatin method,
fluctuating hu mid ity may also cause peeling; gelatin, which is very hygro­
scopic, swells at high h umidity and shri n ks when the air dries up. As the
glass is dimensionally stable, some tensions arise between the gelatin and
its base which may encl in a separation of the material s . In the collodion
processes, excessive concentration of the solvents used for the manufacture
results i n deteriorations : as ether is very volatile, i t favours fast dryin g and
resu l ts in the shrinkage of the collodion which causes the reti c ulation of the
i mage; 26 58 addition of too m uc h alcohol wil l give a thin and brittle collodion
film without any resistance. 36

Chemical Deteriorations

The chemical deteriorations can be seen on the d i fferent components of the

negative, except on glass which is considered to be rather stable. The protec­
t ive varn ish laid on the i mage may decompose: it becomes yellow or sticky
an d peels off. The colloclion or cellulose n itrate is an u nstable product, espe­
cially at high h u m id i ty. I 8·26 •36 I t sets nitrogen oxi des free which attack the
cellulose chain and the silver of the image. It becomes yellow and gradu ­
a l ly crum bles. For t h e varnished negatives the decomposition i s accelerated
because the protective layer prevents the gases from volatizing.
The ye llowing and fading of the image is often caused by residual salts
coming from a too old fixing bath or poor ri nsing. The sul phurous products
based on thiosulphate react with the silver of the image a n d produce sil­
ver sulphide; the negative then turns brown-yellow, or may be full of spots
of the same colour. I 3. I 3.2 u6·46• 58 Air poll ution i n the form of sulphur dioxide
 R e a d i n g 39 G I L L E T , G A R N I E R , A N D F L I E D E R

and n itrogen dioxide and al l other oxidizing agents being i n contact with
the negatives (adhesives, envelopes, paints and varnishes of storage cabinets,
etc . . . . ) cause an oxidation of the silver and a fading of the i mage. S ilver
stains often appear on the edges of old glass p l ate negatives. They are cal led
dichroic on account of their many different colours depending on the way
they are seen: they may look grey or metallic in reflected light, but yel low or
sometimes red or brown-green in transmitted light. They consist of a thin
layer of colloidal silver c reated around the s ilver sulphide molecules.
In the old collections, the existence of small c raters may also be noted,
the origin and formation of whi c h are u n known .

B iological Deteriorations

The gelatin a nd collodion negatives are excellent fungus and bacteria culture
media that thrive best when the h u midity at the storage place is h igh and
exceeds 60% R. J-I . 26•4654 They go through deteriorations, now a n d aga i n irre­
versible: white f ilaments on the surface, coloured spots c aused by p igments
released by spores, decomposition of the gelatin whi c h has become sticky
a n d water-soluble.

References

Manufacturing Processes

Barger, S . : B ibliography of photographic processes in use before 1 880. 17iei.r

mat.erials, processing an.cl conservation . Rochester, Graph i c Arts Research
Center, Rochester I n st i t u te of Tec hnology, 1 980.
2 B e n nett, C h . : A sen.sitit'e gelatin ein.ulsion process. B ri t i s h Journal of
Photography, vol . 25, no. 934 ( M arch 29, 1 878), 1 46-147.
3 Calmels, H. & C lerc, L. P.: Les procecles au collodion lmmi.de, Paris,
Le procede, 1905.
4 Davanne, A.: La photographie, vol. I et 1 1 , New York, Arno Press, 1979.
H ercock, R . J . : Ea rly emu lsion nrnbng. Journal of Photographic Science,
31 ( 1 ), 43-44 ( 1 983).
6 Lande, A.: Ai.de-niemoire pmti.que de photographi.e, 2e edition, Paris,
Librairie J . B . Bail lere et Fils, 1 897.
7 M addox, R. L.: An experi1nen.l with gelati.no-broniide. British Journal of
P hotography, vol . 18, no. 592, 422-423 ( 1871 ) .
8 M i ron, F . : Pliotogra71hie, Paris, P . Vicq-Dunod et C i e E d . , 1 897.
9 Morrison, R. C.: A chen·i.ical history of nineteen.th century photography,
Australian photography conference: Departm e n t of adult education, U n i versity
of Sydney, ( Sept. 1 977) 86-106. Copyright 1 980.
10 N a m i as, H.: Ch.i·m ie photograph ique , trad u i t de la 2e ed. italienne par
E. Jaquez, Paris, C . Naud Ed., 1902.

347
Part V P H O T O G R A P H I C N E G A T I V E S

11 Scott Archer: The collodion process on glass. The C hemist, ( M a rch 1 8 5 1 ) .

1 2 Valicourt, E . d e : Ph.otogwp/1ie s u r 111etal, s u r papier et s u r verre, M anucls
Rorer, Paris, Ed. Leoncc Lager, 1977.

Preservation and Restoration

1 3 American national st.andard pract.ice for st.o rage of processed phot:ographic plat:es,
norme A N S I PH 1 .45, ( 1 972) 14 p.
14 American national standard require1nent.s for ph.ot:ographic filing enclosures for
storing p mcessed phot: ographic films, p lates and papers, norme A N S l PH 1 . 53,
( 1 978) (rev. eel. of A N S I PH 4.20, 1958, 1970), 1 1 p.
15 Bensusan, A. D.: Detaiorat.ion i n pmcessed photograpliic emulsions and
the p reservat ion and restorat ion of old negatives and prints. Sou th African
M useums Association B u l letin, 8, 6, 1 89-196 (April 1 965).
16 Booth, L . : Restoring historical ph.otogrnphs. The Rangefinder, (Aug. 197 1 )
p p . 4o-43.
17 Booth, L. & Boot h , J : Duplicat.ion of cellulose n it.rate negat:ives. Picturescopc,
vol . 30, no. 1, 1 2-18 (Spring 1982).
18 Clark, \N. : /-low lost i 1nages are recc171t.med. College of graphic arts and
photography, Rochester. Preservation and restoration of p hotographic i mages
(seminar), Rochester I nstitute of Tech n ology, 1 980.
19 Coll i ngs, T. J.: The st.orage of glass negatives. Photograph Conservation, 3 ( 1 ),
I & 3, 1 98 1 .

2 0 Col l i ngs, T. J . : Some practical aspect.s of t.he storage and display of st:ill
photographs. " P reprints," 6th Triannual Congress of l ' l . C . O . M . , Committee For
Conservation, Ottawa; 198 1 , (3), 8 1 / 1 4/22, 15 p.
21 Crabtree, J. I. & Henn, R. \�I.: Scun1s, sludges and stains. Thei r sou rces,
p revention and removal. Photographic Society of America Journal, vol. 1 4 ,
201-209 (April 1948).
22 Eaton1 G . T.: Preserva t ion, det.eriorat.iou, restoratio-n of 11hotograph.ic i: inages.
The Library Quarterly 40, 1, 85-98 Uan. 1 970).
23 Enyeart, J . L . : Cleanin.g glass plale n.egat.ives. Sen1 inar Report, Exposure 1 2 , (2)
pp. 6-7.
24 Fassett, D. W., Kolb, F. J . & Weige l , E. N I . : Practical .film cleaning for safety
and effect iveness. Journal of the Society of Motion Picture and Television
Engineers, vol . 67, 572-589 ( Sept. 1958).
25 Galambos, J : La conservat.ion et: la restaurat.ion des mat.tfriaux photographiq ues
et des m.icrofilms . iVl uzeu m , vol . 20, no. 4, 209-223 ( 1 975).
26 Garztecki, J . : 1\1/ethode c n1 collodion et conserva t ion. des negatif' a u collodion.
Ochrona Zabytkow (Warzawa), vol . 24, no. 1, 25-34 ( 197 1 ) .
2 7 Gear, ] . L . , Mac C laren, R . 1-1 . & Mac Kiel , NI . : Film recovery of so1n.e
deteriorated blcich and whit.e negatives. The American Archivist, vol . 40, no. 3,
363-368 (j u ly I 977) .
28 H a i g, R. N . : Fif.. i n. clea ning solvents. Journal of the Society of Motion Picture
a n d Television Engineers, vol . 85, 739-742 ( Sept. 1 976).
29 H aig, R . N.: Fil:1n. clean i ng by 1Jlt.rasonic liquid cavitation and acceptable
solve n ts . Journal of the Society of Motion Picture and Television Engineers,
vol . 89, 240-243 (April 1980).
30 Henn, R . VI/. & Crabtree, J. I . : Sulfide stain . Its n a t n re, cause and met hods of
 R e a d i n g 39 G I L L E T , G A R N I E B , A N D r: L I E D E R

prevention . Photographic Society of America Journal, vol . 1 3 , 752-758

( Nov. 1 947).
31 H e n n , R . \�1. , Crabtree, J . I . & Russel l , H . D . : A n annnon.iu1n hypo reducer.
Photograph i c Society of America J ournal, 1 7 B , 1 1 0-1 1 3 ( N ov. 1 9 5 1 ) .
32 Heusinger, L . : Die Erhalt.u ng Hn.d Pflege fot:ografischer Negat:i.ve. D e r Archivar,
33, (2) col. 273-275 ( M ai 1 980).
33 Johnsen, J. Stub.: Die Resta H rienmg vergilbter ZellHlosenit rat.- un.d
Clasplatten.negative. M altech n i k Restauro 90, 57-68 (1 J a n . 1984).
34 Knight, N . 1-1 . : The c/.eanin.g of 'fl'1.icrofonn.s. Journal of M icrograp h i cs, 1 1 9- 1 22
( November-December 1978).
35 Methode de n1.esure cle l'efficacil.e cles fil tres a u moyen cl'un. aerosol cl'uranin.e
(fl.uoresceine), Norme AF N O R N F x 4460 J J , ( M a i 1972).
36 Moor, I . : The ambrotype research into its restoration an.cl conservat:i.on..
The Paper Conservator, vol. 1 , 22-25 ( 1 976) (part I ) ; vol. 2, 36-43 ( 1 977)
(part I I ) .
37 i\1 u nson, D . : Du-plication of glass negatives. Picturescope, vol. 30, n o . 1 , 19-23
(Spring 1982).
38 National Geographic, Negat ive t ransfer. Tech n i c a l Photography M agazine,
vol . 9, no. 2 , 39 ( Fcv. 19 7 7).
39 Nedughii, S . A . : Ultrasonic cleaning oj 1l'w gnetic tapes an.cl photographic
'l'l'taterials. Tekni ka kino i televidenija, 1 2, no. 2, 72-78 ( 1 968).
40 N e lson, C. \V. : Neut:ron activation. offadecl photographs ancl clocu'f1'1.ents.
American Archivist, 32, 285 ( 1 969).
41 Orraca, J.: T'h.e preservaLi.on aJid restoration of glass plate -negat: ives. l n1age,
Rochester, vol . 1 6, no. 2, 8-9 Q u ne 1973).
42 Ostroff, E.: Consei-vin.g an.cl 1·estoring photogrnphic collections. \�lashington,
American Association of M useums, 1 976.
43 Ostroff, E . : Rescuing nitrale negat .ives. M useum N ews, 57, no. 1 , 34-42
(Sept.-Oct. 1 978).
.
44 Pliotograpliie, directives pour / 'arch.ivage cles plaques photographiques a image
a rgentique, norme A F N O R N F 20.0 1 8, ( Nov. 1 979) 10 p.
45 Photographie, plaques ph.01ographiques a hnage argentique pour arch.ivage
conditions cle con.sen1ation, normc ISO 3897, ( 1 976) 7 p.
46 Preservat.ion. of phot.ogmphs, Eastman Kodak, Rochester, Publ ication F 30,
( 1 979).
47 Prevention and rernoval offungus on pri-nts and fi.lnis, Eastman Kodak,
Rochester, Pubication AE 22, ( 1 969) (rev. 1974).
48 Heed, \/. L . : How to wo,./t rest.oral.ion ·111.agic on wrinlded negatives . Photograph
Conservation, 3, (4) 4-6 ( Dec. 1 98 1 ) . Reprinted from the Professional
Photographer, Q u ly 1 980).
49 Rempel, S : Le soi.n des collect.ions de plwt.ographies en. noir et. blanc, 11ett.oyage
et stabilisation.. Ottawa, l ns i t u t Canadien de Conservation, ( 1 980).
50 Homan, D . : Restoration. of old faded photographs. Arch ives and Man uscripts,
4 , no. 8, 7-1 0 (August 1972).
51 Salvaging blach and whit.e phot.ographic images, Eastman Kodak, Rochester,
Customer tec h n i cal services, C I S 12, ( Feb. 1982).
52 Scott . ] . R.: Cleaning glass negatives. The Canadian Arc hivist, vol. 2, no. 5,
1 00-102 ( 1 974).

349
P art V P H O T O G R A P H I C N E GAT I V E S

53 Scott J . R . : Microfilming glass negat.ives. Arc h i varia, no. 5, ( W i nter 1 977-78) .

54 S t: orage and. preser11at.ion of motion picture film., a se/.ec/.i.ve reprinting, Kodak,
Rochester, S 1 543 AP, ( 1 957) .
55 S t rydom, H . J . : Tiw copying of old photographs and. d.oc11nwnts with reference to
u/.t;ra-violet and. infra-red light. South African M u seums Association Bulleti n ,
Cape Town, vol . 1 1 , n o . 1 , 28-33 ( 1 974 ) .
56 Swan , A . : The care of d1y plate negatives (ge lat i n. o n . glass), M an uscript,
(April 1 976) .
57 Taylor, G . : F r o m the archives. T11e photographic collection. at R . f.T. Photograph
Conservation, vol . 5, (4), 7 ( Dec. 1 983).
58 Thomas, D. B . : Tiw co/.l.oclion process. Sem i nar R . l .T.: Preservation and
restora t i o n of photographic i m ages/Col lege of gra p h . arts and p h oto., ( 1 980)
part 1 1 .
59 Tilson, C . : Preservation., conservation an.cl rest.oration. of photographi.c materials.
Ka lori, 5 1 , 5 1-55 ( M ay 1 9 7 6) .
60 Van Ravenswaay, C h . : An improved -rnethocl for tJw res/:oration. of daguerreotypes.
I mage, 5, 1 56- 1 5 9 ( 1 956) .
61 \�lagner, R. W.: Preservation an.cl restoration of photographic materials through
n uclear aud u l t rasonic methods. I l l i nois L i b raries, 53, ( 1 ) , p p . 1 0- 1 7 (Ja n . 1 9 7 1 ) .
6 2 Wei n stein, R . & Booth, L . : Collection., tISe a n d care of historical p hotographs.
Nashvi l l e , American Assoc i ation for State a n d Local H istory, ( 1 978).
63 Weyde, E.: A sim:p/.e test to iden t ify gases which dest roy silver hnages.
Photographic Science and E ngineering, vol . 1 6 , ( 4 ) 283-286 (J u l .-Aug. 1 972).

D u p l i cation

64 Ask i n s , 13. S., Speich, D . M., W h i t ing, i\'l . Y. & Akridge, K.: A n.ucleai·
chem.ist:ry teclmiqu e fo r restoring faded phot.ographic i·1n.ages. The American
Arc h ivist, vol. 4 1 , ( 2 ) (April 1 978).
65 C h atters, R . i\'1 . & Jacobs, C . : Recove1y offaded phol: ographs by nuclear
techniques. Photographic Applications in Science, Tec hnology a n d Medicin e ,
(V) 2 6 , 27, 47 (Jan . 1 970).
66 Ostroff, E . : Restorat ion of- photographs by n eu t ron. activation. Sci e nce, vol . 1 54 ,
1 1 9- 1 2 3 (Oct. 1 966).
67 Thackray, i\11. & Roman, D.: Intensification offaded photographs a n d
underexposed negatives using radioisotopes. Atomic E nergy, 24-30 (April 1 972).
 R e a d n g 40

MARK H . M c C o RM I C K- Go o D HART

An Analysis of I mage Deterioration

in Wet-plate Negatives from the
Mathew Brady Studios ( 1 992)

The following reacling by J\!Iarh McCormiclz-Gooclhart (see also Reading 63 )

exemplifies the consiclerable value of instrun1-ental analysis in enhancing our
u nclerstancling of the complex clegraclation mechanisms associatecl with early
colloclion wet-plate negatives. JVIarh J\!IcCormich-Gooclhart is currently the
clirector of Aarclenburg Imagi.ng & Archives. During th-is st;ucly McConnich­
Gooclhart was a photographic research scientist at the Smit:li sonian Institution
and evaluat:ecl wet-plate negatives from the Meserve Collection at the National
Po1irai.t Gallery in Washington, D. C. Multiple analytical techniques, inclucl­
ing Fourier transform infrarecl spectroscopy ancl electron microprobe analy­
sis, were usecl to characterize several glass substrates. f\l/cCormiclz-Gooclha1i's
investigative worh clemonstrated a strong correlation between glass co1nposi­
tion (higher levels of soclimn) ancl the cleterioration of collocli.on images on
glass-specifically varnish saponification ancl coating aclhesion failure. 17ie
author continuecl to stucly the effect ofglass composition on wet-plate image sta­
bility after publishing the reacling reprocluced here. That aclcUtional 1vorh was
summarizecl in his article "Glass Corrosion and its Relation to Image Deterio­
ration in Colloclion Wet-Plate Negatives, " published in The I mperfect I mage :
P hotographs, Their Past, Present an d F u t ur e in 1 992. These publications, com­
bined with research concluctecl by Constance McCabe at the National Archives
and Records Administration ( "Preservation of 1 9th-Century Negatives in the
National Archives, " Journal of the American I n stitute for Conservation 30,

MAHK 1-1 . M cCOHMICK-C OoDHART, "An A n alysis of I mage Deterioration in \�let-plate

Negatives from t he Mathew Brady Studios," in The hnpe1fecl. 111•1.age: Phot.ograpb. Their
Past, Presen t. and Fut.ure ( London: Centre for P h otograph i c Conservation, 1 992), 245-55.
Co nference Proceedi ngs, \>\lindemere, 6th-10th A pr i l , 1 992. © The Centre for Photo­
graphic Conservation. Text and i mages reprinted b y perm ission .
P art V P ll O T O G H A P ll l C N E G A T I V E S

no. l,
1 9 9 1 : 4 1-73), drew increased attent ion. to the urgent preservation. needs of
ra m collodion wet-11late negat ive collect ions and the vi. ta! iinportance of envi­

ron mental cont rol (specifically relat:ive h u midity) and proper housing.

I n trod uction

l n 1 98 1 the National Portrai t Gal lery acqu i red 5 4 4 5 glass plate negatives
made by M at hew Brady's \Vash i ngton and New York studios d uri ng the
years 1 86 1- 1 866. These origi nal negatives were c reated entirely by the col lo­
dion wet-pl ate process and comprise what is now referred to as the Meserve
Collection. Brady's stud ios prod uced finely crafted portraits a n d attracted
the affluent and celebrities of the ti mes. The im ages of many pro m i nent 1 9th
century figures are featured i n extraordi nary deta i l withi n the Collect ion :
Abraha m Lincoln, U lysses S . G rant, Jefferson Davis, \Vil l iam Tecu mseh
S herman , H enry Wadsworth Longfellow, Ol iver Wendell H ol mes, Nathaniel
H awthorne, P .T. Barnu m , Samuel Morse, and so forth . The p lates are com­
pelling testimony to Mathew Brady's ge nius and to the skills of the crafts­
men employed by h i m . Due to their provenance they also form a un ique
study group in wh ich to examine the craft and image stab i l i ty of the wet
collodion process. A brief history of the Meserve Col lection is reprinted i n
Appen d ix. 1
The need for a better u ndersta nding of deterioration mechanisms
arose from concerns that appeared at the time the collection was acquired . A
small, b u t signi ficant, nu mber of plates (�1-2%) were set aside from the oth­
ers because the varnish layers were tac ky. Many dirt particles and fibers from
the paper enclosures had become embedded . Discoloration, small cracks
and i mage l osses as wel l as local ized "spotti ng" or "mottling" patterns in the
i mage silver were quite apparent. The tacky varnish coati n gs also exh i b i ted
a strong response to relative humidity. After the affected p lates had been
transferred to their new storage enviro n ment, where the relative h u 111 i d i ty
does not exceed 50%, they did not reta i n the h igh tack leve l . Figure 1 shows
a modern pri nt made from an affected plate, side by side wit h a print from a
plate i n excellent cond ition. Figu re 2 i l l u strates 5mm x 5mm section details
from the same plates. The macrophotos were recorded using a combination
of transmitted and reflected l ight to reveal both negative transmission den­
sity as wel l as the present condition of each plate's surface.
Environmental h istory was ruled out as a cause for differences between
t h e plates. The \Vashi ngton and New York p lates were merged very early,
because prints were made for sale to the public by E. & H . T. Anthony i n New
York. The pop u lar carte-de-visite format exp loited m u ltiple-exposure camera

352
 Reading 40 M C C 0 H M I C K - G 0 0 D I I t\ H T

Figure 1
Contact print From a deteriorated
Brady studios negative
( N PC 5296: 18), Rev. Farley), left.
and one in excellent condition
( N PC 3050 : 1 02, U11ide111:ified
female), rig h t . Heavily embedded
paper r'ibcrs and opaque retouched
cracks on the deteriorated negative
appear as low density values in the
contact print. The bright streak
seen on the good plate is a tn)ical
edge nonuniformity From the hand­
coatcd sensitization method of
wet-plate p hotography. It is not a
sign of age or deterioration.

backs, which yielded several poses on a s ingle large p late. Because each plate
was fin ished i n a continuous method of coating, sensitizing, exposing, and
processing, the multiple exposures possess equi valent materials and process
quality. They were then typically c u t apart to carte-de-visite size and did not
always stay filed side by side. One practice that increased the opport un i ty
for separation was ga ng printing. Various small plates wou l d be mou nted
in sequences to a larger backi ng glass in order to fac i l i tate contact print­
i ng. Nevertheless, when mates are l ocated an d j udged side by side today,
the present manner and degree of deterioration are remarkably the same.
Th us, the mul tiple-exposure i mage mates provided reasonable evi dence that
the present image qua l i ty of i nd ividual p lates in the Meserve Collection was
rel ated to material and/or c raft, rather than to m icrocl i mate or other envi­
ron mental d i fferences.

Experim e n ta l

All negatives i n the col lection have varnish overcoats. Varni s h i ng was a
c ustomary and indeed essential aspect of the wet collodion c raft. An u nvar­
nished wet-plate negative did not su rvive contact printing procedures very
long before severe scratches and abrasion occ u rred, because the collodion
b i nder (cel lu lose nitrate) i s about 2 ::+:: 1 µ,111 thick and the developed si lver
particles are concentrated at the col l odion s urface. The va rnish th ickness
is typically 4-8 µ,m. 2 · 3 A scanning electron m icroscopic cross-sectional view
of a wet-plate negative's collodion-silver b i nder and varnish layers is shown
i n Figu re 3. No distinct boundary is evident between the varnish and col-

353
 Part V P H O T O G R A P H I C N E G AT I V E S

( a)

Figure 2
5 X 5 mm seclion detail of
(a) the deteriorated ne gat ive (NPG
5296: 1851 ReF. Farley ), revealing
fine coating cracks and image
losses as well as embedded dirt
and fibers. (b) ( N PG 3050:1 02,
Unidentified female). where t he
i mage structure is clean and
completely i n tact, revealing even
the grain structure of wood in the
back of the chair used by the s i t ter. (b)

lodion, although some vertical fracture l ines seem to be characteristic of

the varn i s h layer's cross-sectional face. F igure 3 also reveals that some of
the silver particles are only loosely boun d and can be freed i n to the varnish
region when the varni s h i s poured. This situation is not s urprising when the
close sol u b i li ty parameters of the varnish and the collodion b i n der layer are
considered.

354
 Reading 40 M C C O R M I C K - G O O D H A R T

'top Surface

of Varnish

Varnish

Sliver
particle
matrix

Collodlon

'"oriQ1nal '."·/ '. ·

>( •( ,,._ ·.,.� ·:

"loeatfort . · ·, . ·
/�
· . .

, ';.. :....; ·-... . "x ,,_ "•·\::: ·,

' , ...
. •

.¢.9f�� •. . ' . ' .

Va rnish Analysis Figure 3

SEM micrograph of a wet collodion

Varnish condition was exami ned by Fourier transform infrared ( FTIR) negative in cross section a t 8000 X
magnification.
spectroscopy. M icrogram samples of varn ish were removed with a dissect­ The sample was a coating flake
i ng needle from three p lates exh i biting once-tacky varnish layers and from separated From its glass support.

four ran domly selected p lates wherein the varni sh coati ngs appeared to be
in fine condition . The varnish was separated from the col lodion-silver region
with the aid of a 35-50 X stereoscope focused on a high-image density area.
A sufficiently p u re sample of the varn i s h resin was removed by taking care
not to disturb the silver i m age. The deteriorated p lates presented more dif­
ficulty, because the silver matrix had started to break up and d isperse, which
accou nts for much of the mottled and clum ped-grai n appearance of the
affected plates. Tran s mission I R spectra were obtained using a Cygnus 1 00
FTI R spectrometer fitted with a S pectra Tech I R-Plan'M microscope acces­
sory. It was thus possible to keep the amount of varnish required for analysis
to microgram levels, and vital image content was u n d isturbed.
The FTIR spectra of varn ish extracts from the good quality p lates a ll
displayed a characteristic signature of shellac. Th e Brady studios choice of
a shellac formulation is i n agreement with the apparent popu larity of shel­
lac at the time. D uring the Col lodion E ra of p hotography many natural res-

355
 Part V P ll O T O G H A P ll l C N E G A T I V E S

FTIR Analysis of Collodion Wet Plate

Saponified Varnish

b Fresh Shellac

Figure 4
FTI H spectra of' ( a ) deteriorated
va rn is h c.'\ lTactcd from the plate
N PG )296 : 1 8), (b) a freshly C Fresh Shellac
prepared shel lac sample, and + NaOH

( e ) fresh shel lac sapuniGed by

the addit ion of' o . 1 9g NaOH
p e r g shel lac resin.
2000 1 800 1600 1400 1200 1000 800

WAVENUMBER

i ns, such as shel lac, sandarac, copal, dammar, mastic, benzoin, elemi, etc .,
were recommended i n photograph i c varn ish form u las 4 ·'-6·7·8 but recipes made
largely of shellac d issolved in alcohol were prevalent.9·1 0· 1 1 · 1 2 Spirit varnishes
were fast drying and preferred over oil -based varnishes, because they allowed
the negatives to be contact-pri n ted short ly after varnishing.
FTI R spectra of the degraded varnish samples revealed stro ng peaks
at approximately t 564 cm- 1 and 1 400 cm - 1 which are not associated with
natura l res i n , 1 3 · 1 4 spectra, cellu lose n itrate, or potential collodion era plas­
ticizers, such as camphor, bergamot oil, lavender oi l , etc. These peaks are
characteristic of ca rboxylic acid metal salts. Figure 4(a) shows the I R spec­
trum of varn ish from deteriorated p late # N PG 5296: 1 8 5 and, for comparison,
F igure 4(b) shows a freshly made sample of shellac. The presence of m etal
ions in the extracted varni s h samples was then con fi rmed by scann i ng elec­
tron m icroscopy with si mu l taneous energy d i spersive x-ray analysis ( S E M ­
E DS ) . Analyses were conducted on a J E O L 840A S E M w i t h a Tracor
Northern 5502 energy dispersive spectroscopy system. The degraded varni s h
samples contai ned eas ily detectable sod i u m , whereas sod i u m was n o t foun d
i n the good varn ish samples, F igures 5( a ) a n d 5(b). The presence of sodi u m
i n t h e degraded varn ish samples is cons istent with t h e FTI R i n terpretation
of carboxylic acid metal salts. The varni s h deterioration i nvolved the alkali n e
hydrolysis o f ester groups i n t h e resi n . A carboxylic ester is hydrolysed t o a
carboxylic acid, which u nder alka li n e conditions is obtained as its salt. The
 Reading 40 M C C 0 B J\I J C I{ - c ; 0 0 I J 1 1 A H T

Series I I Smi t.hson i an Ins"t.i t.u t. i on

Cursor: 0 . 000KeV = 0

a ,

Seri es II Smi thsoni a.n Ins ti tuti on

Cursor : 0 . rz00KeV = 0

b
Figure 5
S E M - E DS data l'or (a) varnish
's
sample removed from a
deteriorated plate ( N PG 5296 : 1 8;,
y IG Rev. Farley) and (b) varnish rrom a

rn " �'.
plate in excel l ent condition ( N PC

" · '"�
2999: 1 0 1 , EJJ1111a \Vebb).
'��b "" ��
203

deteriorated plate varn i s hes had thus become saponified over time, causing
their present hygroscopi c n ature. VVit h respect to sodium, alkaline hydrolysis
of the ester groups this may be i l l u strated thus:

RCOOR' + Na+ + 01-1 - H Rcoo- N a+ + R ' O l-l

The in terpretation of the FTIR and S EM - EDS data was verified by mak­
i ng freshly saponified shellac coati ngs to compare with the h istorical plate
samples. Solutions of shellac dissolved in alcohol were prepared and var­
ied amou n ts of sodium hydroxide were then added. The reaction with the
NaOl-I was i mmediate and could be observed by the darkening of the shellac
color. Films were cast o n glass su bstrates and FTI R a nalysis of the dry films
was accomplished as previously described. \Nit h an appropriate amou nt
o f NaOl-I , the spectrum of o n e freshly sapo n i fied shellac sample, Figure
4(c), closely matched the I R spectrum of degraded plate #N PG 5296: 1 85,

3 57
P art V P II 0 T 0 G R f\ P H I C N E G f\ T I V E S

Figure 4(a), providing good experi menta l proof of the postu lated varn ish
degradation mechanism.

An. Allwli Source

Various pathways to an alkaline environment were considered. SEM-EDS

detection of both sodium and sulfu r suggested h igh residual fixer m ight be pres­
ent. However, it was fou nd that the 1-3 µm co11odion layer does not retain the
fixer at the levels encountered here. U nder the poorest conditions, a wet-plate
photographer would h ave at least rinsed the plates, because unri nsed plates
presented i mmediate practical problems. An experiment was undertaken to
verify what sodium and sulfu r levels would be fou nd by the SEM-EDS instru­
mentation u nder these circ umstances. A new wet plate was made and pro­
cessed, adhering to traditional form ulas, 1 5• 1 6•1 7 with sodium thiosulfate as the
fixing agent. At the end of the fixing operation only a brief rinse was performed.
The collodion-silver layer was then sampled and evaluated by SEM-EDS for
the presence of sulfur and sodium, and was found to be below detection l i mits
for both elements. Additionally, a sod i u m thiosu lfate fixer acting alone cou ld
not establish the necessary p H level req uired to saponify the varnish. When
sodium thiosu lfate was u sed to fix wet-plate negatives (potassium cyanide was
also common), photographers prepared a h ighly concentrated and u n buffered
formula. The p H decreased in contact with the wet plate.
No other process components seemed capab le of leadi ng to an alka li n e
regi me, either. Bo t h the silver n itrate sensitizing b a t h and the pyrogallic acid
or ferrous su lfate developers were adj usted to pH val ues typically between
4 . 5 and 5.8 with citric acid, acetic acid, or drops of n i tric acid specified i n
various formu las. \Vet-plate technology did not use any a l kaline develop­
ers. Also, wet-plate p hotography was a solution p hysical development pro­
cess. The si lver ions needed for development were supplied by the excess
s i lver n itrate from the sensitizing bath, rather than through the chemical
development mechanism associated with modern fi lms and developers. The
large, non-filamentary parti cle shape, as shown in F igure 3, can be attrib­
u ted in part to the physical deve lopment activity. The cellu lose n i trate and
the varn is h resi ns were also, by nature, sl ightly acidic. Because no wet-plate
chemistry that m ight lead to an a l kaline environment was identified, and any
external sources of sod i u m woul d be l i kely to come i nto contact with the
plates i n a more non-uniform m a nner, the probable source of the sod i u m
a n d corresponding h igh p H level was reasoned t o b e from i nteractions wi th
the collodion negatives ' own glass s ubstrates.
Simple nondestructive screening methods util izing UV fluorescence
and x-ray fluorescence (XRF ) spectroscopy were then undertaken to look for
a correlation between glass compos ition and coating deterioration. Twelve
 Reading 40 M C C O R M I C K - G O O D HA R T

CAL Sm i thson i an I n s t i tuti on

Cursor: 0. 000keV = 0

Figure 6
X B F "signature" of t h e uncoated
b glass s urface for a negative
(a) wit h saponified varnish
coating (NPG 5356 : 1 87, Alpheus
Hyatt) and (b) with a coating i n
excellent condition ( N PG ;46:20,
David G . Farragut). i\llolybdenum
peaks are a n artifact of the
x-ray emission source.

p lates with saponified varnish were compared wit h 1 5 randomly selected

p lates in good condition. UV fluorescence proved inconclusive, because both
varnish coatings and glass substrates f luoresced simu ltaneously, making it
difficult to sort varying glass compositions i n to any defined categories. XRF
( United Scientific Dubois Object Analyzer with Tracor-Northern 5502 instru­
mentation) was used without vacu u m to examine the u n coated side of the
p lates. The spectra revealed a unique "signature" for the deteriorated plates.
Two aspects of this signatur e can be seen by comparing F igures 6(a) and
6(b); Figure 6(a) shows a strong arsenic peak and an apparently l ower cal­
cium signal than that of Figure 6(b), the nonsaponified p late.
The method is semiquantitative. Relative peak heights of differen t ele­
ments do not indicate elemental quantity ratios. For example, AS 2 03 is not
a larger component than CaO wit h respect to its actual percentage of the
bulk glass composition. The strong signal simply reflects the higher XRF
detector sensi tivity to arsenic than to calci u m . N evertheless, a 1 00% corre­
lation between the XRF pattern and a saponifi ed coati ng on the reverse of

359
Part V P 11 0 T 0 G B A P 1-1 I C N E G A T I V E S

the glass was determ ined. All saponified varnish plates could be sorted from
p lates with good varnish by si mply observ i ng the consistent XRF s ignature. l t
must be noted that sod i u m i s not a detectable element with the nonvacu u m­
mou nted XRF apparatus u sed, but potassium i s . No major potassium peak
was detected by XRF i n any of the test samples which i mpl ied that Brady
studio p lates were predom i nantly soda l i me glasses. One specialty glass was
detected by UV Auorescence among 27 samp les and con firmed by XRF to
h ave a high lead oxide component .

G lass Composition Analysis

Accurate glass composition data were determined by wavelength dispersive

electron microprobe analysis. An ARL S E M Q E lectron M icroprobe was
u sed . Beam size was defocused to 40µ,m to i mprove b u l k composition statis­
tics. Small chips of glass were removed from corners of six saponifiecl varn i s h
p lates and s i x plates w i t h good varn i s h . T h e s i x plates w i t h good varnish were
randomly selected from the popu lation of plates i n good condition, a lthough
m u ltip le-exposure i mage mates were not a l lowed, because they wou ld obvi­
ously have the same glass composition . The sapon ified varni s h p late samples
were also randomly chosen, but with one exception. An encampment scene
was delibera tely included, because it had been processed outside of the stu­
dio emrironment, yet was exh ibiting the same mode of deterioration. The
glass chips were cut using a d iamon d-studded copper wire, embedded i n
epoxy, and pol ished to expose a Fresh su rface indicative o f b u l k composition.
A chip from an N B S #620 soda l i me Aat glass standard was a l so prepared at
the same time and analyzed at the begin n i ng, mi clclle, and encl of mach i ne
t i me t o verify accuracy and repeatabil ity of t h e resu lts. The glass composition
results are l isted in the Appe ndix table [ i n this reading] . The varied composi­
tions were then pl otted on a ternary phase d iagram , as shown i n Figu re 7,
by grouping appropriate species a nd norma l izing the percentages to total
1 00%. Such graphical representat ion c learly reveals how the glass substrates
of "good" images versus those with deteriorated i mages cluster i n d i fferent
composi tional regions. Two good plates rough ly matc hed the modern soda
l i me glass form u lation, and the other good plates had h igher a l kaline earth
oxide (CaO and MgO ) and lower alkali oxide (Na 2 0 and K 2 0) quantities
than did modern plate glass. Wit h i n the l i mits of experimental acc uracy, a l l
sapo n i fied va rnish plates tested h a d t h e same b u l k composition, c haracter­
ized by h igher alkal i oxides and lower a l kaline earth oxides in the glass for­
mu lation. The standard deviation assoc iated with the electron microprobe
analys is is small and accou nts for the minor compositional variances of the
saponifiecl samples reported in the Append ix table [ i n this reading] .
 Reading 40 M C C O B M I C K - G O O D ll A B T

85%

10% 80%
\
Ssponified
"'
<82.
0
Good t/
0
t "
NBS
oO 1620 \Severely Figure 7
cracked B u l k composition data from the
70%
Appendix table plotted on a ternary
phase diagram. \.\'eight percent
values \\·ere normalized to total
100%. FeO was divided equally
between glass formers and
alkaline earth oxides.
15% 20% 25% 30%

Increasing Na2o + K2o --..

The chemical durability of sil icate glasses has been i nvesti­

gated . 1 8· 1 9·2 0·2 1 ·2 2 N u merous factors such as glass homogenei ty, su rface rough­
ness, thermal h istory, etc . , make the issue of durability more comp lex than
can be ex'j)ressed solely in terms of bulk composition. However, i n general,
the addition of alkali oxides red uces the melting temperature and i mproves
manufacturin g economics, but corrosion resistance rapidly decreases as the
alkali oxide concentration is increased . On the other hand, the addit ion of
alkaline earth oxides improves the glass durability. It can be seen that the
condition of the i mage coati ngs correlates with the chemical durability of
the glass substrates as inAuencecl by the bulk glass composition.

Wet-plate Coating Condition Correlated to Glass Co1nposi.ti.on

Corrosion of soda-s ilica glass has been characterized in two bas ic stages by
the following general equations. 23 I n Stage 1 sod i u m leaches from the glass
i n an ion exchange process, resu lting i n a " sil ica-rich " layer with hydrated
m icropores:

SiONa (�I""' + 1-1 2 0 H S i OH (gla><) + NaOI-1

During S tage 2 the breakdown of the s i l ica network occurs, resulting in

dissol u tion:
Part V P H 0 T 0 G H A P II I C N E G t\ T I V E S

-
+ 4 OH (solution)

[
(glass)

J
-
I
- 0 - S l - OH +

� (glass)

Because the O H - ion excess at the glass su rface promotes Stage 2, p H va l­

ues h igher than 9 at the glass su rface have been foun d to be a basic thresh­
old for the onset of Stage 2 . \l\fhen Stage 1 predomi n ates, the th ickness of
the hydrated su rface layer continues to i ncrease, and when the S tage 2 reac­
t ion occ u rs congruently the ratios of the d issolving species approach that of
the bulk composition. The extent of S tage 1 and Stage 2 reactions are also a
function of the enviro nmental conditions to which the glass su rface is sub­
jected. G lass corros ion studies often model one or more of fou r common
environ mental regi mes: static aqueous corrosion, dynamic aqueous corro­
sion, static weathering, or dyna mic weathering. For example, the glass sur­
faces i n a tightly enc losed space, such as foun d on pla tes that were attached
to backing glasses i n the Meserve Collection, u ndergo primari ly static
weathering. Stage 2 of the reaction is accelerated, because high pH corro­
sion products from Stage 1 rema i n trapped at the glass su rface. The packag­
i ng construction of daguerreotypes is another example of this environment,
and the corrosion prod ucts of 1 9th century daguerreotype cover glasses have
been characterizecl . 24 The weathering of the glass is recognized by local ized
pitting, haze, and other dencl ritic deposits on the glass su rface. The saponi­
fiecl varnish plates d id exhibit an overa l l haze on the rear surface, but corro­
sion produ cts on the back of col locl ion negatives i n excel lent condition could
also be identified. Weathering on the u ncoated side of the glass negative was
therefore fou nd to offer only indirect, but not conclusive, evidence of i mage
deterioration clue to the gl ass su pport. The coated side and the uncoa ted
side represent signi ficantly d i fferent potential corrosion environments.
As long as the varn ish and col locl ion layers are adhered ( i .e . , no cracks
or flaking which expose the glass su rface ), the glass corrosion environment is
analogous to a static aqueous environment. Corrosion at the col lod ion-glass
interface was apparently confi ned to the growth of a hydrated glass layer,
and corrosion prod ucts associated with weathered glass were not observed
u nderneath adhered coating areas.
 Reading 40 M C C O H M I C K - G O O D ll A H T

The average th ickness of the hydrated glass layer was not measured i n
this i nvestigation. However, an approximation of the t hickness, wh i c h c a n be
derived from the shellac sapo n i fication experiment, provides some i nsight to
the extent of the glass corrosion . The freshly saponi fied shellac samples were
m ixed with 0.03 to 0. 1 9 g sodi u m hydroxide per g of s hellac. These concentra­
tions are equ ivalent to sod i u m amou nts which could be supplied by the 1 8%
Na20 ( 13.4% Na) component of the bulk glass material from leac h i ng depths
ranging from 0.5µ to 31w1 and taken u p u n i formly by 2-µm collodion and
6-µm varn ish layers. The spectrum shown in F igure 4(c) conta i ned the same
sod i um concentration that would be available from a fully leached 3µm glass
layer, and lower concentrations prod uced smaller, but easi ly detectable, car­
boxyl ic acid metal salt peaks in the shellac I R spectra. Hydrated su rface lay­
ers on the order of a few m icrometers th ick do not represent large amounts
of glass corrosion on soda l i me plate glass. For example, Clark, Pa ntano, and
Hench 2 3 reported the formation of a 1 2.7µm hydrated silica layer i n a ternary
soda-li me-silica glass (20Na2 0-1 0Ca0-70Si0 2 mo!%) from static aqueous
attack at 1 00°C in a 3-hour reaction time. The t hickness i ncreased to 29 µ m
after 1 2 hours at 100°C.

Conc l u sions

The most severely deteriorated wet-plates i n the M eserve Collection were

concluded to have h igh sod i u m glass su bstrates of the same bulk composi­
tion. Over time, enough sod i u m leached from the glass to cause considerable
sapon ification of the varnish. Despite our 20th century views about the hand
crafted variabili ty of the wet-plate process, the most chemica l l y deteriorated
Brady studios negatives had poor i mage stability through no fault of the pho­
tographers nor one that they could have eas i ly foreseen. The glass analyses
ind icate some sign i ficant manufacturing variabili ty i n 19th century soda l i me
glass, but t he lot-to-lot variability from a single manufacturer is not known.
S t i l l , the fact that all sapo n ified plates share identical glass composition sug­
gests that one of the Brady studios purchased this high sod i u m glass as stock
fro m a single lot. NPG 5330: 1 86 is especi a l ly i n teresting because it is one of a
few Civil \!Var encampment scenes in the Meserve Collection. The collod ion
craft was performed at a remote location away from either studio; yet this
p late has s hared the same fate as its studio- made counterparts, because of
its glass su bstrate.
Although the poorest qual ity plates in the M eserve Col lection might
be regarded as an isolated bad batch of glass, one additional sample from
the col lection that was i ncluded in the analyses suggests that glass substrate
compositions may have a larger role in collodion wet-plate i mage stability.
Part V P H O T O G R A P H I C N E G A T I V E S

Thi s sample, N PG 5306: 1 85, differed from the saponi fied varni sh p lates. l t
d i d not show overall d iscoloration o r tac ki ness. I nstead, severe c racking and
Aaking of the coat ing layers had occu rred. A modern prin t from this plate
and one of its m u ltiple-ex'j)osure i mage mates is reproduced in F igure 8 [not
reproduced here ] . Due to the tenuous adhesion of the i m age to the sub­
strate, samp l i ng the varni sh for FTIR analysis was not attempted. The glass
composition of NPG 5306: 1 85 is identified on the ternary p h ase d iagram of
F igure 7 by the notation "Severely cracked . " At 1 6.8 wt% Na 2 0, the sod i u m
content is h igher t h a n fou n d i n a n y o f t h e p lates with coatings i n excel­
lent cond ition. N ineteenth centu ry glass procu red for wet-plate p hotography
may have a range of compositions that d i rectly i n Auences long-term coating
adhesion ch aracteristics through the rate of hydrated glass formation and
correspond i ng al kali leaching at the collod ion-glass i n terface.
More samples in various stages of cracking and adhesion failure defi­
n i tely exist in the Meserve Collection. During a recent p roject to rehouse
the negatives i n acid- an d l i gn in-free qu ality paper envelopes, the curato­
rial staff made a conscientious effort to note the present condition of each
i tem in the collection. Si,xty-eight percent of the negatives were fou n d to
be i n very good condition and demonstrate the i nherent stability of the
wet-plate process. Fifty-two p lates ( 1 %) are broken, an often lamented dis­
advantage of glass su bstrates. Thirteen percent were l isted as "damaged ,"
mean ing mechanically scratched, abraded, e t c . El even percent were ju dged
to be "deteriorated," whereas another 6% were reported as "deteriorated and
flaked" or "deteriorated, flaki ng, a n d might benefit from i m mediate conser­
vation measures." The sur vey therefore indicated that 1 7% of the collection
had some coating problems associated with chemical deterioration, cracking
and adhesion problems. Additional glass analyses from samples in this group
of wet-p late negatives are required i n order t o val idate whether a more subtle
correlation exists between glass composi tion and coatin g adhesion.

Acknowle dgements

The author thanks E ugen e J arosewich and Joseph Nelen ( Department of

M inera l Sci ences at the M useu m of Natural H istory) and Pamela Vandiver
(Conservation Analytical Laboratory) for the i r assistance with the electron
microprobe analyses . \!\falter Hopwood and M elanie Feather (Conservation
Analytical Laboratory) provided invaluable help with the FTI R spectroscopy
and S E M - E D S a nalyses. The author also than ks Will Stapp ( I n ternational
M useum of Photography at the George Eastman H ouse) and Ann Shu mard
( National Portrait Gallery) for their knowledge of and assistance with the
M eserve Collection materials.
 Reading 40 M C C O R M I C K - G O O D H A R T

A P P E N D I X TA B L E

G lass Composition Data (Wt% ) ·'·

SAM P L E ( c o n dition) S i 02 Al,O, FeO MgO Cao K,O Na,O TOTAL

N BS #620 G lass Std. 72 . 1 1.8 .04 Fe,O:i 3·7 7. 1 ·4 1 -J . 4 99· 5.J

Specifications
N B S 11620 G lass Std. 7 1 .o (.59) 1 . 7 ( .09) BDL 3 · 9 (. 10) 7·3 ( . 1 2) ·4 (.02) l.J · 9 ( . 2 1 ) 99·2
Micropmbe data
N PG 9 5 1 :33 (Good) 7 1 .0 ( . 59) ·5 (.04) ·3 ( .02) BDL 1 4 . 1 (. 14) .I (.02) 12.6 ( . 1 6 ) 98.7
Lee, 1-/enry W.
N PG 546:20 (Good) 73·3 ( . 59) ·9 ( .o9) .I (.02) ·3 ( .04) 9.8 ( . 1 0) 1 . 3 (.08) 13.2 ( . 19) 99.0
Farragut., David C.
N PG 1 993:69 (Good) Newell, 7o. 2 ( . 59) . 6 ( .06) . I ( . 02) . 2 ( .02) 15.9 (.18) ·3 (.o3) 1 1 .0 ( . 1 5 ) 98.3
Maj. Edward & another

N PG 3050: 1 02 (Good) 7o.6 ( . 54 ) · 3 ( . 06) .2 ( . 02) BDL 13.8 (. 18) .I (.02) 1 p ( . 1 9) 98.3
Unident ified je ll'lale
N PG 1 240:43 (Good) 7o.8 ( . 53) -4 (. 03) . 2 ( .03) BDL 13.5 (.2) .I (,02) 1 3-4 ( . 20) 98-4
Pat.t.on, ]ohn
N PG 3 1 68 : 1 09 (Good) 72 . 1 ( . 68) . 8 ( .05) . I ( .02) · 3 ( .o5) 9 · 9 ( . i 9) 1 .9 (.o7) 12.8 ( . 1 7 ) 97.8
Joseph, t he French Giant.

N PG 26 1 7 ' 89 ( Sa p . ) 74·5 ( .77) BDL BDL BDL 5 . 6 (. 13) .I ( . 02) 1 8 . 1 ( . 1 8) 98.3

Uniclen.t.ified ·male
N PG 5330: 1 86 (Sap.) 74 -9 ( .72) BDL BDL BDL 5 . 8 ( . 09) ,J ( . 02) 1 8 .3 ( . 16) 99 · 1
Carn.p Scene/N . Y. 7th Reg.

N PG 5359: 187 (Sap. ) 75.6 ( . 6 1 ) BDL BDL BDL 5 - 4 ( .o9) , J (.02) 18.5 (. 18) 99.6
Lennon, Ware/ /-Ii.I./
N PG 536 1 : 1 8 7 ( Sa p . ) 74·9 ( . 63) BDL BDL BDL 5 - 4 ( .o7) .I ( . 02 ) 1 8 . 1 ( . 37) 98.6
Leffe rts, Marshall

N PG 5356: 1 8 7 (Sap.) 7 + 8 ( .73) BDL BDL BDL 5·9 ( . I O ) .I (.02) 1 8.0 ( . 23) 98.9
Hyat. t , Alpheus
N PG 5296: 185 ( S a p . ) 7 + 7 ( . 70) BDL BDL BDL 5-4 ( . 1 1) .I (.02) 18.4 ( . 1 9 ) 98.6
Farlq, Rev.
N PG 5306: 1 8 5 ( S evere 7 1 . 1 ( -48) . 2 ( .05) . I ( .02) . 2 ( .03) 9.0 ( . 1 1 ) -4 (.04) 1 6 . 8 ( . 26) 97·7
cracking) lngralia 11i, D . P . , Jr.

"" Data i n Parentheses = standard deviation

B D L, below detection limit

A P P E N D I X

The M eserve Collection

A B ri.ef History
Frederick H ill Meserve ( 1 866-1 962) fi rst became i n terested in h istorical pho­
tographs while searc h i ng for images with which to i l l ustrate the Civil \!\far
memoirs of h i s father, a U n ion army vetera n . I n 1 897 Meserve purchased a
small packet of salt print p hotographs for $ 1 . 1 0 at a New York auction house
Part V P H O T O G R A P H I C N E G A T I V E S

and thereby embarked on a course that u l timately led hi m to amass one of

the largest and most i mportant private collections of 19th century Ameri­
can p hotograph s. The core of this collection was a large group of Mathew
B rady carte-de-visite negatives, which Meserve purchased i n 1902, sti l l i n
their origi nal wooden storage boxes, from Anthony, Scov i ll and Company,
the successor firm to E. & H . T. Anthony, which had acqui red the negatives
from M athew B rady h imself. Meserve, a dedicated amateur h i storian, spent
the remainder of his l i fe worki ng with these n egatives, organizing and study­
i ng them, as wel l as pri n t i ng them, to produce the i l l u strations for Histori­
cal Portraits-his privately published 28 volume iconography of notable 1 9th
century American subjects. \,Yhen Frederick H i l l M eserve died at the age of
96, his extensive collection was i n herited by his daughter, Dorothy Meserve
Kunhardt, who shared her father's passion for the material and continued
his work.
I n 1 98 1 , with the assi stance of the U n i ted States Congress, the National
Portrai t Gallery p urchased a group of more than 5400 Meserve Collection
negatives from the Dorothy Meserve Kun hardt Trust. These original collo­
dion glass-plate negatives, nearly all of which were made i n either Mathew
Brady's New York or Washi ngton galleries, comprise a remarkably com­
prehensive p ictorial i ndex of the prominent personalities of the C ivil \Var
era, i n cl u d i ng Abraham Li ncoln and many of his contemporaries. With the
acqu isition of this portion of the original Meserve Collection, the National
Portrait Gallery joined the Library of Congress and the National Archives as
a major repository for original Brady negatives.

References

1 A . S h u mard, reprinted by perm ission from exh i b i t broc hure, "Lincoln and /-/is
Conte mporaries," National Portrait Gal lery, Washington, DC, 1 990.
2 M . M cCormick-Goodhart, 91.h Trien nial Meeting, Dresden , Germany, August
26-3 1 , 1 990, Prepri nts vol . 1, I C O M Committee for Conservation, 262 ( 1 990).
3 M. McCormick-Goodhart, Topics i n Photographic Conservation , ATC
Photographic Materials Group, 3: 1 35 ( 1 989).
4 iVl . S . Barger, Bibliography of Photographic Processes in Use before 1880,
G raphic Arts Hesearch Center, Hochester, New York, 1 980.
]. Mart i n , Brit:. ]. Photogr. 8 : 304 ( 1 86 1 ) .
6 ] . G . Vail , Phot.ographic Mosaics 3 2 ( 1 878).
7 ] . Sang, Photograph . ] . ; : 226 ( 1 8 59 ) .
8 H . H . N i cols, Photogr. News 6: 1 7 ( 1 862).
9 M. Carey Lea, Philadelphia Photogr. 4 : 1 6 7 ( 1 867).
1 0 Anonymous, Photogr. News 1 4 : 522 ( 1 870).
11 Anonymous, Brit. ] . Photogr. 2 4 : 279 ( 1 877) .
1 2 Anonymous, B rit . ] . Photogr. 2 5 : 575 ( 1 878).
13 M. Derrick, ]. A I C 28: -13 ( 1 989).
 Reading 40 M C C 0 R M I C K - G 0 0 D I I A 11 T

14 The Sadtler Standard Spectra, Sadlier Hesearch Laboratories, P h i ladelphia,

PA, 1 965.
15 J. Towler, The Silver Sunbea'l'l't, Facsilllile 1 864 Edition , M organ & Morga n ,
New York, 1 969.
16 F . S . Archer, T71.e Collodion P rocess on Glass, 2nd ed. (printed for the a u t hor),
London, England, 1 854.
17 T. F. H ardwich, A Manual of Photographic Chem istry, Including t: he Pmclice of
the Collodion Process, 6th e d . , J . C h urch i l l , London, England, 1 8 6 1 .
18 F . H . Bacon, G lass Ind. 49:438 ( 1 968).
19 A . K. Lyle , ]. Amer. Ceram. Soc. 26: 2 0 1 ( 1 943).
20 H . W. Douglas a n d T. M . E l -S h a llly , J . Arner. Cerani. Soc. 50: 1 ( 1 967).
21 T. i\11 . E l- S h amy and R. W. Douglas, Glass Teclinol. 13: 77 ( 1 972).
22 S . Tsu c h i hashi and E . Sekido, Bull. Chem. Soc. Jpn . 32: 868 ( 1 959).
23 D . E . C lark, C. G . Pantano, J r. , a n d L. L. Hench, Corrosion of Glass,
Magazines for I n dustry, I nc . , New York, 1 979.
24 iVI . S . Barger, D . K. S m i th , and W. 13. Whi te, ]. Mater. Sci. 24: 1 343 ( 1 989).
 R e a d n g 41

JOHN M. CALHOUN

Storage of Nitrate Amateur

S till-C amera Film N egatives ( 1 953)

John Calhoun ( 1 9 1 2-1999) has been described as an early pioneer of photo­

graph preservation. Most of his research at Kodahfocused on the physical prop­
erties and dhnensional stability of fiJm and greatly influenced future research
and practice in the preservation offilm-based photographic 1naterials, includ­
ing the use of cold storage. Beginning with cellulose nitrate in the late 1880s,
flexible film supports rapidly superseded glass as the principal support for
photographic negatives. Despite its exceptional physical properties, including
superior diniensional stability, cellulose nitrate is highly flammable and can
be chemically unstable-becoming brittle, discolored, eventually stichy, and
finally deteriorating into a brown powder. The degradation of amateur and
professional cellulose nitrate film has been studied extensively. TI1e devastating
effects of degradation by-products and the tendency of motion-picture films to
ignite spontaneously at high temperatures have given nitrate films a longstand­
ing reputation as a dangerous material. Calhoun's 1953 comprehensive review
of the hazards and preservation of cellulose nitrate film documents its history,
decomposition, and methods of ident;ificat:ion. Jn this article, Calhoun pre­
scribes proper storage conditions (including refrigeration with activated silica
gel J;o control moisture content), regular inspection, and duplication. Impor­
tant distinctions between preservation rishs associated with amateur nitrate
and professional film collections are identified. Calhoun 's paper represents
the state of hnowledge in the 1 950s. Subsequent research on cellulose nitrate,

From J o1-1N i\1 1 . CALHOUN , "Storage of N i t rate Amateu r Sti l l -Camera F i l m Negatives,''
Journal of the Biological Photographic Assoc iation 2 1 , no. 3 (Augus t 1 9 53 ) : 1 - 1 1 ( 1-6
excerpted here). Heprin ted by permission .

3 68
 Reading 41 C A L H O U N

particularly at the Image Permanence Institute in the i 9 9 os, highlighted the

extreme variability in nitrate filni stability and demonstrated the effectiveness
of cold storage in the long-term preservation of nitrate negatives.

The hazard i nvolved in handl i ng or stori ng any appreciable q uantity of n itrate

base p hotograph ic fi l m has been recognized for a great many years. As a result,
q uestions are frequently asked abou t the possible hazard in storing small
q uantities of the so-called "amateur" still-camera negatives o n n itrate base.
These were u sed in past years i n a variety of roll film sizes such as 1 35, 616, foo,
828, etc. as wel l as in the form of fi l m pack and sheet film. As far as the author
knows, these types of film are no longer produced o n nitrate support i n the
U n i ted States. H owever, many people h ave small collections of n i trate nega­
tives of various ages up to 20 or 30 years, and a few even 40 or 50 years old. They
are usually stored in desks or cupboards without any special precautions.
Small quantities of amateur n itrate negatives have never been con ­
sidered h azardous but the chemical stability of cellulose n i trate is low. The
degree of stabil ity depends on the particular fi l m, i ts h istory, and i ts storage
conditio n . For these reasons it is not possible to assure the p hotographer,
either that decomposition or spontaneous combustion will never occu r or, on
the other hand, that all n itrate negatives are dangerous and should be copied
and then destroyed. The truth l ies somewhere between these two extremes.
It is the purpose of this article to attempt to answer some of the q ues­
tions that arise concerning the storage of small q uantities of n itrate fi l m
negati ves from both the hazard a n d preservation standpoin t . Are these
n itrate negatives l i kely to cause a fi re? What quantity does constitute a haz­
ard? \Nhere and how should they be stored? What are the signs of incipient
decompos ition? What special precautions are necessary to preserve val u able
n i trate negatives? Should they be copied on safety film? These q uestions are
of i nterest, not only to amateur photograp hers, b u t also to those in science
and i n d ustry who have small collections of n itrate stil l -camera negatives con­
tain i ng valuable records.
The storage of large quantities of n itrate films such as aerial fi l m,
motion picture film, or professional s heet fil m will not be considered here.

H istory of N i trate F i l m

Cellulose n i trate contain i n g over 1 3% n itrogen is known a s guncotton and

was first u sed i n explosives about 1 845. 1 Cellulose n i trate containing 1 0 . 5 to
1 2% n itrogen is called pyro:-')'li n and has been used in p lastics since about
1 870. Pyro:-')'li n is very flammable but i s not explosive. Nitrate p lastics, com­
monly known as "ce l l u loid," are sti l l used for many household articles such
Part V P l- I O T O G B A P l l l C N E G A T I V E S

as fou nta i n pens, spectacle frames, drawing i nstruments, p i n g pong balls,

brush h and les, cases, buttons, and many others. These articles are Aamma­
ble but are not considered hazardous in ord i nary household quantities.
Cellu lose n itrate made for film base contains abou t 1 2% n itrogen and,
l i ke cel l u loid, is very Aammable but not explosive. It was fi rst used for roll
film i n 1 889 and for the first commercial motion p icture fi l m i n 1 895. 2 As the
motion picture in d ustry grew and quantities of n i trate fil m accumulated in
fi l m exchanges a number of serious film fires occurred. Following the Fergu­
son b u il d i n g fi l m exchange fire i n P ittsburgh i n September 1 909 the National
Board of Fire U nderwriters establ ished rigid regu lations governi ng the han­
dling and storage of n itrate motion picture fi l m . S imilar regulations were
establi shed for the storage of n itrate X-ray a n d other n i trate photograph i c
fi l m s about 1 925. These regu lations with some revisions are still i n force
today, implemented i n many cases by state laws and local ordinances.
Another mi lestone in the h i story of n itrate film from the hazard stand­
poi nt was the Cleveland C l i n ic d isaster which occurred in May 1 929 as the
result of the storage of large qua ntit ies of n i trate base X-ray film u n der
unsafe con di tions. The standards of the National Board of Fire U nderwriters
for the storage of n itra te X-ray fi l m and nitrate sheet and rol l fi l m were then
strengthened.'
About this same time research work o n cellulose acetate or "safety"
fil m base which the fil m manufacturers had been conducting for many years
made it possi ble to supply safety X-ray fi l m . The period 1 930 to 1 940 saw the
gradual replacement of n itrate by safety base for most photograph ic films
except motion picture film, amateur rol l film, and film pack. Following World
War l l add i t ional improvements were made i n safety film base which permit­
ted most manufacturers to replace n i trate base for these p roducts.
Although the fol lowi n g tabl e applies only to film manufactured by the
Eastman Kodak Company, i t may be useful as a n i ndication of the approxi­
mate time when the use of n itrate film base was discontinued.

Date of Last N i trate F i l m M a nufactured by the

Eastman Kodak Company in the U n ited States Type of F i l m
1933 X-ray fil m
1938 R o l l f i l m in size 1 3 5
1 939 Portrai t a n d commercial sheet f i l m
1942 Aeria l fil m
1 949 F i l m pack
1 950 Roll fil m in sizes 6 1 6, 620, 828, etc.
1951 M otion picture f i l m (35mm)¥·

>t- 1 6m m motion picture film was never made on n i t rate base.

 Reading 41 C A L ll O U N

Safety fil m was i n ge neral u se several years earl ier than these dates
in d icate beca use the transit ion from nitrate fil m was made gradual ly. At the
present time n itrate film base has almost ceased to be used i n the U n i ted
S ta tes although a few n itrate films may still be supplied by some manufac­
turers. The s i tuation is q u ite d i fferen t i n most of E u rope and Asia where
n i trate is sti l l the predominant base for photographic fi l m . Of course, the
s u bstitution of safety for n itrate fi l m base in manufacturing does not solve
the problem of storing existing n itrate negatives.

F i lm U se d in Amateur S ti l l Cameras

Roll fi lm, with the exception of the 135 size, has approximately 0.0035- inch
thick support coated o n the back with a gelat i n non-curl i ng layer. Film packs
are generally made with the same type of fil m as this rol l fi l m . The gelatin
backi ng on the fi l m tends to reduce Flammability a n d improve stabil ity.
Film in the r 3 5 size for 35mm m i n iature camera use is physical ly the
same as motion picture fil m . Tt has a base approximately 0.0055-i nch thick
without a gela t i n backing and is cut and perforated similarly to 35mm motion
picture fi lm . As a result it was possible for dealers or photographers to buy
and respool i t in 135 magazi nes. For this reason there are probably more
nitra te 1 35 negatives i n existence than would otherwise be the case.
N itrate commercial and portra i t sheet fil m was made on base approxi­
mately 0.008-inch thick with a gelatin an ti-curl layer on the back.
The d i fference i n base th ickness between t hese several types of film is
of practical i mportance in n itrate fi l m storage because the t h icker the base,
the greater the amou nt of cellu lose n itrate in the film. The th icker films are
more hazardous and more l ikely to decompose with age.

Hazardous Properties of N i t rate F i l m

The hazardous properties of n itrate fi l m are described i n detail i n the

l iterature45·6 and are o n ly brieAy reviewed here. The most dangerous aspects
of n itrate fil m are:

1 ) Ease of ignition ( i ncluding spontaneous igni t ion) .

2 ) H igh rate o f com bustion.
3) Toxicity of combustion products.

The ignition temperature of stable n i trate film is only abou t 300°F

compared with 6oo°F to 700° F for paper, and 8oo°F to 1 0oo° F for safety fi l m .
Contact w i t h a heated electric l ight b u l b or a l ighted cigarette c a n cause the
ign ition of n itrate fi l m . N i trate films which are u nstable as a resu l t of partial
deco mposition with age or i mproper storage conditions may ign ite spontane-

371
Part V P l l O T O G B 1\ P H I C N E G ,\ T I V E S

ously at temperatures as low as 1 20° F. Spontaneous ignition is bel ieved to be

responsible for a nu mber of fires in n itrate motion picture fi l m storage vau lts
fol lowing periods of hot s u m mer weather. 5
Once ign ition occ urs, n i trate film burns so rapidly that i t i s difficult to
exti ngu ish except by concen trated jets of water. Cell ulose n itrate contains
enough oxygen i n the molecule that a fire cannot be stopped by the exclu­
sion of ai r. The nitrogen oxides and ca rbon monoxide given off by burning
n i trate film are very dangerous if the quantity of fi l m is sufficient to produce
toxic or explos ive concentrations of gas. Collections of amateur fi lm nega­
tives are ord i narily not large enough to fa l l in this category.
Still-camera n itrate negatives are much less hazardous than motion
picture films, for exa mple, because the former are usually stored i n enve­
lopes, which reduces the mass of fi l m in i nti mate contact a n d decreases the
l i kel i hood of decomposition or igni t i on. Mention has a lso been made of the
advantage of the gelatin backing on some types of rnl l film and on sheet
fi l m . However, the most i mportant d i fference in hazard between amateur
and commercial nitrate film storage is the very much smaller quantity usu­
al ly involved.

Decomposition of N itrate F i l m

I t is necessary to review some of the fac tors involved i n the decompos ition
of n i trate film before discuss i ng the storage problem in order that the pri n­
ciples i nvolved will be u nderstood. The chemical sta b i l i ty of cellulose n itrate
depends a great deal on how it is made a nd on its purity. H owever, the most
stable cel l u l ose n itrate decomposes slowly even at room temperature with
the evolut ion of n itric oxide, nitrogen d i oxide, and other gases . 1
The decomposition o f cel lu lose n itrate i s a utocatalytic, the evolved
gases acting as catalysts to accelerate further decomposition . This means
that as decomposition proceeds the reaction goes faster and faster u n l ess
these gases are al lowed to escape. Th is is a very i mportant factor in film
storage beca use it means that the life of n itrate fi l m depends on the ready
escape of these fu mes. This is one of the reasons why the thicker sheet fi l m
negatives are more l i kely to decompose t h a n rol l fi l m or fil m pack negatives.
L t also exp lains why a quant ity of fi l m i n close contact with itself, as i n a
rol l of motion picture fi l m or a stack of u n i nterleaved negatives, is more apt
to decompose than i n d ividual fi lms stored in envelopes where the n itrogen
oxides have a better chance to escape to t he air.
The rate of deco mpos ition of cellu lose nitrate is also very dependent on
tem perature and moisture content. Th e temperature coeffici e nt of the reac­
tion is about 4 per J0°C or 2 per J0°F which means that the rate of decompo-

37 2
 Reading 41 C A L H O U N

sition approxi mately doubles for every 1 0°f increase i n storage temperature.
M o isture absorbed from the air, the amount of whi c h i s deter m ined by the
relative h u m idi ty, also accelerates the decomposition reaction. The n itro­
gen dioxide given off by the slow decomposition of n itrate film is a power­
fu l oxidizin g agen t a n d also forms n i tric acid in the presence of moisture .
I t attacks the fi l m base, the gelatin of t h e e m u lsion, and the s ilver i n t he
i mage. T he f i lm base gradually becomes yel low, then brown i n color, brittle
and fi nally turns to powder. The gelatin is gradually hydrolyzed and degraded
u ntil it becomes sticky an d is rendered water soluble. The silver i mage also
becomes d iscolored and faded and finally di sappears because of various com­
plex chemical reactions with the cellu lose n itrate and gelatin decomposition
products. N itra te film decomposition products will also attack and damage
safety films stored n earby.
Cu mm i n gs et al. 5 describe the fol l owing five stages of n itrate motion pic­
ture fi lm decompos i ti o n which are useful for comparison, although the appear­
ance of stil I-camera negatives may differ from that of film i n 3 5 m m rolls.

First Stage-Amber discoloration with fading of the p icture i mage .

Second Stage-The emulsion becomes adhesive and the films tend to
stick together.
Third Stage-The film con tains gas bub bles and emi ts a noxious odor.
Fou rth Stage-The fi l m is soft, welded to adjacent fi l m and frequently
covered with a viscous froth.
Fifth Stage-The fi l m m ass degenerates partially or entirely i nto a
brownish acrid powder.

Film in the second and third stages of decomposition is often brit­

tle. Th is type of film brittleness i s permanent and severe in contrast to the
temporary decrease in flexibility which occurs when film is kept at very low
relat ive h u midities. The odor m e ntioned u nder the t hird stage is very char­
acteristic of decomposing cellulose n itrate or n itric acid and once known
is eas i ly recognized . It is l ess pronou n ced but still n oticeable i n the second
s�ge of decompo� tion.
Film in the first and secon d stages of decomposition can be copied
photographically but o n ly portions of film in the third stage may be reprod uc­
i ble. Film i n the fourth or fifth stages is useless and should be immediately
destroyed because of the danger of spontaneous combustion and chemical
attack on other negatives.
One other factor concerni n g the decomposition of n itrate film dese rves
mention. l t is gen erally believed that faulty processing- inadequate Fixi ng
a nd/or wash i ng-hastens the decompos ition of n itrate fi l m . Fixing sol utions
are generally acidic i n n ature and it seems reasonable that any acid re main-

37 3
Part V P H O T O G R A P H I C N E G AT I V E S

i ng i n the fi l m after processi ng wou l d certain ly tend to speed u p decompo­

sition. At the same time there is little direct experimental evidence of the
effect of p hotographic processing on the stability of n i trate fil m .
T h e poss ible effect o f processing on the decomposition o f n i trate fi l m
base should not be confu sed wit h the very real effect o f processin g o n the
permanence of the photograph ic i mage, regardless of whether the support is
n itrate base, safety base, or paper. I nsufficient fixing or washing causes dis­
coloration and fading of the photographic i mage with age, particu l arly u n der
warm h u m i d conditions. 7 ·8 This and other types of chemical stain which
occur o n negatives may be confused with the early stages of deterioration
cau sed by decomposition of n i trate base.
There are a n u m ber of facts about n itrate fi l m decomposition which
cannot be satisfactorily explained. For example, why are some n itrate fil m s
4 0 or 5 0 years o l d st il l i n good condition whi le other have decomposed t o
the fifth stage i n less than five years u n der simi l a r storage conditions? \Vhy
do n itrate fi l ms of the same source and age i n the same storage area differ
widely in degree of decomposition ? The only safe lesson to be drawn is that
one can n ever be entirely sure how long nitrate fil m wi l l last. Decomposition
is not always gradual, since film which has rem a i ned in apparently good con­
dition for many years may badly decompose in the course of another year.

References

1 "
Worden, Te c h no l ogy of C e l l ulose Es t ers . Vol . I, Part 3, N i t roc e l l u los e The o ry
a n d Pra c t ic e , " D. VanNostra n d Company, I nc . , 1 92 1 .
2 S u lze r , Albert F., "The Epoch of P rog res s i n F i l m F i re Pre ve n t i o n , " ] . Soc.
Mot . Pic t. . Eng., 34, 398-408, April 1 940.
3 "Standards of the N a t i o na l Board of F i re U nderwriters for the S torage and
H a nd l i ng ol' Pho t og rap h ic a n d X- Ray N i trocel l u lose F i l ms as Recommended
by t he National F i re Protection Association," N . 13 . F . U . Pamphl et No. 4 1 ,
J u ly 1 5, 1 930.
4 N uckol l s , A . H . , a n d Matso n , A . F . , "Some H a za rdo us Properties of Motion
Picture F i l m , " ] . Soc. Mot. . Pic t . Eng., 27, 657-66 1 , December 1 936.
C u m m i ngs , J .W., H u tton, A.C., and S i l fi n , H., "S pontaneous l g n i ti o n of
..
De co m po s ing Cellulose N itrate F i l m , " ] . Soc. Mot Pict. and Tel.. Eng . , 54,
268-274, M a rch 1 950.
6 " H azard i n the H a nd l i n g and Storage of N i trate and Safety Motion Picture
F i l m , " Eastman Kodak Company, Rochester, New York, 1 95 1 .
7 Crabtree, J . 1 . , Eato n , G.T., a n d M e u h ler, L . E . , 'The E l i m ination of Hypo from
Ph o t ogra p hi c I m ages," }. Phot. Soc. A m . 6, 6- 1 3, October 1 940.
8 '' S t a i n s on Negatives and Prints, " East man Kodak Company, Rochester, N e w
York, 1 945.

3 74
 R e a d i n g 42

VILIA L . R E E D

H ow to Work Restoration M agic

on Wrinkled N egatives ( 1 980)

The restoration treatment of channeled cellulose acetate fil m base by image

pellicle transfer described in this reading-the fi rst of two reproduced here (see
also Reading 43 ) on the same topic-was popularized in the early 1 980s and is
used on a very liniitecl basis today clue to the hazardous nature of the technique.
Originated by Vilia Reed of Eastman Koda/< Co. in the 1970s and refined by
others-including Douglas Munson (see Reading 43 )-this technique allowed
for the rescue and preservation of severely degraded acetate negative materials
of great historical and artifactual value. Although Reed describes her initial
process with confidence and ease, it is far from sim1Jle and requires consider­
able sh-ill. Frequent health and safety warnings stimulated the development of
modifi ed treatment methods.

Separate E m u l sion from D i acetate B ase

It may seem s u rprising, but i t's possible to take off the t h i n emulsion
layer from a negative and tran sfer i t to another film base. Naturally, you
h ave to handle the delicate emulsion careful ly, b u t rea l ly there's no magic
involved. You simply dissolve the l ayer that holds the e mulsion onto
the original base.

V 1 uA L. REED, " How to work restoration magic on wrinkled negatives," The Professional.
Pliol;ograplier 1 07, no. 201 8 Q u l y 1 980) : 87-89; rep ri n ted in Pliotographiconservation 3,
no. 4 ( 198 1 ) : 4-6. Reprinted by permission of the publisher and the Rochester I nstitute
of Technology.

375
Part V P 11 0 T 0 G B r\ P 11 I C 8 E G A T I \' E S

First, make a prin t or a cl uplicale negative of the old negative as it

exists, wrinkles and a l l . This wi l l be your " i nsura nce" copy i f th ere are prob­
lems d u ring the restoration process. And. of course, practice restoration
with u n i m portant n egatives of the same type, before you try transferri ng a
va l uable antique i mage.
I F yo u 're dealing with negatives on cliacetate safety base-let's just call
it ''acetate" base-the solvent needed is cal led 2-butanone. Like trichloroeth­
yle ne, 2-butanone, Eastman's organic chemical 383, is ava i lable from chemi­
cal suppl iers. (Check for them u nder "Chemicals" i n the Yellow Pages. )
1- lancl le 2-butanone with respect. l t i s Aa mmable, s o do n o t smoke near
it, and keep it away from heat, spa rks, and open Aames. I t also causes irrita­
tion, so wear ru bber gloves (not plast ic, they will d issolve), safety glasses,
and a ru bber lab apro n . The besl work arrangement is a fu me hood equ ipped
with an exp losion-proof exhaust fa n ; u n l i ke a spray booth, this is designed to
pick up heavy fu mes near the work su rface. Check local fire codes for safe­
hanclling and d isposal proced ures for Aammable materials.
Don't let these precau tions scare yo u . I 've been using 2-butanone in
t h i s process for several years, and I haven't had any problems.
To separate the e m ulsion layer from its base, tri m a small strip-one­
th i rty-seconcl-i nch wide-from a 11 fou r edges of the negative. Th is lets solve n t
penetrate and d issolve the adhesive sub layer between emu lsion a nd base.
Next, place the tri m med negative in a sta i n l ess steel, enameled, or glass
tray. Do not use a plastic t ray-the solvent will dissolve i t . Pou r in just e nough
2-butanone to cover the fi l m . The emu lsion should be loosened in three to
four mi nutes. You may ge ntly separate it from the base at the corners to help
t h i ngs along. If the solven t alone does not loosen the emu lsion, transfer the
negative to a tray of extra-strong Kodak Photo-Flo 2 0 0 sol ution, d i l uted 1 : 1 0
with water i nstead o f the n ormal d i l u t ion, and let i t soak. Use the Photo- Flo
solution at about 75°F. If the emulsion still does not come loose i n about five
m i n u tes, acid more P hoto- Flo to the tray.
Someti mes the acetate base is so d ried-out that it will fal l apart when
the emulsion layer comes off. Don't panic! The e m u lsion is the important
thi ng, and it should be i n tact even i f the base isn't.
The next step i s Aattening out the emu lsion . But first, let's see what to
do i f you r problem negative is on n i trate base.

Separate E m u l s ion from N i trate Base

\Vith n it rate-base negatives the procedure is a little different. 2-butanone

dissolves the base as wel l as the sub layer. In addition, we have to remove
the gelatin backing with a c h lori ne bleach; this calls for protect i ng the e mu!-
 Reading 42 11 E E D

sion. B u t that isn't complicated ; just place the n egative on a clean piece
of plate glass, emulsion side aga i nst the glass, and tape all fou r sides. U se
solvent-resistant tape l i ke Scotch brand polyester fi l m tape No. 850 or 853,
three-fou rth- i nch wide. B u rn i s h the tape carefu l l y so that no solution can
penetrate to the emulsion.
Aga i n , use a sta i n less stee l , enameled, or glass tray. Place the glass­
protectecl negative into the tray. Pou r i n the bleach to dissolve the gelatin
backi ng-this can be household l iquid chlori n e b leach such as Clorox,
Sunny Sol, or r o 1 b leach , or a five percent solution of sod i u m hypochlorite.
Wear rubber gloves.
Spread the bleach over the entire p iece of fi l m . As the backing dissolves,
a white foam w i l l appear. Remove the bleach and di sso lved gelatin backin g
with facial tissues or wipe material such as Webril \!\fipes or Kim \!\fipes.
Next, dissolve the n itrate film base. Do this in a wel l -ven tilated,
explosion-proof fu me hood. Wear rubber gloves, safety glasses or goggles,
and a rubber lab apron. The solvent-laden n itrate waste material is extremely
flammable ; be sure to d iscard it i n a fireproof con tainer in accordance with
local fire codes. In addition, i f it is legal in yo ur commun ity to d iscard 2-bu­
tanone clown t he sewer, be sure you r studio does not have any p lastic drain
pipes that wou l d be d issolved by this solvent!
After wiping off the b leach a n d disso lved gelatin from the negative and
d i scarding the bleach bath, put the glass p late back i n the tray and pour
2-butanone solvent over the film. You o nly n eed enough to cover the s urface.
I n a few momen ts, the n itrate base wil l begin to d issolve . Its consis­
tency will be very thick, l i ke gelatin dessert that has al most set . Gently scrape
off this base with a stiff cardboard sq ueegee u n ti l it has been completely
removed from the emulsion. Then l i ft the glass out of the tray and careful ly
wipe clown the emulsion with 2-butanone to remove any res idual smudges of
d issolved n itrate base.
Final ly, after wiping off any rema i n i ng solvent, gently peel away the
tape from the glass and the emulsion layer. The emu lsion wi l l b e u nder ten­
sion, so work careful ly. \!\!hen the emulsion l ayer i s free, tri m off the thick
edge of nitrate base that was protected by the tape. The em ulsion is now
ready for i ts new base.
During this process the emu lsion may stretc h . B u t this isn't norm a l ly
a prob lem because i t stretches equally i n all directions. If you wan t to avoid
stretc h i ng the emulsion from n itrate-base n egatives, lacq uer the fron t of the
e m u lsion before begi nning. Then, after the n itrate base has been removed,
lacquer the back of the emulsion, to equalize stresses. One su itable lacquer
i s S igma Protect-0-Cote. Some standard pri n t lacquers do not work for this
use. If you lacquer the emu lsion, you w i l l need to add a solution of Knox

377
P art V P H O T O G R A P H I C N E G A T I V E S

gelatin to cement the e m u lsion to the new fil m base. I f you do not lacquer,
residual ge latin i n the e m ulsion wil l adhere i t to its new base.

F latten E m u lsion onto New Base

Prepare a s mooth, c lean surface for the e m u lsion by taping a p iece of Kodak
rol ler transport cleanup fi l m 4955 to the plate glass. The cleanup sheet is
Estar base coated with gelatin. P lace the e m ulsion mem brane that you
l i fted from old base i n the center of clean-up material and s lowly apply
concentrated 1: 10 Kodak Photo- Flo solution with a n eye-dropper. The
emu lsion will crinl<le u p at first, then "relax" and flatten as the Photo-Flo
solution penetrates.
l f the emu lsion has been lacquered, use gelatin sol ution in stead of
Photo- Flo and water. D i ssolve a seven-gram packet of Knox gelatin i n sixteen
ou nces of hot water. Wait for it to cool before u sing.
Jf wri nlJes are severe and the e m ulsion is stuck together, treat it with
steam from a n ord i nary room vaporizer. Hold the emu lsion about fo urteen
inches away. Very careful ly, p u l l apart the wrin lJes wh ile the emu lsion i s in
the steam.

M a ke a Sandwich

Once the e m u lsion membrane i s flat o n the Estar base, protect it by covering
i t with a nother p iece of fi l m-to make a n emulsion sandwich. For this, use
a special graphic arts fi l m , 3 M t ranslucent stripping film. Prepare the strip­
p i ng fi l m in advance by fixing to clear it, wash a n d dry it. \11/e simply wan t
t o use the stripping fi l m e m ulsion a s a physical protection for the antique
negative emulsion.
Peel off the dry emul sion layer of the strippi n g film; start with a piece of
adhesive tape in one corner. Then place the stripping film emu lsion against
the flattened-out emu lsion membrane. S mooth it gently with a ru b ber squee­
gee, working from the center to the o u tside. If there are rips i n the old e m u l ­
s i o n mem brane bei n g restored, carefu l l y l ift a corner o f t h e stripping fi l m
emu lsion and move t h e ripped edges together with the t i p of a stylus o r the
encl of a retouching brush. Replace the stripping film and gen tly squeegee.
At the e n d of this step, you have a restored, flattened emu lsion layer
protectively sandwic hed between the two fi l m bases: the cleanup film base
on one side, the strippin g fi l m e m ulsion on the other. Now n otch the usual
corner of the fi l m sandwich so people will lrnow which side should be up
when i t's pri n ted.
 Reading 42 B E E D

Print I t

Originally t h i s process was i ntended o n ly to temporarily rescue crinkled

n egatives. After the emu lsion had been transferred to its new base, d u p l i ­
cate negatives were m a d e . B u t t h e restored sandwich negatives have been
s u rprisi ngly permanent. Those we restored this way three years ago are sti l l
i n excellent s hape, making poss i ble prints from the origi nal negative. Sti l l ,
there's n o guarantee how long these restored negatives w i l l last. To b e safe,
p romptly make duplicate negatives from restored ones on a fi l m l i ke Kodak
professional direct duplicating film ( Estar thick base) S0-0 1 5. I t comes in
standard s heet fi l m sizes and makes a duplicate negative directly from a neg­
ative (or a posi tive from a posi tive) when developed i n Kodak Dektol deve l­
oper or Kodak developer D K-50. It may be exposed by contact or with an
enlarger. I f small duplicate negatives are adequate , a somewhat similar fi l m
is Kodak rapi d process 3 5 m m copy fi lm. This can b e exposed b y placing t h e
restored negative on a l i g h t box or i l l u m inator, on a copy stand, b u t i t s s low
speed will call for long ex'Posures.

Retouch, or Not?

For family photographs, c ustomers very often wil l want the usual kinds of
retouching to enhance prints from the salvaged negative. However, if the
negatives belong to a m u seu m , h istorical society, or u niversity collection , be
sure to get specific written permission before you do any hand retouching on
the negative. To the h is tori a n , any kind of later h a nd-correction on a photo­
graph may compromise i ts value as a record . If prints are wan ted for p u blic
d isplay and the negatives h ave Aaws, it may be safer to retouch the pri nts.
Whether you offer this service for fam i ly h eirlooms or museum pieces,
or both, you'll find that restoring antique negatives on deteriorating bases
by transferring the e m ulsion layer, is an exciting way to b u i l d you r copy and
restoration business.

379
 R e a d n g 43

D O U G LAS M U N S O N

The Pellicular B urles q ue ( 1 997)

Douglas M u nson is the fou nder and director of C hicago Alb u men Works. The
procedures used by M u nson to t reat c hanneled cellulose acetate film deviate
signifi cantly frnm Reed 's (see Reading 42) and are disc ussed in detail in the full
c i ta tion. /- lowever, the excerpt reproduced here focuses on M u nson 's methodol­
ogy for mod�fying t h.e previously reconimended tech nique. Pairing Reed's and
Niu nson 's worlzs toget her illustrates a progression in t reatnie n t meth.odology­
a primary goal of t h is volume. M u nson 's approach is more eff1-c ient and cost
effective with. niore limited rish.

I n readi n g the scant l i tera tu re devoted to the conservation of deteriorated

gelatine n egatives, whether they be glass plates, or n i trate or acetate films, a
n um ber of themes recur-first, that u n s u pported gel atine i mage p e l licles are
l iable to shred or even dissolve d u ri n g the proposed treatments; second, that
the goal of adhering a pel l i c l e to a new support is d i fficult to achieve and
such p roced u res have never been p u t to a true test of arc h ival permanence;
t hird, that the man i p u lations req u i red for any tec h n ique requ i re extreme
dexterity; and, fo urth, given all the above , a ny routine for retrievin g a dete­
riorated negative must be prohibitively costly.

From DOUGLAS M U NSON, "The Pellicular Bu rlesq ue," Topics i11 Pl10tograpl1ic Preservatoion
7 (\•Vashi ngton , DC: American I nstitu te for Conservation, Photographic Materials Group,
1 997). 56-65 ( 56-58 excerpted here). Reprinted bv perm ission ol' Douglas M unson. The
Chicago Albumen \Narks.
 R e a d i n g 43 J\J U N S 0 N

The routi nes i nvoked at the Albumen Works address each of th ese
issues, as wel l as speakin g d i rectly to the three faces of i mage conservation:
fidel ity, security, and reversibility. The proced u res we have developed over
the past ten yea rs provide an approach to the preservation of these objects
and images wh ich is cost effective, provides a worki ng rou t i n e which can
accommodate s u bstantial quantities of deteriorated material, a n d involves
a treatment environment wh ich p u ts the deteriorated origi n a l material at
very little risk.
As you w i l l see i n the description below, the preva i l i n g concept i n our
proced ure is to never allow the pellicle, whether still s upported or loose, to
become wet in a n aqueous solution. Once a pellicle i s in a sol ution contain­
ing more than about 10 % water, i t swells, loses i ts d imensional stabi l i ty and
stre ngth , becomes s usceptible to silver migration, and begins to behave more
as a sheet of gelati ne adhesive, ready to glom onto a nything.
The a b i l i ty to separate an i mage pe llicle from a deteriorated acetate
fi l m base re lies on the presence of ce l l u lose n itrate s u b b i ng layers between
the emu lsion and a n ti-curl l ayers a n d the acetate film base. The i n itial sepa­
ration of the pell icle from its deteriorated acetate base can be accomplished
by d issolvi ng away these n itrate l ayers in a non-aqueous solven t com bina­
tion. S u bseq uent solvent baths perform three tasks. They clean the pel l i ­
cle o f residual cellu lose n itrate reta i ned from t h e first stripping b a t h , they
al low a progression from dangerous solve nt chemicals to the use of a pota ble
alcoho l , a n d they i n troduce a controlled amount of water to the pellicle to
al low i t to relax and be temporari ly f l attened , without evi dence of its previ­
ous furrowi ng.
The secon d place where we deviate from most previously publ ished
rou t i n es is that we do not re-mount the pel l icle. Rather, we dry it of i ts sol­
vents and m i n i ma l water content a n d return it to the i nstitution- fl attened,
i n a fo lded pouch, between stiffen ers, i n a normal archival paper enclosure .
A dry, unsupported gelatine pel l i c l e is amazingly tough a n d strong, rather
l i ke cellophane.
\Vh ile re-supportin g pellicles may seem l i ke a n obvious encl goa l , in
practice, i t rarely serves a benefic ial fu nction for the i nstitutions wh ich own
deteriorated n egatives. Some published procedu res call for re-adhering to
glass. Th is seems u ni q uely reci d ivist, creating a whole new collection of
objects with just the sort of preservation problems c o llections wo uld l i ke to
avoid. Other tec h n i ques of ad heri n g the pe l l icle to coated polyester sheets
are u n tested for arc h ival stab i l i ty, as we l l as being t i me con s u m i n g and deli­
cate, hence costly.
\i\fh i l e we have developed a method for re-ad heri ng pellicles which we
feel is both perman e n t and revers i ble, we do not recommend it for these
Part V P H O T O G R A P H I C N E G A T I V E S

sarne reasons: i t is a delicate procedure, wou ld be relatively costly, and p u ts

the pel licle to u ndo risk d u ri ng t he process.
As a p ract ical rnatter, it is difficult to conceive of any i nstitutional
need which can not be rnet perfectly wel l wi th an accurate du plicate of the
origi nal i rn age pel l icle. Any pri n t i ng, whether, on vintage or conternporary
rnecl ia, can be clone frorn such a d u plicate, and it has been our experience
that whether an institution requires reference pri nts or exh ibition prints, it i s
t h e quality o f t h e print t h a t is im porta nt, not the generation which produced
it. The a u ra requ iring a prin t to be de rived d i rectly from an original negative
is, thankful ly, one restricted to the corn rnerce of photography.
Should a true need arise, however, the store pell icle could be re-ad­
hered at a later date, espec ially i f a rnounting proced u re were developed
which was tested to be sec u re and reversible. I t should be noted, however,
that cornpared to duplicating, re-ad heri ng will produce a less satisfactory
resu l t in all cases where the pell icle is cracked or torn, which u n fortunately,
is re latively oft e n . In a dupl icat i ng procedure, rnany cracks and breaks can
be butted together nearly perfectly, as will be seen i n some of the later slides,
but in any re-ad hering tech nique there i nevitably will be a sl ight shrinkage
upon dryi ng, which will re-open the cracks.
 R e a d n g 44

PETER Z. ADELSTEI N

From M etal to Polyester: History

of Picture-Taking Supports ( 1 987)

Peter Adelstein (see also Readings 1 9 a nd 49), senior research associate a t the
Tmage Permanence i nstitute, is an a u t hority on film-based niateri.als and their
preservation. f-Je has pu blished nwre than eighty papers related to his research.
For the past twenty-five years he has been Chairman of the A merican National
Standards I nstitute (ANS I ) a nd the I n ternational 01ganization for Standard­
ization ( I S 0) comm:ittees dealing ·with t he permanence of iniaging media. This
writing is an essent ial reference to u nderstanding the history, nian ufactu re,
materials, and deterioration of all photographic negative supports. Adelstein
offers a coherent and detailed overviei11 of the mechanical, optical, physi­
cal, and cheniical properties of negative supports, which fu rther informs our
u nderstanding of these com11lex rnaterials and better prepares us to meet t heir
1nesen1ation challenge.

Photographic fi l m wou l d have a much simpler construction if i t consisted

o n ly of a photograph i c emulsion without a fi l m support, adhesive layers ,
backing layers, and so fort h . H owever, this construction is not possi b le
because the physical characteristics of a photographic emu lsion are not con­
sistent with those reg u i red for the complete p hotographic fi l m . For example,
a photographic emu lsion must read i ly a bsorb agueous solutions for photo­
graphic processing, but such a h ighly hydroph i l ic e m u lsion b i nder cannot

PETER Z. ADELSTEIN, "From M etal to Polyester: H istory of P i c t u re-Taking Su pports,"

i n Pioneers of Phol.ograpliy: Their Achievements in Science and Technology, ed. Eugene
Ostroff (Springfield, VA: S P S E-The Society f'or I maging Science and Technology/North­
eastern U n i versity Press, 1987), 30-36. Text and images reprinted by permission of I S&T:
The Society For I maging Science and Technology, sole copyright owners of Pioneers of
Photograpl1y: Their Ach.ieve111e11.l.s i n Science and Tech nology.
P art V P 11 0 T 0 G H A P 1-1 I C 1'\1 E C A T I \! E S

have the wet mechanical strength to go through processing machi nes. Like­
wise, it is not possible to obtain good dimensional stabi lity with a hydroph i l i c
binder since this property requires a fil m that is hydrophobic. T h e hydropho­
bic photographic fil m base provides the physical properties that cannot be
provided by the emulsion layer alone.
Despite the i mportance of the film base i n the fu nctioning of photo­
graphic fi l m , it is the forgotten component. I ts impact is much less apparent
than the c haracteristics of the p hotographic emulsion, and its p hysical prop­
erties generally receive attention only when they do not meet req u i re ments
or expectations. For this reason, the changes in photograph ic fi l m su pport
over the past century are not familia r to m a ny people in t h is industry. M u c h
greater attention i s given to the deficiencies of fil m support, such as t h e flam­
mability of cell ulose nitrate or the che m ical instabil ity of safety film when
stored u nder adverse conditions. H owever in recent decades, very significant
i mprovements h ave been obta i ned with newer fi l m supports which resu l t in
photographic fi l ms being used in new and demanding applications.

N onplastic S upport

The p hotographic indu stry h as always requ ired the use of materials from
other i n du stries as a s upport for fi l m . The early inventors of the photo­
graphic process had access to relatively few materials. Niepce u sed glass in
1 822, stone in 1 824, and s u bsequently pewter and copper. I n 1 839, Daguerre
disclosed the Daguerreotype process, which was the fi rst practical photo­
graphic p rocess and made u se of copper as the su pport. Eight years later,
C laude Felix Able N iepce de Saint-Victor emp loyed a l b u men as the pho­
tographic binder on glass p lates, and i n 1 85 1 Frederick Scott Arc her coated
collodion on glass. The l atter proved to be very s uccessfu l , and was known
as the wet collodion process. I n the post-Civi l Wa r period, ambrotypes-wet
collod ion photograph s on glass s upport with black backing, viewed by re flec­
tion-were very popular. B lackened metal plates were also u sed in place of
glass, and these were known as tintypes. All these su pports had some obvi­
ous disadvantages. \!\Tith the exception of glass, they were not transparent
and none were flexible. Both characteristics are necessary for photographic
fi lms as we know them today.
The first attempt to produ ce a fl exible fi l m support was made in 1 884
when George Eastman introdu ced Eastman negative paper, consisting of
a photographic e m ulsion coated on paper that was made tran sl ucent after
development by treatment with hot castor o i l . Th is allowed it to be printed .
I n that same year, Eastman produced a rol l holder which made possible the
u se of negative paper in rol l s with the standard p late cameras of that time.
Th is was the first roll film camera, and it c hanged the course of photogra-
 Reading 44 A D E L S T E I N

phy. A second attempt to obtain a flexible photographic fi l m was made the

fol lowi ng year, with the i n troduction of Eastman American fi l m . Paper was
u sed as a temporary support for the emu lsion, which was stripped off after
photographic development. This thin photographic emu lsion skin was then
mounted on a glass support and u sed for making prints. As can be i magined,
neither the transl ucent paper nor the strippi ng fi l m were very satisfactory
answers for a Flexible p hotographic fi l m . This was wel l recogn ized, and i n
1 886 Eastman employed a fu ll-time research scientist to develop a Flexible,
transparent film base.

C e l l u l ose N itrate Base

Tech n ical deve lopment in one i ndustry is frequently very dependent upon
developments in another field. This is very evident today i n the electronics
i nd ustry. I t was also true i n the 1 88o's, with the development of a Flexible
photographic fi l m base and the consequent explosive growth of the photo­
graphic industry. The l atter was completely dependent upon i nventions i n
the field o f p lastics, which a t that t i m e was i n a nascent state. Cellu lose
n itrate was one of the few existing p lastics at that ti me, and it was u sed
for maki ng b i l l iard ball s and men's s h i rt col lars. The fi rst u se of plastic for
photographic fi l m base was marketed by the Cellu loid Company in 1 878.
Sheets of cel l u lose n i trate were cut from solid blocks and then sold to p ho­
tographers who s u bsequently coated them with photographic e m u lsions and
u sed them as dry p lates. About ten years later they were manufactured as
e m u lsion-coated p lates by John Carbutt of P h i ladelphia.
I n 1 887, H a n n i bal Goodwin , a m i ni ster from Newark, lew Jersey,
applied for a patent for making photographic fi l m i n long strips on a Flexible
su pport of cel l u lose n i trate. This patent was not granted until 1 898. 1 H ow­
ever, a U . S . patent for a transparent fi l m base was granted to Kodak in 1 8892
and these two patents resu l ted in a long legal battle wh ich was not settled
u n t i l 1 9 1 4 . Kodak also introd uced its first com mercial photographic ro l l fi l m
on transparent cel l u lose nitrate i n 1 889. This deve lopment made possible the
invention of the motion picture camera by Thomas E dison several years later.
The i n itial fi l m s upports were manufactured from "dopes" of cel l u lose
n i trate d i ssolved in wood alcohol . Evaporation of the wood alcohol left a t h i n
transparent cel l u lose n i trate base. The early supports were very brittle, b u t
l-1 . Reichenbach, the Koda k chemist, succeeded i n p lasticizing them b y add­
i ng camphor and fusel oil. The film base was manufactured on tables 2001 X
4011 wide ( Figure 1 ) .
The n itro-ce l l u lose dope was spread o n these tables from a hopper which
was pul led along the table by chains trave l i ng at the edges. The dope was
coated in late afternoon and radiators i n t he room s aided evaporation. There
 Part V P H O T O G R A P H I C N E G A T I V E S

Figure 1
Film cast ing table, 1 889.

was no solve n t recovery system and air movement was accom p lished by fan s
s uspended from t h e ceil i ng. The next morni n g the fi l m s upport was coated
with a n adhes ive layer and the emu lsion was coated using a h opper similar to
that u sed for coating the dope. By noon the emulsion was dry enough for the
f il m to be stripped from the tables, rol led, s l i t and wou n d i nto rol l s for cus­
tomer use. This batch-type process of manufacturing photograph ic fi l m was
used for ten years, although its shortcom i ngs were q u i te obvious.
A patent for a continuous cast i ng mach i n e for the m a nu facture of film
s upport was fi led i n 1 893 by B lair and \Vaterman 3 and was gran ted in 1897. It
described "the formation of a co ntin uous strip of basic film o n the periphera l
su rface o f a cyli n der which u nder rotation d raws o u t the strip a s the com­
position or dope is fed onto the surface of the cyli n der" ( Figu re 2). In 1 898,
the first p i l ot machine based on this pri nciple was constructed at Kodak.
It consisted of a wheel, 20 11 wide and 91 in d ia meter, over which the dope
from a hopper was poured . The wheel was turned, hot air evaporated the
solvent, and the film base was stripped from the wheel after one revolution.
This p ilot p l a n t proved quite successful and the first production mach i n e
was subsequently insta l led, using a wheel 3011 wide, 1 2 1 i n diam eter, made
by G leason Works in Rochester. Although the principle of dope-cast i ng
 Reading 44 A D E L S T E I N

Figure 2
Cont i nu ou s rilm casting machine,
T. 1-1 . Blair and S. E. \1\ /aterman,
patent filed 1 893.

appears q u i te s i mple, there were many serious problems i n the early years
of its manufactu re. Wheel defects occu rred d u e to corros ion or fau l ty plat­
i ng, res u l t i ng in support imperfections. G reat difficulty was experienced in
provid i ng proper emu lsion adhes ion. Solvents applied to faci l i tate adhesion
wou l d cut through thin spots or pinholes in the s upport and cause smears
on the opposite side. S lugs of partially d i ssolved nitrocell ulose would some­
t i mes stick i n the hopper slot, causing support streaks. These problems were
eventual ly overcome, and solvent cast support is manufactured today u s i ng
the same principle, al though either large polished wheels or end less moving
metal belts are used, along with solvent curing sections, a solvent recovery
system, and h ighly sophisticated con trol equipment.
Cellu lose ni trate is manufactured using cell u lose as the starting mate­
ria l . Cellu lose is fou n d i n cotton ! i nters, wood p u l p and other nat urally
occu rri ng materials. The cel l u lose molecule consists of a long chain of glu­
cose u n its l i n ked together by oxygen . Each glucose u n i t i n the cel l u lose mol­
ecule conta i n s three hyd roxyl groups which may be esterified to p rodu ce the
cel l u lose esters used as a film base. Esterification of these hyclroxic groups
with a m ixture of n itric acid and s u lfuric acid produ ce cellulose n i trate. The
cel l u lose n i trate used as the first flexi ble p hotograph ic fil m contained two
and a fraction (out of a maximum of three) n itrate groups per glu cose u n i t .
A satisfactory fi l m base m u s t meet m a n y exacting requ i rements, as
outlined in Figure 3 . Very few plastics meet most of these n ecessary criteria.
I t is rather remarkable and coincidenta l that cel l u lose n itrate, which was
 Part V P 11 0 T 0 G 11 i\ P H I C N E G A T I V E S

Characteristic Comments

Mechanical Properties
strength
tear resistance
} use in cameras, projectors, readers.
flexibility
stiffness to resist contracting force of emulsion.

Optical Properties
transparency for printing and viewing.
low haze

Thermal Properties
flexibility at low temperatures for use at sub-zero temperatures.
high softening temperature to prevent distortion at elevated temperatures, such as
drying after processing.

Dimensional Properties
low aging shrinkage
low thermal coefficient
} required for graphic arts, aerial, motion picture and
industrial applications.
low humidity coefficient

Flatness
low curl for ease of handling, projection or printing.
freedom from distortion after aging

Moisture Properties
low water pickup to maintain strength in processing machines and to provide
dimensional stabil ity.

Static Properties
low charging capability to reduce dust attraction.

Solvent Susceptibility
soluble in non-toxic solvents for production by solvent casting,

Chemical Stability for solvent splicing of morion picture films.

Low Flammability for archival storage

Figure 3
Dcsirnble propenies of
photographic f ilm base.
the only pract ica l , available p lastic i n the 1 88o's, had most of the req u i red
propert ies. It was used as a photographic film base for a period of a l most
60 years. I ts major d rawbacks were i ts lack of chem ical sta b i l ity and its high
flamma b i l i ty. These c haracteristics were known very early and the photo­
graphic i n d ustry is s t i l l cop i ng with these two serious shortcom i ngs. Because
of its chemical i nsta b i l i ty, practically all t he major ll lm arc h ives today have
programs to copy cel l u lose n itrate ll l m onto safety base. It w i l l be many years
before this work is completed.
Many of the early motion pictures have been lost because of the sup­
port degradation, and it is a race agai nst t i me to preserve many of the rema in­
i n g lllm records on n itrate base. The flammabil i ty of cellu lose n itrate is still
causing concern because of the large quantit ies of cel l u lose nitrate stock
still in film arch ives. \Vi t h i n the past decade, two of the most i mportant fi lm
arch ives i n this country experienced bad conflagrations.
 Reading 44 A D E L S T E I N

Safety C e l l u lose Ester Film S upport

Work to correct the stab i l i ty and Aammabi l i ty of cel l u lose ni trate com­
me nced early in the 20th century. Coati ngs of viscose (cellophane) were
made in 1 9 1 5, b u t this material showed excessive swe l l i n g i n processing solu­
tions and was not satisfactory.
Et hyl c e l l u lose was i nven ted in Vienna and was the s u bject of consider­
able i nvestigational work i mmediately after World War I. However, the costs
of this material were high, the properties were poor, and it n ever became a
commercial fi l m support.
The most pro m i s i ng approach was the esteri fication of cellu lose with
a mixture of acidic acid, acidic a n hyd ride, and a catalyst such as s u lphu­
ric acid. Fu l l esterification was rea lized when the three hydroxyl groups on
each glu cose unit were reacted, prod ucing cellulose triacetate. H owever,
by partia lly hydrolyzi ng the cel l u lose triacetate, a product with about 2 1/2
acetyl groups per glu cose u n i t was obtained . Th is polymer, referred to as
cellu lose d i acetate, had i mproved sol u b i l ity over c e l l u lose triacetate i n the
solvents available at that time. The early cellu lose acetates had the ten ­
dency of becomi n g brittle w i t h age and showed a h igh degree of d istortion
cl ue to its h igh moisture a bsorpt ion. During World \Var I, cellu lose acetate
was man ufactured for coating the fabric wings of ai rcraft, and experience
was ga i ned both in its manufacture and i n the use of plasticizers. However,
it was not u n t i l 1 923, when Kodak i ntroduced 16 mm home m ovies, that cel­
l u lose acetate was used as a commercial fi lm base.
Development work continued on the esterification of cellu lose d u ri ng
the 1 920's. I n 1 927 H . T. C larke and C . T. M a l m produ ced the first m ixed acid
ester of cellu lose u s i ng p ropionic acid with acidic a nhyd ride in t he esteri­
fication reaction. The res u l ting polymer was cellu lose acetate propionate,
which had both acetyl and propionyl groups o n each glucose u n it . S u bse­
quent work using b utyric acid lead to the manufacture of ce l l u lose acetate
butyrate.4 A wide variety of m ixed cellulose esters are poss i b le, depe n d i ng
on the particu lar ester groups, the ratio of acetyl to propionyl or bu tyryl,
the degree of esterification of the hydroxyl groups in each glucose unit, and
the length of the cellulose chai n . ; Duri ng the 193o's, a cel l ulose acetate pro­
pionate f i l m support was u sed for amateur color films and amateur movie
films, wh i le cel l ulose acetate b utyrate su pport fou n d application in x-ray fil m
and professi onal s heet fi l m . However, these m ixed cellu lose esters d i d not
have the mec hanical strength propert ies req u i red for motion picture s u p­
port. Heplacement of cellu lose n i trate base for this product l i n e req u i red
additional developme n t work.
l m mecl ia tely prior to and d u ring World War I I , there was considerable
activity i n Kodak development laboratories on cel l u lose u -iacetate. However,
P art V P II 0 T 0 G H A P H I C N E G r\ T I V E S

the solvent casting process req u i res good solu b i l i ty i n solvents, and this poly­
mer is soluble only i n a restricted group of them. M oreover, the res u l t i ng
fi lms from most of the solvents are rather brittle and are not s u i table for pho­
tographic fi l m . Methylene chloride was fou n d to be the only practical coat­
i ng solve n t for cell ulose triacetate, and it was not ava i lable in commercial
quanti ties and at a n acceptable price u n t i l after Word War I I. Th is difficulty
retarded the use of c e l l u lose triacetate fil m s upport for a n u mber of years .
H owever, i n 1 948, Kodak i ntroduced cel l u lose triacetate safety base fi l m for
professional motion p ictures.6 This m aterial h ad the req u i red stre ngth and
di mensional stabil i ty properties req u i red for this fam i ly of products. As a
resu lt, Kodak ceased m a nufacture of cell u lose n itrate i n the U n ited States i n
1 9 5 1 a n d manufacture worldwide was essentially ter m i nated i n the 1 95o's.
Although cel l u lose n i trate base film is no lo nger manufactured, it is
still of concern to the p hotograph i c i n d ustry because of the large quant ities
of this material that rem a i n i n storage. This consti tutes a potential fire haz­
ard , and the chemical i n stability results i n the loss of valuable h istorical and
a rtistic records . IVloreover, decomposing cel l u lose n i trate releases nitrogen
oxide gases i n to the e nvironment that have a very deleterious effect on other
fi l ms stored in the same area . 7 I t i s imperative that cel l u lose n itrate films be
stored by themse lves in areas with proper fire protection.

Vi nyl Supports

Alt hough the i n trod uction of cel l ulose triacetate permitted the photographic
ind ustry to use only safety fi l m s upport, cel l u l ose triacetate did not prove to
be the ultimate film base for all applications. None of the cel l u lose esters
materials possessed the d imensional requ i rements needed for the exacting
applications described below.
Photographic films u sed for aerial survey p u rposes req u i re not only
very small d i mensional changes, b u t the same d i mensional cha nges i n a l l
d i rections so t h a t d istortions will not be i n troduced i n the res u l ti ng map.
S i nce 1 94 1 , the majori ty of topographic aerial films were on cellu lose acetate
butyrate base, which was spec ifically manufactu red to have s i m i la r properties
in all planar d irections. However, this fi l m had a h igher humid ity coefficient
of expansion than desi red because of the moisture a bsorption of the support.
This req u i red appropriate p recautions and corrections in map preparation .
Engi neering d rawings requ i re very exacti ng dimensional stabil ity
because of the large size sheets emp loyed. This appl ication also necessi tates
high tear strength to resist handli n g damage. Cel l u lose ester base fi l ms could
not be used for this p u rpose becau se of these req u i rements. D u ri ng \Vorld
\Va r I I , sensitized emu lsion layers were applied to metal supports such as
steel and a l u m i n um to achieve good d i mensional sta b i l i ty.
 R e a d i n g 44 A D E L S T E I N

Photographic fi l m i s used as a n i n termediate i n the graphic arts indus­

try to make printing plates. Color work requ ires exact registration of the dif­
ferent colors during p ri n ti ng, a n d hence tight dimensional stability of the
film intermediate. Considerable difficulty was experienced making color
printing plates, as exacting humidity control was required.
All t hese appl ications i ndicated the n eed for a more moisture-resistant
support than was possible with the derivatives of cellu lose. A hyd rophobic film
s upport was required, a n d this wou l d have to come from a syn thetic polymer
with very low affinity for water. An excellent review of the need for s uch a mate­
rial and the resulting developments is given in a 1 960 paper by ] . M . Calhoun.8
I n 1925, polyvinyl chloride was discovered, which has very low mois­
ture adsorption . This res u l ted in considerable efforts to develop a dimen­
sionally stable polyv i nyl chloride film base. Although it met the necessary
moisture-resistant requirements for a stable base, the material had some
serious shortcomings . While it was soluble i n solve n ts suitable for casting, it
was very diffic u l t to remove the last traces of solve n t and the support showed
high agi n g shri n kage due to subsequent solve n t loss. Polyvi nyl chloride sup­
port could also be made by the calendaring process in which the p lastic is
squeezed between heated steel rol lers to form a s heet. Although this m ate­
rial is free of solvent, it h as a m atte surface, so that the base is translucent
rather than transpare n t. It also s uffers from relatively high brittleness a n d a
low soften i ng temperature. Nevertheless, it did fi n d limited app l ication for a
dimensio n a l ly stable graphic arts fi l m b etween 1 94 5 and 1 955.
In 1 948, glass c loth impregnated with a polyester resin was i n trod uced
i n the U n i ted States. However, l i ke polyvinyl c hloride, this material was
translucent rather than transparent. M oreover, it showed a large difference
i n properties between the machine and cross d i rections. I t did n ot find sig­
nificant application .
Polystyrene was the second synthetic resin to fi nd use as a moisture­
res istant fi l m base. This material had b ee n u sed for molded articles since
1935 but it had not been considered as a film base because of its brittle­
ness. H owever, a change in its method of manufact ure resu l ted in a marked
decrease in its brittle behavior. Like polyvinyl c hloride, it was not practical to
cast polystyren e from solvents. I ns tead, i t was cast from a melt through a dye
havi ng a long, narrow slot, and then cooled to form a sheet. I n this form, it is
a very brittle materia l . H owever, in 1 946, F. E. Wiley9• 1 0 patented a process i n
which a polystyrene sheet was biaxially oriented b y stretching i n b o t h direc­
tions while heated. A machine called a drafter was used to apply l engthwise
orien tation, and a tenter gave widthwise ori e n tation. The sheet was then
cooled while mechanical l y restrained. This treatment uncoi led the long chain
polystyren e molecules a n d oriented them para l l e l to the thickness direction
of the sheet. The resu l t was a laminated structure with polymer chain s ori-

39 1
Part V P H O T O G R A P H I C N E G AT I V E S

e n ted i n the plane of the sheeting with a res u l ta n t increase i n mechanical

strength and flexibi l i ty. Thi s material was manufactured by the Plax Cor­
poration i n the U nited S tates and was coated to graphic arts emul sions by
Eastman Kodak Company. I t was i ntrod uced i n 1 954 1 1 and was s u bsequently
marketed by other companies. l t had markedly improved d i mensional stabil­
i ty over the cellulose ester films and fou n d wide acceptance i n the graphic
arts industry. Its moisture resista nce and physical properties were satisfac­
tory for this pu rpose, a lthough the latter was i nsufficient for use as an aerial
or motion picture fil m . Polystyren e is su sceptible to stress c razing if stressed
by sharp bends or kin ks . This sensitivity is increased by certain c le a n i ng sol­
vents and stagi ng paint. I t also has a re latively l ow soften ing te mperature,
although it is superior to polyvinyl c h loride in this respect. l t was eventually
replaced by the n ewer polyester film support.

Polyester F i l m Base

The i ntrod uctio n of the polyester polyethylene terephthalate marked a major

advance i n the technology of film su pports. Polyethylene terephthalate is
a polymer that was discovered by Wi n field and D i ckson in G reat Brita i n . 1 2
I t is made fro m the reaction of ethylene glycol a n d d i methyl terephthalate.
The inventors d iscovered that this polymer produced a fiber with very high
strength if i t was oriented by stretc h i ng. Commercial development of this
fiber occu rred after World \Var I I , first i n the U nited Kingdom and then i n
the U n i ted States. \,York fol l owed t o prod uce a p lastic sheeting. Si nce t his
polyester was i nsoluble i n common solvents, it was not practical to convert
it to a sheeting by solve n t casti ng. I nstead it was cast from a melt similar to
the process u sed with p olystyrene. As with biaxially oriented po lystyrene, the
extruded sheet was s u bjected to biaxial orientation. At this poi n t the simi­
larity with biaxia l ly oriented polystyre ne ceases. A fundamental difference
between the two polymers is that polystyrene contains the b u l ky benzene
rings branching out from the main polymer chain, whi c h prevent close pack­
i n g and crystal l ization. However, in polyethylene tereph th alate, the benzene
rings form a part of the m a i n polymer chain and this polymer can be closely
packed and crystallized. Crystal l ization imparts thermal stabi lity to the
biaxially oriented sheet and is carried out in a n operation called "heat set­
ting" after the dra fter and ten te r operat ions. The b iaxially oriented sheet is
mechan ically restrained and heated cons iderably above the orientation tem­
perature . This allows the growth of polymer crystallites and has the practical
effect of locking the polymer chains together so as to provide d i mensional
stabil ity at e levated temperatures.
After it was manufactu red as plastic sheeting, E I. Du Po nt Co. intro­
d uced polyethylene terephthalate base as a graphic arts photographic fi l m 1 3 · 1 4

3 92
 Reading 44 A D E L S T E I N

i n t955. Its excel lent mechanical properties a n d dimensional stabil i ty resu l ted
in very quick accepta nce i n the graphic arts field and it soon replaced poly­
styrene fi l m support. These properties also proved advantageous for i ndus­
trial fi l m s u sed for the reproduction of mechanical drawings and maps. Its
mechanical properties at room temperature are su perior to those of any
other commercial film base and i ts h igh tear strength is a marked advan tage
i n prolonging the l i fe of large s heets of fil m which must be handled fre­
q uently. It also proved very s uitable for aerial fi l m s 1 5 beca use of its toughness
and d imensional stability. I ts excellent mechanical properties proved to be
of benefit to i nstrumentation films and m icrofi lms. For the latter p roduct,
i t also has the added advantage of even greater c hem ical sta b i l i ty than cel­
l ulose triacetate. Polyethylene terephthal ate fi l m s upport is also widely used
for X-ray fi lms because of greater ease of transport thro ugh automatic pro­
cessing machines.

P o lycarbonate Film Base

A second polyester polymer that h as been u sed as p hotographic film base is

bisphenol A polycarbonate. 1 6 I n 1 957, i t was i ntroduced by Agfa as a graphic
arts fil m base and later by Ansco for graphic arts and aerial fi l m s .
T h i s polymer is sol uble i n methylene c hloride and could b e m a n u ­
factured by t h e solvent casti ng process u s e d f o r t h e cel l u lose esters . I t
therefore h a d a n advantage over polyethylene terephthalate i n t h a t t h e man­
u facturer did not requ i re a completely new manufacturi ng plant to produce
this material.
Polycarbonate had better moisture resistance than pol yethylene
terephthalate and consequently good d imensional stab i l i ty with respect to
h u m i d i ty. H owever, it d i d not have the sti ffness, toughness and low thermal
coefficient of polyethylene tereph thalate and was also h igher in cost. Conse­
quently, it never fou n d wide acceptance and is not used today.

C urren t Status

The change in film base technology is i l l u s trated by Figu re 4 , taken from

Calhou n 's 1 960 paper. 1 7 However, of t he many materials that have been used,
today practically all p hotographic films are on either cel l u lose triacetate or
polyethylene terephthalate supports.
The relative comparison of some of the salient properties of polyester
and cell u lose triacetate base is s hown by the bar graphs in F igure 5. These
properties obviously govern the produ c ts for which these two s upports are
used. All graphic arts fi l m s are now on polyester base becau se of their s upe­
rior d i mensional stability. Aeria l films and industrial fi lms are also on this

393
Part V P 11 0 T 0 G H A P II I C N E G r\ T I V E S

1980

1970

1960
POLYCARBONATE
POLYETHYLENE TEREPHTHALATE
POLYSTYRENE
1950
GLASS CLOTH
CELLULOSE TAIACETATE
POLYVINYL CHLORIDE

1940 CELLULOSE ACETATE BUTYRATE

CELLULOSE ACETATE PROPIONATE

1930

CELLULOSE DIACETATE
1920 STRENGTH TEAR WET
STIFFNESS

1910

�0 �D o�
1900

1890 CELLULOSE NITRATE

TRANSLUCENT PAPER
HUMIDITY THERMAL CORE SET
1880 COEFF. COEFF RETENTION

Figure 4 Figure 5
F i l m base m i lesloncs. H<.:lalivc physical properties uF cellu lose
lriacctatc and polyester.

s u pport beca use of excellent d i mensional sta b i l i ty and high mechanical

strength. The advantage of polyester s u pport for X-ray films is the greater
stiffness of the polyester base while wet, which allows easier tra nsport
through a u tomatic process i ng mac h i nes.
1\11 icrofi I ms are manufactured on both eel I u lose triacetate and polyester
bases, but the latter have the advantage of greater c hemical sta b i l i ty u nder
adverse storage cond itions and greater strength and stiffness of the polyester
base, al lowing it to be u sed in thin ner gauges with a consequent savi ng of
storage space. Sheet films are manufactured on both supports, the polyes­
ter base provid i ng much greater protection from edge tears caused by han­
d l i ng. However, the triacetate base material is preferred in some appl ications
where the fi l m is scored and broken so that areas can be removed and u sed
i n compositional layouts. An al ternate proced ure, which also requ i res triac­
etate base, is to dissolve the s upport layer and use the emulsion skin to make
compos ites. Professional movie films are also marketed on both cel l u lose tri­
acetate and polyester bases, although the former is predominant. One of the
disadvantages of motion picture film on polyester base has been the inability

39-l
 Read i n g 44 A D E L S T E I N

to use solvent splici ng, which has been widely used i n this i ndustry. l t is only
i n recen t years that tape splicing of polyester base fi l m has been accepted.
Cellu lose triacetate base is predomina n tly u sed for amateur rol l Fi l m
because o f its core set p roperties, i . e . , the tenden cy o f the material t o con­
form to the d ia meter of a core after winding a n d storage. Although ce l l u lose
triacetate base takes o n core set more readily than polyester base, i t also
loses its core set more readily, particu larly when wet i n processing sol utions.
Consequently, although the amate ur consumer uses fi l m after it has been in
roll form for many months and h as a h igh degree of core set, this core set is
removed upon processing, enabling the con s u mer to have Aat negatives or
sl i des. Cel l u lose triacetate base is also u sed for 8 mm and 16 m m movie fil m .
Core set i s a consideration o f the former a n d solvent splicing o f the latter.
I t should be noted that there can be no such thi ng as a u n iversal Film
support, s i nce the properties req u i red in one product l i n e can sometimes
be detri menta l i n a nother. For example, it i s contradictory to have the high
strength characteristics needed in aerial and i n d ustrial Fi l ms and also have
easy scoring and breaking of the Fi l m desired i n some sheet fi l m applications.
Another example is the easy removal of the core set of amateur ro l l Fi l m ,
which i s partia l ly d u e t o t h e water adsorption of t h e cellu lose triacetate base.
However, this water adsorption is a very u ndesirable property for applica­
tions that req u i re high dimensional stability.
Although the needs of the photographic i n d ustry are very adequately
met by the use of either cel l u l ose triacetate or polyethyl ene terephthalate
Fi l m supports, there a re still areas where properties can be im proved. Wh i le
the dimensional sta b i l i ty of polyethylene terephthalate i s excelle nt, i t still
has some moi sture adsorption. D imensional stabi l i ty wou l d be still Fu rther
improved i f the moisture p ickup could be reduced or its stiffness increased.
Solvent spl icea bility of a polyester Film wou l d offer a nother degree of free­
dom for the consumer. There are also special applications where it wou ld
be very desirable to have greater res istance to d istortio n at elevated tempera­
tures than is currently offered by either cellu l ose triacetate or polyet hylene
terephtha late. \Vh i le vast improve ments have been obtained in the pro perties
of photographic Fi l m base since the clays of pewter, glass or cellu lose n itrate,
there is still room for further, a l t ho ugh less d ramatic, improvements.

References

1 Goodwin, 1-1 ., U . S . Patent l/ 6 1 0,861 ( 1 898).

2 Reichenbach, H . i\11 . , U .S . Pate n t # 4 17,202 ( 1 889).
3 Bla i r, T. 1-1. and Waterman, S . E., " Method oF and Apparatus for r-.11 aking
Photographic Films," U . S . Patent 11588,790 ( 1 897).

395
P art V P H O T O G R A P H I C N E G A T I V E S

4 Clarke, 1 -1 . T. and M a l m , C . T. , " M aking Cellu lose Esters and the Products
Res u l t i ng Therefrom , " U .S . Patent /'2,0 4 8,685 (J u ly 1936).
M a l m , C. T., Fordyce, C. FL and Tanner, 1- 1 . A., "Properties of C e l l ulose
Esters oF Acetic, Propionic and B u tyric Acids, " J. Ind. Eng. Che m . , 34:
430-435 (April 1 942).
6 Fordyce, C. R . , " I mproved Safety Motion Picture F i l m Support," J . Soc.
Motion Picl 1 1 re Engineers, 5 1 : 3 3 1 -350 (Oct. 1 948).
7 Carro l l , J. F. and Calhoun, J . M . , "Effect of N it rogen Oxide Gases on
Processed Acetate F i l m , '' J . Soc . Motion Picl. 11. re Television Engrs . , 64: 501 -507
(Sept. i 955).
8 Calhou n , J . M . , "Tech n ology of New Film Bases,'' Perspective, 2(3): ( 1 960).
9 \Viley, F. E., Canfield, R. W., Jesionowski, R. S. a nd Bai ley, J . , " Process and
Apparatus for Producing C o n t i n uous Sheets of B iaxially Oriented Organic
Polymer," U . S . Patent #2,4 1 2 , 1 8 7 ( 1 946).
10 Bai ley, J., "Stretch Orientation of Polystyrene and its I n teresting Resu lts,"
I ndia Hu.bber World, 1 1 8: 225-231 ( May 1 948).
11 Farre l l , T. J., Kugler, R. F. and Mayne, D. ] . , "Photographic E lement I-lavi ng a
Polystyrene Support," U .S. Patent #2,81 6,027 ( Dec. 1957).
12 Winfield, J. R. and D ickson , ] . T., " Improvements Relating to the M a n u facture
of Polymeric Su bstances," British Patent //578,079 (J u l y 194 1 ) ; "Polymeric
Li near Terephthalic Esters," U .S. Patent //2,465,3 1 9 ( M arch 1 949).
13 Centa, J. M ., " Performance C haracteristics of C RO NAR Polyester
Photographic F i l m Base,'' Pholog m m . Eng., 2 1 : 539-542 ( Sept. 1 955).
14 Centa, J. J\!l., " E ffect of Base and E m u l sion Thickness on D i mensional
Stabi l i ty of G raphic Arts Film," Proc. Tech. Ass n . G raphic Arts, Part A , 8:
75-79 ( May 1 956).
15 Calhoun, J. iVI . , Adelstein , P . Z. and Parker, J. T., "Physical Properties of
ESTAR Polyester Base Aerial F i l m s for Topographic Mapping,'' Photogrnm.
E ng. , 27: 46 1-470 (J une 196 1 ).
16 Schnel l , H . , " L i n ear Aromatic Polyesters of Carbonic Aci d , " } . Ind. Eng.
Ch.em , 5 1 : 1 57-160 ( Feb . 1959).
..

17 Calhoun, J. M . , op. cit .

 R e a d n g 45

D AV I D H O R V A T H

The Acetate N egative Survey:

Final Report ( 1 988)

Th is excerpt summarizes the first conipreliensive analysis of cellu lose acetate

film collections in an effort to better characterize and understand their dis­
q uieting degradation, which was described in 1 984 by David Horvath-then
c u rator a t the University of Low isvUle Photographic A rchives-as the "n-igh t­
·mare in my closet. " 17ie port-ion of the su rvey report reproduced here includes
r lorva t h 's method for distinguishing six diffe rent "levels" of cellu lose acetate
deterioration. I71is characterization has served as a principal g uide for pho­
togra1?h conservators in evaluat i ng and discussing t he condit ion of cellu lose
acet;a.t;e collections. 1-lorvath 's s urvey also led to a better understanding of the
causes of cellu lose acetate deteri.orat-ion including environmental influences,
storage with n-i t rate film and/or in acidic sleeves, and mi.croenvi.ronment . f-J.is
pivotal worh drew a ttention to t he u rgent need for further analysis and study
of cellu lose acetate film. I71al need was ·met du ring t he period 1 988-1 993 by
/;he I mage Permanence Institute in Rochester, New Yorh, and summa rized in
t he ! P l Storage G u i de for Acetate F i l m, an important tool for evaluat i ng a nd
planning storage environnien ts for all types of acetate base film, cinema film,
an.cl microfi. lm.

From DAVID l-IOBVATH, "The Acetate Negative S u rvey: Final Report," Topics in Plwto­
graphic Preservation 2 (v\lash ington, DC: American I nstitute for Conservation, Photo­
graphic M a terials Group, 1 988), 25-39 (25-28 excerpted here). Reprin ted by perm ission
of David Horvath. ''The Acetate Negative Survey: Final Report" is a project Fu nded by the
U n iversity of Louisville and the National Museum Act a n d i s ava i lable on line at /.i t t p:!I
/011 isvi LIe.ed11/lihra rylehstro111/special/fi Ies/Ac et a I es.

397
Part V P H O T O G R A P H I C N E G A T I V E S

M e thodology

The pri me focu s of this study was a survey of film collection s and a deter­
mination of the exte nt of cellu lose acetate degradation. Institutions were
sel ected for the survey based on their holdings of negatives from the period
1 925- 1 9 5 5 . Collections incl u ded had accurate documentation for the elates

of particular negatives ava ilable either directly on the n egative sleeves or

through the use of i ndexes or other fi nding aids. A variety of collections were
included in the samp l i ng to get the best possible variety of fi l m types, u ses,
and formats. I n stitutions were also selected which presented a variety of
storage and environmenta l conditions.
The site surveys themselves consisted of two steps. First, worksheets
were completed for each col l ection. E ntries were made on the worksheets for
negatives which fit the project's chrono logy. Samples were incluclecl for both
degraded and non-degraded exa mples and for a l l m a nufact u rers and fi l m
types ( notches) represented . The total n u mber o f samples wou l d vary with
each collection depending on the arrangemen t of the negatives, the size of
the collection, and the ease of dating particular samples.
The worksheet con tai ned the fol lowing items of data:
C o ll e c tion/Neg #: This column was used to record a collection spec ific
n umber for each i ndividual sample i n c l u ded. A two to fou r letter prefix
designating the i ns t i t u t ion was i n c l uded with the i nstituti o n 's own nega­
tive n u m ber (location ) .

Manufacturer & N umber: The man u facturer of a particular negative

sample was recorded here with any n u mber that appeared em bossed i n
the fi l m edge with t h e m a n u factu rer's name. This nu mber, referred to
as t h e " m a c h i n e n u m ber," is gen e ra l l y cons idered to be the n u mber of
a part i c u l a r notch i n g m a c h i ne used in the fi n i s h i ng of t h e fil m . H i s tori­
cally, these n u m bers have been used by various m a n u factu rers to follow
the move m e n t of raw fi l m stock, or to i n d icate the n umber of an i nspec­
tor of a part i c u l a r fi l m batc h . M o re recently Kodak has used t h e n u mber
to i d e ntify the fi l m product itself.

Notch : F i l m notch codes are cuts on the edges of sheet fi l m that c a n be

used to i dentify the fi l m t)1Je, as we l l as locate t h e e m u ls i o n side of the
film when fi l m holders are loaded in t h e dark. The sample's "NOTC H
R E F E R E N C E " (see Appendix B) [not reproduced here] was recorded
or, if not known, the actual notch was carefu l ly traced i n p e nc i l . A notch
referen c e wou l d then l a ter be assigned.
 Reading 45 H O H V A T l-I

Notch Reference: A u n ique a l p hanu meric designation was assigned to

each notch. For Kodak negatives this referen c e refers to Kodak's own
notch designation as recorded by their Patent Office. This was useful
for their own records and kee ping track of n o t c h usage and c h ronology.
U n fortunately, these records are not available from other m a n u factur­
ers. For these examples a notch reference design a t i o n was assigned for
this s u rvey. A l isting of notch references is i n c l u ded i n Appe n d ix 13 [not
reproduced h e re ] .

Level of Deterioration: Each negative was assigned a n u m ber from 1 -6

descri b i n g its p hysical condition at the time of t h e s u rvey. These six lev­
els can be described as fol lows:

Level 1 -N o deteriora t i o n ; Aat negative.

Level 2-Negative exh ib i ts s l ight or moderate edge c u rl with

smooth s u rfaces o n both e m u l s ion and base s i des. Edge c u rl i s
al ways symmetrical o n t h e two o r fou r s i des affected.

Level 3 - S m e l l ; the negative s mells d i s t i n c tl y of acetic or butyric

acid. This determ ination is d i ffi c u l t to make if there are large
n u m bers of degraded negatives in a confined area s u c h as a box
or drawer where the acid odor permeates. Usually i n these cases
there is level 4-6 degrad ation evident as wel l .

Level 4-Warpage; wavy portions i n edges a n d su rface o f the

negative; not sym metri c a l ; no separation of e m u l s i o n o r base .
One of t h e first signs that a negative may be degrading is that i t
wil l show signs of warpage. S light warpage o r deformation can
also be caused by the u neven loss of solvents from t h e negative.
The type of warpage w h i c h i n d icates serious degradation is most
often verified by the existence of other further degraded samples
in t h e i mmediate vicin ity of the warped negative.

Level 5-Bubbles; occasionally when an acetate negative

degrades, b u b b l es may form between t h e emuls i o n a n d base or
between the base and the a nti-curl backing of t h e fi l m . These
bubbles vary i n size and may appear in a c i rcu lar pattern from
t h e center of t h e negative out to the edges. Occas i o n a l ly these
bubbles are filled with a volatile l i q u i d .

Level 6-Separation of the e m u l s i o n , b a s e , and anti-curl layers.

This can be evident i n varying degrees, from s light local ized sepa­
ration to massive separation. A white crysta l l i ne exudate is often
seen under the separated portions of the base material. This s u b ­
stance i s most l i ke l y to be the plasticizer used to m a n u facture t h e
fi l m b a s e s u c h as tri phenol phosphate.

3 99
Part V P H O T O G R A P H I C N E G A T I V E S

Date: This col u m n was used to record the date of the negative as c l osely
as it can be determ i ned from t h e photographer's records. To be i n c l uded
i n the final data analysis, the elate s h o u l d be reasonably verifiable with i n
a year.

F i l m Thickness: I n i t i a l l y the th ickness of each negative s a m p l e was

recorded using a d i a l type c a l i per. Little variation was noted between the
sheet fi l m negatives in va rious conditions, with t h icknesses ra nging from
.008 to . 0 1 0 i n ches in a l l samples in various conditions. Afte r several s i te
su rveys t h i s measurement was disco n t i n u ed .

F i l m S ize : The n o m i n a l size o f the s h eet f i l m b e i n g sampled.

Notes: Observati ons were recorded h e re for any special conditions of

a parti c u l a r sample, i n c l uding additional comments about cond i t i o n ,
a p pearance, or environ ment, as well as qualificat ions for elate o r notch
i n format ion.

The second portion of t he s i te or i n stitutional surveys consisted of an

i n terview with the c u rator or caretaker of the collection to record the stor­
age and e nvironmental h istory of the material surveyed. Th is i nformation
wou ld i n c l u de , if known, how and where the negatives were stored before
they arrived at the i nstitution and the same i nformation for the institution's
own storage. Of partic u lar i n terest wou l d be any trauma the collection may
have suffered, such as fire, Rood, or warehouse storage, that wou l d affect the
present condition of the negatives .
 R e a d i n g 46

MONIQUE C . FISCHER
A N D ANDREW R O B B

Guidelines for C are &

I dentification of Film- Base
Photographic Materials ( 1 993)

"Guidelines for Care & Identification of Film-Base Photographic Materials " by

photograph conservators Monique Fischer of the Northeast Document Conser­
vation Center and Andrew Robb of the L ibrary of Congress summarizes han­
dling procedures as well as environmental and storage g uidelines, and offers a
b rief introduction to factors governing duplication, rehousing, and treatment.
Tiii.s reference is f1-equently cited for the value of the associated "Identification
of Film-Base Photographic Materials: Instructions and Chart " that appears in
Appendix C of this volume. Compiled by Fischer ancl Robb as graduate stu­
dents in the Winterthur!University of Delaware Progra·1n in Art Conservation,
this streamlined publication offers practical, easy-to-understand preservation
advice to conservators, a rchivists, librarians, ancl other individuals responsi­
ble for negative holdings, including cellulose n itrate, cellulose acetate, and
11olyester films.

Background

There are three broad types of film-base p hotographic materials: cellu lose
n i trate, the cellulose acetates, and polyester. These materials have been u sed
as a support for n egatives, positive transparencies, motion pictures, micro­
fi l m , and other p hotographic products. U n fort u nately, cellulose n i trate and

From MONIQUE C . F 1 s C H E H a n d f\NDHEW ROBB, "G u i de l ines for Care & I denti fication of
F i l m- Base P hotographic Materials," Topics in Photographic Preservation 5 (\Vash ington,
DC: American Tnstitu te for Conservation, Photographic M a terials Group, 1 993), 1 1 7-22
( 1 1 7- 1 8 excerpted here). Reprinted by permission of the authors.
Part V P H O T O G R A P H I C N E G A T I V E S

the cell u lose acetates are unstable. Their degradation prod ucts can severely
harm and even destroy photograph ic col lections, in addi tion to posing seri ­
ous health and safety hazards. In particu lar , institutions s h o u ld isolate
and properly store cellulose nitrate materials because of their extreme
flammab-i lity, especially when i n a deteriorated condition .
The many fires caused by i mp roper storage of c e l l u lose n i trate
prompted the advent of the various types of ce l l u lose acetate fi l m -base. Even
i n their deteriorated state, the cel l u l ose acetates do not have the flammable
character of cellu lose n i trate and became known as "Safety" film. However,
the cel l u lose acetates do have stability problems. The deterioration of cellu­
lose acetate is a u tocata lytic, l i ke that of cellu lose n itrate; once deterioration
has begu n the degradation products i nduce fu rther deterioration. Because
of its increased sta b i l i ty, polyester has replaced the cellu lose acetates as a
s upport for some, but not a l l , fi l m products. A large amoun t of sheet and
roll fi l m rem ains acetate based becau se the cel l u lose acetates can be solvent
wel ded and easily flattened.
The problems associ a ted with both cel l u lose n i trate and the cel l u l ose
acetates have been known for many decades and are wel l doc u me nted .3·45
The instability of fi lm-bases produced before the m i d - 1 95o's is particularly
problematic.9 Many of these materials are presently at risk, and t heir dete­
rioration may place otherwise stable p hotographic materials at risk as wel l .

U s e o f This Handout

The care and preservation of fi l m-based negatives is d ivided i n to fou r broad

categories-I dentification; H an d l i ng Proced ures; E nvironment & Storage;
and Dupl ication, Rehousi ng, & Treatment. Th is essay discusses the last
three topics; accompa nying c harts [see Appendix C J can be u sed for identify­
i ng i ndividual fil m-base materials, as wel l as for surveyi ng large collections.
A preservation plan should i nvolve the carefu l consideration of these fou r
areas. Ide n t ification i s crucial because sto rage , duplication , rehousing,
and treatment decis ions are based on accurate identification.

Handling Procedures

F i lm -base materials can be damaged easi ly, even when in good condition. All
three fi l m types, and the gelatin b i n der on them, can be scratched , abraded,
and creased. Oils and d i rt from your hands can also da mage t he s u pport and
binder, as well as the fi nal image material.
Once deterioration has begun, fi l m-base materials are even more
prone to handling damage . Deteriorated materials can become q uite brit­
tle; in this state, repeated removal from a housing can cause considerable
 Reading 46 F I S C II E R A N D R 0 BB

harm . Furthermore, deteriorated materials may become sticky and adhere to

other materials.
\!\!hen h an dling fi l m-base materials, wear clean cotton gloves a n d work
in a clean, well-lit, a n d we l l-venti lated area with enough room for p rocess­
i ng. Do not a l l ow eating, drinking, or smoking in the processing/examination
a rea. Prolonged exposure to deteriorated negatives can be dangero u s ,
especially w h e n i n large c o llections . Protect yourself b y wearing c o t t o n
glove s , maintaining g o o d a i r circulation, u s i n g a respirator, n o t wearing
contact lens es , and limiting exposure time . \!\!h e n handl ing or examining
materials establish a system for setting aside or locating damaged materials.
These materials should be exa m i ned and possibly treated by a conservator.

Environment & Storage

Maintenance of a proper environment is extremely important to the lon­

gevity of all fi lm-based materials . Presen t recommendations a re for a con­
stant environment of 68°F ( 20°C) between 20% and 30% relative h umidity.
C u rrent research has fou nd that deterioration is heavily dependent on both
temperature and relative humid ity. For example, by lowering temperature
and relative h u midity conditions from 6o°F ( 1 5°C )/50% RH to 40°F (5°Ch5%
RH the rate of deterioration for cellu lose triacetate can be slowed by
i o times . 1 1
Ideally, each type offilm-base material sho uld be stored separately,
isolated from other types of fi lm s upport s . Organizing storage in this way
p rotects other photographic materials from h armfu l degradation products
of cel l ulose nitrate and the cel l u lose acetates. I n partic u lar, the nitric acid
formed by the degradation of cel lulose nitrate can fade si lver i mages, cause
ge latin b i n ders to become soft or even tacky, and corrode metal contain­
ers and cabinets. This type of material-based organization also makes moni­
tori ng the condition of the collection more efficient and effective. D u e to
the llre hazards associated with cellulose n itrate n egatives , it is especially
i m portant to i solate any cel l u lose n i trate materials; i n fact, this i s requi red
by many i ns u rance pol icies.
\Vhile it is important to separate different types of material i f possible,
it is also important to segregate deteriorating m aterials from those in good
condition. As mentioned earl ier, deteriorati n g materials produce degradation
products that can induce deterioration in other photographic material s .
Three layers of protection are recommended for t h e storage o f fi l m ­
based p hotograph ic materia ls. F l a t materials s h o u l d b e p laced i n s leeves,
sleeves i n a box or d rawer, and these boxes or d rawers on shelves or in a
cabinet. Roll materials such as motion picture fi l m and microfilm should be
stored i n u nsealed containers in cabi nets or on shelves. Both Aat a n d roll
Part V P H O T O G R A P H I C N E G A T I V E S

materials should be kept i n a dark area with good a i r c i rc ulatio n . I deally, the
storage area should h ave an exhaust system.
All e nclosures s hould pass the Photo Act ivity Test ( PAT) as described
in AN S I standard IT9.2- 1 988. 2 This stri ngent test evaluates the effect of
housing materials on photographic materials. Many m a nufacturers and sup­
pli ers of housing materials now conduct this test o n their products. If at all
possible, p u rc hase products that have passed the PAT or speci fy that any
housing p u rchased m ust pass the PAT.
Sleeves should be made of u n b u ffered, h igh a lp ha cellulose content
paper. I deally this sleeve should be seamless and have n o adhesive , although
a side seam may be acceptable. The porous nature of paper allows the deg­
radation products to escape from the enclosure, u nl ike a p l astic enclosure
which traps those harmful products and accelerates the deteriorati o n of
the fil m materia l . For the same reason, contai ners for roll m aterials shou l d
b e made o f card stock o r corrugated board, a l though other concerns may
req u i re u se of metal conta i n ers. If Aat materials are u sed frequently, a plas­
tic sleeve may be des i rable; hand l i ng damages are red uced s ince the material
can be seen without removi ng it.

D uplication, Rehousing, & Treatment

The specific procedu res and extent of dupl ication, rehousing, & treatment
will vary tremendously from collection to collection. However, any approach
should rest on a solid fou n d ation of accu rate identification of the film-base
materials in t he collection, a good u nderstanding of the collection's present
and fu ture u ses, and m a in tenance of a good enviro n ment. Without this k i n d
o f fou n dation considerable effort, ti me, and money w i l l b e wasted . In plan­
ning duplication, rehousing, & treatment, fac tors t o be considered are :
de terioration lev els , size and use of the collect i o n , space available for
storage ' and financial reso urce s . 6.7,8. 9 . 1 0. 1 1 . 1 2. 1 3 . 1 4

Hecent research i n dicates that the chem ical stability of cellulose

n i trate and the cellu l ose acetates i s very simi lar. Nei ther cellulose n i trate
nor cellulose d i acetate appear to deteriorate significantly faster than other
cel l u losic fi l m m aterials. 1 1 This research suggests that negative condition
and not n egative type should be the criterion for duplication.
Decisions concerni n g dupl ication, rehousi ng, and treatment should be
considered with a conservator who is fa mi l i ar with you r collection and i nsti­
tution. The deteriorati o n levels outl i ned by Horvath are especially helpful i n
determ i n ing preservation priorities.9 These deterioration levels h ave been
l i sted i n the accompanyin g identification chart [ see Appen d ix CJ. I tems from
Deterioration Levels 5 and 6 (and poss i bly 4) should be brought to a conser-
 R e a d i n g 46 F I S C H E B /\ N D R O B B

vator's attention. Water damaged materials, and those with mold or signs of
i nsect i n festation should also receive a conservator's attention .
I n some situations original fi lm-base materials are d isposed of fo l­
lowing d u p l ication. I f disposal is considered appropriate, i t should only be
done after the original and duplicate negatives h ave been compared, and the
duplicate is considered acceptable. Consult with you r local fire department
before d isposing of fi lm-base materials, especial l y cel1ulose nitrate.
lt is vital to continually monitor the condition of the fi l m - base mate­
rials in you r collectio n . At this time there is no s i mple testing procedure
for detecting i n cipient fi l m- base deterioration . The o n ly way to control this
problem is to maintain as good a n environment as possible and to catch
deterioration as soon as it occu rs and then isolate the deteriorating materi­
als. This is particu larly true of cel lu lose acetates; their condition can go from
an u ndeteriorated state to a badly deteriorated one i n a matter of months,
even in fairly good environments. As Horvath concludes in The Acetate
Negative S urvey, "every i nstitution which contai n s a s u bstantial q ua ntity
of safety fi l m dating from 1 925- 1 9 5 5 w i l l fin d problems with degraded fi l m
base somewhere i n their collecti o n sooner o r later. "9 Monitori ng your col lec­
tion will allow you to catch the deterioration sooner rather than later. The
importance of vigilant monitoring of t h e co llection and its environment
cannot b e overstated.

Bibliography

Adelstein, P . Z. and ] . L. M c C rea. ( 1 98 1 ) . "Stabi l i ty of processed polyeste1· base photo­

graphic films. "" )onrnal of Applied Photographic Engineering 7 (6, August): 1 60-1 67.
2 American N a tional Standards I nstitute. ( 1 988). American National Stcmdard for
/ waging Meclia-Plwtographi.c Processed Films, Plates, and Papers-Filing Enclosures
and Storage Containers. No. ANSI IT9.2-1988. This standard i s revised periodical ly; be
sure to consult the most recent version.
3 Calhoun, J . iVI . ( 1 953). "Storage of n itrnte amateur s t i l l-camera negatives." Journal of
t.he Biological Photographic Association 2 1 (3, Aug.): 1 - 1 3 .
4 Carro l l , ] . F. and J. iVI . Calhou n. ( 1 955). " Effect of n i t rogen oxide gases on processed
acetate f i l m ." Journal of /.he SM PTE 64 ( Sep. ) : 50 1 -507.
C u m m i ngs, ] . \N. , A. C. H utton, and H. S i lfin. ( 1 950) . "Spontaneous ignition of
decomposing cellu lose n itrate Fil m . " Journal of the S MPTE 54 ( March): 268-274.
6 Eastman Kodak. ( 1 985). Consen1atio11 of Photographs. Kodak P u b lication F-40.
Rochester, NY.
7 Eastman Kodak. ( 1 984) . Copying and D11plicaling in Blach-and- \¥hi.t.e and Color.
Kodak Publication M - 1 . Hochester, NY.
8 Hendriks, K. B. ct al. ( 1 99 1 ) . Fundamenlnls of Photogrnph.ic Conservatio n : A S t udy
Guide. Toronto: Lugus Publications.
9 Horvath, D. G. ( 1987). The Acetate Negat ive S u 111ey Final Report. Lou isvi l le, KY:
Ekstrom Library Photograph i c Archives, U n iversity of Louisvi l le.
Part V P II 0 T 0 C H A P 1-1 I C N E G AT I \! E S

1 0 Puglia, S . T. ( 1 989). "Negative d up l ication: evaluating the reproduction a n d

preservation needs of collections." Topics i n Ph otog ra p li ic Conservation 3 : 1 23-1 34. See
also CAN 38: 8-9.
11 Heil ly. J . M . , P. Z. Adelstein , and D. N i sh i mu ra. ( 1 99 1 ) . Preservation of Safety Film.
Hochester. NY: I mage Permanence I nstitulc, Hochestcr I n st it u te of Tech nology.
12 Sturge. J . i\ I . , eel. ( 1 9 77 ) . Neblette's 1-/andbooh of Photography and Reprograpliy­
Materials, Processes, and Sys t e 11 1s , Seve n t h Edition. New York: Van Nostrand H e i n ­
holcl Co.
13 Wei nste i n , H . A . and L. Booth . ( 1 977). Collect io11, Use, and Care of Historical
Phot.ographs. Nashville, TN: AAS L H .
14 Young, C. ( 1 989). " N i t rate fll m i n p u b l i c institutions. " H ist.01-y News 44 (4 , J u ly/August
1989).

406
 R e a d i n g 47

j EAN- LO U I S B I G O UR DAN

S tability of Acetate Film Base:

Accelerated-Aging Data
Revisited (2006)

Jean-Lou-is Bigourdan worhs a t the Image Permanence Institute, where his

research. has focused on the effects of enclosures and microenvironments on
the stability of 11/iotograph.ic films. This article on the stability of cellulose tri­
acetate film describes the use of accelerated-aging techniques to predict the
long-term behavior offilm-base materials and the resu lts of ten years of natural
aging of cellulose triacetate film. The results underscore a direct correlation
between accelerated aging 11rocedures and data obtained by natural aging at
rooni and subfreezing temperature, th.us validating conclusions based on pre­
viously published accelerated-aging tests. The importance of environmental
conditions-specifically low-temperature storage-in p reserving photographic
filni is affirmed. Bigourdan demonstrates that temperature and humidity tran­
sitions do not cause extra chemical decay in cellulose triacetate films and th.at
enclosure type offers little protection.

I n troduction

Accelerated-agi ng data came into use to aid archivists who were fac i n g the
problem of i n formation loss caused by irreversible decay in their col lectio ns.
Since 1 988, the I m age Permanence I nstitute ( I P I ) has been engaged in a
series of research projects i nvolvi n g the study of p hotographic material sta-

J EAN-Louis 8 1 G O U R DAN, "'Stability of Acetate Film Base: Accelerated-Aging Data Hevis­

ited," Journal of hnaging Science and Technology 50, no. 5 (2006): 4 94-50 1 . © 2006 Society
for I magi ng Science and Technology. Hepri nted by permission of I S &T: The Society for
I maging Science and Technology, sole copyright owners of journal of Imaging Science and
Tech nology.
P art V P H O T O G H A P H I C r'\1 E G A T I V E S

b ility. I P ! has foc used on the development of preservation strategies and has
prod uced a series of management tools for dea l i ng with media collections,
i n cl u d i ng the I Pl Storage Guide for Acetate Fil1n, 1 the Storage Guide for
Color Phot:ogmphic Materials, 2 and the IPI Media Storage Quich R eference .3
These p u b l ications were designed as m anagement tools for archivists to use
in assessing the effective ness of their storage conditions in contro l ling the
decay of cellu lose acetate film and color photographic material s or collec­
tions of m ixed media. The vast m ajori ty of the i n formation included in these
publications is based on data produced by accelera ted-aging tests, which
were conducted primarily on p hotographic materials at steady elevated tem­
peratures and at constant moisture content. l n recent years, I P I has focused
on develop i ng data at lower temperatures. I n an earlier paper, IPI published
Jong-term data on the stab i l ity of n itrate, cel l u lose triacetate (CTA), and
polyester fi l m su pports at 50°C obtai ned from a 1 0-year incubation period . 4
This paper revisits common accelerated-agi ng procedures used for
the study of fi l m stab i l i ty, reporting data obtai ned by natural agin g at room
and subfreezing temperatures, and u nder changing temperature and relative
h um idity ( R H ) condition. Common acce lerated-aging practices a n d l i mita­
tions are d iscu ssed first.

Accelerated-Aging Studies-Background

Using T-/igh Te·m.peratures

Accelerated aging at h igh temperature was used i n early comparative stud­

ies of n i trate and acetate fi l m supports . 5 Later, a predictive method, based
on the approach advanced by the Swedi s h chemist Svante Arrhenius, 6 was
developed thro ugh successive studies of the stability of photographic fi l m .
Adel stei n pioneered t h e u s e o f t h e method t o quantify the stab i l i ty o f color
dyes.7 Later accelerated aging studies on nitrate,8·9 acetate, 4· 1 0· 1 1 · 1 2 · 1 3•1 4· 1 5 and
polyester16·1 7 plastic s upports, and on color dyes 1 8· 1 9 fu rther demonstrated
the releva nce of the Arrhenius equation for i nvestigating photographic fil m
stability. Through extrapolation o f Arrhenius plots, these studies made it
possible to quantify the relationsh i p between temperature and the rate of
degradation of materials at various h u m id ity leve ls. I n practice, some mea­
surement of t he rates of chemical reaction, e.g., free acidity or p hysical prop­
erty changes d u ring CTA fi l m decay, 1 2 is determi ned at several temperatu res
and constant fi l m moisture content. The logarit h m of those rates is p lotted
versus the reciprocal of the absolute temperature ( K) . The data obtained
at elevated temperatures can be u sed to esti mate the rate of decay at other
temperatures.20 Th us, the method provides a way to analyze the experimen­
tal data and translate them i nto terms of l i fe expectancy ( LE ) for the tested
 Reading 47 B I G O U n O A N

materials, expressed i n years stored at 2 1 °C, 50% R H . The I nternational

Organ ization for Standardization ( I SO ) has standardized this method . 2 1 The
method has been usefu l for developing effective p reservation strategies for
fi l m and color materi a l s . Data published in the IPI S torage G u ide for Ace­
tate Fil m 1 and in the Storage Guide for Color Photographic Materials2 were
obtai ned using this type of data analysis.
A legit imate and frequently e.JqJressed concern i s the possi ble distortion
of the real-life behavior of the test materials t hrough the use of accelerated­
aging conditions. The studies mentioned above were commonly condu cted
a t h igh temperatures (70°C and above) . Can artificially created agi ng condi­
t ions reflect the materials' natural behavior? One response to this concern i s
to u s e only moderately accelerated conditions o r even room conditions for
testing materials decay rate. H owever, this req u i res l o nger incu bation peri­
ods , which can be i mpractical .

Using Moderately Accelerated Aging

\!Vi t h the above concerns in m ind, i nvestigators have used m oderately accel­
erated agi ng conditions, ei ther by extending the d u ration of i nvestigation or
by modifying the preparation of test samples. I PI's l ong-term collection of
data on fi l m supports4 is an example of the former approach ; its i nvestiga­
tion of the role of m icroenviron ments in controll i n g vinegar syndrome i s an
example of the latter. 22
I P I incubated test materials at 50°C for 10 years in order to eval uate
earl ier LE predictions for n i t rate, acetate, and polyester fi l m supports. The
data from these tests, reported by Aclelstein, 4 are i mportant because they
can be s u perimposed onto the i nitial Arrhenius plots, which were based on
h igher temperatures (70°C and above ) . These resu l ts provided a pre l i m i n ary
answer to the question of whether the earlier LE predictions were rea l istic.
In fact, the data obtained to elate at 50°C do not conflict with the previous
LE pred ictions in any way, giving them added credence. Data published in
the 1 Pf Storage Guide for Acetate Film are consistent with the latest long­
term agi ng i nvestigation, which provides new gro u n ds for lo ng-term fi l m
storage recommendations a n d u nderscores t h e benefit o f cold storage t o fi l m
chemical stabili ty.
To study the benefits to CTA fi l m base stabi l i ty of mi c roenvironments
created by addi n g acid scavengers (silica gel and molecular sieves) to sealed
enclosures, i nc ubation temperatures as low as 35°C were used. The method
i nvolved preclegracling the CTA fi l m by incubating it for a s hort time at 90°C
prior to incubation at 35°C. This approach was based on earl ier research ,
which h a d demonstrated ( 1 ) that film acidity level i s t h e best i n d icator o f
CTA fi l m decay a n d ( 2 ) that, beyond an acidity level o f 0.5 m L 0. 1 N a O H per
Part V P H O T O G R A P H I C N E G A T I V E S

gram of fil m , the rate of deterioration progresses at an ever faster pace. That
acidity level characterizes the a u tocatalytic point of acetate base chemical
decay. Figu re 1 [not reproduced here] illustrates the relationship between
fi l m free acid ity and time. lt also reflects the evolving condition of the fil m .
Any increase in fi l m acid content reflects the advance o f CTA fi l m base chem­
ical degradation. As i l l u strated in Figure 1 , the rate of decay is slower before
the autocatalytic point than it is after that critical point is reached. Th is
behavior was the basis for predegrading the fil m samples p rior to incubation
at moderate ly accelerated condition s . The condition of newly p rocessed CTA
fi l m was thermally al tered at 90°C u ntil the film acidity reached the autocat­
alytic point. The newly processed fi l m was in i tially moisture conditioned to
2 1 °C, 50% RH and then was enc losed i nside two sealed a l u m i n u m -foil bags
prior to the fi rst incubation a t 90° C . Th is approach was successfully u sed to
i nvestigate the effective ness of adsorbents (sil ica gel and molec u l ar sieves),
fil m enclosures, and moisture preconditioning to low RH i n controlling ace­
tate fil m base degradation . The method prod uced telling results at 35°C and
reduced the required i n c u bation length to less than two years. 2 3 F u rther data
were obta i ned at 2 1 ° C , using the same methodology. 23

Natural Aging of Collections

S u rveying media col lections may be the best way to quantify the effects of
environ ment on fil m stab il ity. I n recent years, survey tec h n iques for acetate
base collections have been significantly improved by the use of acid detec­
tors such as A- D Strips. 24 Such tools can identif·y materials in various states
of deterioration, but they also can p rovide a general view of the state of pres­
ervation of large collections, on the basis of which efficient p reservation
strategies can be determined. I t is recognized that knowing the condition of
a collection is a necessary step i n u nderstanding the envi ronmenta l needs of
that collection. By definition, condition survey res u l ts reflect how fast ace­
tate collections are naturally decaying. The attention given recently-si nce
d i agnostic tools such as A-D S trips have becomes avail a ble-to assessing
the state of preservation of collections on acetate fi l m base has provided
strong evidence that most holdings are in part actively decayin g if they have
been kept in an in appropriate environment for several decades. This si tua­
tion is consistent with predictions based on accelerated-aging data, which
suggest that 40-year-old acetate materials may now be at the a utocatalytic
point o f acetate degradation if t hey have been stored at room conditions
( 2 1 °C, 50% R H ) . Accelerated-aging data a lso suggest that collections stored
at colder temperatu res are in better condition than those stored in warmer
temperatures. U n fortu n ately, pre-existi ng, and often c urrent, storage cli­
m ate conditions are guesses at best, and they a re rarely ful ly documented .

4 10
 Reading 47 BIGOUHDAN

Anecdotal evidence from the field, only partia l ly documented, suggests

that colder temperatures postpone further acetate base chemica l decay. I n
reaction t o these uncertainties, I P I has been monitoring the condition of a
series of acetate-base fi l m rolls kept at both room and s ubfreezin g storage
temperatures.

N atural Aging Study

Expe1·inient

A series of fourteen 400 ft. 35 m m color motion picture prin t rol l s on CTA
s upport were preincubated i n order to i nitiate the vinegar syndrome. The
fi l m was first moisture conditioned to 21°C, 50% RH and then e nclosed i n
two heat sealed aluminum-fo i l bags. I t was t h e n preinc ubated at 90°C for
long e nough to produce an acidity level n ear the autocatalytic poi n t of ace­
tate base decay. Using the water-leaching determi nation m ethod, 2 5 the ini ­
tial ac idity level for each 400 ft. fi l m rol l was determin e d by titration. E ach
fil m rol l was placed i n s ide e ither a metal can or a vented polypropylene can.
E ight samples were stored inside a frost-free freezer (average temperature:
-r6°C ). S ix samples were kept at room conditions ( 2 1 ° C, 50%-55% R I-I ) .

Results

Effect of Storage Temperature

The acidity of each roll was meas u red after 5 years of storage, after 6.5
years of storage, and again after 1 0 years and 3 months of storage. Each rol l
was tested i n three locations (10, 200, and 390 ft . from the encl of the rol l ) .
The va lues listed in Tabl e 1 [ n o t reproduced here] are average acidities based
on these three measu rements. Aii of the acidity measurements were made
u s i ng the same method. 1 9 F igures 2-4 [ not reproduced here] report the ini­
tial acid i ty leve ls and i ll ustrate the acid i ty changes observed after 5, 6.5, and
I O years and 3 months, respectively.
No s igni ficant change i n fil m free acidity was detected i n the samples
kept i n frozen storage. The variations observed in the resu lts reflect only the
variabili ty of the determination method. By contrast, all fi l m rol l s kept at
2 1 °C , 50%-55% RH displayed major acid i ty i ncreases. After just 5 years, the
acid ity levels had i ncreased by a factor of 2 or 3. Data obtai n ed after 6.5 years
of storage at room conditions i nd icated that the deterioration had progressed
fu rther at an even faster rate. After more than IO years of storage at 2 1 ° C , the
fi l m aci dity was foun d to be 9-1 3 t imes greater than the initial acidity levels.
These resu lts a re strong evidence of the i mpact of temperature on CTA fi l m
base stability. Table 2 [not reproduced here] underscores t h e real benefit of
P art V P H O T O G R A P H I C N E G A T I V E S

frozen storage i n postponing Fu rther chemical degradation of acetate m ate­

rials. Furthermore, these empirical resu l ts are consistent with predictions
based on accelerated-aging data for degradin g acetate fil m base publ ished
i n the IP/ Storage G uide for Acetate Film, i . e . , that film acidity at the a uto­
catalytic poin t ( i .e., 0.5 mL 0. 1 NaO H per gram of fi l m ) would double after
5 years of storage at 2 1 °C, 50% R H .

Effect o f F i l m Enclosures

S ince no signi ficant acidity change was detected i n frozen storage,

only the data obtained at room temperature were of i nterest for assessing the
i mpact of enclosure design on CTA fi l m base stab i l i ty. F igure 5 [not repro­
d uced here] i l l ustrates the fi lm acidity i ncrease over time for each test sam­
ple stored at 21°C. Films stored i n metal cans and vented plastic cans al ike
displayed drastic acid ity changes. F i l ms in both types of containers decayed
rapidly at room cond itions and displayed no significant condition cha nge i n
frozen storage after more than 1 0 years. These data i ndicate that the type of
enclosure p l ays only a marginal role in controlling vinegar syndrome, con­
firming fin d ings from earlier researc h . 1 7

Practical Significance

This study is of great practical i mporta nce because i t shows that actively
degrading fil m s can be successfu lly stabi lized in frozen storage wh i le await­
ing dupl ication or reformatting. These data demonstrate that acetate fil ms
t h at have started to decay w i ll be i n an adva nced state of decay after only a
few years of storage at room temperature, and w i l l l i kely be damaged. Th is is
a strong argument for u si ng cold storage temperatures for the benefit of a l l
fi l m materials. Th e data al so show t h a t materials t h a t have started to degrade
can be stab i lized for many decades. The sta b i l i ty of materials showing no
signs of chemical decay wi l l be optim ized and those materials wi l l last for
h undreds of years. As stated above, the type of enclosure p lays no signifi­
cant role in preventing vinegar syndrome. Providing cold storage is the best
option for protecting vulnerable photographic fi l m from chemical decay.

Effect of Cyc l i ng Environments on CTA F i l m B ase Stab i l i ty

Changing Temperature and R J-1

Every collection is exposed t o temperature and R H changes t o a greater o r

lesser extent. A poorly control led storage c l i mate i s n o t t h e sole cause of
temperature and RH A uctuations. Even materials stored i n a well-control led

412
 Reading 47 B I G O U R D A N

storage space can ell.']Jerience enviro nmental changes due to equipment fai l ­
ures or transitions i n and o u t of storage. ( I n fact, t h e colder t h e collection
storage is, and therefore the better for chemical stabi lity, the more extreme
the transition to room conditions is for the fil m . ) Th is raises two questions:
( 1 ) To what extent are macroenvi ronmental changes transmitted to the
m ic roenvi ronments surrou nding the collection materials within their enclo­
sures, u l t imately causing changes i n the materials themselves? and ( 2 ) How
can the long-term effect of changing e nvironments on the rate of chemical
decay be predicted? I P I has addressed the first q uestion by developing data
on thermal and moisture equi libration for a variety of situations. Some of
the data have been reported. 2 6 I P I has addressed the second question both
by developing predictive models for acetate fi l m base ' and color dye 2 decay
and by creating the t ime-weighted preservation i n dex (T\VPI ) , a calculation
model that quanti fies the i mpact of changing e nvironments o n chemical
stability.27 All of these developments are based on the knowledge that tem­
perature and moisture content govern the chemical degradation of organic
materials according to recognized thermodynamic principles.
Few studies have looked at the i mpact of cycling environments on the
rate of chemical decay. S hahani28 pioneered this type of i nvestigation by
exposi ng paper to cycling RH at constant temperature. Res u l ts led to the
conclusion that cycling R H has the potential for i ncreasing chemical decay.
Thi s earlier i nvestigation seemed to i ndicate that cyc l i ng environments
cause decay mechanisms that cannot be explai ned by commonly recognized
thermodynamic principles. The study data showed that at 90°C paper decays
faster u nder cycling R H than at the steady u pper limit of the given h u mid­
ity cycle. H ofenk de G raaff condu cted several accelerated-aging experiments
i mplementing both cycling RH and cycl ing temperature in order to study
the discoloration of paper materials.29 Resu lts suggested that cycling tem­
peratu re at constant RH could cause d i scoloration (i.e., yel lowing). These
paper test res u l ts prompted a re-eva l uation of paper and photographic fi l m
behavior. I t was judged i mportan t t o determine i f changing temperature and
RH conditions are inherently detrimental to the stab i l i ty of archived materi­
als. Toward that encl, the q uestion of whether changing envi ro nments cause
extra chemical decay i n paper and CTA fi l m base was addressed. The behav­
ior of several papers and CTA fi l m base was studied; the paper results have
been reportecl .30 Data obtained on CTA photograph ic fil m base are discussed
in the fol lowing sections.
Although the stabi l i ty of CTA fi l m base had been extensively studied at
constant temperature/RH conditions, the effect of cycling cond i tions on fi l m
base stability h a d not been i nvestigated . The present study was conducted
primarily to i nvestigate ( 1 ) the effect of cycling RH at constant temperature
and (2) the effect of cycli ng temperature at constant moi sture conten t . A
P a rt V P H O T O G R A P H I C N E G A T I V E S

t h i rd approach explori ng the effect of an i ncreasing number of temperature

cycles was conducted by i mplementing t h ree d i fferent cycl e times within the
same i ncubation period.

Experimental and Results

Samples

The material tested was processed 35 m m motion picture fi l m on CTA

fi l m base. [ n order to conduct the i n vestigation at the lowest possible tem­
perature, the film was thermally preclegracled prior to incubation. Several
solid 1 000 ft. film rolls were first moisture preconditioned to 2 r °C, 50% R H
an d then p laced i n sealed bags a n d pre incubatecl a t 90°C. After preincuba­
tion, the 1 000 ft. ro lls were broken clown i nto several series of 100 ft. rolls, a l l
w i t h s i m i lar acid content. Free acidity l evel s were determined b y u s i n g the
water-leaching method. 15

Effect of Cyc l ing RH at Constant Temperature

Th ree series of predegracled roo ft. rolls were i nc ubated i n this portion
of the study. Arch ival cardboard boxes were selected for the study because,
being porous, t hey wou l d provide opt i m u m moisture equi li bration between
the fi l m material and the cycling environment. Three h u mi d i ty conditions
were se lected : steady 55% R H , steady 70% R H , and cyc l i ng between 40% and
70% R H with a 2-week cycling t i me [ . . . ] .
The 55% R H level corresponds to the m i d ra nge of the 40%-70% R H
cycles, a n d t h e 70% R H level corresponds t o t h e upper l i m i t o f t h e cycle.
Incubation temperature was set at 35°C, based on moisture equi l ibration
data i ndicat i ng that 90% equilibration can be reached after 5 clays of condi­
tion i n g at that temperature. 3 1 One week each at the upper and lower l im i ts
of the R H cycle resulted i n a significant change in fil m moisture content
during the cycle. The fi l m 's degradation rate was determined by moni toring
its free acidity over time. Results were ana lyzed by compari ng the rates of
acidity i ncrease obtained under the three h u m id ity conditions.
The com parison i s i l l u strated in F igure 7 [ not reproduced here ] , which
shows the acid content in the fi l m versus i ncubation time un der the three
R H conditions. I ncubations were conducted for al most 2 years. Each data
poi n t corresponds to one sample p u l l and reflects the free acidity of an i ndi­
vidual rol l , as measu red at three locations along the length of the rol l ( i .e .,
1 0, 50, and 9 0 ft. from t h e en cl ).
As expected, the h ighest rate of decay was observed at the h i gh est
steady h u m i d ity condition (70% R H , the upper l imi t of the R H cycl e profile).
 Reading 47 B I G O U H D A N

Th is confirms t hat h igh water content i n acetate fi l m base has a detrimen­

tal effect on the fil m's stab i l i ty. Films incubated at a steady 55% HH and a t
cycling h u m i d ity between 4 0 % and 70% R H (2-week cycle time) degraded at
slower rates. A sl ightly fas ter rate of decay was seen under the cycling R H
conditions than at steady 55% R H (the m idrange of the H I-I cyc le) as s hown
by the rise in acidity in the cycled film after 500 clays of incubation. Changes
in film acid content were small throughout the entire incubation period, and
t herefore the results were variable. This eJ1.'Periment did not show that the
decay rate u nder cycling RH conditions was greater than at the u pper l i m i t
of t h e Ii 1-l cycle profile.

Effect of Cyc l i ng Temperatu re at Constant Moisture Content

Three series of preincubated 1 00 ft. roll s were moisture preconditioned

to 2 1 °C, 50% H J-I and enclosed i n sealed metal cans prior to incubation at
three temperature conditions: steady 35°C, steady 50°C, and daily cycling
between 20 and 50°C . [ . . . J Because of the small free space i n the sealed
cans and the resu l ti ng small moisture absorption capacity of the air com­
pared to the total water content i n the fi l m , the i ncubations essentially were
conducted at constant fi l m moisture content. The short 1 -day cycle was cho­
sen based on previous demonstrations that thermal equ i l i bration i s much
faster than moisture equilibratio n . Full temperature equ i l i bration occurred
within two hours for a 100 ft . rol l of 35 mm fi l m enclosed in a metal can . 2 7
Film samples were incubated for variou s periods up to al most 2 years
at 35° C . For each temperature condition, the rate of decay was determined
by mon itoring the free acidity of the fil m , using the approach described i n
the previous ell.'Periment. F igure 9 [ not reproduced here] i l l ustrates t h e acid
content in the film versus incubation time u nder the three temperature con­
ditions stud ied.
As expected, the h ighest rate of decay was observed at the h ighest
steady temperature condition (so°C, the upper l i m i t of the temperature cycle
profi le studied). Th is is i l l ustrated i n F igu re 9 by the fast acidity i ncrease at
steady 50°C compared to the smaller acidity changes observed a t steady 35°C
and at temperatures cycling between 35 and 50°C . The rate of decay un der
cycling temperatures was faster than that at the steady midrange tempera­
ture but slower than that at the u pper l i m i t of the cycle.

Effect of the N u mber of Temperature Cycles

The study was extended to i n c l u de assessment of the i m pact of the fre­

quency of temperature cycles wit h i n a given period on the decay rate of CTA
fi l m base. F i l m samples were ell.'Posed to several temperature cycles. Three

415
P art V P 1-1 0 T 0 G B A P II I C N E C 1\ T I V E S

series of predegraded c oo ft. fi lm rol l s were moisture conditioned to 2 1 °C, 50%

H I-I , enclosed in sealed metal cans, and then i n c u bated for 6 months under
tem peratures cycling between 20 and 50°C . Three cycle times were used: 1
day, 1 week, and 3 months. After 6 months, the effects of 1 80 1 -day cycles, 24
1 -week cycles, and two 3-month cycles were compared with respect to their
impact on CTA fi l m base stability at constant moisture content. F igure 1 0
[not reproduced here] reports no sign ificant differences among the rates of
acid generation caused by the three experimental conditions. These data do
not su pport the assu mption that i ncreasi ng the frequency of temperature
cycl ing m ight cause extra chemical decay i n CTA fi l m base.

Discussion

The res ults of the ex'Periments compari ng the effects of cyc l i ng temperature
and RH and the effects of steady temperatu re/RI-I do not s u pport the i dea
that environmental A u ctuations cause extra chemical decay. F i l m samples
d id not decay faster u n der cycling conditions than at the steady h igh l i m i t
of t h e cycle. O n t h e contrary, t h e rate of decay under hum idity that cycled
between 40% and 70% HH was slower than at s teady 70% H I-I , the upper
l i m i t of the h u mi di ty cycle. The same behavior was observed i n the study of
tem perature cyc ling. The rate of decay meas u red under temperature cycling
between 20 and 50°C was slower than that measured at steady 50°C, the
u pper l i m i t of the temperature cycle.
I t should be noted that i n the R I-I-cycling i nvestigation the relatively
long time requ i red for the fi l m to reach moisture equilibrium m i t igated the
effect of changing R I-I . H owever, this situation occ urs i n real life as wel l .
Due t o t h e rapid thermal eq u i l i bration o f t h e fi l m , the effect o f tempera­
ture changes was m i tigated to a lesser extent during the temperature cycling
experi ment. Despite these u ncertainties, i t can be concluded, based on these
two sets of data, that neither cyc l i ng H l-1 nor cycli n g temperature appeared
to be i n herently detrimental to CTA fil m base stab i l i ty.
These data do not inva l idate the principle that forms the basis
of pred iction models l i ke TWP I . The fact that the rate of fi l m decay was
fas ter u nder cycling temperature than at steady 35°C, the midrange tem­
perature of the cycle, supports the principle that the worst condition has
a greater i m pact than the best condition in determi ni ng overal l fi l m base
stability. In that regard, the TWP I model i s consistent with the behavior
observed i n this study.
I nvestigation of the effect of cycling temperature with cycl e times of
1 clay, 1 week, and 3 months indicated that decay rate is u naffected by the
number of cyc les within a given period of time. This suggests that the rate of
 Reading 47 B I G O U B D A N

decay is dependent only on the total amount of t i m e spent at each tempera­

ture of the cyc le. I ncubating the fi l m samples through two, 24, and 1 80 tem­
peratu re cycles between 20 and 50°C over a period of 6 months produced no
noticeable differences in the rates of degradation; free acid ity i ncreased at
the same rate for a l l t h ree sample series. The total time spent at 20 and 50°C
was considered to be essential ly the same for all three series. Therefore, we
can conclude that the time spent at each temperature is the determi n i ng
factor of the rate of decay. Th i s observation rei n forces the va l i dity of TWPI
model , which i s based on this p re m i se.

Conc l u s ions

The data presented m this paper reaffirm the importance of environ­

mental conditions in preserving p hotographic fi l m . Data obtai ned u nder
n atural -agi ng conditions on CTA-base p hotographic fi l m are consistent
with earlier predictions based u pon accelerated-aging studies. These l at­
est data underscore the effectiveness of cold-temperature storage for sta­
b i l izing CTA fi lm that has already started to decay and for optimizing fil m
base stability overa ll. The second objective of this paper was to i nvestigate
the possibil ity that temperat ure and h u m idity tra nsitions might cause extra
chem ical decay in CTA fi l m supports. With i n the fra mework of this s tudy,
the rates of decay observed under cycling R H and cycling temperature offer
no evi dence that transitions from one R H to another or From one tempera­
ture to another cause a new mechanism of deterioration or accelerate deg­
radation more than would be expected by current thermodynamic mode l s.
These data va l idate t h e TvV P I model , wi t h wh i ch t he changing conditions
in real-life storage enviro n ments can be analyzed to reach an overal l esti­
mate of the chemical decay rate in collections. Further, t he data rei nforce
the potential value of TWP ! in i n forming s torage decisions through the
assessment of curre n t s ituations or in s i mulating n ew storage spaces with­
out neglecti ng unexpected chemical degradation caused by temperature and
R H transitions.

Aclmowl edgments

Data reported in this paper were developed through the support of the D ivi­
sion of Preservation and Access of the National E ndowment for the H u man­
ities ( N E I-1 ) and the Andrew Mellon Foundation. The study of the effect of
cycling e nviro n ments on acetate film stability was part of a 3-year research
project condu cted under grants from N E B and The I n st itute of Museum
and Library Services.

417
Part V P l-I O T O G R A P H I C N E G .<\ T I V E S

References

1 J . M . Reil ly, IP/ St.orage Cu.idefor Acetate Fi.Im ( I mage Permanence I nstitute,
Rochester I nstitute of Technology, Rochester, NY, 1 993).
2 J. M. R e i lly, Storage Guide for Co/01· Photographic Materials ( U niversity of the
State of New York, New York State Library, Albany, NY, 1 998).
3 P. Z. Adelstei n , IP/ Media Storage Quiel< Reference ( I mage Permanence
I nstitute, Rochester I nstitute of Technology, Rochester, NY, 2004).
4 P. Z. Adelstein , J. M. Reilly, and F . G . E m m i n gs, "Stability of' photographi c
fi l m : Part VI-Long-term aging studies," SMPTE J . 1 1 1 , 1 36-143 (2002).
J. R . H i l l and C. G. Weber, " S tabi lity of motion picture films as determi n ed by
accelerated aging," SM PTE J . 27, 677-690 ( 1936).
6 S. Arrhenius, " U ber die Reaktionsgeschwi n d i gkei t beider I nversion von
Rohrzucker <lurch Sauren," Z. Phys. Chem. 4, 226-248 ( 1 889).
7 P. Z. Adelstein, C . L. Graham, and L. E . West, "Preservation of motion­
picture color fi l ms having permanent value," S M PTE ) . 79, 1 0 1 1 - I 0 1 8 ( 1970).
8 P. Z. Adelstein, J. M. Reilly, D. W. N i s h i m u ra, and C. J. Erbland, "Stabil i ty of
cellulose ester base photograp h i c fil m : Part IV-Behavior of nitrate base fil m , "
SMPTE }. 104, 359-369 ( 1995) .
9 P. Z. Adelstei n , "Optim izing n itrate fil m storage," Preserve Then Show (Danish
Film I nstitute, Copenhagen, 2000, 52-66).
10 A. T. Ram and J . L. McCrea, "Stability of processed cellu lose ester
photographic films," SM PTE ]. 97, 474-483 ( 1 988).
11 A. T. Ram, S. M asaryk-Morris, D. Kopper!, and R. VJ. Bauer, " S i m ulated aging
of processed cellulose triacetate motion picture fil ms," ) . J.,,·1agi.ng Sci. Technol.
36, 2 1-28 ( 1992).
12 P. Z. Adelstein , J . M . Reilly, D. v\I. N i s h i m u ra , and C. J . Erbland, "Stab i l i ty of
cellulose ester base photographic fi l m : Part I - Laboratory testing procedu res,"
SMPTE J . IOI, 336-346 ( 1992).
13 P. Z. Adelstein, ] . i\!I . Hei lly, D. W. Nishimura, and C . .J . Erbland, "Stab i l i ty
of cellulose ester base photographic film: Part I I I - M easurement of' film
degradation," SM PTE J . 1 04, 28 1-29 1 ( 1995) .
14 P. Z. Adelste i n , ] . \
i !1 . Heil ly, D. \II/. N i s h im u ra, and C. J . Erbland, "Stabi l i ty
of cell u lose ester base photographic film: Part I I -Practical storage
considerations," S M PTE J . 1 0 1 , 347-353 ( 1 992).
15 P. Z. Adelstei n , J. M. Heil ly, D. W. N i sh i m u ra, C. J. Erbland, and J .-L.
B igourdan, "Stab i l ity of cellu lose ester base p hotographic fil m : Part \I-Recent
fin d ings," SMPTE J . 1 0 4 , 439-447 ( 1 995).
16 P. Z. Adelstein and J. L. McCrea, "Sta b il i ty of processed polyester base
photographic films, " ] . Appl. Phot.ogr. Eng. 7, 1 60-1 67 ( 198 1 ) .
17 M . Edge, i\11 . M ohammadian, i\!I . Hayes, and N . S . Allen, "Aspects o f polyester
degradation: Motion picture fi l m and videotape materials , " ] . Imaging Sci .
Teclmol . 36, 1 3-20 ( 1 992).
18 H . J . Tui te, " I mage stability i n color photography," J . Appl. Phot.ogr. Eng. 5,
200-207 ( 1979).
19 B. Lavedrine, C. Trannois, and E. F lieder, " E tude experimentale de la stabi l ite
clans l'obscurite de d ix films c i n cmatographigues couleurs," Studies i n
Conservation 3 1 , 1 71 - 1 74 ( 1986).
20 J. M . Reilly, "Accelerated aging tests," Research Techniques in Phot.ographic
Conservation ( Danish Film I nstitute, Copenhagen, 1995) 77-84, 1 996.
 Reading 47 B I G O U H D A N

21 ISO 1 8924-2000, lu1aging Materials-Test. Method for A rrhenim-type

Pred-ict ions ( I nternational Organization for Standardization, Geneva,
Switzerland, 2000),
22 J . - L. B i gourdan, P. Z. Adelstei n , and J . M . R e i l ly, " Use of m icroenvironments
for t he preservation of cel l ulose triacetate photographic fil m , " ] . lmaging Sci,
Teclmol. 42, 1 55-1 62 ( 1 998) ,
23 J .-L. Bigourdan and J . M . Rei l ly, "Effectiveness of storage conditions in
controlling the vi negar syndrome: Preservation strategies for acetate base
motion-picture f i l m col lections," Proc. ] TS , (2000), pp. 14-3 4 .
24 www.i magepermanenceinstitute.org/sub_pages/8page9.htm
25 P. Z. Adelstein , J . M . Rei l ly, D. W. lishi m u ra, and C. J. Erbland, "Sta b i l i ty
of cellu lose ester base photographic film: Part III-Measurement of film
degradation," S M PTE J 104 , 28 1-291 ( 1995),
26 J .-L. B igourdan, P. Z. Adelstein , and J . NI . R e i lly, "Moisture a n d temperature
equ i li bration: Behavior and practical signi ficance i n photograph i c film
preservation," Proc. A HSAG 1 54-164 ( 1997).
27 J. M. R e i l ly, D. \A/, N i s h i m ura, and E. Zin n , New Tools for Preservation :
Assessing Long-Term Environmental Effects on Library and A rchives Collec t ions
(The Commission on Preservation and Access, \Vashi ngton, DC, 1 995).
28 C . S hahani, F. Henge m i h le, and N. Weberg, "The effect of variations i n
relative hu m i dity o n the accelerated aging of paper, H istoric Texti l e and Paper
Materials I I ," ACS Symposiurn Series, Vol . 4 w, edited by. S . Zeronian and
1- L Needles (American Chemical Society, Was h i ngton, DC, 1 989), pp. 63-80.
29 J. Hofenk de G raafT, " Research i nto the cause of browning of paper mou nted
i n mats," Contribut.ions of t he Cen t ral Hesearcli Laborat.ory to the Field of
Conservation and Hestomtion, Central Research Laboratory for Objects of Art
and Science, Amsterdam, Netherlands ( 1 994), pp. 2 1-42,
30 J . - L. B igourdan and J . M . Reilly, "Effects of Auctuating environments on paper
materials-Sta b i li ty and practical sign i ficance for preservat i o n , " Proc. A HSAG
1 80-192 (2002),
31 J .- L. B i gourdan and J. M . R e i l ly, " E nvironment and enclosures i n fil m
preservation," Final Report t o t he Office of Preservation, National E ndowment
for the H u ma n i t ies, Grant No. P S 20802-94 (Sept. 1 5, 1997).
 P A R T V I

The Preservation of
Color Photography

Color p hotography presents a un ique challenge in the field of photograph

conservation in that m u ch of the color p hotograph ic material s that exist
today are in herently u nstable at room temperature. When c h romogenic
color photography became the dominant p hotographic med i u m in the i96os,
concerns arose about the preservation of color materials, in both still and
motion picture formats . The stability of b lack-and-whi te materials was con­
s idered wel l p roven, so the widely accepted solution to color preservation
in the 1 960s was the creation of b lack-and-white separation masters . This
was an obvious solution in light of recent color p hotographic h i story-black­
a nd-white separation negatives had been the preferred method of producing
color photograp h s p rior to the commercia lization of chromogenic p hoto­
graphy i n the 1 930s and '40s. H owever, the creation of separations and the
fu ture recombination of these separa tions into a fu l l color image is a time­
consuming process with many potential problems. Our readi ngs begin in the
late 1 960s, as color i mage stabil ity testing procedu res were becoming more
standardized and widely discussed, and continue through the 1 970s, 'Sos, and
'90s . Over these three decades, conservation scientists and other research­
ers developed a n in-depth knowledge of color deterioration mechanisms and
their driving forces. As time progressed, it became increasingly evident that
the primary solution to color preservation was not separations but cold tem­
peratures and lower h u midity. Such a n environment preserves the origin a l
object, rather than only t h e information i t contains v i a copying, a n d i n this
way is sympathetic with the p hilosophy of conservation.

\•Vi lliam Eggleston (American. born 1939). J\llem phis. ca. 1 97 1 . D ye LransFer pri n t , 4 6 X 3 1 c m ( 1 8 1/s X
1 2.Y1 <> in.). Gift of Caldecot C h ubb. Los Angeles, J. Paul Ccuy Museum, 98.x�1.232.2
© £ggleslo11 Artist,ic Tr11st
 R e a d i n g 48

D AV I D c . H U B B E L L , R O B E RT G .
M c K I N N EY, A N D L LOYD E . WEST

M ethods for Testing I mage

S tability of Color Photographic
Products ( 1 967)

In this reading David H ubbell, R obert Mc Kinney, and Lloyd West describe
a variety of light and t hermal stability tests as practiced in the Photographic
Technology Division of the Eastman Kodah Company in 1 967. T11eir primary
cancan was accelerated test methods suitable for t he testing of Kodah color
11hotographic materials and their stated objective was "to determine the com­
parative or absolute stability of the products under act ual conditions of use . . .
by the custmner. " To this end, each of their test wiet hods is an accelerated
analogue to smne real-life condition. For exmnple, t:he authors com11are 100°F,
90% R f-1 thermal testing to tropical lzeeping conditions, and they use 50,000
foot:candles to test the stability of color slides in a project or. The first color
image stability standard, ANS I PI-I 1.42-1969, "Method for com11a ring the color
stabilities of photographs, " was based largely on t he ·worh of Hubbell, McKin­
ney, and \Vest. Kodah's resea rch in the area of c ustomer heeping conditions
has continued to t h e 11resent day and provides valuable data in optimizing dye
stability in color photographic materials.

Introduction

I m age stability testing is schematically i l l ustrated in the image fading vs. age
of material plot shown i n Figure 1 [not reproduced here] . The dyes in color

DAVID C. H U B B E L L , HoBEHT G . M c KINNEY, and LLOYD E. WEST, " M e t hods For Testing
I mage Stability of' Color Photographic Products,'' Pho1ographic Science and Engineering
1 1 , no. 5 ( September-October 1 96 7 ), 295-305. H eprinted by perm ission of I S &T: The Soci­
ety for I 111aging Science and Technology, sole copyright owners of Photographic Science
and Engineering.

422
 Reading 48 1-I U B B E L L , M C KINN EY, AND \:V E S T

p hotographic products w il l , i n time, change or fade and may reach a point

when the material i s n o longer acceptable for the use i ntended.
We have been investigating methods for testing the stability of dye
i mages i n our laboratory for the past several years. We have repeatedly made
changes and will u n doubtedly continue to do so as we fi n d methods that are
more u seful in predicting the life of the p hotographic images.
These methods are presented as a starting point from which the manu­
facturers, processors, and customers may b u ild better tests. Certa i n ly new
uses of p hotographic products will req uire revisions in the tests or perhaps
req u i re radically different tests . The manufacturer, processor, and customer
would benefit by knowin g how long a given product "'ril l remain p hotographi­
cally acceptable i n actual use.
The U . S .A. S tandards Institute Sectional Committee P H 1 on Pho­
tographic Films, Plates, and Papers and Commi ttee PH4 on P hotographic
Processing h ave discussed the need for test methods. The Committees have
considered the feasibility of writing standard test methods.
A primary objective of accelerated stability testing of processed film or
paper is to determin e the comparative or absolute stability of the products
u n der actual conditions of use. The test procedu res and conditions must be
rigidly controlled to allow a test to be reproducible from day to day, month to
month, or year to year.
A second objective is to have the tests short enough and obtainable
at low enough cost to be practical. Most tests can be s hortened by
acceleration-that is by h igher temperature, h u m idity, or light inte nsity.
H owever, any acceleration over c ustomer usage runs the risk of the result
not correlating with the most c ustomers' intended usage of the product.
The accelerated test conditions and test times proposed here are reason­
ably short, yet show good correlation with the mild conditions u sed by most
cu stomers. They show i n hours, days, or weeks the c hanges in a product nor­
mally experienced by the customer after weeks, months, or years. The resu l ts
from mild test conditions i n our laboratory are compared periodically with
those from accelerated tests. The test times have been selected such that
some p roducts show measu rable changes. The times and conditions should
be reviewed as c ustomer u sage changes and as new or improved products
come onto the market. Some prod ucts that are manufactured today may not
be manufactured for very many years without b eing drastically altered or
even discontinued. H owever, there may still be valu e in knowing the stability
of some products even though their manufacture is discontinued.
The slight color and density of film base L1Sual ly change a negligible
amount compared with the changes in the e m ulsion, with time. There are
some cases of significant increases in density of film base that tend to offset
or hide the fading of one or more dyes. Strictly speaking, one is interested in
P a rt V I T H E P H E S E H VAT I O N O F C O L O H P H O T O G H A P H Y

the net cha nge of emu lsion plu s base. Th us cha nges should be reported as
i mage stability rather than dye stability.
These test conditions do not measure such properties as brittleness,
tackiness, scratc h resistance, or resistance to mold or fu ngus a ttack. The test
conditions apply only to processed film or paper and not to raw stock.

General Nature of Tests

The required test chart exposures are made on the material to be tested,
then the film or paper is processed, densities are measured, the material
is given the appropriate image stability test treat ments, and densities are
remeasu red to show any change that has occu rred .
The acceptability of color p hotographs depends upon the scene, the
viewing conditions, the use to which the product wi l l be put, the i ndivid ual
doing the _j udgi ng, and other factors. Th is paper describes image stability test
methods on ly.
Man u facturers of color p hotographic papers and fi l m s u sually attach
a disclai mer to their products indicating that the dyes in processed products
may, in time, change.
No two dyes are equ a l ly stable u nder a ll conditions. This u nequal sta­
bility among the three dyes in color p roducts is especially objectionable in a
neutral (gray) area of a photographic image.

Preparation of Test Samples

Test chart expos u res are m ade on a noni ntermittent intensity scale ( l b) sen­
sitometer. Six special tablets were designed to make single-layer exposures
of cyan, magenta, and yellow areas as well as neu tral and m i n i m u m density
areas. The construction an d use of t hese tablets are described i n Appendix A
[at the encl of this reading] . A test chart of this type with individu a l neu­
tral and dye patches gives more quantitative i n formation about the image
stability than do actual pictures . H owever, for visual demonstrations actual
pictures may be more mea n in gfu l . \Nith pictures, however, there w i l l usually
be difficulty in selecting a s u itable subject. Differe nces in the original color
balance of pictu re comparisons represen ting different processes, emulsions,
etc. , add additional risk in making eval uations from j u st pict u res.
The sensitometric exposures a re processed in a normal process for the
particular fil m or paper u nder test, u n less a proposed change in processing
chemistry or met hod is the basis for the test.
I n tegral density measu rements are made before and after the dye sta­
bility test. Appropriate s harp cutting red, green, and blue fil ters are u sed
whose transmittance c u rves peak close to the peak absorption regions of the
 R e a d i n g 48 l-I U B B E L L , M C K I N N E Y , A N D \•V E S T

three dyes i n the color product. Densitometer filters used for Kodak prod­
ucts are as fol lows:

1. Color paper products are read with status 0 1 reel, green , and blue
fi l ters.
2. Reversal color film products are read with status N reel, green , and
blue fil ters.
3. Color preprin t fil m p roducts, through which pri nting is clone, are read
with status l\!12 reel, green, and blue pri n t i ng density filters.
4. A heat-absorbing glass and dich roic i nterference filter are a lways used
in optical tandem with each of the densitometer filters referred to
above.

\Vhen more thorough i nvestigation of the h u e shifts, stain , print-out,

etc. , is requ i red, spectrophotometry i s also employed.

Radiant E nergy Test Conditions

The rad iant energy test conditions are those that we believe best simulate
the cu stomers' most common u se of the product. The cho ice of a tungsten
projector for testing 3 5 mm transparency materials, or fl uorescent i l l u m i ­
nation for professional sheet fi l m s , is obvious. T h e choice of t h e type
and i ntensity of energy for testing reflection print materials has been more
difficult. The i ntensity and spectral c haracteristics of rad iant energy from
the sun vary with l atitude, season, t i me of day, and atmospheric conta m ina­
tion. For those reasons, an d the fact that few customers subject products to
d irect s u n l ight, the s u n i s not a satisfactory direct energy sou rce for i mage
stabi l i ty testi ng.
Table 1 [ not reproduced here] specifies the test equ ipment and i n ten­
sity i n footcandles. Thi s table also shows the temperature and relative
h u mi dity at which the u nits are controlled.

3 5 mm Slide Projectors

An image stabi lity test using any particular 35 mm tu ngsten lamp projector
for a given time of projection is, at best, a rough approxi mation of average
c ustomer projection . One customer may project h i s transparencies for only
a few m i nu tes in 1 0 or 20 yrs, whereas a second cu stomer may project his
transparencies several hours each year. The m i ni m u m i mage stability char­
acteristics that would satisfy the first cu stomer wou l d not satisfy the second.
Depending on the lamp rating and optics of the projectors, one cus­
tomer m ight project h is samples in a projector at less than a level of 5000 ft-c
while another c ustomer m ight be subjecting h is samples to over 200,000 ft-c.
Part VI T l- I E P R E S E RVAT I O N O F C O L O R P l-I O T O C R A P l- I Y

Fu rthermore, the i mage fad i ng of some prod ucts va ries considerably with
the sample temperature, which is dependent o n the cooling system of the
p rojector as we l l as on lamp wattage.
Another variable is i n termi ttency of projection . One set of slides may
be projected q u i te frequen tly, but o n ly for 5 to 10 sec/exposu re. Another set
of sl ides, althou gh p rojected i n frequen tly, may be p rojected for an i n terval as
long as several m i n u tes.
Figu re 2 [not reproduced here] i l l ustrates the fading of the cyan dyes
of two 35 mm color products in projectors at two different temperatures.
Product 1 shows the same straight-l i n e cyan dye fad i ng with acc u m ulated
time of projection at eac h of two temperatures of projection. The cyan
dye fad ing of Product 2 i s dependent upon the slide temperatu re. D i ffer­
ent conclusions woul d be d rawn concern ing the relative sta b i l i ty of the two
prod ucts-depending upon the temperature of projection and the acc u m u ­
lated t i m e o f projection.
Sa mples are projected with the l ight striking either the base or the
emu lsion-depending upon normal use of the product.
For radiant energy tests of 35 mm prod ucts, two types of p rojectors
are used. A Kodak Carousel a utomatic s lide projector with a 500-w tungsten
lamp is con nected through a variable au totransformer to maintain the i n ten­
s i ty level at 50,000 ft-c of white light, as measured at 550 mµ. The change
i n spectral energy distribution over the requ i red range of voltages neces­
sary to maintain consta n t lamp i n tensity is small and of no signi ficance i n
i mage fad i n g tests. The attract ive features of this projector a re d u rab i lity and
a cyl i ndrical s l i de magazine that holds up to So slides-35 m m . By p roper
sett ing of a selector switch and pl uggi ng i nto the power through a n e lectri­
cal timer, the machine can be set to i n termi tten tly project the So sl ides for
20 sec at a time until eac h sample has accu mulated the desired total e)qJosu re.
The other type of projector is a specially modified Kodak Master M odel
projector using a con t i n uously circulating 1 6- i n . dru m t hat holds fou r 3 5 m m
o r 1 6 m m strips u p to 1 2 i n . long. Th is al lows u s to test continuous-wedge
control strips without havi ng to chop and mount samples. The i n tensity of
this projector is mainta i ned at 1 00,000 ft-c by a variable a u totransformer.
Both types of projectors are operated by ti mers that stop a test at a predeter­
m i ned t i me . The timer that records the acc u m ul ated test time is also val u ­
a b l e in case o f lamp fai l u re.
The methods of measu ring the light i n tensi ty in the projector gate and
s l ide fi lm temperature in the gate a re discussed in Appendix B [at the encl of
this read i ng] .
The i n te ns i ty of A uorescent i l l u m i nators found in the trade for u se
with color sheet films, and sometimes with 35 m m tra nsparency films, usu­
ally ranges from 200 to 500 ft-c; a few a re as h igh as 1 000 ft-c. ReAection
 Reading 48 J- 1 U B B E L L , M C K I N N E Y , J\ N 0 \V E S T

color prints are frequently ill u m i n ated with fluorescent lamps, the i ntens ity
for normal viewing seldom being higher than 1 50 ft-c.
F igu re 4 [not reprod uced here] shows a fluorescent test u n i t that sub­
jects fi l m samples to 1 500 ft-c . A s i m ilar test u n i t with fewe r lamps is operated
at 500 ft-c for testing paper products. The Deluxe Cool White Fl uorescent
Lamps used in these u n its s i mu late natural daylight. They are commonly
used i n the trade for viewing p hotographic materials. It has been found
that d i ffe rences i n the spectral energy distribution of these lamps made
by different manufactu rers or normal manufacturi ng variations of any one
manufacturer a re not la rge enough to cause sign i ficant differences i n i m age
stability tests.
Opal ized glass (opal coati ng on glass) , diffuse Luc ite, and diffuse
Plexiglas are common diffus i ng materials. They may have different transmit­
tances as shown i n the spectrophotometric curves in F igu re 5 [ not repro­
d uced here] . These diffusers may affect the fad i ng rate of a magenta dye as
shown in F igure 6 [not reproduced here] . \Ne use the diffuse Plexiglas i n the
test u n i ts described here because it most nearly matches the d i ffusers used
i n the trade.
A detai led description of one of the F luorescen t I l l u m i n ator Test U n its
i s fou nd in Appendix C [at the end of this read ing] .
Test ti mes vary for the different products accord i ng to the expected
use by the cu stomer. The products are tested for the times shown in Table 2
[not reprod uced here ] .

Tungsten Fadi ng Unit:

For testi ng F il m to tu ngsten i rradiation, other than that of 35 m m projection,

we use a Tu ngsten Fading U ni t , show n in F igure 7 [not reproduced here ] .
This u n i t s i m ulates 1 6 m m projection, exposure i n printers, a n d tu ngsten
viewers . This u nit, u n li ke an ordinary projector, i l l u m i nates a l arge n u m be r
of samples simu ltaneously.
This u n i t has two 2000-w l a mps, positioned on the same opt ica l axis so
as to give with i n r% equal radiation over the entire 1 0- i n . wide sample plane.
The sample carriage, as i n most of our i nstru mentation, revolves around the
source, i ntegrating any d i fferences i n i n tensity that cou l d result from b lack­
e n i ng of the lamps . A housing arranged i n the form of a du odecagon a ro u nd
the lamps contains 1 2 panels of Vs-in P ittsbu rgh 2043 heat-absorbing glass.
Samples i n the unit are con tinuously receiving 5000 ft-c of energy.
The Tu ngsten Fading Unit, like all the major items of i nstrumentation
for radiant energy testing, has a barrier-layer cell o n the sample plane which
i s connected electrically to a light i ntegrator. The probe is simil ar to that
used for monitoring the projectors except that a Weston hermetically sealed
Part VI TH E P R ES E H V A T I 0 N 0 F C 0 L 0 R P H 0 T 0 G R f\ P I I Y

photoelectric cell is u sed which contains a Vi scor filter marketed by \Veston

El ectrical Instru ment Corp . , Newark, N .J . 07 1 1 2. The equipment rep rod u ces
the segment of the energy distr ib u tion fou nd in the C I E l u m i nosity curve.
The i ntegrator is an Acromag Inc. series 1 20 1 Digital Type E lectrical I ntegra­
tor with a single-stage amplifier, Acromag Model 392.

Xenon-Arc Equipment

One of the curves in Figu re 8 [not reproduced here] shows the relative e nergy
d istribution of daylight. The small vertical line i n d icates where window glass
would cut out the u l traviolet e nergy. The rest of the energy distribution is
a reasonable s i m ulation of the energy that wou ld strike prin ts fra med and
h u n g i n the home.
An early dayl ight test unit was an Atlas Carbon-Arc Fade-Ometer,
where carbons b u rned i n a c losed Pyrex globe. Thi s u n i t has been widely
u sed by the textile i n d u stry, but for our pu rposes gave energy too high in the
u l traviolet regi o n and too low in the visible region to match actual daylight,
also shown in Figure 8 [not reproduced here ] .
A n Atlas Weather-Ometer was tested with "daylight carbons" that
bu rned in air. The light was fi l tered through plate glass. The energy distribu­
tion, Figu re 8 [ n ot reprod uced here ] , shows that i t still did not adequately
match daylight.
The i ntensity level of the natural light stri ki ng color prints in homes,
offices, etc., is usually low and i s fil tered through window glass. Color
pri nts are often several feet from a w indow and seldom receive direct s u n ­
l igh t rays.
Franc Grum, Kodak Research Laboratories, determi ned the energy
d istribution of average northern skylight throu gh window glass. H e and oth­
ers designed a u n i t s i m i lar to that shown in Figu re 9 [not reprodu ced here] .
Th is test unit consists of a 6000-w water-cooled, Osram Xenon XBF lamp
filtered through 4 m m of Pi ttsburgh 2043 heat-absorbi ng glass.
The i l l u m i nance at the sample plane of the xenon-arc test u n i t is con­
tro l led at 500 ft-c to ach ieve moderately accelerated fad ing. F igure 10 [ not
reproduced here] shows the c lose spectrophotometric match between actual
northligh t through window glass and the test unit through P i ttsburgh 2043
heat-absorbi n g glass.
The xenon-arc simu lated northlight test is also used for color sheet
fi l ms to s i m ulate fading cau sed by northlight (daylight) fa l l i ng on trans­
parencies being displayed on viewers. This condition has a lso been of
merit in s i m u lating the fadi n g of negatives which might be l eft u n p rotected
on a table top.
 Reading 48 II U H B E L L , M C K I N N E Y , A N D \V E S T

For special tests where d i rect s u n light through window glass i s to be

simulated, a n Atlas Fade-Ometer with a xenon-arc source i s used. This u n i t
a l s o h a s a 6000-w, water-cooled xenon l a m p . T h e fi l ter housing uses 2 m m
o f Pitts b u rgh 2043 heat-absorbing glass a n d 4 m m o f plate glass. With the
sample plane m u c h c loser to the lamp, the i l l u m i nance at the sample plane
is 5400 ft-c, thus approac hing the i nte nsity of actual s u n l ight.

Combined Radiant Energy and Heat and Humidity

H igh u ncon trolled heat and h u m i di ty d u ring a rad iant energy test might lead
to variable test results.
Figure 1 1 [not reproduced here] shows a modified A m inco " C l imate
Lab," Type P-C, i n which a wide range of heat and h u m i d i ty conditions,
above ambient room conditions, can be selected and maintained. For
these tests, samples were subjected to 750 ft-c of fluorescent e nergy from
a bank of 1 5- i n . fl uorescent lamps m o u n ted on a glass door of the cabinet.
Figure 12 [not reproduced here] shows the effect of a change i n the re la­
tive h u m i d ity when testing two prod ucts to fl uorescent i l l u mination. \!\The n
tested at moderate relative h u mi d i ty ( 50% R H ) , Prod uct B was noted t o have
better magenta dye s ta bi l i ty than Product A, whereas, when tested at h igh
h u mid ity ( 85% R H ) , it showed poorer magenta dye stab i l i ty. Thu s the rel­
ative h u m i d ity of the test condition may affect the comparative stabi l i ties
of the products.

H eat and H u m i d i ty Test Conditions

N o s i ngle accelera ted heat and h u m i d ity test condition can b e expected
to serve for all uses of one given prod uct. The choice of one or more condi­
tions is complicated by the diverse u ses of d i fferent color products. Several
accelerated cond itions have been u sed and abandoned because the res u l ts
Fai led to correlate with those at more moderate conditions. The test cond i ­
tions selected ( l isted i n Table 1 [ n o t reprod uced here) ) are a compromise
but have been shown to be excel lent i n pred icting stabil i ty to certai n actual
storage conditions.
The relative h u mi d i ty of a n oven that does not have forced-air c i rcu la­
tion has been found to be non-un i form. S. Martin s howed that atmospheric
cham bers consisting of air above sat u rated solut ions of ammon i u m n i trate
(65% RH at 20°C) are qu i te variable depend i ng on the load ( test material) i n
t h e chamber.3 The effect i s reduced when t h e atmosphere i s c i rcu lated .
For most products, keepi n g at 1 40° F-70% R H i n a forced-air rec i r­
cu lated oven4 is the best test condition for s i m u lating long term storage.
Part VI T l- I E P H E S E H V AT I O N OF C O L O R P l-I O T O G H A P I-I Y

Resu lts from this unit have shown the best correlation with i mage stabil­
ity p roblems resu lting from process variations such as ineffective washing. 5
The 140°F-70% RH accelerated test has also s hown the best correlation
with i mage stabil ity problems resulting from process changes that c hange
the emulsion p H .6 Emulsion p H i s the measurement of acidity or basicity
of the residual chemicals i n the fi l m or paper after processing. Figure 1 3
[ not reprodu ced here] shows the stabi lity of the three dyes i n a fi l m product
over a range of emu lsion p H values. I t is a general pattern for subtrac­
tive color products with this type of dye system to show primarily poorer
cyan dye stab i l i ty at h igh em ulsion p H and poorer yellow dye stability at low
e mulsion p H .
The J Oo°F-90% R H keeping test i n a forced-air recircu lated oven h as
been a val u able test for simulating "tropical keeping" where h igh h umid­
ity is primarily responsible for l oss in i mage stabi l ity. F igure 14 [not repro­
d uced here] shows a den si ty-log E curve of a negative color fi l m that was
processed with and without the required stabi l izing bath, after 7 days' keep­
ing at 1 00°F-90% RI-I . The large h ue s hift of the u nused colored coupler area
is caused by the h igh h umidity but does not occur significantly if the stabi l iz­
ing bath is u sed properly.
The 1 70° F-dry test condition is especially useful in s howing the tem­
perature sensitivi ty of dyes and also in produ c i ng a c hange of the unused
colored coupler in some products in the green-sensitive layer. This occurs
when there is insufficient stabilization by forma l i n . The pattern of fading i s
often referred t o a s "pink-toe fade" s ince i t i s magenta dye fading mainly i n
t h e toe portion o f the D-log E curve. Figure 1 5 [not reproduced here] shows
the cu rve for a color print fi l m processed with and without the requ ired for­
m a l i n stabi lizing bath after 1 day's keeping at the 1 70°F-dry condition.
Samples of fi l m and paper stored in an air-con ditioned office at 75°F-
40% RI-I are examined annually and compared with the test results from
accelerated heat and h um idity tests.

Reporti n g Data

Whenever the a i m of a test is to compare the quality or acceptabil ity of two

or more materials after dye stability test conditions, modified trilinear paper
is u sed as shown in Figure 16 [not reproduced here ] . The points p lotted
along the yellow-bl ue axis, the magenta-green axis, and the cyan-red axis
show peak absorption changes, or dye fading of s ingle-layer exposures a t a
density of 1 .0. The points plotted i n the remaining areas show the hue shift
of the neutra l and c lear areas. The amount of h ue shift acceptable i n a neu­
tral area i s considera bly l ess than a n equ ivalent dens ity c hange of the peak
 Reading 48 1-1 U B B E L L , J\11 C K I N N E Y , A i\1 D \\I E S T

absorption region of cyan, magenta, or yellow color patches . For example, a

20% yellow dye loss i n a gray i mage area , such as a road, is more d isturbing
to the viewer than a 20% yellow dye loss i n an i mage of a lemon.
To s how clearly how the tri l inear p lotting works, the hypot hetical data
of two products used on F i gu re 1 6 [not reproduced hereJ are shown i n Table 3
[not reproduced here ] . The data may also be plotted as shown i n the bar
chart on Figu re 17 [ not reproduced here] .
The data s how Product 1 to have poorer s tab i l i ty of a l l three dyes to this
accelerated test. Despi te a density loss, however, the neutral patch retains
its neutral balance. Product 2 on the other hand shows more stable dyes but
a s ign i ficant hue s hift i n the reel d i rection.
Depending on the p u rpose of a speci fic i m age sta b i l i ty st udy, other
m ethods of reporti ng data are used. vVhen a d i rect comparison of image sta­
b i l i ty behavior against t i me i s needed, a n u m ber of plots l i ke those shown
in Figu re 6 [not reproduced here] may be s u fficient. Sometimes the fading
comparisons of sensitometric process control s trips are sufficient when one
i s partic u larly i nterested in speed and gamma changes in a neutral sca le.

Summary

For the past several years we have been establishing contro l led, reproduc­
i ble, accelerated radi a n t energy and heat and h u mi di ty test conditions. They
attempt to s i m u late i n hours , days, or weeks i mage stability effects normally
ex'Perienced by the c ustomer after months and years.
There are many p itfall s in trying to match the nebulous "norma l " use
by the customer. The m a i n risk i s i n trying to average a wide d ivergence of
u ses of a product i n to one normal or average condition and then compound­
i n g it by accelerating the laboratory test condition. Despite this, resu l ts of
these tests have s hown good correlation with m ilder tests and actual use of
the products.
The i mage stability tests amount to making special sensitometric ex'}JO­
s u res on the test material, obtai n i n g representative processi ng, measuring
densities, s u bjecting samples to the appropriate test cond itions, remeasuring
the densities, and reporti ng the density changes that have occu rred.
The i mage stability test conditions used depend on the prod ucts to be
tested. The radiant energy test conditions most frequently used are 35 m m
s lide projection (50,000 o r 1 00,000 ft-c), Tungsten Fading U n i t ( 5000 ft-c),
Fluorescent Viewers ( 1 500 and 500 ft-c), an d xenon -arc s i m u lated average
northern skylight (500 ft-c) . The heat and hu m i d i ty test conditions most fre­
quently used are 140°F'-70% R H , 1 00°F-90% R H , and 1 70°F'-clry, a l l in con­
tro l led forced-a ir c irculated ovens.

431
Part VI T ll E P H E S E H V ,\ T I O N OF C O L O R P ll O T O G R A P H Y

Acknowledgme nts

The authors wish to express their appreciation to G . W. Larso n , 0. E .

M il ler, \1\1. 1-1 . Bebb, A. ] . S a n t , E . 1-1 . Spra gue, J . H . Kerr, K. E . Dodds, and
A. ] . Leta, Photograph i c Technology Division, Eastman Kodak Co., as well as
F. G rum, E . A. Geier, W. E . VVh ite, and T. Wigh tman of the Research Labo­
ratories of the Eastman Kodak Co. for the engineering and design of the
i mage stab i l i ty testing equipment.

Appendix A-Sensitometric Tablets

Each of fo ur sensi tometric tables- 1 , 2, 4, and 5 of Ta ble Ar [not reprod uced

here]-has a wedge neutral scale and each has three ,,,, edge color pa tches.
Two other tab lets, 3 and 6, have u n i form densities. Selection is made in
accordance with the type of p roduct. Ta ble A2 [ not reprodu ced here] shows
the color filters used i n these tablets for selectively eX']JOSi n g the cya n ,
magenta, a n d yellow layers o f most color p hotographic fi l m s or papers.
Tablets 1 , 2, 4 , and 5 were designed spec ifically to take advantage of
automatic desitometry, i nc l u d i ng d igital ized data for tran sparency prod ucts.
Ta blets 3 and 6 are u sed i f the material is to be cut and mounted as
3 5 mm s l ides for tes t i ng. These tablets are used to produce u n i form color

patc hes of 1 .0 density and u niform neu tra l patc hes of densi ties 1 .0, 0.5, and
m i n i m u m dens ity. Trial ex'j)osures are made u n t i l the densities, ::t: 1 0% , are
obtained.
'vVhen dea l i ng with a n u n fa m i l iar prod uct, trial ex'jJOSu res are neces­
sary to obta i n correct speed and balance. Adjusting for the neu tral scale bal­
ance can be made with Kodak Color Compensating F i l ters between the light
sou rce of the sensitometer and the tablet.

Appendix B-Measurement and C on tro l

of the In tens it)' of I l lumination

The intens ity is monitored by a convenient selen i u m barrier-laye r cell in ten­

sity probe shown i n Figu re B 1 [not reproduced here ] . Over the cell is a Kodak
\1\lratten Filter No. 1 02 for converting the energy to foot-candles, a neutral
niter to reduce the l ight i n tensity on the cell, a white plastic d i ffuser, and a
metal screen attenuator to further reduce the light i n tensi ty sufficiently to
keep the m icroa m meter o n scale. The probe is con nected to a m ic roam meter
with its scale cali brated to i n d icate 50,000 or 1 00,000 ft-c i l l u m i nation.
The Kodak Wratten F i lter No. 1 02 modi fies the light energy mea­
su red to that fo u nd i n the C I E l u m i nosity curve, peaking at about 550 mµ.
Reporting the en ergy level from such a na rrow sample of the total energy

-f 32
 Reading 48 11 U B B E L L , l\ I C K I NNEY , A N 0 \V E S T

d istri bution does not l i m i t our information about total energy. S i nce energy
d istri bution is held essentially constant in our equipment, a si mple multipli­
cation of the e nergy u nder the d istri bution curve by the probe reading gives
the total energy.

Cont rol of Eniulsion. Tempera t u re

A thermocouple of N o . 36 B rown and S harpe ga uge wire is cemented to the

ce nter of the emulsion side of a sl ide with a u niform neutral dens ity of 1 .0 or
greater. The slide i s p laced i n the projector with the thermocouple away from
the l ight source. The slide is inserted in the projector after the projector has
operated for at least 1 5 min to thoroughly warm up. The sl ide temperature
measurement is read after the thermocouple slide has been i n the projector
gate for 5 m i n . The thermocouple is connected to a potentiometer.

Appendix C-Fluorescent I l l umi nator Test U n i ts

The lamps a re conventional 40-w, 48- i n . , Deluxe Cool White Fluorescent

lamps. Construction details for the 1 500 ft-c u ni t are shown i n Figu re C 1
[ not reprod uced here ] . The lamp separation i s 1 Y4 i n . on the center and the
d istance from the center of the lamp to the in side of the d i ffuser is 1 Y2 in. It
was necessary to put a m asking fra me arou n d the perimeter of the test u n i t
s o that t h e i ntensity over t h e sample plane d i d n o t vary over ::!::: 2 1/i % . The
mask covers at least 7 in. of the glass portion at the ends of the lamps as
well as at least half the d i ameter of the bottom and top lamps. There is an
air space of 1/4 i n . between the outside of the diffuser and the sample plane
to keep the sample plane temperature low. The sample plane consists of
grooved s l i ts i nto which 1 1 -i n . long card board sample holders a re placed. The
sample area ava i lable is determined by the n u m ber of lamps used i n the unit.
Better effic iency of sample space after masking could be had by using 8-ft
lamps.
The diffuser material used is Ys-in. thick white transl ucent Rohm
and Haas Plexiglas \i\12447. The inside of the unit ( back, sides, and i n side
of masking frame) i s pai nted with a Flat white paint contain i ng titani u m
dioxide pigment.
The i n tensity at the sample plane of the test u n i t at normal line voltage
is greater than 1 500 ft-c. A variable a u totransformer al lows voltage adj ust­
ments to compensate for aging of the lamps and maintain a constant i nten­
sity level at the sample plane. The change in spectral energy d istribution
over the req u i red range of vol tages is small and is of no sign i fica nce i n dye
fading tests. An intensity probe and microammeter similar to that used with
the projectors monitors the l ight intensity.

4 33
Part VI T H E P H E S E H V A T I O N O F C O L O H P H O T O G H A P H Y

The 500 ft-c u n i t differs form the 1 500 ft-c u n i t mainly i n lamp sepa­
ration and d istance of lamps from the sample plane. Other specifications
are the same.

N otes

Description available from the Eastman Kodak Co. upon request. Tech nical
bulletin PC- 3 , September, 1965.
2 Described by 0. E . M i l ler and S . A. Powers, " I mproved Pri nting Density
Filters For Densitometry of Color Preprint Materials," J. SMPTE , 72: 695-700
( 1 963).
3 S . Mart i n , ) . Sci. Inslr111n., 29: 370 ( 1 962).
4 Aminco Constant Te111peralurc- H u 111 idity Catalog No. 560.
C. W. Larson, D . C. H u bbel l , and L. E. Wes t , ) . SM PTE, 7 1 : 495 ( 1 962).
6 P . Horowitz and W. R . Weller, ) . SMPTE , 67: 401 ( 1 958).

434
 R e a d i n g 49

PETER Z. ADELSTEIN, C . LOREN

G RA H A M , A N D L L OY D E . W E ST

Preservation of Motion-Picture
C olor Films Having Permanent
Value ( 1 970)

1 970 was a lan.dmarh year in i·mage stability research.. For the first time
researchers at Kodah published the results of an accelerated stability test using
the Arrhen ius equation., which has since become the foundation. for the pres­
en1ation. of color materials. This m.eth.od made it possible to predict the fading
behavior of a dye over very long periods and at nearly any temperature. Conse­
quently, -it was possible for the first time to calculate with some accuracy h.ow
long a color dye would last at; 40 °F, 30°F, or even 20°F, and the results were
renia rlzable. Color dyes could last for thousands of years at freezing ten-ipera­
tures. Adelstein (see also Readings 1 9 and 44) recalls that th.ere was a debate
at l<odah at the time about whether or not to in.elude the cold storage recom­
mendation. Tt was clearly the right thing to do, and the best ·m ethod for long­
term preservation, but they were concerned that no one would do it. It was
expensive, and th.ere was no precedent for it. Of course, they did include the
cold storage recommendation. This led-as the story goes-to the establish­
m.enf; of one of the first subzero storage facilities for the preservation of color
photographs at the John F. Kennedy Library, after ]Ff( Library arclii11ist Alan
Goodrich read the article and in.eluded a cold storage faci lity in th.e planning
of th.e library's construction..

PETEB z. ADELSTEIN, C. LOREN C IV\HAM, and LLOYD E . \�IEsT, " P reservation o r Motion­
Picture Color F i l 111s H aving Per111anent Value," Journal of the SMPTE 79 ( N ove111ber
1 970): 1 0 1 1 - 1 0 1 8 . This paper was a con t ribution su b111i t ted to S M PTE o n Augu st 3 1 , 1 970,
by P. Z. Adel stei n , C . Loren Graham, and L. E. West, Photographic Tech nology Div. East­

man Kodak Co. © 1 970 by the Society ol· M otion Picture and Te]e,�sion Engineers I nc .
Reprinted b y per111ission.

435
P a rt V I T H E P H E S E H V AT I O N or C O L O H P l-I O T O G H A P H Y

I n troduction

The need for a rc h ival preservation of i n formation stored on motion-picture

fi l m has been recognized for many years, both by commercial enterprises
and govern mental agencies. 1 An example is the i ndefin ite keepi n g req u ired
for film of historical events, copies of documents h aving perma nent com­
mercial i n terest, and records of space exploration. A considerable body of
l i terature has been concerned with the chemical i n s tabil ity of the cell ul ose
n i trate film support that was used i n the early clays of the motion-picture
industry.2•3·4·5·6 These fi l m s cannot be preserved i ndefinitely. H owever, the
i ntrod uction of acetate fil m su pports gave a h igh degree of chemical stabi lity
to motion-pictu re records. 7·8
Equally as i mportan t as the sta b i l i ty of the fi l m support is the perma­
nence of the photograph ic image. The excellent keeping characteristics of
the si lve r i mage in b lack-and-wh ite photograph i c fi l m s are easily confirmed
by the rem arkable condition of i m ages on photograph ic glass plates that are
over 100 years old. H owever, the widespread u se of color i n recen t years has
caused concern about i mage permanence because of dye facl i ng.3 In many
fields, black-and-white films are less common than they were a decade ago,
while the quant ity of color films that are of archival i n terest has i ncreased at
a tremendous rate. Thi s s u bject has been discussed by Gale and vVil liams9
and more recen tly by Calhou n . 1 0 General storage req u i rements are outlined
in several other publications. 1 1 · 1 2· 1 3 H u bbell, et al., 1 4 have described the test
equ ipment and procedu res requ i red to evaluate the image stability of color
fi lms. The widely accepted proced u re of storing silver- i mage separation mas­
ter posit ives or master negatives 1 5 has been given recen t attention .
This paper attempts to discuss long-term preservation of color fi l m s
i n somewhat more detail t h a n previ ous articles. I t i s d i rected towards those
who have large quantities of color motion-pictu re fi l m to store for indefinite
ti mes and where their arch ival value j ustifies extra storage preca u tions. I t is
not primarily i n tended for those i n terested i n normal commercial storage.

Definition of Archival

The American National Standards Instit ute has iss ued spec i fications o n
both archival fi l m a n d arc h ival storage conditions. Arch ival record fi l m s a re
records which have permanent va lue. For the u l t i mate in fi l m preservation,
a rc h ival fi lms must be stored u nder arc hival conditions.
The AN standard on arc hi.val photographic film 1 6 specifies a black-and­
white s i lver i mage on a cel l u lose ester support, and a simi lar specification for
fi l m on polyester support is now u nder consideratio n . However, at the pres­
ent time color i mages are not considered by AN S I to be arc h ival materials.
 Reading 49 J\ O E L S T E I N , G B A H A M , A N D W E S T

Although many color fil ms manufactured over 2 5 years ago are still in excel­
lent cond ition, some color films have shown dye fad ing, particularly i f stored
u nder non-recommended conditions.
There is also an AN standard on archival storage conditions which
applies to m icrofilms, 1 7 and a second AN standard is i n draft form on the
recommended storage conditions for al l other fi l ms, including color fil ms. I n
both these documents, arch ival storage conditions are considered those suit­
able for the storage of f i l m having permanent val u e. While such con ditions
will not necessarily res u l t i n all color fi l ms remaining in usable condition for
h u ndreds of years, there is no doubt that recommended storage conditions
wil l prolong their u seful l i fe tremendously.

S upport M aterials

The stability of c urren t safety f i l m supports is sufficiently h igh so that there

is no longer cause for concern. H owever, this is not the case with cel l u lose
n itrate base. Although the manufacture of nitrate stock was discontinued in
the U nited States i n 1 9 5 1 , considerable quantities of n itrate base film still
remain in storage. M otion-picture color films on n itrate support should be
dupl icated onto safety fi l m as rapidly as possible. While ideal storage condi­
tions can retard the degradation of n itrate films, their useful l ife is l i m ited.
Such materials do not have adequate keeping behavior for records of va l ue.
I t is recognized that some storage of n itrate base film may be requ i red u ntil
either fu nds or fac i l i ties are available for duplication. Storage recommenda­
tions for nitrate fil m s have been d isc ussed previously.5 • 1 0• 1 1
The introduction of the cel l u lose acetate type of fi l m support marked
a major advance in the permanence properties of photographic fil ms. Such
Films genera l ly conform to the ANSI requ i rements for safety fi 1 m 1 8 and i n the
case of black-an d-whi te i mages, for archival record fil m . 1 6
More recently p hotographic films have been i n troduced on polyes­
ter base, 19 particu l arly for applications where high strength or exceptional
d i mensional stab i l i ty is required. \Vhile polyester support is not yet used
for theater prints in the m otion-picture entertainment in d ustry, it will be
encou ntered in special applications such as h igh-speed photography, contin­
uous loop projection, or w here very thin films are desired as i n m i litary and
space photography. Chemical stabi l ity tests on this type of base20 h ave shown
excellent behavior. I t has been predicted that the permanence of polyester
base fi l m is somewhat superior to that of fil m on cellulose triacetate base. I t
i s for this reason that work i s u nder way i n ANSI t o prepare a spec i fication
for arch ival fi l m on polyester support .
A characteristic of the film support associated with permanence
i s the di mensional behavior of the film. In earlier days of motion-picture

437
 Part VI T ll E P H E S E RV AT I O N O F C O L O H P l-I O T O G H A P l- I Y

TIT]-·o ··-,- -1 11 I 1 1 1-- ---r--1 TTl I TII --,----r

-ri rrrl
- I

. ( . "'�-) - --j1
1.0

o-e 0.8
Safety film
., (circa 1 940)
"'

� 0.6
p�''"° Mm '"OC""'
-�
.:::
Figure 1 (f)
0.4
Aging shrinkage oF processed

I
motion-picture film, after keeping Negative film
(triacetate base) _
0.2

·--L-���[
�� �����l���I
at 78'F, 60% H I -I ; controlled
tests on strips Freely exposed to
__ LLUilJJJ
I
c irculat ing air. 0
0.1 10 100
T i m e , years

fil m , a high aging shrinkage caused problems i n projection performance2 1

and in physical d istortion .22 I n addition, color records that are stored as
s i lver separations m u st be repri nted i n register to reconstitute the color
image. Differences i n aging shrin kage between the separations may cause
registration problems and for this reason all separations must be stored alike.
L i kewise a h igh-agin g shrinkage could cause prin t i ng difficu lties. I f a nega­
tive has shrinkage i n excess of 0'4%, the resulting prin ts made on a continu­
ous pri nter wil l show l ac k of sharpness and u nsteadiness when projected.
Fortunately, the shrinkage characteristics of most c u rrent 3 5 m m motion­
picture fi l m supports h ave i mproved to the poi n t where this is no longer of
major concern.23
Figure 1 s hows l o ng-ti me aging shrinkage of several types of Kodak
fi lms. The current motion-picture positive film has a maxi m u m aging shrink­
age of o.6%. Thi s is also true for some 1 6m m color reversal fi l m . The maxi­
mum size change is reached only after at least twenty years of storage, a n d
this fi l m is considerably m ore di mensionally stable than the early safety fi l m
w h i c h shrank approxi mately 1 .0% within five years .24 The maxi m u m shrink­
age of Kodak motion-picture negative fi l m o n triacetate base is only about
0.2% .25 All Eastman fi l ms that a re recom mended for use as silver separa­
tion masters in a su bsequent section of this paper are on the triacetate sup­
port u sed for negative film to insure excel lent registration upon printing. The
remarkable d i mensional stabil ity of polyester base film i s well recognized and
is very evident i n Figu re 1 .

Storage of B lack-and-White Separation Masters

Al though there is no substitute for preserving the original color films which
themselves are h istorical or i mportan t records, the most accepted procedure
 Reading 49 A D E L S TE I N , C BA II A M , A N D \V E S ·1·

for the preservation of color fi l m records of permanent value has been the
preparation and storage of three silver i m age separations. Not only are prop­
erly prepared silver images inhe rently more stable than most dye i mages, but
the many years of experience with them have provided the archivist with the
assurance that a usable record can survive beyond most anticipated req u i re­
ments. Silver i m ages are relatively stable and properly processed b lack-and­
white fi lms contain very few free che micals that m ight degrade the i mage.
However, balanced agai nst the i mp roved sta bil ity of si lver i m ages is the fact
that any system using pri nting of separation negatives or positives may pres­
ent printing problems. Good commercial laboratories have developed the
necessary ski l l , b u t even i n the best l aboratories some degradation of i m age
quality cannot be avoided in a 111 u l t iple-stage printing system.
This quality consi deration, coupled with the added cost of making
and using separations, will encourage attempts to store the color origi nal.
Color fil 111s a re i n a state of rapid evol ution, with i m proved types being i n tro­
d uced every year. Such i111prove ments often provide i nc reased dye stabil ity
as well as other advantages. However, none of the i 111provements now envi­
sioned is of such 111agn itude as to make dye i mages equal to s ilver images i n
keepi ng quality.

A. Printing

The preparation of separations s u i table for long-term storage requires care

in printing. All separations should be printed onto the same fil m s tock. The
cost and complexity of prin ting wil l be depe ndent on the q u al i ty req u i re-
111ents of the reconstituted i 111age. If o n ly a record is requ i red, such as 111 ight
be the case i n some doc u 111entaries or n ewsreels, and color quality and i 111age
steadi ness are only of secondary i mportance, some shortcuts are someti111es
taken. l f good quality is req u i red in the reconstituted i 111age, more elaborate
procedu res are necessary. The separation pos itive shou Id be made on a regis­
tration printer to ass u re exact registration of the three i111ages. Usual ly, best
definition and registration can be ach ieved on a step registration printer.
'vVhen the image is reconstituted by printing onto in termediate film, step
registration is aga i n advisable for exact image registration and as a compen­
sation for any differences in di111ensions t hat may have occurred.
Step registration printing is costly beca use it is slow and exacting.
Sometimes for economy, continuous con tact printing is substituted in one of
the steps. This may result i n inferior i mage registration and steadi ness and
the qua lity m ay be u naccepta ble. Most continuous contact printers do not
provide exact registration. In addition, any differences from the opti 111 u 111
differential i n p itch between the raw stock and the printing origin a l (or mas-

439
P a rt VI T H E P H E S E H V J\ T I O N O F C O L O H l' H O T O G H A P l-I Y

ter) can be co111pensated for only by s l i ppage between the two fil111s. Thi s can
cause detectable b l u rring or displace111ent in parts of the i 111age.
The pictu re infor111ation 111ust be properly placed on the sensito111et­
ric scale of the fi l 111 . In addition, the contrasts of the three i 111ages 111 ust be
carefu lly controlled to provide properly 111atched colors in all parts of the
scale of the reconstituted color i 111ages. The only reliable check for good
separation qual ity is, u n fortunately, the reco nstitution of the i111age as a
color dupl icate negative and t he s ubsequent pri nting as a color posit ive. Thi s
checking i s often 0 111 itted for economic reasons but should not be if a good­
quality color i 111age is expected to be reconstituted after archival storage.

B. Processing

Of para111ou n t i 111portance 1 11 the processing of b lack-and-white fil 111s for

arch ival storage is the residual t hiosulfate con tent. Residual thiosu lfate
reacts with metal l i c si lver grains during storage and causes d iscoloration
and fad i ng of the i mage . M aximum thios u l fate levels are specified i n the
AN standard for arch iva l film, 1 6 using test procedures given in the appropri­
ate AN standard 111ethod25 and in the l iterature.26·27 Residual t h ios u l fate i s
i n fl uenced by t h e nature of t h e fixi ng bath and c a n b e lowered by adequate
washi ng. The t hiosulfate ion is retai ned 111ore tenaciously i n an acid harden­
i ng bath than in a non-hardening fixin g bath. H owever, the latter may cause
abrasion problems should the gelatin layer become soft. R esidual si lver com­
pounds should also be kept to a l ow level. This can be ach ieved if film is
fixed in a fresh fixer and thoroughly washed so that i t meets the archival
th iosulfate l i m i ts Y'
The processing of the three separations also must be carefully con­
trolled to assure properly matched contrasts and to mainta i n d i 111ensional
precision. Special care must be taken i n the d ryin g stage of a process in
order that a l l three will h ave the same degree of shrinkage. With 111odern
low-shrinkage films, this can be ach ieved.

C. S torage Conditions

To preserve the black-and-white i m ages of the separation masters, a storage

temperature of 70° F or less and a relative h u 111 i d i ty of approximately 50% i s
reco111 mended . The latter is close t o the relative h u 111i cl i ty m a i n ta i ned b y most
printing l a boratories and therefore m i n i 111izes d i 111ensiona l c hange of the sep­
arations with consequent registration proble111s. A more detai led d iscussion
of the ram i fications of re lative h u m i d i ty control and 111oisture cond ition i ng is
given in the Appen d ix [at the encl of this read i ng] . The storage conditions of
the three separa t ions should be identical to maintain equal dimensions.
 Read i ng 49 t\ IJ E L s T E I N l G H A J-1 ;\ i\I ' t\ N IJ \V E s T

(A) 35rrm Separation Positives

5235 ,. �
�
5254 5235 5235 � 5358

�
5235 -

(B) 16nm Reversal Separation Positives

7276
8

7252 7276 7252 � 7387

R
7272 J
7271-7 7385

(C) 16nm Separation Negatives

"" �
�:: : �
7J 7234
7385 ·� 7387

7271 � 7385

(D) 16rrm Separation Negatives

""' �
�: : 7
� 7234
"" --'> '"'
Figure 2
Schematic d i agn1m s of' system l'or
production of master separations.

0. Pre71a ration of 3 5 mrn. Separations

The color records of 35mm mot ion-picture color negatives can be preserved
as reel, green and blue separation positives. These are often made d u ri ng the
preparation of a motion picture as a safeguard against possi ble loss or dam­
age of the original negative, and procedures for their preparat ion have been
well esta bl ished. Satisfactory procedu res have been described by Gale and
Kisner28 and area also i nc l u ded i n t he Eastman Kodak Company processi ng
manual .29 Co lor-separation films are not i nexpensive to make and use, how­
ever, and in the case of long-term storage they also acid substantially to the
storage cost by requ iring three t i mes as much space. A common proced ure
begins with the printing of the t h ree separat ion positives t h rough reel, green
and blue fi lters onto a b lack-and-white du plicating fil m , such as East man
Panchromatic Separation F i l m 5235, using a registration pri nter ( F igu re 2A) .

-H '
Part VI T ll E P H E S E H VAT I O N O F C O L O H P ll O T O G H A P ll Y

After storage these could be reconstituted i n to a color duplicate negative

by pri nting with the same tricolor fil ters onto an i n termediate film, such as
Eastman Color I ntermediate Film 5253. The d u pl icate negative can be used
to make pri nts on a pri nt fi l m , such as Eastman Color Print F i l m 5385.

£ . Preparation of 16nmi Separations

The preparation of separations from 1 6m m fi l m s has not had very wide com­
mercial u sage i n the past. H owever, recent improvements i n 16mm color
films seem to be encouragi ng the use of t h is film for the prod uction of more
i m portant pictures. Therefore, it seems reasonable to expect the need for,
and use of, 1 6m m separations to i ncrease. The procedu res for 16mm color
negatives a re the same as with 35mm fi l m . H owever, reversal 1 6m m origi nals
a re more com monplace, and the procedu re is somewhat more complicated.
There can be a choice between three major systems, u s i ng e i ther rever­
sal separation pos itives or separation negatives. These systems have been
described by Schafe r and Zuidema. 1 5
l n the fi rst system ( Figure 2B), separation positives t hrough tricolor
filters can be made on Kodak Plus-X Reversal Film 7276. The color i mage
can be reconstructed by pri n t i ng through the same tricolor fil ters onto
Eastman Ektachrome Commercial F i l m 7252. I f multiple prints are requ i red,
the Ektac h rome Commercial F i l m is u sed as a pri nting master for print­
i ng onto Eastman Reversal Color Print F i l m 7387. When a large n u m ber
of prints is req u i red, a more economical met hod wou ld be to make an
internegative from the E ktachrome printing master using Eastman Color
l n ternegative Film 727 1 followed by pri nti ng onto Eastman Color Print Film
7385 or 738 1 .
I n the second system ( Figure 2c), sepa ration negatives a re made by
printing t hrough tricolor fi l ters onto Eastman F i ne G rain Dupl icating Pan­
chromatic N egative Film 723+ The separation negatives should be pro­
cessed i n a b lack-a nd-white process in which the contrast can be con trolled
by deve loper time. If the separations are of proper matched contrast, a few
release prints can be made through the tricolor filters on Eastman Color
Pri nt Film 7385. When a n u mber of release prints is anticipated, the separa­
tions should be made at lower contrast, so that a 7385 pri n t may be used as a
printing master to prepare reversal prints on 7387 or an internegative on 727 1
film, From which a large n u m ber of prints can be made.
Another system s uitable for a large n u m ber of pri nts, but req u i ri ng one
less pri nting stage, makes u se of Color Reversal I ntermediate F i l m 7249 to
make a color negative from 1 6 m m separati on negatives ( F igure 20). The 7249
negative can be used to make contact prin ts onto 7385.

-1-12
 Reading 49 A D E L S T E I N , C R A l-I A iVI , A N D W E S T

Storage of Color Originals a n d Color Prints

The u se of black-an d-wh i te separations is t he most reliable way known at

the present time to store the photographic i n formation i n a color origi n a l
negative o r color original reversal, but someti mes t h e color original is itself
of h istorical val u e and must be stored, or the expense of making separations
m ust be avoided. When color film m ust be kept for long periods of time i t i s
of u tmost i mportance t h a t storage conditions be c hosen t o m i n i m ize dye fad­
i ng. The storage of color records requires less expense i n the preparation of
the materials s ince separation masters need not be m a de nor does the color
i mage have to be reconstituted after storage. However, this m u st be balanced
agai nst a n i ncreased cost i n obta i n i ng the desi red storage conditions.

A. Processing

Proper process ing i s certainly as i mportant for color films as it is for b lack­
and-white if satisfactory storage is to be obtained. However, deta iled
i n structions can not be given i n this paper because of the d i fferen t proce­
dures required for differen t color fi lms. O n ly generalized precau tions can be
stated.
U ndesirable residual chemicals m ust be removed by proper chemi­
cal treatment and thorough washing in the process. Test m ethods and rec­
om mended upper l im i ts for res idual chemicals i n some fi l m s are reported
by v\/est.30 The fi l m manufacturer's spec i fications for pH and stabilization
m u st be fol lowed carefully. U nder some conditions, too m uch was h i ng to
remove resid u al chemicals can be detrimental to opti m u m dye sta b i l i ty.
Gale and Williams9 h ave d iscussed and i l l ustrated some dye stab i l i ty prob­
lems when these fac tors are neglected . Some analytical tests are helpfu l i n
determ i n i ng whether t h e fi l m has had proper treatment, b u t they cannot be
considered a complete safeguard . There is no s u bstitute for a relia ble pro­
cess ing la boratory.

B. Storage Conditions

One of the most critical properties of concern i n the storage of color fi l m is

the stabil ity of the dyes. Many dyes will decompose slowly with a res u l t i n g
change i n color. I t i s i mportant i n fi lm storage to h ave condi tions t h a t will
delay or prevent any dye degradation. A vital variable i s the relative humidity
of the storage area. There is ample evidence that organ i c dyes have better
stabil ity when in equilibrium with air at low relative h u m id i ty. This is i l l us­
trated i n Figure 3 for a processed color negative film. The shift i n reel dens ity

44 3
 Part VI T l- I E P R E S E R V A T I O N O F C O L O R P l-I O T O G R ;\ P l l Y

+ O.I �---·-
-- ----�

.,
°'
c
0
.c
u
>-
.,
·� 0 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - "'

c c:
0
., .c
'O
u - 0. 1
>.

·;;;
c: Red
I year at 90° F. 0
.,
60 % RH 40 % RH

- 0.1

-0.2 �----�----�
0 20 40 60 ea 0 4 0
Storage relative humid ity, % Time , years

Figure 3 Figure 4
Effect of' relative h u m i di t y on red density s t a b i l i t y or a Effect of rclalivc h u m id i ty upon lhe dye s t a b i l i t y of' a
processed molion-picturc color negative film. Density change processed motion·picture negative film at 70°F. Density cha nge
determined rrom an original n e u t ra l density of 1 .0. dclermincd f'rom a n original n e u t ra l density or 1 .0.

3 .7
20 1 -

� :: � ::rr
fil
l
3
.....
80 -
A
0 g. 3 .3 0

g� 3. 2 � 100
-
.� 3. 1 : 120 �

�-:�� I::��
Vl ISO
h

t::_ __L___ 1
IO
_ __ _
100
_1-..J---1�
I 2
� � � �-� �-
5 10 20 50 IOO 500 1000 10 20 50
Days Years Hours
Time for 10% cyan dye fading T ime

Figure 5 Figure 6
E ffect of' tcmpcrnt u rc on the dye stabi l i ty of processed mntion­ Hate of warm·up of Pdm i n trade packages. C u rves arc
p i c t u rc East m a n Color Negative Film a n d East m a n Color Print F i l m . l'or 40°F t e m pera t u re d i fference. Packages placed
Typical d a t a l'or f i l m s m : rn u fact u rcd between 1963-1967; 40% BH. on edge d u ri ng wcirm·up period.

is lower at the low h u m i d i t ies, regardless of the i ncubation temperatu re. A

simila r effect for the t h ree color densit ies is shown i n Figure 4 a fter longer
ti mes at a more moderate temperature .
These dye stabil ity data were all obtai ned at room temperatures or
h igher. I n formation is not yet avai lable on the i mportance of re lative h u m i d ­
i ty at low te m peratures. S u c h i n fo rmation is d i fficu l t t o obta i n because o f
t h e Jong time periods requ i red before measurable changes a re observed . The
conservat ive approach i n storage is to assume that h igh relat ive h u m id i ties

-+4-f
 Reading 49 A D E L S T E l i\1 , G H A H A M , A N D \,V E S T

are to be avoided, even at low temperatures, although any adverse effects

wo uld be slow. Storage recommendations have su bseq uently been made on
the basis of such an assumption. However, there is a possi b ility that high
h u m id i ties may not be a sign ificant factor if the temperatu re is low enough .
Examples of good keeping of fi l m after long-ti m e agi ng i n a rctic conditions
have been ci ted . I n low-temperature storage, the user must balance the risks
of h igh h u mi d ity against the cost or i nconven ience of h u m i d i ty control.
In addi tion to relative h u m id ity control, temperature control is very
i mportant for dye images. Experi mental work to determ ine the opti m u m stor­
age temperature has made use of a c lassical method of extrapolation. Years
ago, Arrh e n i u s measured chemical rate changes as a fu nction of tempera­
t u re. He fou n d the results fel l in a straight l i n e when p lotting a function of
the temperature against the l ogarit h m of the reaction rate. By extrapolation
he predicted how fast the reactions wou l d take place at lower temperatures.
A simi lar experi ment was performed using processed motion-picture
color negative and color print films, storing them in dark cabinets at a n u m ­
b e r o f elevated temperatures. The relative h u m i d ity was held at 40% i n each
case. The cyan, magenta and yel low color-patch test strips, origi nally at a
density of 1 . 0, were removed from storage period ically to measu re the dye
fad i ng. The time requ i red for objectionable fad i ng was recorded when the
l east stable dye faded 1 0% . In these experi ments the cyan dye was fou n d to
be the least stable to heat. I n Figure 5 the temperature is p lotted in equal
i nc rements as the reciprocal of degrees Kelvi n . For convenience the tem­
perature is also s hown in Fahrenheit. Time for JO% cyan dye fad i ng i s plotted
as a log fu nction. The resu lts fall c lose to a straight l i ne . Extrapolation of the
data, especially as far out as J OO or more years, m ust be made with caution .
I n a practical test the fi l m s might be removed from storage periodically for
viewing, thus being s u bject to l ight fad ing. I n addition, the extrapolations
m ay not hold at relative h umidity values higher than 40%. Nevertheless, the
advan tage of low temperatures is striki ng.
It can be concluded that for optim u m storage, very low temperatures
a n d moderate to l ow relative h um i dities are des i rable. These h u m i dities can
be more economically controlled in a n air-conditioned storage area if the
temperature is above freezing. Therefore, the archivist is faced with several
poss i b i lities.
One approach i s storage at below freezi ng temperatu res, storing the
film in hermetically sealed containers. It is recognized that this approach
may not be practical s ince the writers are not aware that such containers
are read i ly avai lable at this time. A practical alternative i s the com b i n ation
of taped cans and heat-sealed foi l bags, as discussed later in this paper. Th is
method has the advantages of excellent protection for the dyes with easy
availabil ity and low cost of freezer u n i ts . I t has the d i sadvantages that the

445
P a rt V I T H E P H E S E H V AT I O N O F C O L O H P l-I O T O G H A P l l Y

container m ay not remain completely moistu re-proof, the container is cum­

bersome, and the fi l m is not eas i ly accessible.
Another approach is the use of an air-cond itioned storage vau l t or cab­
i net at 35°F with the relat ive hu mid ity controlled between 1 5 and 30%. This
method has the advantage of ready accessi b i l i ty of the fi l m , storage of fi lm i n
regu lar cans, and greater certa in ty of contro l led h u m idity. I t h a s t h e d isad­
vantage that these a i r-co nd itioned u n i ts are more expensive than deep-freeze
u n i ts and that dye stabil ity at 35°F is not as good as at o°F to -10°F.
A less expensive and more conve n i e n t m ethod of fi l m storage is to place
the taped film cans in a freezer at o°F. H owever, as poin ted out previou sly,
there is the risk that a resulting h igh h u midity may cause adverse effects over
a very long time period. For relatively s hort test times, for example, one year,
the dye stabili ties of all prod ucts stored i n heat-sealed metal envelope at o°F
were equal to or better than those for products stored at 75° F-45% R H .
\!\Then fi l m i s removed from a cold-storage area, moisture condensation
will take place if the fi l m is below the clew point of the ambient a i r. M oisture
condensation is a pote ntial problem. This might l ead to fi lm blocking or to
a su bsequent return of the f il m to storage in a h igh-moist u re cond ition. For
this reason film should not; be removed from its contai ner until sufficient
warm-up time has perm itted the fi lm temperature to rise above the clew­
point temperature. The req u i red warm-up time will depend upon the tem­
peratu re differential between the fi l m and the ambient a i r, the clew poi n t of
the latter, and the size and i nsu lation of the film container. The effect of the
l atter i s i l lustrated i n Figu re 6 for a 40°F temperature difference, represent­
i ng the difference between 35°F storage and room conditi ons.

C. Effect of Light

Dyes may fade on exposure to light, and for this reason films for archival
storage should not be projected if it is avoidable, and films which have been
projected should not be selected for s torage i f others are available. The fad­
i n g of the three dyes cl ue to radiant energy may be u n re lated to the compara­
tive fad i ng of the same dyes when stored for long periods of time in the dark.
D i fferent dyes may fade at d i fferent rates, causing a change in color balance.
However, l ight fad i ng is not a problem associated with dead storage si nce
film should be stored i n closed contai ners and not be exposed to rad iant
energy. Light fading may be a problem , however, i n freq uent projection of
motion-pict u re fi lms.
Personnel responsible for maintaining p roper storage conditions for
films may have l i ttle or no control over the projection of the fi l ms. H owever,
good storage is to l i ttle ava i l if the film is not treated properly by the u ser.
The val u e of a motion-picture fi l m , even when stored under ideal condi-
 Reading 49 A D E L S T E I N , G B A H A M , A N D \V E S T

tions, i s i n i ts viewing. The use of h igh-q u al i ty projectors, wel l m a i n ta ined, is

essential to long l i fe.
One use of motion-picture films is to view s ingle frames while the fil m
is stationary i n the projector gate. I f a single frame i s viewed for a n extended
length of time, it w i l l fade more than the adjacent frames, even though the
projector may provide s upplementary cooling. Thus, when the film is aga i n
projected as a motion picture t h e single-frame fading wi l l produce objection­
able effects. Motion-picture fi l m should not be used for si ngle-frame projec­
tion i f it is of permanent val ue.

Storage Materials

All motion-pictu re fil m should be p laced in closed contai ners, the most read­
ily ava ilable being the cans in which the raw fi l m is sold. Care should be
taken with any material placed in the can with the film . The reels, cores, and
paper supplied with the fi l m can generally be considered safe; other m ateri­
als may n ot be. The time and cost of long-term keepi n g tests preclu de exten­
s ive scree n i ng of materials for safety in archival storage.
The degree of sea l i ng of the fi l m cans that is required depends upon
the type of storage condition and the degree of protection desired. Tap­
i ng the fi l m can provide protection agai nst d i rt and dust, and at least some
protection agai nst gaseous contami nants. The tape should be flexible enough
to seal irregularities of the can. H owever, as s hown i n the Append ix [at the
encl of this read ing] , cloth tape is not completely a ir-tight . Moreover, it may
deteriorate with time, with consequent loss of effectiveness. The effect of
the latter can be m i n i m ized by periodic retap ing. Taped cans can be used
in a vau l t where the h u m i di ty is contro lled, but cannot be relied upon to
prevent moisture-exchange. At o°F storage, an approach is to place the
fi l m in a taped can, which i s then heat-sealed i nside a foi l envelope. This
type of package is very c umbersome, but in addition to i mproved moisture­
protection, i t w i l l m i n i m ize the possibility of rusting of the can, which wou ld
eventually destroy the can.

Air Purity

Air purity h as only recently become a real concern to the general population,
but i t has long been recognized as an importan t factor i n material storage.3 1
The atmosphere in many industrial areas contains small amounts of gases
such as s ulfur d ioxide, ozone, hydrogen sulfide, and oxides of n i trogen. These
compounds are i nj u rious to p hotograph i c fi l m and can cause i mage fad ing
and eventual chemical degradation of the e m ul s i o n and support. A va ult
for longtime storage of fi l m should be situated i n locations where the a i r

4 47
Part VI T 1-1 E P H E S E ll V A T I 0 N 0 F C 0 L 0 H P 1-1 0 T 0 G H A P II Y

is clean, or else the a i r supplied to the storage area should be purified . ln

addition to remova l of gaseous i mp u ri ties, this air s upply should be fi ltered
to remove dust and air-borne d i rt . The p resence of dirt in a storage area can
cause serious film-abrasion problems.
I t has been suggested t hat dyes may be more stable i f film is stored i n
a n inert atmosphere. H owever, some color films are more stable i n a i r than
i n n itrogen or argon.
l n addition to d i rt and contaminants fro m the air supply, precautions
must be taken to i n s u re that i mp urities are not produced from any other
materials stored i n the fi l m-storage area. Of particular concern is the pres­
ence of cellu lose n itrate base fi l m . Any gaseous degradation products of cel­
l u lose n itrate will cause dye fad i ng and ulti mately b ase degradation of safety
fi l m stored nearby.32 Cellu lose n itrate base fi l m should not be stored in the
same area with any safety films.

Recommendations

Out of the foregoing d i scussion a n u m ber of p rocedures for long term stor­
age of color m otion-picture fi l m on safety base can be formu lated . Unfortu­
nately, t hose provi d i ng the greatest assurance are also the least convenient
and more costly. The fo llowi ng recommendations are l is ted i n the probable
order of decreasing assurance, and in the order of i ncreasing conven ience.
Assurance of perfect keepi ng quality cannot be attai ned by any system, and
i f efforts and costs a re cut the assurance is l i kely to decrease. It will be up
to the i ndividual arc h ivist to decide which is the most practical to meet h is
requ i rements.
When m u l tiple copies of very valuable material are avai lable, it wou ld
seem essential to store more than one copy and use more than one system
of storage.

( 1) Mahe Blach-ancl-VVh ite Separation Masters

This method is the u l t i m ate for longtime preservation of color photograph ic

records although the cost of making b lack-and-white separations is h igh. Al l
three separations m ust be stored a l i ke and should be at a temperature of
70°F or Jess and a relative h u m i d ity of approxi mately 50%. This proced u re i s
n o t applicable i f t h e objective i s t o preserve t h e original record i tself.

(2) Store i n Hermetically Sealed Containers at o°F or Beluw

This is the best possible condition when the color fi l m itse lf must be
preserved. Films should be moisture cond i tioned to a re lative h u m idity
 R e a d i n g 49 A D E L S T E I N , G B A l-I A M , A N D \•V E S T

between 1 5 and 30% prior to placing i n hermetically sealed contai ners. H ow­
ever, hermetically sealed contai ners for motion-picture fi l m are not read i ly
available at present.

(3 ) Store in. Vault at 3 5°F, 1 5 to 30% Rf-I

This method provides excellent keep i ng conditions. It also prO\rides con­

ve nience in fi l m packagin g and Film retrieval si nce film can be stored in
u n tapped cans. However, the physical i nstal lation is expensive.

(4) Store in. Ta1?ed Cans a t o°F or Below

Film should be moisture-cond itioned as described in recom mendation (2)

and placed in cans sealed with several laps of a moisture-resistant tape. This
procedure is simple an d allows the u se of low-cost freezer u nits. H owever,
moisture leakage w ill occur in time. For improved protection, fi l m should be
reconditioned and repackaged after a period of years. Better moisture resis­
tance is obtai ned if the taped cans are heat-sealed i n foi l envelopes. How­
ever, this additional film packagi ng is time consuming and the package is
c u m bersome. These wou ld be problems when the fil m quantities are large.
The use of film in u n taped cans offers no hu midity contro l . There is the
risk that h igh hu m idities may eventually have adverse effects, even at low
temperatures.

Appendix

Effe cts of T-/u·inidity

The need for relative h u m id i ty control for archival storage was poi nted out
i n the body of this paper. ln add ition to the specific recommendations which
were made, there are several additional ram i fications to h u m id i ty control
which should be presented .
This subject i s i mporta nt si nce it is the relative h u m id ity of the ambi­
ent air with which the film is i n equ i l i bri u m (not the abso l u te h u m i dity)
which determi nes the quantity of moisture held. The relationship between
re lative h u m i d i ty and the moisture content of the components of a motion­
picture fi l m on cellulose triacetate base i s shown in F igure 7. These c u rves
show that the emulsion layer takes up considerably more water per u n i t
weight than the triacetate fi l m base.
l t is important to recognize that the dependence of the moisture con­
tent of fi l m on relative h um id i ty of the ambient air is not greatly i n f l uenced
by temperature. Figu re 8 shows the percentage of water in a motion-picture

4 49
 Part VI T H E P R E S E H V A T I O N O F C O L O H P H O T O G R A P l- I Y

-- 1 20 F
70 F I
-C
- · - ·-
45 F I.
6/ .
�4 /
3
Emulsion only
c
Q)
c
0
u
� 2
:::>
Ui
"6
2

20 40 60 80 0 20 40 60 80
o ���� �����

Relative humidit y , % Relative humidit y , %

figure 7 figure 8
Moisture content of typical motion-picture rtlm Effect of temperature on moisture content oF typical
on cellu lose triacetate base a t 70°F. motion-picture ne gative film on cel lulose Lriacetate base.

negative fi l m over the temperature range of 45 to 120°F. Even though the

abso l u te h u mi d i ty of air at 1 20°F - 50% R H is considerably greater than at
45°F - 50% RH, the water content of films i n equi l ibri u m with these condi­
tions is essen t i ally the same. Evidence has also been obtai ned showing that
this relat ionship is also true a t temperatures below freezing.
For this reason, moisture content is expressed i n terms of the relative
h umidity of air with which the fi l m is in equ i li b r iu m , rather than as percent
water content. The former u nits are much more meani ngful to those con­
cerned with storage conditions.

A. High Humidity Limits

The upper l i m i t of 30% R H was recom mended for color i mages because of
hydrolys is of dyes at h igh rel ative h u m i d ities. I n addition, h u m i d i ti es above
60% RH a re favorable for fu ngus growth wi th a resulting color change and
eventually complete destruction of the photograph i c image. Elevated h u m i d ­
i ties may also cause the convolutions of the fi l m i n t h e roll t o s t i c k together
or block. The recommendation for the upper l i m i t for black-and-wh i te sepa­
rations, where dye stabil ity is not a factor, was 50% R H .

450
 Reading 49 A D E L S T E I N , G R t\ l l A i\1 , A N D \V E S T

Cl)
"'
.c .30
u
.s
"'
.06 �------..
:E
E
;;:: .20
.c
u
:;;:
3'
0
"O
c:
"'
.c
.10
0
�

�
"'
Lower l i mit

E of test
0
i5
·a
0 20 40 60 BO 0 20 40 60 80
Relative humidity , % Rela tive humidity, %

Figure 9 Figure 10
Effect of relative h u m idity on curl of 1 6m 111 motion-picL urc color film. E lfecL or relative h u m idity on brittleness of motion-picture color film.

B. Low H u m idity Liniits

A lower l i m it of 1 5% R H was recom mended because of poss ible problems

with either curl or b rittleness.
An example of the i ncrease in fi l m curl of a 1 6 m m motion-picture color
print film with decreasing h u m i d ity is i l l ustrated in F igure 9. H igh film c u rl
may give p roblems i n projection performance a n d cause handling diffic u l­
ties. Th is can be overcome by cond itioning the fi l m to a h igher h u m i d i ty
prior to u se s i nce the i nc rease i n fi l m c u rl at low h u midi ties is revers ible.
The most serious problem associated with storage of motion-pict u re fi l m i n a
h ighly c u rled configuration is the occu rrence of "spokiness . "22 A spoky rol l is
a fi l m roll i n the shape of a polygon rather than round when viewed from the
side. It occ u rs because a h ighly c u rled fi lm resists being bent i n the length
d i rection when i t is already bent i n the width direction. This causes the film
to behave l i ke a steel tape and bend sharply when wou nd i n rol l form. S poki­
ness occurs more readily i n loosely wou nd rol ls stored at very low h u m i d i ­
ties. When it occurs, it is more severe w i t h films wou nd emu lsion-out. The
res u l t i ng roll has radial l i nes on its side, rese m b l i ng the spokes of a wheel .
When a spoky rol l is stored for long periods of time, the fi l m permanently
Aows i nto this spoky condition with a resulting film d istortion. Th is is not
removed by s u bsequent h u m idity condition i ng of the fi l m and may cause
projection difficu l ties.
Another property associated with low h u m i dity i s fi l m bri ttleness. Film
britt leness i ncreases m arkedly as the relative h u midity is lowered ( Figure 1 0 ) .

45 1
 Part VI T ll E P H E S E H VAT I O N O F C O L O H P ll O T O G R A P ll Y

100 100 ------------ - ----------- -

- -- ________ ]
� 80 � BO
Single strip
I
E Sing l e strip E
I
I

l5 60 � 60
::>
::>

·5
CT
� 40
"'

::>
v;
� 20 16mm reel
in taped

0 1L----'--'---' ..._ _._..._

metal can

5 10_20_50 I -� 5 10 15 I 2 5 I 2 5 10 I 2
I I 5 10 20 I 2 5 10 I 2 5 2 5 10 20
O '--'---'--'-L-L-<::.-.L_L-_l_L-..L.J.-L---1""°-.L---'-L_l
2 5
Minutes Hours Days Weeks Minutes Hours Days Weeks Years
Time Time

Figure 11 Figure 12
Effect of width on rate of conditioning of' motion-picture film. H o l l s Effect of packaging on rate of conditioning
w o u n d at 2 0 oz t e n s i o n . Tempcrn t u rc 70°F. uf motion-picture f il m al 70°F.

This brittleness may be manifested by emu lsion cracks or comp lete film
breaks i f it is bent e m u lsion-out aro u nd small d ia meter rollers . 33 However,
film britt leness is considered less i mportant than F il m curl since latent brit­
t leness can be e l i m i nated by conditioning the film to a h igher h u m id ity,
wit hout any detrimental effects, provid i ng the fi l m had not been cracked .
The important practical considerat ion is to avoid using fi l m while it is in a
brittle state; otherwise permanent damage may result.
I t is for t hese reasons that a lower l i m i t of 1 5% R H was recommended
for cellu lose ester base fil m s . For polyester base color films, a lower l imi t
of 25% R H was suggested t o lessen any chance of adhesion problems. This
is the cu rrent recommendation of the A N S I commi ttee concerned with
this problem.

C. Moist u re ConcliUon:ing R ates

I t cannot always be assumed that t he relative h u m idity of the air with which
the film reaches moisture equilibri u m is identical with the relative hu mi d i ty
of the storage area si nce moisture condition i ng of fil m i s a t ime-dependent
process, as i l l u strated in Figure 1 1 for cellu lose triacetate base fi l m . Although
a si ngle stri p of film can be completely moist ure conditioned i n sl ightly more
than one hour, it requ i res only about 1 5 min for 75% conditioning to be
reached. H owever, it takes considerably longer for motion-picture film in ro l l
form. as t h e n t he moisture m ust d i ffuse from the sides of the film ro ll with
conseq uently a much longer diffusion pa th. A 1 6mm film rol l req u i res over
two weeks, a 35m111 rol l over five weeks, and a 7omm rol l over several months.
 Read i n g 49 A D E L S T E I N , G H A H A M , 1\ N D \V E S T

100 ------------------- ---------------

�
- 80
E
.2
@ 60
70°F - I 0°F
·:;
C"
<l>

�
ii
40

'i5
::2' 20 Figure 13
Ef-'f'ect oF temperature on rate of
o ������ conditioning of film (single strip).
1 2 5 10 20 2 5 10 20 50 100
Minutes Hours
Time

Conditioning t imes are somewhat dependent on air velocity and w i n d­

i ng tension, b u t are i n dependent of roll length. The form of the film package is
a nother very i mportant factor i n the rate of moisture conditioning ( Figure 1 2 ) .
I t takes about three times a s long for a 1 6 m m rol l i n a n u n taped metal
can to reach moisture e q u i l i bri u m as a fi l m roll exposed to the air. Of par­
ticular i n terest is that tap i n g metal cans is n o guarantee that the fi l m w i l l
remain at a constant moisture content. I n the study reported i n F igure 1 2,
the fi l m reached 50% of the way toward equ il i briu m with the relative h u m id­
i ty of the storage air after two years when stored i n a can sealed with an
adhesive cloth tape . This, of cou rse, is very dependent upon the quality and
quantity of the tape used to seal the can. From a practica l viewpo int, i t i ncli ­
cates that we cannot depend o n taped cans t o keep the moistu re content of
a roll of fi l m consta n t for long periods of time. Some type of hermetically
sealed container is req ui red i f the ambient air is not control led at the recom­
mended h u m i d ity.
Low temperatu res are recommended for optim u m dye stabil i ty.
Although the rate of moisture cond itioni n g i s very m uc h slower at - 1 0° F than
at room temperature ( Figure 1 3 ) , fil m will sti l l u n dergo a moisture change.
The factors d iscussed above that affect moisture conditioning a lso apply at
temperatures below freezing.

D. Moisture Conditioning Methods

The optim u m method of controlling the relative h u m i d i ty of the storage

room is by a ir-conditioning with fu lly a utomatic re lative h u m idity control .
An alternative procedure is the use of a refrigeration-type deh u midifier34
con trolled by a h u m id istat, although this does not provide as acc urate con­
trol of relative h u m i di ty.

453
Part VI T l-I E P R E S E R V AT I O N OF C O L O B P l l O T O G H A P l- I Y

The use of desiccant-type room dehumidifiers is not recommended

because of poss ible problems with d i rt and consequent abras ion or chemical
contamination effects. Calci um ch loride i s particu larly bad as it creates fine
dust particles when dry, and is corrosive when moist.
The optim u m method of conditioning fil m to the desire d moisture
leve l is by running the film thro ugh a su itable condition ing cabinet, with
a condition i ng time of about 20 min. Alternatively, film can be placed i n
u ntaped c a n s i n a controlled-h umidity storage area and al l owed t o condi­
tion for an extended period of t i me to the desi red h u midity. H owever, i f the
h u m id ity d i fference between the fil m and storage area is large, some fi l m
d i stortion m ay occur.
When there is no other means of l owering the moisture content of the
fi lm, the use of sil ica gel h as been suggested. 1 1 . 1 3 Thi s method is practical
only when the quantities of fi lm are small. It a lso suffers the disadvantages
of possible film d istortion and of d ifficul ty in controlling the final moisture
content precisely so that the film i s not overd ried. O nce the fi l m is condi­
t ioned to a s u i table moisture level , then i t must be p laced i n a hermetically
sealed container. As was d iscussed earlier in this paper, hermetical sealing of
containers is difficult to achieve .

Acknowledgment

The authors wish to thank G . W. Larson for fu rnishing the dye stability data
that was reported.

References

E. H. L i nd g ren , " Preservation o F c i n e 111atograph fil 111 i n the National F i l 111

Arc h ive," 81-. fGneniat:. Sound and T\!, 50: 290-292, Oct. 1 968; see also Ibid.,
]our. SM PTE, 78: Oct. 1 969.
2 G . L. H u tc h ison, L. E l l i s and S . A. Ashmore, " F i l m decompos ition tests, " ]011r.
SM PTE, 54 : 38 1-383, M ar. 1 950.
3 H . C. Brown, " Problems of stori n g film for archive p u rposes , " B r. Kinemat.,
20 : 1 50-162, May 1952.
4 J. W . C u m 111ings, A. C . H u tton a n d H. S i l fi n , "Spontaneous ign ition of
deco111posing cellulose n i t rate fi l 111 , " ]our. SMPTE, 54: 268-274 , Mar. 1950.
Standard for the Storage and H an d l i n g of C e l l u lose N itrate Motion Picture
F i l 111, N F PA No. 40, 1 967, National F i re Protection Ass n . , 60 Batte ry111arch S t . ,
Boston, M A 02 1 1 0.
6 G . L. H u tc h ison, L. E l l i s a nd S . A. Ashmore, "The s u rvei l lance of
c i n ematograph record f i l 111 d u ri n g storage,"]. Applied Chem., 8 : 24-34 , J a n .
1 958.
7 J. H . H i l l and C. G . Weber, "Stability of motion-picture f i l m s as determ i ned by
accelerated aging," ]our. SM PTE, 27: 677-690, Dec. 1 936.

4 54
 Reading 49 A D E L S T E I N , G H A ll A M , A N D W E S T

8 C . R . Fordyce, " I mproved safety motion-picture fil m support ," )0111'. SMPTE,
5 1 : 331-350, Oct. 1948.
9 R . 0 . Gale and A. L. W i l l iams, " Factors affecting color film dye stabi l i ty:
Related printing problems and release pri n t q u a l i ty," j ol l r . SMPTE, 7 2 :
804-809, Oct. 1 963.
1 0 J. M. Calhoun, "The preservation of motion-picture fi lm," A 11 1. Archv., 30:
5 1 7-525, J u ly 1 967.
11 Storage and Preserva l. io11 of !Vlolion-Pic " 1 1 re Fil11i, 1 957, East111an Kodak Co.,
Rochester, NY 1 4650.
12 Eastman Koclah Mot.ion Pic t u re Fillllsfor Professional Use, 1 968, Pub. No. H - 1 :
43-44, 1 968, Eastman Kodak Co., Rochester, NY 14650.
1 3 Storage and Care of Kodah Color Films, 1969, Pub. No. E-30, Eastman Kodak
Co., Rochester, NY 1 4650.
14 D. C. H ubbe l l , R. G . M c K i n ney and L. E . West, "M ethods for test ing image
stabil ity of color photographic products," Phot. Sci . & E11.g . , " : 295-305,
Sept.-Oct. 1 967.
15 R. K. Schafer and J. 'vV. Zuidema, "Si lver protection masters for 1 6 m m color­
reversal originals, " }ollr. SMPTE, 7 6 : 1 oc8- 1 0 1 0 , Oct. 1 967.
1 6 American National Standard Speci fications for Photographic F i l m for Archival
Records, Si lver-Gelatin Type, on Cel l u lose Ester Base, P H 1 .28- 1 969, American
National Standards I nstitute, I nc . , 1 430 Broadway, New York, NY 10018.
17 American National Standard Practice for Storage of' M icrof i l m , Pl-1 5.4- 1957,
American National Standards I n stitute, I nc . , 1 430 B roadway, New York, NY
10018.
1 8 American National Sta ndard Specifications for Safety Photographic F i l m ,
P H 1 .25- 1 965, American National Standards I nstitute, I nc . , 1 430 Broadway,
New York, NY 1 00 1 8 .
1 9 D . R . White, C . J . Gass, E. Meschter a n d W . R . H o l m , " Polyester
photographic f i l m base,"joHr. SMPTE, 64: 674-678, Dec. 1 955.
20 P . Z. Adelstein and J . L. M cCrea, " Permanence of processed Estar polyester
base photographic films," Pho t . Sci & E 11g., 9 : 305-3 13, Sept.-Oct. 1 965.
21 R . H. Talbot, "The projection l i fe of f i l m , " Jo11r. SMPTE, -1 5 : 78- 1 0 1 , Aug. 1 945.
22 E. K. Carver, R . H . Talbot and H . A. Loom is, "Film distortions and their clTcct
u pon projection quality," .Joi"" SM PTE, 4 1 : 88-93, J u l y 1943.
23 P. Z. Adelstein and J. M Cal hou n , " I nterpretation of d i mensional changes in
cell u lose ester base mot ion-picture films," .Jorn" S M PTE, 69: 1 57-1 63, Mar.
1 960.
2-J J . M . Calhoun, "The p hysical properties and d imens ional behavior of motion­
picture f i l m ," }ollr. SM PTE, -13: 227-266, Oct. 1 944.
25 American National Standard Met hod for Determ i n i ng the · rh iosu l Fate Content
of Processed Photographic F i l m , P l- 14.8-1 953, American National Standards
I nstitute, I nc., 1430 Broadway, New York NY 1 00 1 8 .
2 6 C. D. \Varburton a n d E. P. P1-zybylowicz, "A n e w test method for t he
measurement of residual thiosulf'ate i n processed fil m based on borohydride
reduction to s u l fide and methvlene blue formation," P/101 . Sci. & Eng . , 1 0 :
86-92, Mar.-Apr. 1966.
27 G. 'vV. Larson , D. C. H u bbe l l and L. E. West, "Appl ication oF two analytical
test methods to predict processed i mage stabi l ity," ./o u r. S M PTE, 7 1 : 495-50 1 ,
J uly 1 962.

-155
P art VI T ll E P R E S E H V /\ T J O N O F C O L O R P l l O T O G H A P l-I Y

28 R. 0. Gale and \<\/. I. Kisner, 'Tech n i q ues in color d u pl ication," Jorn- .

S M PTE, 69: 874-88 1 , Dec. 1960.
29 Prod11ctio11 of J\ll o t io11 Pic t u res i n Color Usi11g East111rm Color Fil111s,
East111an
Kodak, Co., Rochester, NY 14650.
30 L. E . \Vest, "\1\ /atcr conservation in photographic processing," I mage Tech . ,
Nov.-Dec. 1 969.
31 A. E. K i 111bcrly, S u JJw1c11y Report of Nat.io11al B u reau of S ta11.dards Research
on Prese111at.ion of Records, National B ureau of Standards M i scellaneous
Publication M 1 54 , Mar. 1937.
32 J. F. Carroll and J . M . Calhou n , " E ffect of ni trogen oxide gases on processed
acetate fil m , " )our. SM PTE, 64: 501-50 7 , Sept. 1 955.
33 P. Z. Adelstei n , "\<\ledge brittleness test for photographic film," Pho t . Sci. &
E ng . , 1 : 63-68, Oct. 1957.

34 1- 1 . Pollak, " Dehu111i d i rlcation for the preservation of docu ments," J\ll e c/1.
\!\forlcl, 1 4 1 : 268-270, Aug. 1 9 6 1 ; 302-304, Sept. 1 96 1 .
 R e a d i n g 50

H E N RY WI L H E LM

C olor Print Instability:

A Problem for C ollectors and
Photographers ( 1 978)

The early 1 970s saw a dramatic rise i n t he study of color photographic penna­
nence. Several symposia ·were orga n.i=ed, among them "Conservat.ion of Colour
Ph.otogra71h:ic Records, " held in London at the Royal Photographic Society on
September 20, 1 973. Another was held in t:he fall of 1 975 at the George East man
/- louse, an.cl yet anot:her at; Nei11 Yorh 's lnterna t ional Center of Photogmph.y on
May 6-71 1 9781 which was ent.it.lecl "Tiie Permanence of Color-Technology's
Challenge, t he Photogra71her's and t he Collector's Dilemnw. " IV/any st udies on
light fading a nd t hermal stability were pu blished throughout the 1 9 70s, and
color impermanence also became a com mon to71ic in the 71opular press. Edi.­
torials a nd feature a rt icles lamented t h e i m mi nent destruction of 11wst color
71lwt.ogra71hs due to their inheren t instabilit ies, and the informat:ion abo11t t he
need for cold ancl moderately clry st.orage conditions was seen more ancl more
in print. The individual who 71erhaps dicl more t han a nyone in 71u.blici=ing the
color problem. and in advocating cold storage was J-/enry \!Vilh.elm (see also
Reading 67 ), who began st udying t:he stability of color photography ·in 1 97+
By 1 978 he began a systenwt ic test i ng of color print stability, wh ich conti.n-
11es today in t he testing of inlzjet prints. He would u lti mately p u blish t.he ·most
co1nprehensive booh to elate on the to71ic1 The Permanence and Care of Color
Photographs ( 1 993) . The a rticle presented here was first published in the jou r­
nal Afterimage in October 1 9781 and early the following year it: a71pea recl i n
M odern Photography. I t offers a looh at Wilhel m 's early research a nd the state
of color stability and preservat ion at t hat t :i 1ne.

1- I ENHY W i L l l E L M , "Color Print I nstabil ity: A Problem for Col lectors and Photographers,"
Afterimage 6, no. 3 (October 1 978) : 1 1- 1 3. Hcpri ntcd by permission oF the aut hor.

457
Part VI T H E l' H E S E H V A T I O N O F C O L O H P l-I O T O G H A P l- I Y

I n spite of the greatly increased interest i n collecting photography in recent

years , many photographers and col lectors in the fine art field have avoided
color p hotography. The reasons for this are nu merous, but probably the
most important shortcoming of color p hotography from a collector's po int
of view is i ts a l leged lack of i mage permanence. Few collectors are wil ling to
pay substantial sums of money for a photograph with t he u n happy prospect
that it might fade away in a re latively s hort period of time. This in turn has
d iscou raged many photographers from worki ng in color. As a result, the evo­
l u tion of color photography as a fine art has been restricted, and even today
most museums and archives have little, if any, color photography in their
collections. H owever, in the past Few years i ncreasing n u m bers of photog­
raphers have produced s u bstantial bodies of work in color (S hore, Cosin­
das, Eggleston, Meyerowitz, Slavi n, B ishop, and Vogt, to name just a few) .
I n general, the current generation of color photogra phers is very concerned
about the i n stability of the prints t hey sell, but the fact that their color prints
may have a much shorter l i fe than silver-gelatin pri nts has not cau sed them
to a bandon their work i n color.
Any discussion of color print stabil i ty must deal with three disti nct and
separate phenomena:

1. I mage fad i ng and/or stai ning caused primari ly by the effects of light
and UV radiation. Virtually all color print processes deteriorate on
ex'Pos ur e to l ight of the visible part of the spectru m eve n if there is
no U V rad iation present. In ge neral, most color materials do not have
the same types of spectral depende nce on fading as do other types of
a rtistic media.
2. I mage fad i ng and/or sta i n i ng that takes place i n the dark. The rate
of dark fad i ng for any give n material is primarily a fu nction of
temperature , with relative h u m id ity being an i mporta nt factor, and
pol l u tants, im proper processing, o m ission of a final stabi lizer bath,
i nadequate wash ing, etc. being other pote ntially important variables.
3. Deterioration of the pri nt su pport material on prolonged exposure to
light and/or UV radiation or deterioration of the support d u ring dark
keeping caused by tempera t u re a n d moisture fluctuations or other
factors. Among c u rrent materials, support deterioration appears to be a
serious problem o n ly with HC pri nts. Collectors wou ld be well advised
to avoid all types of b lack-an d-white and color pri n ts made on resin­
coated su pports.

Color print image deterioration may include any or a l l of the fol lowing:

1. Loss of highlight detail, usually with reduced overa l l dens ity and contrast.
In time, most color pri nt materials will suffer a l most total i mage loss.
 Reading 50 W I L I- I E L M

2. Color balance changes caused by the cyan, magen ta, and yel low i mage
dyes or p igments fad i ng at uneven rates. \Ni t h any given material, the
d irection of the color balance shift is usually different with l ight fad i ng
and dark fad i ng. Dark fad i ng reactions cont i n ue du ring the time a print
is eA'POsed to light and u ndergoing light fad ing; the combi ned effects
of l i ght fad i ng and dark fad i ng are complex and difficult to predict.
3. Stain formation. In correctly processed curren t materials, stains are
usually low-level yellow colorations which are most readily observed
i n highlight regi ons of a pri nt. Such stains may sign i fi cantly al ter the
color balance of low dens ity areas of a prin t in addition to yel lowing the
D-min ( m i n i m u m density) areas. Ye l low stain formation is a serious
problem with many, but not all, of the currently used materials.

The visual changes that take place when a color print deteri orates are
often difficult to describe, but are read i ly apparent i f a faded print is d i rectly
compared to a non-faded print of the same s u bject. 1 n the early stages of
deterioration, a viewer may think there is nothing wrong with a print u n less a
comparison pri nt is avai lable. As fading advances, a poi n t is reached where
most people will say that the quality of the prin t i s poor. I n terpretation of
the point when objectionable fad i ng has occurred often varies depend i ng on
the s u bject matter of a particular photograph. For example, people usually
have a rather fixed concept of what flesh tones should look l i ke and will toler­
ate much less variation i n these colors than they might with an a bstract scene.
An objective method of monitoring color print deterioration has been
devised by the author. This can be u sed by m u seums that would l i ke to dis­
play color prints as long as possible while not exceedi ng a predetermined
degree of i mage deterioration . Th is pri nt monitoring system will be described
i n the a uthor's forthcomi ng book on preservation.
I n many cases there is little relationship between light fad i ng and dark
keeping properties. Some materials have relatively good fad i ng stabi lity but
poor dark fad i ng stabil ity. A n u m be r of p rocesses have excellent dark keep­
i n g stabi l i ty b u t poor l ight fading stabi lity. From a col lector's point of view,
excel lent dark keeping sta b i l i ty is the most i mportant req u i rement i n select­
i ng a color print materia l . As a general statement, it may be said that no c u r­
rent color materia l , with the probable exception of F resson Q uadrichromie,
can be displayed for long periods of time without sign i ficant fad ing taking
place. H owever, the req u i rements of most collectors will be satisfied i f a
color print i s stable i n the dark and i s sufficiently resistant to l ight fad i ng
that i t may be viewed from time to time a n d can be u sed for short term
d isplay (for example, a three or four month m useum exh i b ition, i l l u m i nated
with tungsten l amps with an i ntensity of about 50 footcand les-540 l ux) with
no sign ificant deterioration taki ng place.

459
Part VI T ll E P H E S E n V 1\ T I O N O F C O L O H P ll O T O C H A P ll Y

I t should be n oted that even the most u nstable color materials, when
stored i n the dark at very low refrigerated temperatures and low relat ive
h u m idit ies, can be preserved for a very long time-h u n d reds, and eve n
thousands of years. M u seums and arch ives will have to install color storage
equipment i n the near fu t u re if they i n tend to preserve color transparencies,
negatives, motion pictures, a nd most types of color prints. A small n u m be r
o f collec t i ng i nstitutions i n t h e U . S . and Eu rope already have such fac i l i ­
t i e s . However, most major i nstitutions, s u c h as the M u seu m of Modern Art,
George Eastman House, the U . S . National Arc hives, and The Public Arc h ives
of C anada, do not yet have cold storage faci l ities for their collections.
Most private collectors will not wa nt to go to the expense and trouble
of mainta i n i ng a cold storage vault. Preservation of color images by making
silver separation negatives or posi tives-a procedure which has often been
suggested by the photographic i n d u stry-has many serious d rawbacks i n
addition to h igh cost and potential i mage quality losses, a n d i n t h e author's
opi nion, should not be seriously considered for most applications.
There a re a n u m ber of color pri n t processes cu rrently i n u se by artistic
p hotographers, and each has a distinct set of stabi l i ty characteristics. It is
i mporta nt to collectors that photographers identify their color prints with
the actual process name a n d the date the prints were made. For example:
Kodak Ektacolor 74 RC-Ektaprint 2 Chemicals with Ektaprint 3 Sta­
b i l i ze r-J u ne, 1 978. The commonly u sed terms "Type C Print" a nd "Type R
Print" are al together i ncorrect u n less a print was actually made on Kodak
Color Print Material , Type C (a n egat ive-pos itive chromoge n ic material) or
Kodak Color Print Material, Type R (a reversal c h romogenic material)
d u ring the time t hese materials were ava i lable from 1 955 to about 1 959.
Followi ng is a list of the m ost commonly encou n tered color pri nt
m aterials c u rren tly i n use i n the fine a rt field. Comments o n the l ight fad i n g
sta b i l ity a n d dark keep i n g stability of the materials are based o n a n exte n­
sive series of accelerated and non-accelerated natura l agi ng tests condu cted
by the author d u ring the past several years. The tests and resu lts will be
described in deta i l in the a uthor's forthco m i ng book o n preservation. A few
of the comments given here are from i n d u stry data s upplied to the author.

Kodak Ektacolor 74 RC Paper. Prints made o n this chromoge n ic mate­

rial are usually from color negative origi nals, or color internegatives made
from origi nal color transparencies. This type of paper is capable of excellent
color and tone reproduction when used with origi nal masked color nega­
tives, but the paper has only moderate light fad i ng stabil ity and poor dark
keep ing stability. Significant fad ing will occ u r in the dark u nder typical con­
ditions i n less than 1 0 years time. C u rrent Ektacolor paper has i mage dyes of
closely matched fad i n g rates when exposed to most types of light sources if
 R e ad i n g 50 W I L H E L M

the print or the l ight source is covered with glass. J n accelerated agi ng tests
conducted b y the a u thor, the use of Kodak E ktaprint 2 processing chemicals
without E ktaprint 3 Stabil izer w i l l sign i ficantly i n crease dark fad i ng rates.
The paper has an RC su pport. It is not recom mended for applications where
non-refrigerated Jong-term keeping i s requ i red .

Kodak Ektachrome RC Paper, Type 1 933. Th is chromogenic material is

used to make prin ts d i rectly from color transparencies without the use of
an internegative; color and tone reproduction are generally i n ferior to those
of prints made from masked color n egative originals or internegatives. The
paper is s ignificantly i n ferior to E ktacolor 74 RC in l ight fading sta b i l i ty and
has about the same poor dark keepi n g stability. Type 1 993 is being replaced
i n the U . S . wit h Type 2 2 0 3 , early batches of which had extremely poor yel low
dye light fading stabi lity. Kodak has i n dicated that future batches of 2203
will have light fading stability s i m ilar to E ktacolor 74 R C . The paper has a n
RC support. U s e of t h e paper i s n o t recom mended w h e n non-refrigerated
long-term keepi ng i s req u i red.

Agfacolor MCN 3 3 1 0 , Type 4 . Thi s i s a chro mogeni c negative-posi tive

paper used to make prints from origi nal color negatives or i nternegatives
made from original transparencies. lt is little used i n the U . S . , but is very
common in E u rope. This paper has poor l ight fad i ng stabil i ty and very poor
dark keepi n g stability. This is an RC support materia l , and appears to h ave
inferior dark keeping stab i l i ty compared to the Agfacolor M C N 1 1 1 -Type 7
fiber-based papers i t replaced i n the m i d - 1 97os. Use of this paper is not rec­
om mended when non-refrigerated long-term keeping is requ i red.

Kodak Dye Transfer Prints. Thi s is a s u rvivor of the historic dye-i m b i b ition
process, a n d was i ntrod uced in essentially its present form i n 1 946. Dye
Transfer is the s uccessor to the Kodak \!\!as h-Off Relief Process, i n troduced
i n 1 935, which was Kodak's first color pri n t process. Dye Transfer i s cu rrently
Kodak's o n ly color print process with a conventional fiber-based s u pport.
Dye Transfer pri nts a re generally made from original color transparen­
cies, b u t can also be made from original color negatives or i nternegatives by
any of several procedures, the m ost d i rect being wi th the use of Kodak Pan
Matrix Film. Prints can also be m ade from color negatives with the use of
i n ter-positives or separat ion negatives made from separation positives which
were p repared from the original color n egative. M ost p hotographers wi l l fi n d
it m u c h easier to m a ke h igh quality Dye Transfer prin ts from original color
negatives and Pan M atrix F i l m (a process that avoids the need for making
separation negatives, color and contrast correction masks, etc.) than from
original color transparencies.
Part VI T l- I E P R E S E R V ,\ T I O N O F C O L O R P H OT O G R A P H Y

Dye Transfer is a complex and expensive process. Most pri nts of this
type are made i n com mercial labs, but increasing n u m bers of photographers
are lea rn i ng to make the prin ts themselves. The process is capable of excel­
lent color and tone reproduction; both color saturation and contrast can
be extensively manipu lated i f desi red. Kodak Dye Transfer pri n ts are often
i ncorrectly referred to as " Dye" prints. Kodak sells a l l the necessary materials
and equ ipment for the process, but does not actually make prints for custom­
ers. The process al most disappeared from the market a few years ago, but it
will probably see a major resurgence in the fine art field in the com i ng years.
Dye Transfer prints have excellent dark keepi n g stability; they are far
more stable i n dark storage than any other Kodak color pri n t process. They
will al most certa inly last more than 1 00 years with no sign i ficant cha nge i f
kept i n the dark except for occasional viewi ng or short-term d isplay. How­
ever, the prin ts have relatively poor light fad i ng stabil i ty. The yellow dye i n
particular i s u nstable a n d u nder typical conditions of display the prints will
fade faster than cu rrent E ktacolor 7 4 RC prints. However, because of its
excellent dark keeping stab ili ty and freedom from stain with age, the process
can be considered to be among the first choices for collectors. New prin ts
normally s mell of acetic acid. The prints should never be washed or other­
wise treated i n an attempt to remove the residual acetic acid.

F uj i Dyecolor Pri nt . This i s a dye-i mb i bition process quite si m i lar in con­

cept to the Kodak Dye Transfer Process. The pri nts are currently avai lable
o n ly i n Japan and are made only by a printing service of Fuj i . At the present
time Fuji does not sell the materia l s requi red to make the prints. The prints
are avai lable at low cost i f large n u m bers of the same pri nt are ordered.
Transfers are made au tomatically on a special rotary mac h i ne developed by
Fuj i . Pri nts are made on a conventional fi ber-based paper and visually appear
nearly identical to Kodak Dye Tra nsfer prints. Fuji Dyecolor prints have
been avai lable only in the last few years. Like Kodak Dye Tran sfer prints,
Fuji Dyecolor pri n ts have excellent dark keeping stab i l i ty, but re latively poor
l ight fad i n g stability. Dyecolor prin ts are quite sui table for col lectors and for
edition printing.

C ibachrome C C P-A 1 82U a n d C C P- D 1 8 2 U . C ibachrome prints are the

only current example of the h istoric si lver-dye-b leach process. There are
several versions of the process, all of which are made on pigmented cellu­
lose triacetate su pports except for the recently i ntroduced C i bachrome R C
Paper photofi n ishing material . C i bachrome RC prints should b e avoided by
collectors because of potential i nstability of the support. Ci bachrome was
i ntrod uced in Switzerland in 1 963, but did not come i nto wide use by artistic
photographers until the i ntroduction of the three-solution Type A process i n
 Reading 50 \·V I L l l E L M

1 974. C i bachrome i s perhaps the eas iest of a l l color processes with which to

make prints. It is used to make positive prints d i rectly from color transparen­
cies; however, i t can also be used to make prints from color negative origi nals
by the use of masked i n ter-positives. Cibachrome p roduces pri n ts of h igh
color saturation and, objectively speaking, excessive i m age con trast. Many
p hotographers object to C ibachrome because of the contrast p roblem. Some
artistic p hotographers who work with C i bachrome take p hotographs only in
situations with low-contrast lighting (such as overcast days when the sun is
not s h i n i ng) or restrict their work to studio situations where l i ghting contrast
can be con trolled. It is possible to i mprove the color and tone reproduction
of the materials greatly by the u se of con trast redu ction and color correc­
tion masks, a procedu re which greatly complicates the process. Some com­
mercial labs, such as B oris Color Lab of Boston, Mass., have special ized in
h igh quality m asked C ibachrome printing. Availability of a negative-pos itive
version of C i bachrome whi c h could be used d i rectly with masked color nega­
t i ves wou ld probably solve the contrast and color reproduction properties of
the curre nt materials.
Ci bachrome has excellent dark keeping stabi lity; l i ke Dye Transfer
and Dyecolor, C ibachrome can be considered to be essentially permanent
in dark keepi ng. C ibachrome is the only s i mple process c urrently avai lable
that produces dark-stabl e prints. C i bac hrome has relatively good light fad­
i ng stab i l i ty, though it is by no means permanent on long-term d isplay. I t
has better l ight fad i ng stability than any other color prin t m ateria l tested by
the a u thor except Presson Qu adrichromie. For p hotograph ers who want to
m ake their own prints a n d don't wa nt to get i nvolved with the complexi ties
of the Kodak Dye Transfer Process, C i bachrome is the only process available
that produces dark stable prints. Col lectors should consider the pri nts to be
q u i te acceptable for non-refrigerated l ong-term keepi ng. The prints should
be handled careful l y as they show fingerpri n ts easily. Coating the prints with
lacquer i s not recommended by the a u thor at the present t ime.

Fresson Quadrichromie Prints. At the present ti me, prints made by the

French Q uadrichromie process are the only color p ri n ts ava ilable which may
be considered to be essentially permanent both in dark keeping and on d i s­
p lay u nder typ ical conditions for extended periods of time. H igh i ntens ity
accelerated ligh t fad ing tests conducted by the a u thor i nd icate that u nder
typical conditions of display the prints will probably l ast for a t least 50 years
with only very m i n or deterioration. A more definite projection of the light
fad i ng stability of the prints cannot be made u n t i l lower l i gh t level, long-term
tests have been completed. Other than slight yellowing of the conventional
fiber-base paper support, the pri n ts would appear to be essentially perma­
nent in dark keeping.
Part VI T ll E P H E S E H V AT I O N OF C O L O H P l-I O T O C B A P l-I Y

Quadrichro m ie prints have been produced o n ly since about 1 9 5 1 , b u t

the color process is based on the h i storic monochrome process u sed b y the
Fresson fa m i ly for a great many years. The Q u adrichromie process is so
named because the pri n ts are made with a fou rth "black printer" i mage i n
addition to the usual cyan, magenta, and ye l low colors, so as t o prod uce dark
tones of adequate density. For the same reason, b lack i n k p l u s the other
three colors are gen erally u sed in the p hotomechanical color printing pro­
cesses. Quadrichromie prints are made of separate l ayers of p igments sus­
pe nded i n thin ge latin coati ngs. The compos i tion of the p igments has not
been made p u b l ic, but they are probably inorganic p i gm ents of the same
types used i n l ightfast p a ints.
At present, the prints are made only at the Fresson lab located near
Paris, France. The materia ls for the process are not sold by Fresson and the
exact methods of making the pri n ts have not been d isclosed. Jt is known
that the prints are m ade from separation negatives (usually made from
origi nal color transparencies by contact printing, b u t sometimes made
from original color negatives) and that the dichro mated gelati n layers con­
tai ning the pigments are coated, dried, exposed, and the non-hardened areas
of the i mage are washed off with water conta i n i n g sawd ust as a m i ld abra ­
s ive, one layer a t a t i m e . I n spite o f t h e time-con s u m i ng nature of the pro­
cess, Fresson s u pplies the prints at re lat ively low cost.
Tone reproduction of the process can be q u i te p leasing, but by objective
standards the saturation of the colors and the accuracy of color reproduction
is rather inferior to most other color processes. When 35mm transparencies
or other small format color films are u sed as originals, there is a substan­
tial i ncrease i n gra i n in the final e n larged print due to the use of contact­
s ize separation negatives. H owever, for many artistic photographers, these
shortcomi ngs of exact color reproduction are considered to be an advantage
as the prints have a certai n mellow q u a l i ty that cannot be obtai ned by any
other process. The p ri n ts have a smooth non-glossy s urface and contrary to
what one might expect with a process of this type, the i mage has no visible
p hysical re lief. A n u m ber of fas hion photographers i n E u rope have made
exte ns ive use of the process because t hey believe the quality of the pri n ts
is better s u i ted to their work than the h igh-sat u ration and someti mes harsh
color prints obtained with the standard color processes .
The excellent stabi l i ty of the prints, com bined with the soft colors p ro­
d uced by the process, wil l probably make it increasingly popular with artistic
photographers. There are a n u mber of photographers in the U . S . and Can­
ada who have sta rted to m a ke use of the process. At present, this is the only
color print process that can be considered if it is desired to d isplay prints for
long periods of time.
 Reading 50 \V I L I I E I . M

H a n fstaengl Tricolor Carbro Pri n ts . Tricolor carbro p ri n ts made with

the currently produced pigment tissues s uppl i ed by the Ha n fstaengl firm of
Germany probably have good dark keepi n g stabi l ity, but i n accelerated l ight
fad i ng tests conducted by the au thor, the pri nts proved to be significantly
i n ferior to Cibac hrome prints in stability. The ye l low pigment in parti cular is
subject to l ight fadi ng, and the prints exh i bit serious color balance shifts as
fad i ng progresses. The tricolor carbro process is a complex a n d difficult-to­
control method of printmaking; with the i nstability of the c u rrently available
pigments, there is p robably l ittle reason that a photographer wou l d want to
work with the p rocess. However, the H an fstaengl firm is said to be working
on a new set of pigment tissues an d i t is p robable that the l ight fad i ng stabil­
ity of the process can be greatly improved and could wel l become the equal
of Fresson Quadric hromie. The H an fstaengl tissues and other necessary
su pplies are distributed in the U . S . by Gallery 6 1 4 ( 6 1 4 West Berry Street,
Ft. Wayne, Incl. 46802 ) . There are a n u m ber of photographers i n the U . S .
a n d Canada c urrently using the process; however, a t this time there i s no
commercial lab producing prints by this method.
Tricolor carbro can be used with either original color transparencies or
color negatives. The prints are m ost often made on I Oo% cotton fiber paper,
b u t the color i mage can be applied to a wide variety of materials. Tricolor
carbro i mages have an easi ly detected physical relief. Some very early tricolor
carbro pri n ts are thought to be very resistan t to l ight fading. H owever, the
majority of the tricolor prints i n existence (made si nce the early 1 94os-the
process was in general use until the 1 950s) were made with pigments which
were i mp roved in color reproduction at the expense of l ight fad i ng stabil­
i ty. I t wou l d be very unwise to s u bject a tricolor carbro print to prolonged
d isplay u nless i t has been positivel y identified as having been made with a
stable pigment set.

Kwik- Print. This is a contact speed color prin ti ng process using successively
coated, exposed, and washed off pigment l ayers. The p i n ts are norma lly
made on non-plasticized pigmented wh i te vinyl sheets, though other support
materi als including cloth and paper may be u sed . All the material s neces­
sary for the process along with detailed i nstructions a re ava ilable from Light
I m pressions Corp . , 1 3 1 Gould Street, Rochester, N .Y. 1 4 6 1 0 . Kwik-Pri nt is a
mod i fication of the Kwik-Proof graphic arts p roofi ng system made by D irect
Reprodu c tions Corp. of B rooklyn, N .Y. The mechanics of making a print
with the Kwi k-Print system are somewhat similar i n general concept to the
Fresson Q uadrichromie process. H owever, the p igment solu tions supplied
for use with the Kwik-Pri nt process have very poor l ight fading stabi l i ty and
the pri nts should never be displayed. The prints probably have good dark
Part VI T II E P R E S E R VAT I 0 N 0 F C 0 L 0 H I' I I 0 T 0 C HAPHY

keeping stabil ity. Di rect Reprod uctions and Light I mp ressions are presently
worki ng on a new pigment set and it is possi ble that pigments of greatly
i mproved sta b i l i ty w i l l be made ava i lable in the future. Extensive i mage and
color manipulation is possible with the process and this is one reason the
process appeals to many artistic photographers. Some photographers work­
i ng with the process exercise so many creative controls in making a print
that the res u l t cannot be exactly dupl icated a second time and should be
considered to be a u n ique print. Photographer Bea Nettles had a show at the
\.Vitkin Gallery i n New York in February of this year which featured a large
n u m ber of pri n ts made with the Kwi k-Print process. At present there are no
commercial processi ng labs making pri nts with the process. The author is
not sufficiently fami liar with the use of the process i n non-manipu lated color
pri nting to be able to make spec i fic comments on i mage resol ut ion and the
acc uracy of color and tone reprod uction of which the process is capable.

Polaro i d SX-70 I nstant Prints. SX-70 prints, u nless they are d u pl icate
photographs taken of a static scene, are unique prints with no negative or
transparency which can be used to make add itional prints. lf SX-70 f i l m is
u sed to copy an existing SX-70 pri nt, the resulti ng copy prin t wi ll have severe
color and tone d istortions. Because SX-70 origi nals are u nique pri nts, they
must be hand led with spec ial care and should never be displayed for long
periods of time. SX-70 pri nts are quit e subject to l ight fading, and i n a gen­
eral way may be considered to be somewhat less stable than E ktacolor 74 RC
pri nts. The yellow dye u sed with SX-70 prints is the least stable of the t h ree
i mage dyes and the color balance will shift toward a b l uish-purple as l ight
fad i ng progresses.
The da rk-keeping characteristics of SX-70 prints are not prec isely
known at present. Accelerated dark agi ng tests conducted by the author as
we l l as tests conducted by the Polaroid Corporation i n dicate that, while the
dyes themselves appear to be qu ite stable in t he dark, the p rints have a ten­
de ncy to form yellowish stai n which is very noticeable in D- mi n areas. Stain
formation is accelerated by cond itions of high relative h u mi d i ty. I t may be
years before the actual behavior of the pri nts u nder typical conditions of
dark keeping can be determined with certai nty. Density measurement of
four-year-old SX-70 prints stored i n the dark i n typ ical room conditions show
that some yellow stai n does i ndeed occur d uri ng natural agi ng; however, it
is not yet known just how far the stain formation w i l l progress. Until more is
known about the keep i ng characteristics of the prints, valuable SX-70 pri nts
should be kept i n cold storage at low relat ive h u midities. All SX-70 films
prod uced until t he introd uction late i n 1 977 of the rapid-developing type had
somewhat ye l low D-mi n areas i m mediately after processing.
 Reading 50 \V I L 1 1 E L 1\ I

Study of the aging c haracteristics of both SX-70 and Kodak PR 1 0

instant prints is complicated by the fact that a l l the processing chemicals
and other components of the film rem a i n i n the fi l m beh i nd the i m age layer
after processi n g is completed. M ost of the moisture contai ned in the pro­
cessing reagent diffuses through the polyester cover sheets d u ri n g several
months follovvin g processi ng. SX-70 was i ntrod uced in 1 972; d u ri n g the fol­
lowing years several i mproved versions of the film have been i ntrod uced and
the most recent type has significantly i mproved accu racy of color reprod uc­
tion compared with the original 1 972 fi l m .

Polaroid Polacolor 2 Pri n ts . Polacolor 2, using t h e same types o f metal­

l ized i mage dyes u sed in SX-70, was i ntroduced in 1 975 as a replaceme n t for
the origi nal Polacolor 1 f i l m i ntrod uced i n 1963. I n spite of advertising by the
Polaroid Corporation suggesting that Polacolor 2 prints are very resistant to
light fad i ng, a variety of accelerated and natural l ight fad i ng tests conducted
by the author and others i n d icate that u nder typical conditions of display,
the stab i l i ty of Polacolor 2 prints is relatively poor and is i n ferior to Ekta­
color 74 HC prints.
Like SX-70 and Kodak P R 1 0 pri nts, Polacolor 2 prints are u n ique prints
( u n less they are duplicate photographs taken of a static scene) and do not
have a usable negative or transpare ncy which can be used to make add itional
prints. For this reason, they must be treated with special care and should not
be displayed for more than several mon ths. Like SX-70 prints, Polacolor 2
pri n ts form objectionable stai n i n accelerated dark aging tests. The rate of
stain formation is greatly i ncreased i n conditions of h igh relative h u m i d ity.
Wh i le the actual keeping characteristics under typical dark storage condi­
tions are not yet known with certa i n ty, collectors wou l d be advised to keep
the pri n ts in cold storage with low relative h u m id i ty.
Polacolor 2 Type 808 pri nts in the 8 X 1 0-inch format were i ntrod uced
in 1 977 and this prod uct is l i kely to become popu lar with artistic photogra­
phers. Sta b i l i ty studies with this new p roduct are in progress. To date, there
is no ind ication that Type 808 has better stabil ity than other Polacolor 2
prod ucts, and all the preca utions given previously should be applied to T)1Je
808 prints also. Part of the appeal of the c urrent i nstant color processes to
artistic photographers is the fact that t he pri n ts are u nique i mages. Th is
gives the prints greater i ntrinsic value and i n c reases their identification
with many other types of artistic media, such as oil pai n t ings. However, the
very fact that the i nstant pri n ts are u n iq u e i mages puts greater stress on the
need for i mage permanence. Col lectors and p hotographers should be keenly
aware of the stability l i m itations of the currently available i nstant color
materials.
Part VI T ll E P B E S E H VAT I O N O F C O L O R P ll O T O C R A P ll Y

Polaroid Polaco lor 1 Prints. Polacolor 1 (known s i mp ly as " Polacolor") was

i ntrod uced in 1 963 and was the first i nstant color p rocess 111a rketed. I t pro­
d uced prints of pleas ing tone reproduction but, by objective standards, had
very u nsaturated color reproduction of 111ost colors. H owever, the soft color
rep rod uction appealed to some artistic photographers. Marie Cosi ndas used
it to advan tage i n 111any of her most well-known photographs. Cosi ndas gen ­
era l ly reta ins her Polacolor origi nals and thinks o f t h e m i n 111 uch t h e sa 111e
way as 111ost p hotographers t h i n k of their original color transpa rencies or
negatives. Cosi ndas sells copy prints 111adc fro111 the Polacolor origi nals; 111ost
often the copies are made by the Kodak Dye Tran sfer Process using d i rect
ca 111era sepa ration n egat ives 111ade Fro111 the origi nal Polacolor print.
The Polacolor 2 process, which replaced 111ost Polacolor 1 prod ucts in
1 975, has 111uch-i 111proved color saturation and co111pares favora bly with con­
ventional color processes. Polacolor 1 pri nts have poor l ight fad i ng sta b i l i ty
and should not be d isp layed for 111ore than short periods of t i 111e . However,
accelerated agi ng tests conducted by the aut hor, as well as exa m i nation of
ea rly Polacolor 1 pri nts, i nd icate Polacolor 1 prints have excellent dark keep­
i ng stabil ity and have a l 111ost none of the yel low sta i n formation evident with
the newer Polacolor 2 111aterials. For this reason, Polacolor 1 pri nts can be
considered q u ite su itable for col lectors who do not have l ow- h u 111 idity refrig­
e rated storage facil ities. The manufact u re of Polacolor 1 for general applica­
tions ceased i n 1 976; it was last available as Type 58 fil11 1 in the 4 X 5-inch
format. Polacolor 1 had a strong tendency to c u rl toward the i 111age side after
processing, so Polaroid suppl ied cards coated with a p ressu re sensit ive adhe­
sive with the 111 111 for 111 o u n t i ng the pri nts to keep them flat. The effects of
the adhesive and card stock on the lo ng-ter111 keeping of the prints a re not
cu rrently known . I t is possible to re111ove the prints fro111 the cards using
special techniq ues.

Kodak I nstant Print Film PR10. P R 1 0 print 11 1 111 and cameras for use with
the film were i ntrod uced by Kodak i n 1 976 to co111pete with the establ ished
Polaroid SX-70 syste 111 . Like S X 70 , the prints are a n i n tegral sealed package
-

with all processing che111 icals and other components remai n i n g in the print
after processi ng. Also l i ke SX-70, P R 1 0 prints a re covered on both sides with
polyester sheets. P R 10 has another plastic layer coated o n top of the cover
sheet which is e 111bossed to give it a se111 i-gloss su rface. L i ke all other i nstant
color systems, P H 1 0 prints a re u n iq u e prints u n less duplicate photographs
have been taken of a static scene. For this reason , they must be t reated with
special care.
The author does not know of any seri ous artistic p hotographer who
has done extens ive work with the P R 1 0 syste 111 . While the Polaroid Corpora-
 Reading 50 \V I L I I E L M

tion has encouraged art1st1c appl ications of its products, Kodak has made
no such effort with the P R 1 0 system. I ns tead, Kodak has ai med its extensive
advertising campaign for PR 10 toward the casu a l s napshot user with no s ug­
gestion that the prod uct m ight also be u sed by more serious photographers .
P R 1 0 prints have exceed ingly poor light fadi ng sta bility-probably
m uch worse than any other currently manufactu red color print material in
the world-and in natural aging tests u nder typical home d isplay conditions
i n the home, severe dye fading and color s hifts occu rred in less than eight
months' time. P R 1 0 prints also have poor dark fad i ng sta bi lity with loss of
dye density and stain formation occurring i n a relatively short period of time.
PR10 prints should be avoided by photographers and collectors alike. If a
val uab le P R 1 0 pri nt mu st be preserved, it should be kept i n the dark at low
temperatures and low relative h u m i d i ty.

Photomechan ical Color Printing Processes. The author has clone only
l i m ited research into the stability of the fou r-color ink sets u sed with the
photomechanical pri n t i ng processes such as offset l i thography, gravure, and
letterpress prin ting. AJI of the samples tested t h u s far have poor light fad­
i ng stability. Samples tested to elate i ncl u de randomly se lected posters, book
pages, postcards, catalog pages, etc., as wel l as i n k company sample books.
I n spite of poor l ight fad ing stabil ity, the few samples tested appear to have
excellent dark keeping stability i n accelerated agin g tests. Exa mi nation of old
books and magazines printed in color tend to s upport the general conclu­
sions of these accelerated tests. Due to the i nstability of most color camera
f i l ms and photographic color print materials, i t i s obvious that most color
photographs will not s u rvive in any form u nless t hey happen to be pri nted in
color in a book, magazi ne, or other p u b l ication that is protected from pro­
longed exposure to l ight. Future reproductions w i l l in most cases have to be
made from the printed version, and not the original color photograph. Some
photographers, particularl y i n Europe, have offered portfolios of color photo­
graphs printed by gravure or offset l i thography on h igh quality paper. Assu m ­
i ng that t h e printing paper i s o f a stable type, an d that t h e pri n ted sheets are
kept in the dark except for occasional viewi ng or s hort term d isplay, this use
of printed reproductions i s probably a reasonable method of collecting color
photograph s . However, many coll ectors have val i d objections to col lecting
pri nted reproductions.
In conclusion, of the currently available color pri nt processes, only a
few are s u itable for use when long-term non-refrigerated keeping is requi red
with photographs of persona l , fa m i ly, h istoric, scientific, artistic, com mer­
cial, journalistic, and poss i b le future economic i mporta nce. These are l i sted
in the box on this page [p. 470 in t h i s vol u m e ] .
Part VI T ll E l' H E S E H V A T I O N O F C O L O H P II O T O G H A P H Y

Recommended Color Print Materials

User or L a b Processed C i bachromc (non-RC su pport types only)
Kodak Dye Transfer ( paper support)

Lab Processing 011/y Fuji Dyecolor Print (paper su pport)

Fresson Quadrich romie ( paper support)

I n s t a n t Color Photography Polaroid Polacolor I (obsolete process)

(if required) Polaroid XS-70 (tentative recom mendation)

All or t he six materials l isted arc subject to l ight and U V rad iation caused dete­
rioration: prints should be kept in the dark For long-term keeping. Prints used for dis­
play pu rposes should be monitored lo prevent dctcriorntion beyond pre-set l i mits. Fresson
Quadrichro111ic prints appear to have excellent l ight fad i ng stabil ity and can probably be
displa)'Cd sal'ely for many years. However, Quadrichromie prints should a lso be monitored
ii' very long-term d i splay is plan ned. The recommendation l'or SX-70 is tentative as dark
keeping lest data is i ncomplete.

It should be noted that none of the six recommended pri nt materials

make use of the com mon chromogenic development method of color i mage
formation. A l l cu rre nt chromogenic materials, such as Kodak E ktacolor 74
RC paper, have dark keeping stabil ity which is not nearly adequate for the
req u i rements of col lectors . \t\fh i l e the i n tensity and spectral content of the
l ight in d isplay locations can vary a great deal from place to place, Ektacolor 74
RC paper may be ex1Jected to exhibit sign i ficant l ight fading in 3 or 4 years
and serious deterioration in 1 5 or 20 years when prints are d i splayed u nder
typical conditions fou n d in the home. i\l l ost other chro mogenic and all c ur­
rent instant color print p rocesses may be expected to deteriorate even faster
than Ektacolor 74 RC u n der typical d isplay conditions. The great m ajority of
color photographs i n existence today have been made on chromogenic mate­
rials. All color camera fi l m s curre ntly i n production, with the exception of
the i nstant color materials, make use of chromogenic development.
The only cu rrently availa ble mea ns of prese rving chro mogenic color
photographs is to store them in the dark a t very low temperatures and very
low re lat ive humidity. While to elate only a few large-scale cold-storage fac i l ­
i t i es have been constructed, progress is being ma d e . The U . S . Library of
Congress recently began operation of a large faci l ity n e a r Was h ington, D. C.,
for the storage of color motion pictu res and st i l l photographs ; it has an oper­
ating temperature of 35° F ( 1 . 7° C) at about 30% relative h u midity. The new
John F. Ken nedy Presidential Libra ry now under construction near Boston ,
Massach usetts, will have a o° F (- 18° C) 30% RH vau l t for the storage of its
la rge co l lection of color negat ives and other color photograph s . There are
also a number of other low tempera t ure va u lts in North America and Europe
which are used for the storage of color motion picture fi l m s . Many more
cold storage fac i l it ies need to be b u i l t .

.1 7 0
 R e a d n g 51

RO B E RT J . T U ITE

I mage S tability in C olor

Photography ( 1 979)

R obert Tuite worhed in the Research Laboratories of the Eastman Kodah Com­
pany in Rochester, New Yorh. His 1 979 article "Image Stability in Color Pho­
tography" is a clearly presented overview of the coniplex mechanisms of light
and darh ( thermal) fading of color photographic dyes. In addition to the mech­
anisms of dye fading, Tuite also summarizes color perception and how it is
used in the engineering of color materials as well as some of the historical dye
stabil-ity issues beginning i n the 1 940s. Since the introduction of Kodachrome
in 1 935, the engineering of c hromogenic color materials at Kodalz and the rest
of the 11hotogmphic industry has always been a balancing act between cost,
ease of use, and permanence, among other things. Fro-rn the beginning Kodah
was capable of c reating remarlwbly permanent color materials, as evidenced
by the Kodachrome transparency and print materials. However, the most per­
manent processes were not always the most practical in the marlwt. While the
Zach of permanence of many chromogenic materials is a serious challenge for
conservators, articles lihe Tuite 's demonstrate the complexity of the problem
and show that color instability was not due to careless product development
or the inability to create more permanent products, but rather the result of a
com11lex interaction of raw materials, scientific research, consumer desire, and
economics.

ROBERT J. TUITE, " I mage Stabi l i ty i n Color Photography," Journal of Applied Photographic
Engineering 5, no. 4 ( Fall 1 979) : 200-207. © 1 979 Society of Photographic Scientists and
Engineers. Repri nted by perm i ssion of I S &T: The Society for I maging Science and Tech­
n ology, sole copyright owners of Journal of Applied Photographic Engineeri.ng.

47 1
Part VI T H E P H E S E H V AT I O N OF C O L O H P H O T O G R A P ll Y

I n troduction

I mage stabil ity is one of several i mportant fac tors in the design of a color
photographic product. E m u l sion speed, tone scale, color reproduction,
sharpness, gra i n i ness, shelf stabi lity, and process considerations (simplicity,
compatibil ity, ecology, etc . ) are also some importa n t features. Because there
a re i n herent t radeoffs i n the design of any product, these design factors m u st
be weighted according to their i mportance to the spec ific product. I n a given
prod uct, for exa mple, one may chose to trade a sharp ness advan tage for bet­
ter color reproduction i f that should be both possi ble and desirable.
With regard to i mage stabil i ty, and l ight stabil i ty i n particu lar, the encl
use of the prod uct determines the relative importa nce p laced on this design
feature. For example, i n a n amate u r super-8 motion-pict u re fi l m , a given
frame may not experience even one second of i l l u m in ation from the projec­
tor lamp in its entire l i fetime. A profess ional color enlargement print, on the
other hand, should withstand exposure to light for many years . I n virtually
every color photograph ic product, however, good dark keeping stabil ity ( i . e . ,
t o heat, h u m id i ty, etc . ) i s required.
No color p hotograph i c product yet has arc h ival stabi l i ty u nder all con­
d itions of use. The same m ight be said for virtually any colored materi al.
I n deed, all dyes change in time; it is the rate of change (or fad i ng) that dis­
t inguishes the more stable dyes from those less stable. The progress made i n
prod ucing more stable color images has resu lted from decreasi ng the rate of
change to the poi n t where the stab i l i ty over a reasonable time is acceptable
for most applications. Once we ach ieve a position where fading is not per­
ceived, image stab i lity becomes a scientific rather than a user issue.
I n this paper we i l l ustrate the progress made d u ri ng the past fou r
decades i n im provi ng t h e s tab i l i ty o f color images a n d provide some insight
i n to how this was achieved. \Ve also review some of the methods used for
measuri ng image stab i l i ty u n der acce lerated test conditions and appraise the
u t i l i ty and pitfalls of these tests as pred ict ive tools. Where appropriate, the
tec hnological advances a re i l lustrated by sta b i l i ty data from spec i fic color
products. In most cases, however, the image stabi lity i mprovements a re a
res u l t of generic tec h nology and a re more broadly applicable.

I mage Stabili ty Evaluation

The true meas u re of the adequacy of color image stabili ty is how color images
endure normal keeping conditions set by users of the p hotographic materia l .
However, the chemical reactions involved i n t h e degradation of color i mages
are so complex and so slow that accelerated laboratory test p rocedu res have

472
 Reading 51 TU IT E

been devised. Such tests provide q u ickly the kind of i n formation necessary
for product development progra ms a n d also p rovide a pred ictive tool for
assessing long-term i mage stabi I ity u n der normal conditions.
Accelerated keeping tests can be d ivided into two types: dark fad i ng and
light fad ing. I n the dark fad i ng tests, primarily heat and h u m i d i ty are u sed
to i nfl uence the rates of chemical reactions i nvolved i n image degradation .
Light fad i ng tests measure the photochemistry of the dyes and dye formers;
both the i ntensity and the wavelength d istrib u tion of the l ight source are
i m porta nt. Testing proced u res of these two types h ave been described in sev­
eral previous p ublications . 1 •2
O u r most credible dark keepi ng test uses the classi cal Arrhenius equa­
tion, which describes the rate of a chemical reaction as a fu nction of tem­
perature. Dye loss with t i me can be described by a s i mple first-order kinetic
e>.']Jression, i n which the rate constant (h) varies with tempera ture accordi ng
to the Arrhenius equ ation . Thus,

-d(dye) = h(dye)
dt

and

where A i s the frequency factor, E" is the activation energy of the reaction, R
is the u n ivers a l gas constant, and T is the absolute temperature (°K). Taking
logarithms of both sides of the equation gives a l inear relationship between
In h and 1/T; a lso, -In K is li nearly related to In t 1 110, which is defined as
the ti me req u i red to fade 1 0% of the dye from a n original density of 1 . 0 .
Therefore, in practice In 1: 1 1 1 0 is pl otted against the rec iprocal of the abso l u te
temperature, for several tempera t u res above 24°C (?5°F) ( room tempera­
t ure). By extrapolation of these plots to 24°C (?5°F), the time req u i red for a
0 . 1 density Joss at room temperature is predicted ( F igure 1 ) . Generally such
pred ictions agree wel l with actual keeping data where s ufficient time has
elapsed to obtain such data. For example, the data point i n Figu re r for the
cyan dye sta b ility at 24°C (?5°F) is from actual room temperat u re keepi ng; it
coincides with the extrapolation of the l i ne thro ugh the data poi n ts obtained
i n the accelerated tests. It is i mportant to note that a 0. 1 density loss was
chosen for p u rely scientific reasons. It is enough dye loss to measure with
confidence a n d i s j udged to be just noti ceable visually. Th is i nc rement is not,
however, a measure of the useful l i fe of a color i m age, as is discu ssed i n the
next section.
The temperature dependence of dye fad i ng can be u sed to advantage
to extend the stabi lity of color i mages by keeping the print both cool a n d dry.

4 73
 Part VI T II E P R E S E R V t\ T I 0 N 0 F C 0 L 0 R P 1-1 0 T 0 G R t\ P 1-1 Y

l--3�7�Y�E�A�R�S�M""--AG�E�N�T�A��� / /
19 YEARS YELLOW

()
II
0

d
II
0
<l
.2

0
_,-
Figure 1
Use or t h e Arrhenius equation to

Bs0c 24•c
predict d a r k keeping at 4 0% RH
v t
{ 1 960 in a ge color negative fil m ) .
2.8 3.2 3.4

Table 1
Effect of temperature on s t abil i ty of image dyes. ·'

Predicted t i me (l)
S torage a t 40% R H for
temperature, °C 0 . 1 density loss from D = 1.0

4 . I
1 6 . t.
3 4 0 . t.

Although image dyes i n differen t products vary widely i n their temperature

(and humid ity) response, the effect of temperature on i mage sta b i lity can be
estimated from Table 1.3 Where archival keeping i s demanded, for example,
freezing the color image will generally exten d the time for 0 . 1 densi ty loss by
a fa ctor of more than 3 0 0 .
Light fad i n g of dyes is much more comp lex than dark fad i ng. Possibly
because of the ro le of ox')'gen i n the photochemistry of dyes in the photo­
graphic med i u m , the quantum efficiency of dye fad i n g (Cf>) is not a si ngle-

474
 Reading 51 TU IT E

value parameter, but varies with the i n te nsity ( I ) (as well as the wavelength)
of t he i l l u m i nant. Thu s ,

-d(dve) * ct> . 1
dt

I n t heory, a tenfold i ncrease i n i ntensity should result i n a tenfold increase

i n the rate of dye loss. In fact, this is seldom true, and i t is i mporta nt that
we recognize this so-called rec i proc ity fai l u re in our test proced ures. Any
i m provement observed at high i n tensi ty needs to be confi rmed al lower,
more rea l istic i n tensity levels.
Photographic p roducts can be ra n ked accordi ng to the re lat ive i mpor­
tance of light stab i l i ty in their performance. Products that are i l l u m i nated
either continuousl y or for long t i mes, such as d isplay t ra nsparenc ies and
enlargement prints, are the most demanding for l ight sta b i l i ty. These a re
fol lowed i n order by s n apshots, sl ides, and movies. Color negatives are the
least demanding because they a re seldom v iewed d i rectly and a re usually in
dark storage .
Under actual keeping conditions, some comb ination of light and dark
fad i ng wi 11 determi n e the stabi Ii ty observed, as shown schematica I ly by the
following equation:

observed i mage fade = a ( l ight fad ing) + f3 (dark fad i ng)

where the relative contrib u t ions of a and f3 for a given product a re deter­
m i ned by the keepi n g conditions. H ow stability data from accelerated tests
can be u sed to model long-term keeping by u sers is a complex problem for
which we have no quantitative sol ution. \i\lherever possi ble, however, keep­
i ng data from u sers are gathered to provide i n s ight i nto the relat ive i m por­
tance of these two components of image degradation i n various products.

Perceptual Factors i n I mage Degradation

Before leaving the s u bject of how i mage stabil i ty i s meas u red, some discus­
sion on the perceptual i m pact of i mage degradation is appropriate. As stated
previous ly, a o. r density loss is u sed as a meas u re of dye loss; the visual
i m pact of this change depends upon several perceptual factors:

1. Contrast c ha nge vs. color balance c hange: A r o% contrast cha nge i s

virtually u ndetectable b y our visual system, whereas a color balance cha nge
of the same magnitude is often noticeable. Thus "neutral" fad i ng, where a l l

-1 75
Part VI T ll E P H E S E H V J\ T I O N O F C O L O H P ll O T O G H A P ll Y

t h ree dyes fade at equivalent rates, is prefe rable to selective fad i ng of one
or two of t h e dyes. F u rthermore, i f only one of the dyes fades, we are least
sensit ive to loss of yel low dye and most sensitive to loss of magenta dye for
equ ivalent density losses. 4
2. \lieivi. n g conditions: The eye is most sensitive to cha nges in a reflec­

tion print that is viewed i n a well-l ighted room because t here are many
reference points against which the i mage can be compared . 5 Fad i ng of t rans­
parencies or motion pictures is less noticeable because the eye acco mmo­
dates to small color or con trast cha nges in a darke ned s u rro u n d . For color
negatives (or other printable materia ls), the printer often does a satisfactory
job of compensating for fad i ng of t he negat ive i mage.
3. Single stiniu lus vs. pai red comparison: Changes in the color i mage

a rc most noticeable when an original reference poi nt is avai lable, e.g. , when
half of a pri n t is covered and the other ha lf is faded by e>.lJOSu re to light.
U nder such conditions even a 1 0% u n i form dye loss is usually evident. On the
other hand, i n the absence of the original print as a reference, a u n iform loss
of 1/i of all t h ree dyes m ight sti l l provide a lower quality b u t acceptable print
to most people.
4. Scene dependence: The eye is most sensi tive to changes i n " mem ory"
colors, es pec ially flesh, and in particu lar, flesh that goes cold. C hanges in the
color of sky, grass, and nearly neutra l objects, such as u nstained wood, a re
also more objectionable than are cha nges in brightly colored objects because
of t h is me mory factor.

Thus, aside from scientific and technological considerat ions, t he key

issue in i mage stabi l i ty is how the viewer perceives the subtle changes that
take place i n a color i m age over a period of t i me i n terms of picture q u a l i ty.
These subtle changes m ight in fact be compared to the normal color and
contrast va riab i l i ty encou n tered in the manufact u re , processi ng, and use of
color photographic products. Efforts a re u nderway to eva l u ate i m age degra­
dation psychophysically in order to assess better the i m pact of such changes
on the q u a l i ty of the color i mage as perceived by t he viewer.

I mage S tabi l i ty Technology

I n t rad i t ional color p hotography, the t h ree i mage dyes (ye l low, magenta, and
cyan) arc fo rmed by coupl i ng of the oxid ized developer with a coupler as
follows :
 Reading 51 TU I T E

R'COCCONH-0R"
II

�NR, Yellow
dye
*NH., �Ex posed
< >AAR. [Q:lN-N
©l\-N
o0'
NR,
A gX

NR,�
Magenta
dye
� R' ?-R
0

OH"

�NR,Cyandye
I n the Kodac hrome process, the dyes a re precipitated at the site of the devel­
oping si lver, and the u n u sed couplers are washed out of the fllm. ln this
environment the dyes are very stable to dark keeping. Kodachrome s l i des
made more than 40 years ago have kept extremely well in dark storage and
virtually a l l Kodachrome prod ucts are predi cted not to lose 0 . 1 density for
more than 50 years i n normal storage. 6
I n pro ducts such as Kodacolor a n d Kodak E ktac hrome fl lms, the cou­
plers are ballasted with a h igh-molec u lar-weight fragment to keep them
i m mobile i n the proper layer. Th is i n n ovation greatly simpl ined the pro­
cess ing of color products. As a res ult of this feature, residual couplers are
prese n t i n the image in i nverse proportion to the amount of dye formed.
Therefore, i n such products, we have to be concerned not only with the fad­
ing of the dyes but also with color-form ing reactions of the residual cou­
plers and any u ndesirable i nteractions between the res idual couplers and the
image dyes.

477
Part VI T 1-1 E P R E S E H \I A T I 0 N 0 F C 0 L 0 H P II 0 T 0 G R A P II Y

Early color prod ucts contai ning i ncorporated couplers were less stable
in dark storage (albu ms, fi les, etc . ) than their Kodachrome counterparts. For
exa mple, prints made on Kodak's origi n a l color paper i n the early 1 940s not
only lost dye density, but the borders turned ye llow in a few years of d ark
storage; this situation persisted to some degree i n to the early 1 950s when a
much more stable paper was introd uced. Ea rly Kodak Ektachrome transpar­
encies were also not as stable as Kodachrome transparencies, but the c u r­
re nt E ktachrome films have dark keepi ng sta b i l i ty nearly compa rable to that
of Kodachrome fi lm.6 During this time the l ight sta b i l i ty of such color p hoto­
graphic products has also been greatly i mproved.

Magenta Image Stabilit.y

As stated above, early color prints turned yel low in the borders a n d to some
extent i n the i m age a rea also. Photomicroscopy revealed that the ye l low color
was primarily in the magenta layer and was present wherever magenta dye
was missi ng, thus i m plicating the magenta coup ler.
The m agenta coupler u sed i n earl y color prints reacted to give yel low
materia ls: princ ipa l ly the methynyl bis coupler ( I ) in the dark and the azo dye
( 1 1 ) in the light - two d i fferent reactions, but the same visual res u l t.;

RO
�N-N
O�NHR'
CH
1 OH
R' N H "<Y
N-N
"©lOR
I ( + other products)

II ( + other products)
 Reading 51 T U I T E

S u bstitution of the two ortho positions of the 1 -phenyl ring, e.g.,

Cl '!CJ(' Cl

N
rr -
C
� NHR'
JO

produced magenta couplers whi c h were much less prone to t h is yel lowin g
reaction because o f two factors. F irst, t h e rates of t h e reactions i nvolved
were s lowed down dramatical ly, a n d second, the products that were formed
had their spectral absorption shifted into the u ltraviolet where it i s m u c h
less visible ( Figure 2 ).
Another trou b lesome reaction i n early products was t h e reaction o f the
residual magenta coupler with the magenta dye to form a variety of colorless
products, particularly evident in the toe region of the H and D c u rve because
of the 1:2 stoichiometry i nvolved:

magenta dye + 2 resi d u a l coupler � leuco magenta dye + bis coupler +

other products

The use of aldehydes i n the fi na l processing bath prevented this reaction.8

R "-..
N-N

O� R'

�
+ R"CHO --+ CHR" + other
products
R' O

N-N

l madg;;ta
-......_ R

no reaction

Later, magenta couplers were devised that s howed much lower tendency to
react with their mage nta dyes.9
Because of these technological advances, none of the modern Kodak
color photographic m a terials that use traditional processing are magenta-dye
l i m i ted for dark stab i l i ty, and virt u ally all are predic ted to keep more than
5 0 years i n the dark without exceedi ng 0 . 1 densi ty loss in m agenta dye. 6
H istorical ly, m agenta dyes i n traditional color products have been
l i mi t i ng for light stab i l i ty, a problem aggravated , i n fact, by substituting the
1 -phenyl ring of the coupler as described above . M uc h effort has gone i n to
learn ing the mechanism of this photochemical reaction a n d applying that
knowledge to stab i lize the dyes to light. Although the detailed mechanism

479
 Part VI T H E P H E S E H VA T I O N O F C O L O H P l-I O T O G R A P l-I Y

1.8
A. 1942 Vintage Magenta Coupler
8. Mod e rn Magenta Coupler

?: 0
·u;
c
., E
,, I
0.9 I e - o.3 Kodak Eklacdor
0 I
u 0
I Professional Paper
·� I <J ( 1960 vintage)
0 0.6 I -Q.4
I
\
0.3
',s -o.s
.... - - -
-----------

o - o.s .___�10
�--�"'
2oc-----,3; . ---:t 0 ---;;:;;----c:
4 oa
L-__ L- -...L-��
5 �
0 ---'-
,--
0 s�
--: oo -
=--- -'- �
-., :---­ o- 4� so
,
DAYS
Wovelenglh
Exposure (Xenon ore)

Figure 2 Fig ure 3

Yellowing of residual magenta couplers, as measured Light stability of magenta d y e in color papers, a s measured in color patches
by reflection spectrometry in the border of Kodacolor exposed in a standard, s i m u lated glass-f-iltered daylight facleometcr (5.4 hh
prints made in 195 3 (A) containing 1942 vintage = 500 fc ) . 1 The Ektacolor paper ( 1 960) was processed in P - 1 22 chem istry,

magenta coupler and 1 957 (B). and the Ektacolor 74 paper was processed in Kodak Ektaprint 2 chemistry.

is beyond the scope of this paper, dye is destroyed via an oxidative mecha­
n is m i nvolving both s i nglet and triplet exci ted states of the dye, which are
produced i n the photoc hemical sequence. 1 0 Stabi liza ti on of the dye i nvolves
i ntercepting both the acti n i c radiation with a UV a bsorber and one or more
of the reactive spec ies with a quencher.
hv
Dye - Dye*

�
02
Dye* --+ Products

Dye*
or other Quencher
- Dye
reactive
species

M uc h of the technology for improved magenta l ight stab i l i ty is embod­

ied i n c u rrent Kodak E ktacolor paper. As shown below, the m agenta layer i s
protected from u ltraviolet radiation b o t h from above a n d below b y u ltraviolet
absorbers (some Fad i ng occurs by rad iation re Aected from the support) and
the magenta coupler layer contains stabil izers of the anti oxidant type 1 1 both
as part of the coupler molecule and as a separate addend u m .

CYAN COUPLER
---- -- UV-absorbing layer
MAGENTA COUPLER -- stabilizer-coupler
-
------ - stabilizing addendum
YELLOW COUPLER

-t8o
 Reading 51 TU IT E

Table 2
I m prove ment in l ight stabi l i ty of ye llow dye."·h

Dye dens i ty loss from D = r . o

@-coc-CONH-0
II R'
N

o/'
NR, "'
<CHJ,CCOCCONH-@
II R'
N

o/"
-0 . 1 6

NR1

fc ) fluorescent light. '

"36 days 1 6 hLx ( 1 500
hThe improvement shown is from a comparison of two successive
Kodak Ektacolor print materials/'

Progress m ade i n producing more ligh t-stable magenta i mages via sta­
b i l izer and UV absorber technology is illustrated i n Figu re 3 [see previous
page] , where magenta l ight stabi l i ty for Kodak E ktacolor 74 paper is s hown
to be about double that for a 1 960 vi ntage of E ktacolor paper. 6

Yellow I mage Stability

The largest si ngle i mprovement in yel low dye l ight stabi l i ty came from the
sim ple change from a benzoyl group,

@-co
to a pivalyl group, ( C H3)3CCO, on the yel l ow coupler (Table 2 ) . 1 2
Translation of the technology responsible for both the magenta and
yellow l ight stability improveme nts i n Kodak E ktacolor paper to color fi l m
prod ucts h a s n o t been straigh tforward because of additional tech n i cal
constra i nts. H owever, the new Kodak Vericolor pri nt fi l m 4 1 1 1 has much
improved yel l ow and magenta l ight stability via the above tec h nology relative
to the product that it is replaci ng.
U nder dark keeping cond itions, yellow dyes are the least hyclrolytical ly
stable of the three dyes , a characte ristic that poses a difficult da rk-sta b i l i ty
chal lenge . Aci dic hydrolytic attack occ urs at the azomet h i ne l i n kage ; 1 3 a l ka­
l i ne hydro lysis occurs at the keto l i n kage . 1 4
P a rt V I T H E P R E S E H V /\ T I O N O F C O L O H P l-I O T O G R /\ P H Y

r
-0
c
.,p- '-.

�
c NH
x

¢ N R,

several
products

Yel low dye fading is often the most pH sensitive of all i mage degradation reac­
tions. The final processing pH is c hosen to a great exten t by the need to have
the film pH at the poi nt where the rates of these two reactions are minimized.

9
<CH,1,CCO -Qr ON H
Cl

NHCOR

--©
Cl

COOH cCH3l3CCOCHCONH
m I ,
0 \

©----------��'NHSO,R
IV

Small-format photography, with i ts exact i ng i mage structure demands,

has placed an i ncreasing b u rden on the dark stabi lity of the yel low dye. The
req u irement for ever-thinner yel low layers led to very reactive, carboxy­
solubil ized two-equ ivalent yellow couplers ( l l l ) , 1 5 features which were detri-
 Reading 51 TU IT E

Table 3
Dark stabi li ty of yellow dyes.6

Predicted time (years)"

for 0.1 yellow dye
density loss
in dark keeping
Kodah Ektachrome 40 Movie F i l m (Type A) ( Process E M -25) 3
Eastnian Ektachrome VN Print F i l m 7399 ( Process E M -99) 7
Koci.ah Ektachrome 50 Professional F i l m 6 1 1 8 ( Daylight) 32
( P rocess E-6)
F<odacolor I I F i l m and Koci.ah Vericolor I I P rofessional F i l m
( P rocess C-4 1 )

" Generally ±: 20%.

" Product is cyan-dye limited.

menta l for dark keepi ng. Yellow couplers are now ava ilable with sol u b i l izing
groups of higher p l(,,, such as s ul fonamide ( IV); 1 6 their use has extended the
dark keepi ng stab i l i ty of yel low dyes manyfold.
The improvement in dark keepi n g of yel low dyes is i l lustrated in Table 3 ,
where t h e t imes o f 0 . 1 density losses for a n e w Kodak E ktachrome fil m and
for new Kodacolor a n d Kodak Vericolor films are compared with those for
two older films that contain the old yel low couplers .6

Cyan Image Stability

The cyan dye generally has been the most stable to light of the three dyes,
b u t there has traditionally been a tradeoff between l ight and dark stabil i ty .
The prim ary u ndesired dark reaction of the cyan dye i s reduction by the

o/
residual cyan coupler to the colorless leuco form of the dye. 1 7

c;·· &··
0 OH

R
+ -----+ + ox idation
products
residual
N c o u pler NH

¢ NR,

cyan dye
¢ N R,

leuco dye

Dark keepi ng of the cyans has also been a concern where processi ng control
has been i nadequate. Thus, a ny of a n u m ber of other reducing agents, which
may not be rem oved completely, can also cause this (or a s i mi lar) reaction:
e.g. , retained thiosulfate ( hypo) from the fix bath or ferrous i o n from a poorly
Part VI T II E p n E s E n \I A T I 0 N 0 F c 0 L 0 n p I I 0 T 0 G H A p 1-1 y

regenerated bleach-fix bath . 1 8·19 Even bal lasted hydroqu i nones, which a re

?'R
u sed as incorporated i nterlayer scave ngers in p roducts, can be involved.

colorless products
(dye partially

4NR, .��
regenerable by
+ oxidation )

OH reducing agents
cyan dye

� �:�
This problem has been helped greatly by a change from Kodak color
developi n g age nt C D-2 to C D-3 i n most p rocesses.
H,C,-N C,H, H,C, H � CH,

"""
I
d'
CH3

NH,-HCI NH,·3/2H,SO.-H,O

Kodak color developing Kodak color developing

agent, CD-2 agent, CD-3

But the major i mprovement in dark keeping of the cyan dye has res u lted
from use of couplers that give dyes of generic structure V I I , which contain
the am ide group in the 5-position. Dyes of this type a re much less prone to

4NHO)R
red uction than are the two class ical types \1 a nd V J .
0
AYCONHR'
0

R �

4NR", v
*NR", VJ

!y NHCOjR'
0

RCONH�

�NR",
Vil
 Reading 51 TU I T E

Table 4
Dark sta b i l i ty of cyan dyes."

Predicted time (years)"

for o . 1 cyan dye
density loss
in dark keeping
Kodah Ehtac'1rorne Duplicating Film 6 1 20 ( Process E-3)
Kodah Ehtacolor Print Film 4 1 09 ( Process C-22) 8
Kodalc Ehtaclironw D u p l icating F i l m 6 1 2 1 (Process E-6)
l<odah Vericolor Pr i n t Film 4 1 1 1 ( P rocess C-4 1 )

" G enera l l y ::!: 20%.

h Both products are yellow-dye lim ited.

The i mprovement is illu strated i n Table 4, where Kodak Vericolor

print fi l m 4 1 1 1 and Kodak E ktachrome duplicating film 6 1 2 1 , which conta i n
the new coupler type, are compared with the products t h a t they rep laced.6
The time to 0 . 1 density Joss has been extended from 5-8 years to beyond
50 years.

Overall Progress in Light Stability

The long-term progress i n improving l ight stability i n traditional color

p hotography is best illustrated by the improved l ight stabil ity of several ge n­ Figure 4
erations of Kodak Ektacolor paper (Figure 4). The measu re of stabil i ty used Light stability of selected
professional color papers. The
i n the figure is the time to fade 20% of the l i miting dye i n the standard simu­
lated dayl ight fadeometer (5-4/d:x 500 fc). 1 Whereas the least stable dye i n
bars represent the time required
= for a 20% density loss of the
limiting dye from a neutral patch
exposed i n a stanclard1 simu lated
glass-filtered daylight Fadeometer
( )-4 h/x = 500 fc). 1 A = T)1>e I
Kodacolor paper (P- 1 21 process);
B = T)1>e I I ( UV absorber added)
( P - 1 2 1 process); C = Type C (new
F
£klocolor
magenta and yellow couplers
Kodok 74 Paper _.
( P- 1 22 process): Kodak color
E
developing agent CD-3 replaced
C D - 2) ; D = Kodak Ektacolor
D profess ional paper ( t hree new
couplers; new u ltraviolet absorber)
( P- 1 22 process): E = Kodak
c Ektacolor professional paper
P 1 685 (stabilizer i n magenta layer)
B ( Ektaprint C process); F = C u rrent

I
"'
Kodak Ektacolor paper (stabilizer-

8 A
magenta coupler and stabilizer
+-Type! Kodacolor Paper in magenta layer; new ycl lmv
coupler; UV-absorbing resin-coated
support) ( Ektaprint 2 process).

Year introduced
 Part VI T l-I E P R E S E R V A T I O N O F C O L O R P l-I O T O G H A P l-I Y

- 1
0.

0 -0.2

_g
E
-0.3
Figure 5
0
Light stability of Kodak Ektacolor <J
- 0.4
74 prints vs. dye transfer prints, as Dye Transfer Poper

measured i n color patches exposed Kodak Ektocolor 74 Poper

in a standard, simu lated glass� -o.5

-O.SL----±10----i20,,---f30,-,4';:0---...,5;!;0;--;!60'
fi l tered daylight fadeometer
(5·4 /,h = 500 fc) . '
DAYS
Exposure ( Xenon ore)

the original (Type I ) Kodacolor paper faded to this extent i n �2 days, the l i m ­
iting dye i n the new E ktacolor 7 4 paper requires nearly 1 50 days of contin u ­
ous i l l u m i nation for t h e same a m o u n t of fad i ng t o occur. T h e various bars
on F igure 4 represent a selection of new color papers conta in in g a n um ber of
the aforementioned stabilizing features: n ew U V absorbers, a new developer,
new couplers, and stabi lizers .
A further i l l ustration of the curren t l ight stability position i s the s upe­
rior stabil i ty of prints on Kodak E ktacolor paper relative to dye transfer
prin ts, for m any years the quality standard i n color photography for sta b i l i ty
to light ( Figure 5). Kodak l i teratu re states that E ktacolor paper prin ts h ave a
useful l i fe of 1 5-20 years or more i n typical home display. 3

Masbng Dyes

Before leaving traditional color photography, we should comment on the s ta­

b i li ty of the masking dyes, which i mpart the fam iliar orange hue to color neg­
atives. These dyes are very s table to dark keeping (t 1 n 0> 50 years ) ,6 b u t will
fade under prolonged exposure to light. They are stable enough to survive
many printings, however, a n d s ince negatives were never meant to be dis­
p l ayed, l i tt le effort has been put i nto further i mprovi ng their light stability.

Stability of Koda k lnstant Print Film20

The chemistry of instant color p hotography differs from that of traditional

photography in that preformed i mage dyes are either mobilized or i mmo­
b i l ized (depending on the system ) as a fu nction of development. In the
Kodak system, a mobile i mage dye i s released i magewise from a n i m mobile
dye releaser as a fu nction of s ilver development by a mobi l e cross-oxid izing
developer or electron transfer agent ( ETA) . 2 1
 Reading 51 TU I T E

OH
©Q'"''m' 0

@¢r"'"'"NHSO, dye
dye releaser
()
ETA ETAox NSO, dye
oxidized dye releaser

l ow
0

©Q-'"""'
no dye release

0
NHSO, dye (mobile)

Si lver development converts the ETA i n to i ts oxidized form ( ETA0.J which

i n turn oxidizes the dye releaser to the a lkal i -u n stable qui nonemonoimide,
which hyd rolyzes to yield mobile dye. The modular nature of this chemistry
means that the image dyes can be designed and selected for characteristics
(e.g., color quality) that are i n dependent of the i maging chemistry, thereby
redu cing many of the constraints i m posed by traditional color photography.
There are, however, additional constraints i mposed by the i n tegral no­
throw-away feature of modern i nstant p hotography. After ejection fro m the
camera and for several weeks thereafter, the print remains wet i n ternal ly, a n
enviro n ment detrimental to image stability, particu larly u nder the extreme
conditions of l ight i n tensity and temperature used in acce lerated fading
tests. Such extreme conditions may also produce stain i n border areas that
does not occur under n ormal keepi n g conditions. Moreover, the cont i n uing
wet ness allows m i n u te traces of dye to continue to m igrate to the receiver,
fu rther complicating the gatheri ng of data. Therefore, data on i n stant color
prints may be subject to later revision as we learn more about how to run
accelerated tests i n this format.

Table 5
Light stabi l it y i n Kodak i nstant print fi l m/P R 1 0.'"h

Dye density loss from D = 1.0

Cyan Magenta Ye l low

\,Vet print - -43
Predried print -. 2 7 - .23 -.2 7

" 2 1 days 5.4 hlx (500 fc) s imulated, glass-filtered daylight. '
I.See Ref. 20.
Part VI T H E P R E S E R VA T I O N O F C O L O ll P II O T O G B A P H Y

As for d ark keeping,20 we esti 111ate it will req u i re at least 7-10 years for
a 0 . 1 density loss in Kodak i nstant print fil111/P H 1 0 for the l i 111iting m agenta
dye, 6 putting this product on a par with Kodak Ektacolor 74 paper (wh ich
i s cyan -dye l i 111 iti ng) for dark keepi ng. Our good experience with the a l b u 111
keeping of Ektacolor paper prints gives us confidence that P R 1 0 prints also
have satisfactory albu m-keeping stabi lity.
As for light stab i l i ty,20 the contin ued wetness of the print standard
si111u lated dayl ight fadeometer ()Ahl.x = 500 fc ), 1 the cyan dye faded about

60% 111ore in the wet print than in the predried pri n t, a condition which more
c losely s i 111 u lates the longer tim e and lower in ter111 ittent i ntensity of keep­
i ng by u se rs. Eit her wet or dry, these dyes are less stable to l ight than those
in Ektacolor paper, our 111ost stable trad itional color photographic product,
which, of course, has benefi ted from many years of resea rch . H owever, we
continue to 111ake progress on all fro nts in instant color photography, i nclud­
i ng new i mage dyes that are more light stable than those shown h ere.
\11/e have now had more than two years experie nce with this product
and have periodically 111onitored and evaluated prints kept u nder a variety of
typical home and office d isplay conditions, such as in picture cu bes and on
desk tops (as well as i n a l b u 111s, etc . ) . U nder these conditions, dye loss has
been relatively neutral through m ost of the tone scale and few prints have
shown a percept ual quality l oss due to fad i ng,22 a result consistent with o u r
assignment of the relative i mportance of light and dark keepi ng for a prod uct
of this type.

Summary

G reat progress has been made i n i mproving i mage stabi li ty in color pho­
tography si nce its i nception so111e 40 years ago. This paper reviewed some
of the tech nological accomplish111ents that have made this possible. While
there is still 111 uch work to be done, the i 111age stability of color photographic
prod ucts today is satisfactory for a l l but the most de111anding users. Treated
with the care they deserve ( i . e . , avoiding strong light sources and hot, h u m id
environ111ents), color photographs will last a long t i 111e .

N otes

1 (a) A 111erica11 National Standard J\llet liod Joi· Comparing the Color Stabilities
of Plwtogmphs, ANS I PH 1 .42- 1 969: (b) H u bbell, D. C., R . C. McKinney,
and L . E . 'Nest: '"Methods for Testing I mage S ta b i l ity oF Color Photographic
Prod ucts,"" Photogr. Sci. Eng. 1 1 : 295-305 ( 1 967).
2 Steiger, F . H . : "The Arrhen i u s Equation i n Accelerated Aging Studies,'" Ain.
Dyest11ff Heporter 46: 28 7-290 ( 1 958).
 Reading 51 T U I T E

3 Eastman Kodak Company P u b lication. F-30, " P reservation of Photographs "

( i n press).
4 MacAdam, D. L. : "Visual Sensiti\�ties to Color D i fferences in Daylight,"
J . Opt . Soc. Am. 32: 247-274 ( 1 942).
Evans, R . M . Eye, Film, and Camera i n Color Photography. John v\li ley and
Sons, New York, 1 959, pp. 1 72 , 1 73.
6 Larson, C . \�!., et a l . , Eastman Kodak Co. : u npubli shed work.
7 Rossiter, B. \>\/., Eastman Kodak C o . : u npublished work.
8 Vitt u m , P. W., and F. Duennebier: "The Reaction between Pyrazolones a n d
t h e i r Azomet h i n e Dyes," J . A 1 n . C hern S o c . 7 2 : 1 536-1 538 ( 1 950) .
9 Darlak, R. S . , Eastman Kodak Co.: u n p u b l i s hed work.
10 S m i t h , W. F., J r . , \>\/. G . H erkstroeter, and K. L . Eddy: "Quenc h i ng of S i nglet
M olecular Oxygen in Solution by Azometh i ne Dyes," J . Am . Chern. Soc. .

97' 2764-2770 ( 1 975); "Mechanistic Pathways for Visible Light Fading of

Pyrazolone Azomethine Dyes i n Oil-in-Celation Dispers ions," Phot.ogr. Sci.
Eng. 20: 1 40-1 48 ( 1 976); and u np u b l ished data.
11 Lestina, G . J., a n d \>\/. A Reckhow, Eastman Kodak Co.: u n p u b l i shed work.
12 Weissberger, A., and C. J . K i b ler: U . S . Pat. 3,265,506 ( 1 966).
13 d e H oFfman, E., a n d A. Bruylants: "Syntheses et Proprietes des Bases de
S c h i ff," Bull. Soc. Chim. Beiges 75: 9 1 -106 ( 1 966).
14 Sano, IC "The Alkaline H ydrolysis o f Yellow Azomethine Dyes," J . Org. Chem.
34: 2076-2080 ( 1 969).
15 Fleckenste i n , L . J.: U . S. Pat. 3,408, 1 94 ( 1 968).
16 Ca meron, R . , a n d W. Gass: U.S. Pat. 3,894, 875 ( 1 975).
17 Osborn, H . J . , Eastman Kodak Co.: u npublis hed work.
18 Larson , G. W., D . C. H u bbell, and L . E. West: J . S . M .P.T. E . 7 1 : 495-501
( 1 962).
19 H o rowitz, P . , and W. R . Weller: "Some Considerations o f Eastuwn Color Print
F i l m Dye Stabil i ty, Ibid. 67: 401-404 ( 1 958).
20 Kodak instant p ri n t film h a s s i n ce been replaced by an i m proved vers ion,
Kodak instant color film. Among the fea tures of this new prod uct is improved
i mage stability u nder both dark and l ight keeping conditions.
21 H a nson, \>\/. T., J r . : "A F undamentally New I maging Techno logy for I nstant
Photography," Photogr. S c i. Eng. 20: 1 55- 1 60 ( 1 976).
22 Porter, R . F . , Eastman Kodak C o . : private commun icatio n .
 R e a d i n g 52

C HARLETON C . BARD, G EORGE W.

LARSON, H OWELL HAM M O N D ,
A N D C LA R E N C E P A C KA R D

Predicting Long-Term Dark S torage

Dye Stability Characteristics of
C olor Photographic Products from
Short-Term Tes ts ( 1 980)

Tiiis article was coauthored by several researchers from the Eastman Kodah
Company in Rochester, New Yorh. Charleton Bard and George Larson worhed
in the Photographic Technology Division, Howell Hammond in the Research
Laboratories, and Clarence Paclwrd in the Film Technical Services Division. In
this article, which appeared a decade after the first publication of the use of the
Arrhenius equation for studying dye fading by Adelstein et al. (see Reading 49),
Bard and his coauthors set out the detailed use of the Arrhenius method for the
precise prediction of darh storage dye fading. As they state in the article, when
compared with the 1969 ANSI standard "this new test method is a considerable
improvement over previous methods for predicting the stability of color photo­
graphs to long-term storage at various temperatures. " Tiiat is the fundamen­
tal advantage of the Arrhenius model-by testing at only a few temperatures,
the results can he extrapolated to far lower temperatures. Jn natural aging at
these subzero temperatures, one would have to wait thousands of years to see
a significant change. Tiie adoption of this method has been universal in color
stability testing and provides the justification for cold storage of color 11hoto­
graphic materials as well as other chemically unstable materials such as film
on cellulose nitrate and cellulose acetate supports.

CHARLETON C. BARD, GEORGE \V. LARSON, H OWELL HAMMOND, and CLARENCE PACKARD,
" P redicti ng L o ng -Tenn Dark S torage Dye Stability Ch a ra c te ristics of Color P ho t o gra p h i c
Products from S hort-Term Tests," Journal of Applied Phot.og.-aphic Engineering 6, no. 2
(April 1980): 42-45. © 1980 Society of P h ot ographic Scientists and Engineers. Rep r i n t e d
,
by permission of J S&T: The Society for I maging Science and Te c h no l ogy s o l e copyri g h t
owners of Journal of Applied Phot.ographic Engineering.
 Reading 52 B A R D ET A L .

"All colors fade" like "all men are mortal" are u n fortunate facts of the real
world and are truisms that bear periodic restatement.
The colorants in autumn leaves, in i n ks a n d dyes, in tapestries and
paints, a n d even furniture stains, to name a few, will slowly fade.
Fading can be conveniently divided into two categories: light (photo­
c hemical) and dark (chem ical) keeping. I t is the dark-keeping factors that
are of interest in this paper. They include temperature, h umidity, and atmo­
spheric constituents. The most common atmospheric constituents that cause
colorants to fa de are su lfur oxides, n itrogen oxides, a n d ozon e . These gases
can be a n d have been causes of m arked fading of coloran ts in particular situ­
ations. H owever, overall, they are not of great concern.
More important are the factors [of] temperature a n d h umidity. The
fading of colorants, and specifically [of] the dyes u sed i n color photographs,
is the result of chemical reactions that generally go faster as the tempera­
ture and h u midity are increased. The chemical reactions i nvolved in the dark
fading of photographic dyes are primarily hydrolytic and oxidative-redu ctive.
For example [ Figure 1 , not reprod uced here ] , yellow dyes can hydrolyze via
two rou tes, acidic and basic. On the acidic side, hydrolytic attack takes place
at the azomethine linkage; on the alkaline side, hydrolysis occurs a t the keto
linkage. Ideally, the final processing pH adj usts the emulsion p H to a point
where these two reactions are minimized.
Fading of cyan dyes in the dark can be a reductive-type reaction as
s hown in Figure 2 [not reprodu ced here ] .
B ecause o f these fading reactions, it has been o f i nterest t o both the
manufacturer and the customer to attempt to predict the dark-storage sta­
b i l i ty of color photographs. Accelerated tests such as those described in the
AN S I Sta ndard PH 1 .42-1 969 have been used for this p u rpose . 1 This Stan­
dard recommends the accelerated test conditions of 140°F-70% RH to simu­
late the res ults obtained from long-term storage. Experience has s hown that
in many cases the relationship between the image s tability after a week at
1 40°F-70% RH and years at 75°F-40% RH is not the same for all products.
Consequently, the relative image stability of products as determined by keep­
ing at 140°F-70% R H may not be indicative of the relative i m age stability at
750F-40% R H .
The accelerated tests would b e m uc h more val u able if they could accu­
ratel y predict the actual c hanges that occ u r i n processed color films a n d
papers d u ring s torage at various conditions. T o t h i s e n d , t h e Arrhenius equa­
tion has been applied to the prediction of the dark-storage stability of color
p hotographs. The Arrhenius equation has been used b y others to predict the
aging characteristics of materials.2·3 In his famous paper, Arrhenius4 pro­
posed the followin g relationship between temperature a n d the specific rate
of a reaction :

49 1
Part V I T H E P H E S E H V AT I O N OF C O L O H P l-I O T O G R A P l-I Y

loo"' h a �
T
where h is a measure of the rate of the reaction and T is the temperature i n
degrees Kelvin . Thi s equation says that t h e logari thm of t h e specific rate of a
chemical reaction is proportional to the reciprocal of the temperature.
I f the l ogarithm of the specific rate ( h) of a reaction is plotted against
ZIT for several temperatures and a straight line i s obtained, then, by extrapo­
l ating this straight line, predictions of stabilities (rates of change) at lower
and h igher temperatures can be made.
The Arrhenius equation has commonly been applied to simple, homo­
geneous chemical reactions where the reactants and products are known.
It i s therefore something of a surprise that this equation is also satisfactory
to describe reactions as complex as the dark fading of dyes in color p hoto­
graphs. Nonetheless, in al most all cases so far tested, where the p redicted
fading rates can be compared to the actual long-term rates , the equation
has worked.
There are, of cou rse, l imitations on such an accelerated test. It m ight,
i n a specific case, give the wrong predictions. F u rthermore, the Arrhenius
equation says nothing about the effects of other factors on the rate of fading.
For example, h u midity is one such fac tor whose effect is not accounted for
by the equation . Table 1 [not reproduced here] s hows the effect of h u midity
on the stabil i ty of a particu lar yel low dye. An i ncrease from 40 to 60% R H
causes a two-fold decrease i n the dark stabi l i ty. This i s explicable i n terms of
the hydrolysis mechanism of yel low dye dark fading. I f the RH is reduced to
1 5%, the dark stab i l i ty is i ncreased twofold. These res u l ts i n dicate that opti­
mum storage would be at 1 5% R H ; b u t, since storage at that relative h u midity
m akes the e m ulsion too d ry and brittle, an R H of about 25% is recom mended.
To appl y the Arrhenius equation to the dark fading changes of color
p hotographic materials requ i res that some restrictions . . . be made on the
experimental condition s. We have c hosen to keep the RH at 40%, for exam ­
p l e . W e h ave also chosen to u se t h e density o f a b o u t 1 . o a s the i n itial density
for each dye . This density choice is qu ite arbitrary; the basis for its selection
is simply one of conve n ience.
An actual Arrhenius test is performed as folJows: First, several single­
dye, step-wedge exposures are made. 1 The film is then processed in a stan­
dard process and densities are meas u red. The processed film strips are h u n g
on stainless-steel rods i n s i x ovens a l l at 40% R H a n d at t h e controlled tem­
peratures of 52°, 60°, 68°, 77° , 85°, and 93°C. At appropriate times, density
measurements are made to give cu rves l ike those shown i n Figure 3 [not repro­
d uced here] . All density measurements are corrected for D-min changes. The
changes in the D-min were su btracted from the changes in the dye densities
so that o n ly the fading of the dye itself was being measured. The D-min may

492
 Reading 52 B A R D ET A L .

i ncrease, decrease, or remain unchanged d u ring dark storage. Th is Arrhenius

method can also be u sed to pred ict changes i n the D-min.
The vertica l axis i n Figure 3 [ not reproduced h ere] is the dens ity of the
dye ( i n this case the red d e nsity of the cyan dye ) . The horizon tal axis is the
logarithm of the tim e in days and years . The u se of the logarithm of the time
is si mply to get all the data on one graph and has no other sign i fi cance. In all
cases, the origi nal densi ty of the dye i s 1 .0 .
S mooth curves are then Fitted b y a compu ter calculation t o t h e points
on the fading curves for each cond ition. From these s moothed curves the
part i c u l ar times req ui red a t each condition for the density to decrease 0 . 1 ,
0 . 2, 0 . 3 , and 0 - 4 are determined .
For this cyan dye, these ti mes (tT) are shown i n Table 3 [ not repro­
duced here] . These times (tT) are i nversely proportional to the rate of fad­
i ng (h) at each temperatu re and, therefore, to the reciprocal of the absol ute
temperature.

I
1 /tT ex lz ex -
T
where tr is the time required to lose the i ndicated densi ty at temperature T
and I<. is the specific reaction-rate constant.
If the Arrh e n i u s equation is applicable, then the plot of log l/tT against
UT should yield a straigh t l i ne. These plots are show n in Figu re 4 [ not repro­
d uced here ] . For this product, the points do fal l on straight l i n es .
B y extrapolating these stra ight l i nes t o room temperature, 24°C , a pre­
d iction can b e made of the time requ i red for the cyan dye to lose the speci­
fied density at these conditions; 24°C-40% RH. These pred ictions for the
times req u i red to lose 0 . 1 , 0.2, 0.3, and 0.4 in densi ty are respect ively 5, 13,
25, and 40 years.
I n addition, as previously mentioned, the straight-line extrapolation can
be made to any temperature of i n terest. This a llows the person storing the
photograph to choose a storage temperature that gives a desired stability.
A convenient reference that relates the i ncrease in stability to a
decrease in storage temperature is shown i n Tab l e 4 [not reproduced here] .
For example, freezi n g the color i mage will extend the time for a given density
loss as compared to that at 24°C and 40% R H by a factor of over 300.
It is of u t most i mportance in u s i ng this test procedu re that the manu­
facturer's processing recommendations be followed to the letter i n order that
the data obtained can be compared a mo ng laboratories. F u rthermore, s i nce
the processes are carefully designed to give optim u m dye stabili ty, any pro­
cess ing change could lead to a sign i ficant reduction in stability as predicted
by this test-a prediction that is ulti mately what should occur on long-term,
ambient storage.

49 3
P a rt V I T H E P R E S E R VA T I O N OF C O L O R P l-I O T O G R A P l-I Y

F igu re 3 [not reproduced here] also compares actual room-temperature

fad i ng with pred icted. About 5 years of actual keeping data h ave been accu­
m u lated to date, and t he resu l ts are withi n about 0.02 density u nits of the
predicted dye density.

Precision of the Arrh e n i us Test

It is not possible to q uote a u n i que val u e for the sta ndard deviation for the
predicted t imes for all produ cts. H owever, eJqJerience, based on many years
of using the Arrhenius test on many p roducts, has shown that an overal l
estimate o f the precision o f the predi cted time is about ±20%. For exam­
ple, if the average predicted time for a given densi ty loss at 24°C-40% R H
from many tests i s 1 0 years, the range of the predicted resu l ts wou l d be
8 to 1 2 years.
The use of a compu ter to analyze t he data has i mproved the precision
of the test as compared to the earlier manual methods. The principal source
of vari a b i l i ty now appears to be i n the i n c u bation portion of the test.
The i nc u bation part of the test p rocedure is done in one of two ways.
I n the fi rst, a sufficient n um ber of strips are p u t i n to each oven so that dupli­
cate strips can be removed at each t ime, for a total of about six times. This
procedure can involve from 50 to 1 00 strips depending on the n um ber of
ovens and t he n u m ber of t i mes strips are removed. Each data point for a
given oven is an average of two s trips . Normal ly, the agreement i n dye loss
between the two strips is very good (±0.01 dens ity u nits). Alternatively, two
strips can be put i n to each oven a n d repeatedly taken out, measured, a n d
returned to t h e oven for further incubation. B o t h procedures give compa­
rable res u lts; the choice between them becomes one of conve nience.
F igure 3 [not reproduced here] s hows how wel l the s uccessive data
points fal l along a s mooth curve, which i s , i n a way, a measu re of the prec i­
sion of the test.
The u se of a computer to fit the curves to the data points and to
extrapolate the Arrhen i u s straight-line plots res u l ts in one predicted time for
a specified temperature.
To reiterate, the principal source of variab i l i ty i n the test is most
probably in the repeatability of the specific test conditions of temperature
and h u m i d i ty.

Accuracy of the Arrhenius Test Predictions

A good esti mate of the accu racy of the Arrhen i u s test has yet to be made. The
problem is the long time req u ired for the color photograph to fade signi fi ­
cantly i n the dark at a m b i e n t conditions (24°C-40% R H ) . At present, o n ly a

494
 Reading 52 B t\ B D ET A L .

few comparisons between predic ted and actual dark fad i ng have been accu­
m u l ated, and even in these cases, very l ittle fad i ng has actually occu rred.
One such comparison i s for the cyan dye i n Kodak Vericolor I I professional
film 5025, type S.
Another prod uct for which a comparison can be made is Kodak E ktach­
rome duplicating fi l m 6 1 20 ( Process E-3). The predicted rate of fad i ng for the
cyan dye is within a year or so of the observed, with the actual rate of fading
being slower than the predi cted rate [ F igure 5, not reproduced here] . O n ly
six years of storage at ambient conditions (24°C-40% R H ) has been acc u m u ­
lated for this product at these conditions so t h a t actual total cyan dye loss
from an origi nal density of 1 .0 has just about reached 0. 1 .
A third product for which a comparison can b e made i s Kodak E kta­
color 37 paper. Figure 6 [not reproduced here] shows the data for the accel­
erated tests and the predicted and observed fad i ng for the cyan dye . I n this
case only four years of storage data are available.
The cyan dye i s predicted to lose about 0 . 1 density i n about 10 years
at 24°C-40% R H . In four years, it has lost 0.03 i n density. The agreement
between the predicted a n d observed rate of fad i ng i s aga i n very good.
B ased upon comparisons such as these for a variety of products, the
accuracy of the estimated rates of fad i ng of the dyes in the dark at ambient
conditions is guite good. From a practical standpoi nt, the test method gives
sufficiently accurate predicted rates so that usefu l comparisons can be made
a mong the dark sta b i lities of the dyes within a product or among products.
In conclusion, we have described a n accelerated test for predicti ng the
dark-keeping characteristics of the dyes in color p hotographs. The ava i lable
data on actual storage of products agree wel l with the predicted . Therefore,
based on these results, this new test method is a considerab le i mprovement
over previous methods 1 for pred icting the stab i l i ty of color photographs to
long-term storage at various temperatures.

References

1American National Standard Method for Comparing the Color Stabi lities of
Photographs P H 1 . 42 1 1 969.-

2 Steiger, F. H . : "The Arrhenius Equation i n Accelerated Aging," American

Dyest uff Reporter, 4 6 (9): 287-290 ( 1 958).
3 Adelstein , P. Z. and J. L. M cCrea: "Dark I mage Stab i l i ty of Diazo F i l ms,"
) . Appl. Pliotogr. Eng . , 3 : 1 73- 1 7 8 ( 1 9 77 ) .
4 Arrheni u s , S . : Z . Phys. Ch.e m . , 4 : 226 ( 1 889).

-1 9 5
 R e a d n g 53

PETER KRAUSE

Preservation of Autochrome Plates

in the C ollection of the N ational
Geographic S ociety ( 1 985)

\;\!hen Volmar K. \i\lentzel, archivist; at the National Geographic Society, dis­

covemd l 1 , 000 additive screen plates that had been poorly stored for decades in
a warehouse, he lznew soniething had to be clone. In 1981, when this project was
initiated at the National Geographic Society, no significant research had been
unclertalzen on the deterioration or conservation of autochromes. The National
Geogra phic Society's project brought together the author Peter Krause, an
archivist, a conservator, and scientists from Ciba-Geigy to investigate the light
and darl� stability of autochro w1e plates as well as the best methods for pro­
ducing high-quality photographic reproductions. Krause, a former president of
I/ford, Inc . , had also written and lectured on photographic technology since the
1940s. In this research, the temn pe1formecl a su rvey-in addition f;o the accel­
erated light and darlz aging tests-and gave us our first scientific study of this
fragile color process. One lhnitation of the study, as stated by Krause, is that
the tested plates were at least fifty years old at the time of testing. Thus, testing
m.ay have niissecl initial light or clarh fading, particularly iffading occu rred to
a greater degree initially.

PETEH KBAUSE, " P reservation o f Autochromc Plates in the Col lection of the National Geo­
graphic Society, " Journal of I maging Science 29, no. 5 (September/October 1 985); 1 82-92.
© 1 985 Society of Photographic Scientists and Engi neers. Heprinted by perm ission of
I S&T The Society for I maging Science and Tec h n o logy, sole copyright owners of'Jounwl
of 1-111 .agin.g Science.
 Reading 53 K H /\ U S E

I ntroduction

The debut of the Lumiere Autoch rome process in 1 907 was an h istoric event
in t he an nals of photography, because i t was the first si mple, practical and
reliable process for producing photographs i n n atural colors. Autochrome
p lates, avai lable i n differen t s izes thro ugh normal suppliers of photo m ateri­
als, could be exposed i n conven tional cameras of the day and converted to
positive color transparencies by a 10-12 m i n b lack-a nd-wh ite ( b/w) reversal
processing procedure requ iring only two chemical sol u tions, a developer and
a silver bl eac h .
T h e Autochrome plate, t h e first o f several scree n type, additive color
materials, u t i l ized violet-blue, green and orange-red dyed potato starch gran ­
u les o f about 1 2- 1 6 µ, diameter as color filter elements. T h e gra nules, i n a n
i n itial color ratio o f 7 blue: 8 green : 5 red, were dusted onto a sticky l acquer
coating o n a glass s upport to form a monol ayer of about 5000 colored dots
per mm2• The u navoidable clear spaces between gra n u les were covered with
very fine carbon b lack powder to preve nt color degradation by white light
during camera ex1Josure and subsequ e n t viewing of the image.
After appl ication of the carbon black powder, the spherical starch
gra n u les, held in place by the sticky s u bstrate, were flattened to about 10 µ,
through appl ication of mechanical pressure (about 5000 kg/c m2) and t hereby
rendered more transparent. A clear lacquer overcoating of about 5 µ, th ick­
ness was applied next to protect the water-solu b le tri-phenyl methane type
filter dyes from water a n d moisture during su bsequent man u facturing opera­
tions (emulsion coating, drying, packaging), as well as during later process­
ing and storage . The fine grain, panchromatic emulsion layer coated on top
of this lacquer layer was about 4 µ, t hick. I t was not well hardened by m od­
ern standards and, therefore, was q u i te susceptible to physical damage espe­
cially d u ri ng processing despite the low solution temperature of 1 5°C. For
this reason it was recom mended also that a thin lacquer coating be applied
to the su rface of the processed plate to enhance its abrasion resistance. An
added benefit was a reduction in moistu re sensi tivity.
The reaction of the world to the new Autochrome process was enthu­
s iastic from the very start and was well descri bed by Alfred Stiegl i tz 1 when
he wrote i n 1 907: "All are amazed at the rem arkably beautifu l color render­
ing; the wonderful l u m inosity of the s hadows . . . the rich ness of the deep
colors . . . I n short, soon the world wil l be color-mad and Lumiere w i l l be
responsible." Among those fascinated by the promise and potential of the
new process was G i l bert H . Grosvenor, the p ioneering editor of the J o u rna l
o f t h e u p-and-coming National Geograph ic Society ( N . G . S . ) . H e perceived
i mmediately what great i mpact the use of Autoc h romes would have i n the

497
Part VI T l- I E P H E S E H V AT I O N OF C O L O H P H O T O G H A P l-I Y

Field of photojournalism and how m uc h the accou n ts of far away peoples

and places wou l d gai n from full color illus trations.
And, being a man of action h e soon put h i s idea to work. The N . G . S . ,
i n fu l fi l l ment of one o f i t s primary a i m s , supported Commander Hobert E .
Peary's 1908 expedition to the North P o l e w i t h a $ I Ooo cash gran t and G ros­
ve nor arranged for Peary to carry along a supply of 4 X 5-inch Au tochrome
plates. Peary reached the Pole i n April 1 909 and brought back many b/w pho­
tographs which were p u b lished in the September and October 1 909 issues of
the N . G . S . magazine. H owever, the Au tochromes were not u sed, primarily
because of u nsolved problems with the reproduction of the new color trans­
parencies by p hotomech a nical means. In fact, it was not u n t i l July 1 9 1 4 that
these problems had been m astered to the point that the First Autochrome
could be prin ted successful ly. This was a view of a flower garden in Ghent,
Belgi um, by Pau l G . G u i l l u mette. The caption for this i l l u stration is memo­
rable also and reads in part: "The picture makes one wonder wh ich the more
to admire-the bea u ty of the flowers or the power of the camera to i nter­
pret the l uxuri a n t colors so fai th fu l ly . " H owever, the s ustai ned u se of color
i l l ustrations made from Autochromes d i d not commence until 1 9 1 6 with a
series of 23 photographs by Franklin Price Knott featuring R u t h St. Denis
and Ted S hawn in scenes from the I nd i a n dance, "The G arde n of Kama."
Thereafter, color illustrations were a regular and importan t feature of the
N . G . S . magazine. Altogether, 2355 additive color transparencies were p u b­
l is hed between 1 9 1 6 and 1 938, more than i n any other journal. Most of these
were Autochromes, b u t in the later years they were often supplanted by the
higher speed F i n l aycolor, Agfacolor, and D u faycolor p lates and Fi l ms. And,
many more were acq u i red, but never p u blished.
This p ioneering era of color p hotography reached i ts zen ith and its end
al most s i m u l taneously soon after the 1 936 debu t of the new, h igher speed and
more bri ll iant 35mm Kodachrome Fi l m . Thi s a n d the small, versatile Leica
camera made a combination whi c h promised to open up new domains for
photojournalism. However, the ell.']Jected , gradu a l replacement of an estab­
l is hed system by a new one was i nterrupted by the outbreak of World War I I .
\,Yhen peace came a t last i n 1945, the n e w subtractive type color Fi l ms, made
i n the New World, took over completely.
The Autochromes and other additive color tra nsparencies in the col­
lection of the N . G . S . were put away a n d seldom u sed aga i n . The pu blished
photographs were placed i nto paper envelopes and kept i n Fi ling cabi nets
in a typical office enviro nment . The m u ch more n u merous u npublished
plates and Fi l m s were also placed i n paper envelopes, but then wrapped i n tar
paper and packed in wooden crates. The crates were stored i n a warehouse
for t he next 35 years and s u bjected to the wide fluctuations in temperature
and h u m idity typical of the \,Yashi ngton , D . C . , clim ate. They were retrieved
 Reading 53 K R A U S E

by Vol kmar K. Wen tzel (the present archivist of the N . G . S . ) i n 1 975 while
searc h i ng for material for a bicentenn i al exh i b i t . Among them were eleven
4 X 5-inch Autochromes from the Peary expedition to the North Pole which
had faded in the i n terve n i ng 67 years, b u t still reta ined soft-hued i m ages of
the e)qJl orer's s h ip frozen i n the pack ice so long ago. U nfortunate ly, many
other valuable and i rreplaceable transparencies had deteri orated to a much
greater extent, such as the Autoch romes taken by Dr. J oseph Rock i n C h i n a
and Tibet d u ri ng t h e 1 92o's. I n fact, often only torn envelopes a n d notes i nd i ­
cated what R o c k had s o p a instakingly recorded .
Alarmed by the a l l too evident threat of total loss of this u nique col­
lection of old color photographs, Wentzel called for i m mediate remedial
action . However, it was soon d iscovered that l ittle i nformation was ava i l­
able conce rn i ng the preservation of additive type color transparencies. The
efforts toward u nderstan d i ng the aging behavior of photographs had been
ex'Pended on b lack-and-white and s u b tractive type color p hotographs. In the
end, i t was decided to i ni ti ate a n in-house p rogram aimed at developi ng the
req u i red i n formati o n . Accordingly, a p ilot program was started in June 1981
u nder the d i rection of the a uthor a n d i nvolving the following participants :
Mr. Volkmar K. Wentze l , Arc h ivist a n d Ms. Robin S iegel, Con servation­
ist of the National Geographic Society; Mr. H e n ry A. Shull, P hotograph i c
Consultant; a n d several m em bers of C iba-Geigy Photochemie, Ltd . , notably
Dr. D . B ermane, Mr. H . R . Mannsdorfer, and Dr. M . Schellen berg.
The main objectives of this p i l ot program were:

1 . To collect detailed i n formation o n the condition of the u npublished

additive type color transparencies i n the N . G . S . collection a n d to make
a first, tentative appraisal of their curatorial va lue.
2 . To assess the i n trinsic stabi l i ty and l i fe expectancy of Autochrome
i m ages and to define req u i red restoration proced u res and opt i m u m
long-term storage conditions.
3 . To i nvestigate ava ilable color copying systems and to identify processes,

materials and formats best suite d to the copying of the originals at

h a nd and to the req u i rements of the N . G . S .

S ummary o f F i n d ings

State of Preservation, Tentative Curatorial Value and Major Image Defects

Relevan t data on these quality aspects of the color transparen c ies were
obtained by exa m i n i ng 1 1 , 0 1 3 p lates a n d films. Physical damage, i mage
defects and i mage quality attrib u tes were analyzed and recorded on speci a l
forms. E a c h p l ate was also rated w i t h respect t o overal l state of preservation
and tentative curatorial val u e . Two t hree-step ranking scales were used, with

499
Part VI T H E P H E S E H V AT I O N OF C O L O H P l l O T O G l1 A P l-I Y

1 , representing good; 2, fair; and 3, poor state of preservation; and A, good

curatorial value; B, fair; and C, poor value.
Altogether the fol lowing types and numbers of additive color transpar­
encies were exa m i ned.

Autochromes
Dufaycolor 1 ,252
F i l m color 387
Agfacolor 225
Finlaycolor 56
Other r9
Total

T h e two quality ranking procedures yiel ded t h e followi ng res u l ts :

State of Preservation Curatorial Value

Good 1-892 1 A-1 872
Fair 2 - 1 762 B-44o5
Poor C-4736

I n judging the state of preservation only definite damage to the physi­

cal structure and degradation of the i mage during storage were taken i nto
accou nt. The i dentification of p hysical damage usually was straightforward
and encompassed: broken , chipped or cracked s u pport and cover glass; dete­
riorated fi l m base; damaged or m issing b i nder tape; p u nctured, cracked,
wri nkled, torn or delami n ated i m age or l acquer l ayers.
The assessment of i mage degradation posed a greater chal lenge and
requ ired an i n i t ial i n vestigation of t he l i kely causes of several defects that
might have been formed during m a nufacture or processing of the plates or
by some process of deterioration d u ri n g storage. For example, most of the
Au tochrome i mages were fou n d to h ave irregularly s haped green spots rang­
i ng in size from less than 1 mm to over romm. The questions were: " How and
when were these spots formed?" " H ad they changed with ti me?" "Would they
continue to c hange?" "If so, at what rate and u nder which circu mstances?"
M ic roscop ic exa m i nation revealed that these green spots, and the less
freq uent green l ines, all had a clear central area surrounded by desatura ted
green and grayish fi lter gran ules. The l i terature revealed that the green dye is
the most water soluble of the three fil ter dyes and fu rther microscopic study
proved that the overlying emu lsion and lacquer layers were p u nctured at the
c lear central region of each green spot or l i ne. I t seemed reasonable to con­
clude that small holes or scratches m ade i n the two top layers d u ri ng manu­
facture or processi ng a!Jowed water to penetrate i n to the fi l ter layer during
processing and to extract dye from the green granules. As the dissolved dye
spread ou tward, it i n teracted with the blue and reel granu les ren dering them

500
 Reading 53 K R A U S E

a grayis h color. This assump tion was confirmed by puncturing the layers of
a discarded Autochrome p l ate with a fine needle and placing a d rop of water
over the hole. A c haracteristic green spot formed within seconds. Further
confirmation that the green spots usually had formed during processing was
obtained during examination of black spots. Some of these were found to be
green spots covered by black retouching dye. (The spotting and retouching
of Autoc h rome images was quite common and some photographers habitu­
ally intensified weak i mage colors with retouching dyes in addition to cover­
ing up various blemishes. )
The mechanism which produces green spots more than l ikely also
accou nts for the green discoloration of i mage margins of Autoc h romes stored
without cover glass and those h aving l oose or partia l ly missing binder tape.
Presu mably, moisture can gain access to the l ayers of such plates through
the u nprotected edges and over a prolonged period of ex-posure wil l cause
the green discoloration of the fi l ter layer. U n der some conditions, however,
moisture and heat cause fading of the green dye and lead to a change i n
color balance toward pink.
The net resu lt of this preliminary i nvestigation was that the presence
of green spots and l ines was not a cause for lowering the state of preser­
vation rating, whereas green discoloration near the margins or underneath
cracks in the glass support was considered a n aging defect that prompted
lowering of the qual ity rating from r to 2 or 3 .
B lack spots, as noted, are apt to be retouching marks, but sometimes
t hey are mere pinpoints that cover the entire image area. These so-cal led
pepper spots are metallic si lver specks formed during development as a
res u l t of an acknowledged defect i n the manufacture of the Autoch rome
silver halide emulsion. Other, more n u merous, black marks and smudges
probably evolved du ring storage and had their origi n in fa u l ty processing or
solution contam i nation. Accordi ngly, they were considered aging defects and
recorded as such.
A third type of spots varied i n color from yellow to brown and orange
and in size from pinpoints discernible o n ly under a magnifier, to well defined
discs visible with the n a ked eye. \!\!hen viewed by transm itted l ight under
sufficiently high magnification, these spots have appreciably lower density
than the su rrou nding area and it was thought at first that fad ing of the fi l ter
dyes was responsible for the change in color and the loss in density. H ow­
ever, fu rther m ic roscopic study and c hemical treatment proved that the
blemishes were confined to the silver image layer and that t hey consisted of
metallic s i lver or s ilver s u l fi de. I ndeed, they proved to be the same type of
spots investigated and described by McCamy and Pope,2 H e n n and Wiest,3
\i\feyde, 4 Feldman,' and others and evidently caused by the oxidation of the
image silver to si lver ions, migration and subsequent reduction of the ions
Part VI T H E P H E S E H V i\ T I O N O F C O L O H P l-I O T O G R A P l-I Y

to colloidal silver at preferred sites and occasional further transformation to

silver s u lfide. A magn i fied view of spots found in a n Autochrome i mage of
a Cambodian dancer is shown in Figure 1 . The c haracteristic structure of
these spots can be seen in an emulsion sl iver stripped from another affected
p late i n Figure 2. A photomicrograph revealing the ringlike s tructure of these
spots is reproduced in Figure 3 . At t i mes, t his kind of degradation of the sil­
ver image can also lead to the formation of continuous stains that cover por­
tion s or a l l of the image area.
Autochrome si lver images may be especi a l ly s usceptible to oxidation
because they are fine gra i n and because normal reversal processing did not
include a fixin g step. James6 reported i n 1 965 that developed silver of fine
gra i n emulsions i s more susceptible to changes i n morphology and density
o n storage i n h igh h u mi d i ty when u n fixed than when fixed. On the other
hand, the Autochrome s ilver image occasionally was i n tensified or red uced
and these after treatments requ i red a fi nal fixing step. Moreover, many dif­
ferent formulas and procedu res were employee! , b u t the possible i n fluence of
processi ng variations on oxidation propensity is u n known. In any event, there
are no records on the methods used by N . G . S . p hotographers in the field.
Finally, the lacquer coating normal ly applied after processing should have
provided some protection against moistu re and oxidizing gases, a lthough at
times it may have trapped excessive moisture within the emulsion .
I n view of these u n known varia bles and the u nknown storage condi­
tions, it was to be expected that the inc idence of brown spots or discoloration
wou l d vary from one photographer to another. B ut the exten t of the variation
was a surprise. It ranged from o to 5 1 % . The highest incidence was fou n d in
the Autochrome plates purchased by the N . G . S . from the French photogra­
pher Gervais Courtellemont. I n teresti ngly enough , his p roblem with brown
spots was noted already in 1 93 1 by Frankl i n L. F isher (Chief of the N . G . S .
I l l u strations Section) i n several u n p u b l i s hed Autochro mes made b y Courtel­
lemont in Spain in 1 928. Fisher ret u rned a defective plate to Courtellemont
and suggested that fau l ty p rocessi ng was the li kely cause of the i mage deteri­
oration. H owever, Courtel lemont vigorously defended his processing method
i n a long l etter i n wh ich he wrote i n part: "A sim ilar accident occurred in
1 92 1 for Mr. A lbert Kah n , the great banker and philanthrope who has a
considerable collection of Au toc h romes 9 X 1 2 for scientific projection . H e
consulted t h e professors a t Sorbo nne a n d t h e microbiologists attri b u ted this
accident to a cryptogamic change i n the coloured particles u nder the i n flu­
ence of h umidity. Si nce 1 9 1 2 (sic) I have t herefore made all efforts to avo id
h umidity, b u t duri ng the war my studios in Paris were, owing to lack of coal,
hu mide (sic) and I have lost many plates through these brown spots. I have
sent the damaged pla te of Spain to Lyon and Messrs. L u mi e re confirmed
that this accident was clue to humidi ty. But how can we know when and where

502
 Reading 53 KHAUSE

Figure l
Magnified view of the head and shoulder of a Cambodian dancer from an Auwchrome
plaLe in t h e N.C.S. collection. The orange-brown spots arrayed i n straight l i nes and of'len along
image contours, seen here as low density discs, were found i n many Autochromcs stored u nder
u n fovorablc temperature and h u midity conditions. The spots are located in the silver image layer
and are bel ieved Lo have formed through oxidation of the primary si lver particles followed by
migration of the resultant silver ions and their reduction to colloidal silver a t prcrcrrcd sites.
Part VI T ll E P R E S E R VAT I O N O F C O L O R P JI O T O G B A P H Y

Figure 2
Low-power photomicrogram of a sliver or an Autochrome emulsion layer
affected with brown spot blemishes. Autochrume ernulsion layers can be
stripped off rather easily after incision with a razor blade.

Figure 3
Photom icrogram of a typical brown spot found in the silver image layers
of many Autochrome plates. The ring-like structure, clearly discernible
at this 200X magnitude. is characteristic or these aging blemishes.
 Reading 53 K H A U S E

the germs of this change have appeared i n spite of a l l precautions taken?

In the frame when the p icture was taken? I n the laboratory, before the glazing
and in spite of venti lation?? In the premises where the collection was kept???"
Thus, the probable cause of the problem was correctly ident ified, but
not the nature of the defect nor Courtellemon t's u n in tended contri bution to
its occurrence. And, Courtel l emont kept right o n producing Autochromes
that were exceptionally pron e to form brown spots.
The final tal ly of the major defects that accou n ted for a downgrading
of 2092 plates to C lass 2 or C lass 3 ran k was as follows :

Yel low spots and discoloration 5 7 Y2%

Damaged tape"· 23%

Broken support or cover glass 1 3 1/2%

F i l m base deterioration 6%

B lack spots and smudges 2%

'-· A l though o n ly 501 plates were downgraded
because of damaged tape, about one-th i rd of
all plates, or about 3500, wo u l d benefit from
reb i nd i ng.

These data and others col lected and recorded in the cou rse of the
exami nation of the 1 1 , 0 1 3 plates and films have been the basis for establish­
i ng a priority schedule for the restoration and copyin g of these old color pho­
tographs and, of course, for an i n itial ran ki ng by curatorial value.

Stab i l ity of Autochrome I mages

Although the photographic literature of the Autochrome era contains some

references to the good light sta b i l i ty of Autochrome i mages and although
the ill effects of h igh temperature and moisture were recogn ized, no com­
prehensive investigation of the dark a nd light stabi l i ty of Autochromes
appears to have been carried out. Th is is not to say that the Lum iere broth­
ers were u naware of the i mportance of good keepi ng quality, but rather that
the comp lex l i fe testing procedures used today were u n known at that time.
The i n formation whi c h was available prompted the manufacturer to caution
Autochrome users not to expose processed plates to d i rect s u n l ight or to
heat, lest the i mage layers crack. C ustomers were warned also against the
appl icat ion of a lcohol or alcohol contai n ing fl u i ds to speed u p dryi ng, or
for cleaning, or as a lacquer solvent, because the alcohol would completely
decolorize all three fi lter dyes. And, they were advised to protect the del icate
emulsion layer with a lacquer coat i ng of recom mended form u l ation and with
a cover glass. The Lumiere Company even supplied a special black b i nder
tape coated with a thermoplastic adhesive to forestall the use of more con-
Part VI T H E P H E S E R V AT I O N OF C O L O H P H O T O G R A P H Y

ventional adhesive material s which tended to give off moisture after appli­
cation . The moisture was apt to penetrate into the filter l ayer a n d cause a
reddish discoloration of the image.
U nsophisticated and incomplete as these i nstructions may seem today,
it is evident from our i nvestigations that they covered the main factors
i nvolved in the degradation of Autochrome images. It is evident also that
m a ny 75-year-old Autochromes are i n near perfect condition, giving a mple
proof of the good keeping q uality of properly processed, fi nished and stored
p lates. H owever, at the start of our i nvestigation we were confronted with a
large n u m ber of plates i n less than perfect condition and, as noted, it seemed
i mportan t to gai n better knowledge about the intrinsic dark and l ight stabi l ­
i ty o f Autochromes and a b o u t causes of deterioration . T o t h i s e n d , acceler­
ated aging tests were carried out with the tec hniques used in the evalu ation
of current color photographic products. Of course, the res u l ts of these tests
m u s t be i nterpreted with caution, since the Autochro mes were at least fifty
years old at the start of the tests a n d s ince little or nothing is known about
their processing or storage h istory. However, i ndividual p lates were c u t into
pieces to secure a s ufficient n umber of l i ke samples for the differen t treat­
ment conditions ; and tests were rep licated to verify observed changes a n d
trends. Moreover, samples of Cibachrome Color Transparency fi l m CTD-F7
and of C ibachrome High Resolu tion fil m FT-245.S were included in the
dark and l ight fading test runs to permit direct comparison with two q uite
stable and known color products.
The followi ng test conditions were employed:

Darlz Keeping:
77°C-40% R H-84 days a n d 77°C-60% R H -84 days

Light Stability:
1. F lu orescence i l l u m ination; 10.5 K Lux; 40°C-35% RH a n d

40°C-8o% R H , to a n irradiation level of 20 kJ/cm2

2. Xen o n arc illu mination; 1 00 K Lux; cycled between :
light: 38 h r a t 43°C-55% R H , a n d
darh: J O hr at 28°C-80% R H t o an i rrad iation level of 1 20 kJ/crn2

Data obtained i n these tests are shown i n the graphs reproduced in

Figures 9-1 2 [not reproduced here] .
Additional accelerated aging tests are being carried out i n an effort
to find s u i table adhesive tapes for replacing worn and broken Autochrome
binding tapes. Prel i m inary resu lts of these ongoing tests reveal the same pat­
terns of change as the completed dark keeping tests.
 Reading 53 K H /\ U S E

I n view of the many known factors that may have caused changes i n
the initial densities o f the s ilver i m age a n d the filter dyes, it was dec i ded to
p lot the dark testing data i n terms of density d i fferences lo.D's from the start­
i ng densities D0b, D0g, and D 0 r. The l ight stab i l i ty data, on the other hand,
are presented i n conventional fashion with color densities plotted against
the i rradiance expressed in kJ/cm2.
The following conclusions seem warranted on the basis of the
completed tests:

Darh Stability:

1 . Autochrome i mages e>cposecl to h igh temperature s how a marked

increase i n blue density. The magn i tude of this change is s i m i lar at 40
and 60% R H . The blue density i ncrease is d u e primarily to a yel lowi ng of
the si lver image, b u t some yel lowin g of the lacquer layer may occur also.
2. The fi l ter dyes lose densi ty i n high temperature storage. The loss of
green density i s the greatest and that of blue density the smallest. The
m agn itude of the change is moistu re dependent and is signi ficantly
greater at 60% RH than at 40% R H .
3 . The green filter dye i s the most moisture sensitive.

4 . The color balance of Autochrome i m ages tends to shift toward yellow­

red on exposure to h igh temperature a n d h igh h u m id ity, owi ng to
changes in the s ilver i mage a n d the filter dyes. These c hanges offset
each other to some extent.
5. The dark stability of Au toc hromes i s poorer than that of C i bachrome
film i mages, but is s urprisingl y good and is estimated as being
comparable to that of present Kodachrome film i mages.
6. The Au toch rome e m ulsion layer develops cracks at h igh temperature.

Light Stability:

1 . The stability of Autochrome i m ages u n der Xenon arc i l l u m i nation i s

good a n d s i mi lar t o that of Cibachrome Transparency fi l m CTD-F7
wh ich has better stability than C ibachrome H igh Resolution film FT-
245.S. H owever, severe cracking of the Autochrome i mage layers is
encountered upon prol onged i rradiation to h igh i ntensity i l l u m i nation.
2. E>.'Pos ure to fl u orescent light of 20 kJ/cm2 at 40°C and 35% RH causes
m i nimal fad i ng of Autochrome and CTD-F7 dyes. However, the reel
and green densi ties of FT-245.S fi l m decrease about 10% owi ng to the
fading of the cya n and mage nta dyes.
3 . At the 80% RH leve l , all t hree color films fade more rapidly and

severely. At 20 k]/cm2 the loss in density i s about 20% for the least
stable green dye of Autochrome and about 1 0% for the cyan dye of
Part VI T 11 E P H E S E H VAT I 0 N 0 F C 0 L 0 H P II 0 T 0 G H A P 1-1 Y

C i bachrome C TD - F7 The reel density of FT-245. S fil m decreases by

.

about 65% under these test conditions.

The conclusions that can be d rawn from these and other tests are that
Autochrome i mages have good intrinsic dark and l ight stabi l ity but must be
protected from h igh h u m id i ty, high temperature and exposure to i ntense
i l l u m i nation i n order to m i n i m ize d i scoloration and cracking of the i mage­
forming layers. Low temperature storage at a re lative h u m i dity of from 25 to
40% should be beneficial, as with a l l color photographs. H owever, the rather
poor layer adhesion and consequent emu lsion cracki ng observed at e levated
temperatures may also cause problems at very low temperatures cl ue to dif­
ferential shrinkage of the p late elements. Therefore, it woul d seem prudent
to maintai n storage temperatures near 45°F until longer and more extensive
testing at o° F has been completed.

Color Copying Tests

The ai m of t h i s project p hase was to identify and se lect color copying pro­
cesses, material s and formats best su ited to the origi nals at hand and to the
req u i rements of the National Geographic Soc iety. The basic pre mi se is that
va luable, origi nal photographs should be kept in controlled dark storage to
assure maxi m u m l i fe and that copies should be u sed for most editorial, study
and reproduction purposes. The ch ief req u i rements for the color dupl icates
were defined as:

• C lose duplication of the tone scale and colors of the origi nal i mage
with m i n i mal loss i n sharpness.
• S u perior i mage stab i l i ty of the master copy so that it woul d outlast the
origi na I manyfolcl .
• Formats that wou l d provide the desi red flexibility and accessi b i l ity
and that wou l d m i n i m ize costs and problems of dissemination and
reproduction.

\i\lith t hese criteria 1 11 mi nd, the fol lowing types of color copies were
prepared from a representative sampling of 100 Autochrome origi nals rang­
ing in i mage quality from excellent to poor:

1. Same size transparencies on Ci bachrome Dupl icating film CTD-F7,

Ektachrome Dupl icati ng fi l m E-6.
2 . 35mm tra nsparencies ( 5 X reduction) on Ektachrome Sl ide Duplicating
fi l m E-6, Kodachrome 25 film K- 1 4
3. 35mm transparency of 20-35mm Frames (40X reduction) on Ektachrome
S l ide D u p l icating film E-6, and Kodach rome 25 film K- 14 .

5 08
 Reading 53 K H A U S E

4 . 4 X 6-inch microfiche, 84 i m ages (20X reduction) on C i bachrome H igh

Resolution fil m FT-24 5.S.
5. 4 X 6-inch m icrofiche, 336 i m ages (4o X reduction) on C ibachrome
H igh Resolution film FT-245.S.
6 . Same s ize and 8 X 1 0-inch reAection prints on C i bachrome- 1 1 print
material, P-30.

The 5 X 7-inch color fi l m duplicates and the 8X 1 0-inch Cibach­

rome prints were made by projection pri nting with a n Omega E , 5 X 7-inch
enlarger. The 35mm Ektac hrome dupl icates were made with a n Olym pus
camera and copy stand and the Omega color head servi ng as i l l u m i na­
tor. The 35mm Kodachrome- I I fil m dupl icates were made with a speci a l ly
constructed N . G . S . copy u n i t equipped with an electronic Aash u n i t . The
color microfiche copies on Cibachrome H igh Resolu tion f i l m were made
from the 35mm E ktachro m e d u pl icates by Microcolor Corporation of
M idland Park, N .J .
The perceived advan tages and potential shortcomings o f the materials
i n c l uded i n our tests a re s u m marized below:

Cibachrome Color Duplicating Film, CTD-F7

Advantages:
• very good color reprod uction capability
very good dark and l ight stab i l i ty
stable, 7-mi l polyester base
s i mple, three-step process
Potential shortco m i ngs:
rather h igh i n herent contrast
peak density of cyan dye does not match peak sensitivity of
conventional color print materials

EhtachrO'lne Tn1e E-6 Color Duplicating Fil 1ns

Adva ntages :
• very good tone and color reprod uction capability
i mage su itable for reprod uction by standard tec hniques with
normal color pri nt materials
sheet fi l m and 35mm compatible with standard E-6 process
Pote ntial s hortcomi ngs :
dyes have relat ively poor dark stabil i ty

Kodachrome 25 Cmnera Film

Advan tages:
good dark sta b i l i ty

5° 9
Part VI T H E P H E S E H V A T I O N OF C O L O H P ll O T O G R A P H Y

high speed
Potential shortcom i ngs :
excessive contrast
re lat ively poor color discri m i nation
re latively poor light stabil ity
high cost

Cibachrorne High Resolution Fi.Lin , FT-245.S

Advantages:
exceptionally good i mage sharpness and resolving power
(over 350 line pai rs/m m )
• very good dark stab i l i ty
good l ight stab i l i ty
Potential shortcom i ngs :
modera tely h igh contrast
slow speed

Cibachronie- 1 1 Color Print Material C PSA . 1 K

Advantages :
very good t o n e and color reprod uction capability
• very good dark and l ight stability
stable, 7-mil polyester base
si mple, th ree-step process
Potential shortcom i ngs:
reAection prints cannot match the appearance of a
tra nsparency u n der normal viewing conditions

As expected, i t was not easy to achieve a close match between the

original transparenc ies and the copies, owi ng to the presence of the si lver
i mage and the u n usual h u es of the t h ree Au tochrome fi l ter dyes. In fact,
the characteristic and i n trigu ing appearance of an Autoc h rome i mage can
be dupl icated only by matc h i ng its fai rly h igh reddish mini m u m density a n d
the del icate t o n e modu lation i n the h ighl igh ts. W e approached this appear­
ance with copies made on C ibachrome and E ktac h rome s heet duplicating
films, when combi ned with a t i n ted si lver fi l m . The matc h i ng of certa i n
colors, such as t h e pure Autoc h rome orange-red and violet-blue filter col­
ors, req u i res selective exposure manipu lation or retou c h i ng, i f a neu tral
color balance is to be mai ntained. H owever, for less critical applications,
stra ightforward copying proced u res can be employed. Care m ust be taken,
of cou rse, to prevent overheating of the Autoc hro m e plate (the silver i mage
read ily absorbs infrared radiation) and to observe proper orientation (emul­
sion to e m u lsion contact printing results in side reversa l ) . Light fading need

510
 R eading 53 I\ H A U S E

not be a concern un less a large n u m ber of copies are made, espec ially u nder
high moisture and elevated temperature conditions.

Conclusions

Our i nvestigations confi rmed that Autochrome images have good intrinsic
dark and light stab i l ity, but showed that the si lver i m age as well as the filter
dyes are qu ite s uscept i ble to fad i ng and d iscoloration u nder adverse storage
conditions. The silver i mage layer also is prone to crack on expos u re to d i rect
heat or that generated by in tense i l l u m i nation and the entire layer assembly
is del icate and prone to tear or del a m i nate.
H eat and moisture appear to have been the major cau ses of deterio­
ration of u n published Autochromc pl ates in the N . G . S. collection as man­
ifested by brown spotting and d i scoloration of many si lver i mages and by
discolored margins and the reddish color bala nce of many others. H owever,
major differences in aging behavior were found between plates made by d i f­
ferent photographers, pres umably because of d i fferences in processing and/
or finishing procedures.
The res u l ts of accelerated aging tests ind icate that storage of Auto­
chrome plates at about 45°F and 25% to 40% RH will prolong their l i fe span.
The evi dence also suggests that t he use of a cover glass has been beneficial
on the whole as a sh ield agai nst physical i nj u ry of the del icate image layers
and against moisture or other reactive vapors in the sealed enclosure.
Su itable copies can be made d i rectly from Autochrome originals with
ava ilable d i rect posi t ive color fi l ms and ref-lection print materials, but some
of the tone and color qualities oF the add it ive i mage create reproduction
proble ms not encoun tered i n the copyi ng of pos i t ive color tran sparencies
made with modern subtractive type color fi I ms. The copying cq u i pm en t
must provide excel lent cooling of the Autochrome plate d u ring expos u re to
prevent emu lsion cracking and dcla m i nation.

References

1 f\. S t ieglitz, letter Lo the ediLor ol' Photo1vaphy ( London), daLcd TuL1.i11g,
l\l l u n i c h , J u l y 3 1 . 1 907.
2 C . S . McCamy and C . I. Pope , J . Hes. t\1 . 13.S. G .S.A. ( Pl1ys. and Clie111 . ) 5:
385 ( 1 965).
3 H . W. Henn and D. G . \N i cs t , Plwtugr. Sci . E11g. 9 : 378 ( 1 965).
-l E. Wcydc, Plwtugr. Sci. E11.� . 1 6 : 283 ( 1 972).
L . 1-1. Feldma n , ). Appl. P/10/ogr. E11g. T 1 ( 1 98 1 ) .
6 T. 1-1 . J ames, Pl101ogr. Sci. E11.� . 9: 1 2 1 ( 1 965).

511
 R e a d i n g 54

B E RTRAN D LAVE O R I N E
A N D j EAN - PAU L GAN D O LFO

The Addition of Col or.

Autochrome s : Analysis and
C onservation of a C olor
Photography Process ( 1 998)

/ 1 1 Fra nce, the birth place of t he a11/oc h ro111e, Berl mnd Lavedrine, Jea12-Pa11l
Ga11dolfo, and ot hers have conc/11c1ed exlensive research into the a u toch ro me.
Berl rand Laveclrine is c n rrently di rec/or of the Ce11t re de Recherche sur la Con­
servation des Collections ( C R CC) a11d has co111 pletecl exl.ensive research on the
h istory and techn.iq·ue of t he aulochro111e process. )ea ii-Paul Gandolfo is a pro­
fessor at t he Ecole Nat ionale S11perie11re Lo11is L11111iere, t h e French nation.al
school of pholography. With. access lo I he original L11 11iierefactory noteboohs, the
L11111iere b11siness archives, and other papers, ! he aut hors were able to t race the
design and develop 111ent; of I.he a11 tochro111e i11 a way never before possible.
These reso11rces also allowed 1he111 to ide121ify ! he dyes used in t he 11wm1fact 11re
of ! he a11tocli ro1ne. Alt hough not described i11 1 /iis art icle, this enabled a st 1td)'
of I he fading of autoc h ro111e dyes fro111 t l1eir c reation , leading to a f11/ler 1111der­
slunding of original a u toc11 ro111es a 1 1cl the degree lo tFhich they haFe changed.

Introduction

Photography-and color photogra phy in part icul ar-is one of the most bril­
liant exa mples of the i nti mate re lationship between art and chemistry. I t
would b e ted ious to l ist a l l o f t h e famous chemists, such a s Herschel. Liebig,
Vogel, Land, etc., who played a role i n the history of photography. And it

l k HT H A N D LA\' E D H I N E and J E1\N- PAC I . G A N DOLFO, " L'ad d i 1 i o n des c o u l e u rs . L'a u l oc h ro m c :

Ana lyse c l conserva t ion d ' u n p roeede de photographic en couleurs," Art el c/1in1ie, la
cr111/e11 r . con l'e rencc proceed i ngs e d i ted hy J <1 c q u c s Coupy a n d J ea n - P ierre Mo hen ( C N HS
E d i t i on s , 1998). 1 30-- 3 6.
 Reading 54 LAV[ D B I N E A 1\,' D C. A N D O L F O

wou l d be j u st as ted ious to l ist all of the artists who i m mersed themse lves i n
the field of chemistry i n order t o master a n d i mprove the technique o f p ho­
tography and turn that invention i n to an art.
N i nety years ago, after several years of i ntense research, Louis L u m iere
developed the first indu strial color photography process. The su ccess the
au tochro m e enjoyed in the past, and still enjoys today, honors the memory of
a man whose work reflects a re markable sense of practical i ty combi ned with
extraord i na ry intuition and persevera nce. Th is new process gave the public at
large the opportu n ity to ph otograph in co lor. It was used through the 1 930s
by the photographers of the "Arc hives of the Planet"-a project fina nced by
the banke r Albert Ka h n-which has left us a legacy consisting of more than
72,000 a u toc hrome plates. Severa l years ago, at the request of Jeanne Beau­
soleil, c u rator of the Albert Kahn M u seu m , we undertook a study i n order to
better u nderstand the structure of a u tochromes and their behavior over time.
H ere we will prese nt the main res u l ts of our research , as we p l ace the advent
of color photography in its h istorical and techni cal con text.

Color Photography in the N ineteenth Century

Direct Synthesis of Colors

I t was not long before the enthusiasm that met the 1 839 annou ncemen t of
L. ] . J\1 1 . Daguerre's photograph ic process succu mbed to the fact that those
i mages were mere monoch romatic transcriptions of a colorfu l rea l ity. I n
principle, there was n o reason the q u asi-magical power o f fixing a n i mprint
of l ight should exclude the color element. N icephore N iepce h i mself was
s u rprised by this, and Daguerre uns uccessfu l ly experimented with certai n
phosphorescent compounds. A search began for su bstances or a process
to fix both the i mage and its colors in a si ngle operation. That approach,
which wo uld be termed the "direct method, " was explored i n the ensuing
years, but the d i scoveries barely made it beyond the laboratory stage. For
exa mple, i n 1 848, Edmond Becq uerel recorded a color i mage of the solar
spectru m on a si lver plate, but that photochromy was not stable and d isap­
peared when s u bseq uently exposed to light. In the Un ited States, Levi H i l l
produced daguerreotypes with severa l natura l pigmentations. B u t i t was not
u n til 1 89 1 with the work of Ga briel Li ppma n n-who won the Nobel Prize i n
Physics i n 1 908-that a d i rect met hod was suggested capable o f prod ucing
very bea ut iful color photographs, based on interferential phenomena. I n the
camera, the dry plate comes i n contact with a layer of merc u ry. D u ring expo­
s u re , l ight passes thro ugh the plate and is reflected onto the su rface of the
mercu ry; this forms a reflected wave that , by i n terfering with the incident
wave, produ ces vibration nodes and anti nodes whose spac i ng depends on

513
P a rt V I T ll E P B E � E H VAT I O N O F C O L O H P ll U T O C H A P ll Y

the \\ ave l e ngt h . These fringes of i nterfe rence arc recorded on the photo­
sensit ive layer and, a fter development, when the plate i s v iewed at a cert a i n
angle. the si lver deposit acts as a d i ffract i on screen t h a t restores spectral col­
ors. Fro m a physics perspective, t h e Lippmann process is attractive. For the
genera l p u b l ic, i t is spectac u l ar, b u t d i ff i c u l t to i m plement. Expos u re t i mes
arc very lo ng-sel'e ra l dozen m i n u tes-a nd, in order to recreate the colors ,
the res u l t a n t i m age needs to b e viewed at a part icu lar a ngle .

I r i di reel Sy11.t hes is of Colors

Thus. i n t h e late n i neteenth century, t h e d i rect photochromy met hod d i d

not seem t o h o l d m u c h p ro m ise of a great fu t u re , w h i l e i nstead i nterest i n
t he so-ca l l ed i n d i rect method was renewed. The latter was not held i n high
regard, be i ng considered rather a labora tory m a n i p u lation, m u c h as some
today would feel about colorization. This process for manufact u r i ng color
i mages had been suggested s i m u l taneously i n 1 869 by two personal i t i es or
the clay, Lo u i s Ducos d u H a uron and the poet C h a rles C ro s . It was based
on the principle or t h ree-color separa t i o n . The s u bject was photographed
t h ree t i mes u s i ng a b l u e f i l ter, then a green one, and then a reel one. F rom
the three black-and-wh i te negat ives, t h ree carbon prints were prod uced , col­
ored yel low, reel, and b l ue, respectively. By s u peri mpos i ng the t h ree mas­
ters on a s i ngle base, the s u bject was rep rod uced i n color. This i s the very
principle or color p r i n t i ng with a l l of its in herent d i ffi c u l t ies i n achieving
good tonal re ndering. Because of s u c h d i ffi c u l t ies, many people sa id that the
resu l t i n g i mages could not be cal led color ph otogra phs, since the photogra­
phe r's l a t i t u de in c hoosing the color recom pos i t ion was too great. Regard­
less, D ucos d u H a u ron 's h e l iochromes may be considered the r1 rst exa m p les
or color prints. In his 1 869 book e n t i t led Les cu1 1le11rs en phutugrap/1 ie, sul11-
t iu11 c/11 prublellle [ So l u t io n o f t h e problem of reprod u c i ng colors b y photog­
ra phy J , the i ndeLH igable a n d pro l i fic scien tist suggested a s i m p l i fied method
where color i s recreated by "alternMing red, y elluw, and blue rays, as t.hin as
possible . " This i dea of a m i c roscopic screen was revi s i ted at the turn of the
century, part icu larly by the Lum iere brothers, resu l t i ng i n the a u tochromc.

The Wnrh uf the L11 111iere B rothers

I n the 1 880s, the Lum iere brothers were deeply i nvolved in t h e i r fa t her's fac­
tory and, t h a n ks to the combi ned cf-forts or the e n t i re Fa m i ly, at the e ncl
or the n i n etee n t h c e n t u ry, the L u m iere and Sons company was expa n d i ng,
e m p loying 1 90 people and p rod u c i ng more than 350,000 dozen photogra phic
p lates per year. On the basis of not h i ng e l se but the many patents t hey
r i led, the cu riosity and i nventive ness o f Lou is and Auguste seems to have

5 ' -l
 Reading 54 L 1\ V f D B l i\1 E A N D G A N D O L F O

been bound less. Not only did t hey strive to develop ci nematography, they
were also a l ready i n te rested i n a means of prod ucing color photographs and
eagerly awai ted each new development in that field. Thus in the year fol ­
lowing the i n t roduction of t h e i n feren tial color ph otography process, they
perfected i t and , on May 1 1 , 1893, presen ted prints that made quite a sensa­
tion. Yet, despite all of the improvements t hey made, the l i m itations of the
process made i t impracticable for the gen eral p u b l ic . They then turned to
i n d i rect methods, as i n d icated by their 1 896 paper p u b l ished in the Annuaire
general et international de la photogra11hie, where t hey expressed the "firm
hope that the pri nciple of M essrs. C ros and Du cos du H a u ron wou ld one
clay be the basis for a truly effici e n t m et hod of photographic reproduction of
objects with t heir colors . " The three-color carbon sl ides they produced u s i n g
these tec h n iques were a great h i t at the 1 900 U n iversal Exposi t ion . l-low­
ever, the approach s t i l l d i d not satisfy, their expectations; it requ i red long
and complex manipu lations and the resu lts were u n pred ictable for amateurs.
So they tu rned in the d i rection of what later became the autochrome. The
patent was filed in 1 903 and i n d u strial manufacturi ng, which began in 1 907,
l asted for more than t h i rty years.

The Principle of the Autochrome

The colors in an autochrome a re recreated by addi tive syn thesis, in the

same way as the i mages that form o n a color television scree n . A deve loped
a u toch rome plate comprises a n extremely fine screen of blue-, green-, a n d
red-colored fi bers formed b y t inted grains o f potato starch. Above, a b lack­
and-white slide mod u lates the flow of l ight, allowing va rying amounts of col­
ored l ight to fi lter t h rough . A reel i m age appears reel beca use a l l of the blue
and green grains of starch a re masked, while the color ye l low is achieved by
masking the blue starc h ; i n the white parts, all of the starch gra ins a re vis­
i ble, etc. All color n u an ces are thus restored.
This princ iple of color photography u s i ng a screen was not entirely
new, si nce, late in the n ineteen t h century, i t was a l ready the s u bject of one
patent by the American McDonough and another by the Engl ishman John
J oly. The screen designed by the latter was a succession of col ored li nes,
1 20 m icro n s i n widt h, alternately t i n ted orange, gree n , and blu e-violet. The
i n novation introduced by the Lumieres was a three-color screen composed
of potato starc h , about ten ti mes fi n er than that of the competition. The ran ­
dom distribution o f the starch a lso eliminated any grid effect a n d provided a
very welcome "poi n t i I I ism " effect.
The princ iple was origi nal and simple, but i m plemen ting it proved more
complex. It was necessary to proceed by trial and error and, using t he means
and techn iques of the clay, fi nd a satisfactory sol u t ion at each step along the
Part VI T H E P H E S E l1 V 1\ T I O N OF C: O L O H l' l l O T O G H /\ P H Y

way. The transition from prototype to i n d ustrial man ufact uring took fou r
years o f development, before all o f t h e d i fficulti es were surmo u n ted.

Man ufac turing of Autoch romes

The Starch

During this study, we focused on the st ructu re of the a u tochrome, which

gave us the opportun ity to q uest ion the reasons for the techn ical cho ices that
were made. F i rstly, it was necessary to gather the existing documentation.
\Ne stu d ied publ ications, researc hed first-hand accou n ts and a rchives, and
were q u ickly confro nted with the problem i n herent i n i ndustrial archives.
Duri ng the production period, information was kept secret and scarcely ever
filtered through, other than through patents, which were i nten tionally vague.
'vVhen production ended, either the factory prospered and the arch ives were
destroyed due to lack of space, or the factory d i sappeared along with its
documentation. Th is was the case with the Lumiere factories, which were
destroyed in the 1 970s along with much of their arch ives. Luckily, a few doc­
uments were saved from destruction, often u nder i ncredible c i rcu mstances,
a nd used as a basis for our researc h . These documents consisted of several
factory logs and re m nants of correspondence. Add itional hypotheses and
experi ments a l l owed us to fi l l in the knowledge gap .
T h e Fi rst q u estion t h a t comes to m i nd is: w h y potato starch ? Admit­
ted ly, the a rt of photography was closely re lated to the art of cooking i n the
n ineteenth century, j u dging by some of the photographic formu las of the
clay, which combined sugar, honey, tea, gelatin, egg white, and salt. What's
more, this s i mple gastronomic l ist should remove a l l dou bt as to who actu­
ally i nven ted photography. H owever, that does not ex']Jlain the choice of
potato starc h . Louis Lum iere wa n ted to manufacture transpare n t , colored
microparticles. A Lum iere patent dating to 1 900 entit led "A new type of color"
prese nts a pigment-ma n u facturing method. The Lum iere factories were cer­
ta i n ly not i n terested i n manufact u ri ng pa int, and t h i s patent was therefore a
mere byprod uct of research on manufacturing a color screen . l t describes a
method of tinting mi neral or muci laginous powders using organic dyes.
M a ny co mpou nds capable of fixing dyes were stud ied, but it was not
until 1 903 that Lou i s Lum iere apparently chose starch, wi thout deciding
from what plant it came. l n the month oF Dece m ber, he asked the munici­
pal laboratory of the c i ty of Lyon about the gra i n s izes of various plant
starches. H e also obtai ned i n formation from starch mills i n France, i n the
colonies, and a broad. Starch samples From bananas, rice, yams, pachyrhizus,
taro, and d ioscoreaceae arrived from a round the worl d. In the end, i t was
 Reading 54 L A V E D B I N E A N D G A i\ D O L r o

potato starch that seemed to fl t the b i l l . Adm itted ly, potatoes grow more
readi ly than bananas in the Lyon region, but the experiments that we con­
ducted using other types of starch-such as rice starch, whose gra i n s ize
seems more appropriate-show that only potato starch actually meets all of
the req u i rements of the process. H owever, that choice meant perform ing a
tricky operation that no starch producer was capable of providi ng, i . e . , sort­
ing the grains. ln fact, potato starch grai n size ranges fro m 5 to 1 00 m icrons,
and Lo u is Lum iere wanted to keep only very fine gra i ns with a size smaller
than 15 microns. After m u ltiple experi ments, a p roduction site was set up in
the vil lage of J u re, at the site of an old waterm i l l . Potatoes were purchased
from growers i n the region, then grated and washed in a series of decanta­
tion basins. Swept al ong by the wash water, the heaviest grains prec ipitated
in the fi rst basins, while the l ighter ones remai ned in suspension and then
d ropped i nto s u bsequent basins. The starch for use i n the autochromes was
recovered from the last basins.

Tin ting t he Grains

The foll owing ope ration was to color the gra ins of starc h . The secrecy sur­
rounding the manufacturing process in the L u m iere factories aroused many
a legend about the type of dyes that were u sed (natural dyes, according to
some ) . From a conservation perspective, we wanted to determ i ne the nature
and stabil ity of th ese ti nctorial materials and also whether the manufactu ring
process had evolved over the years. I n fact, when we look at several screens
u nder a microscope, we find different h ues. In some plates, the starch grains
are blue, while i n others they are purple. And the ora nge starch grains con­
tain va rying degrees of reel . \iVas this due to different dyes, to variations i n
the proportions, or else t o agin g phenomena? A chromatographic ana lysis
would provide answers to those questions.
I n order to perform the a nalysis, we needed a n u m ber of reference
dyes. The only accu rate i nformation found in the l i terat u re dates to 1 93 9
( i .e . , 32 years after a u tochrome production started ) . I t is all the more va l u ­
a b l e i n t h a t i t comes from a publ ication b y Seyewetz, t h e chemist w h o spe­
cial ized in dyes for Laboratoires L u miere, and who ind icated "eryt h rosin ,
tartrazi ne, and carm ine blue." The laboratory notebooks a n d t h e annotated
books on dyes that belonged to the Lurniere brothers, housed at the L u mi e re
I n stitute in Lyon, enabled us to establish a l ist of some t h i rty potential dyes .
O u r reference dyes were e ither p u rc hased com mercially, extracted from old
texti le spec i mens, or synthesized in the laboratory. The separation by reverse
phase liquid chromatography req u i red some adjustments, since the acid com­
pounds had to be separated from the base compou nds. By working i n an acid

517
 Part VI T l-I E P R E S E H V A T I O N O F C O L O H P l- I O T O G R J\ P l- I Y

0.0 39
-15-HO
A
Time ( m i n . ) %f\ % 13
Cl: l ') l -10 t'r}thro�in

13
tartra1in<-'

0 90 10 s 0.029
15 25 75 () -1 1 :; :; :;
25 () 1 00 n
l'r\'St:1J dolct

30 0 1 00 ll
0.0 1 9

/\
420=i I
N
0.009 pall'l11 hlt1l'

-0.00 1
0 10 20 30 40
Time (mi n u tes)

Figure 1 med i u m-i n acetonitrile i n the prese nce of chlora te ions-we separated and
H P LC analysis of dyes f'rom an
autochromc plate. detection at
identified dyes of the triphenylmet hane, xanthene, and rnonoazoic fa m i l ies,
530 nm. Chrompack ChromSphcr such as rose bengal, e ryt h rosi n , cl i i oclofl uorescei n , patent b l u e , c rystal violet,
B col u m n , dia meter 3 111111.
metach l oral m alachi te gree n , and Aexo blue 8 1 0 ( Figure 1 ) .
length r o cm. Flow 0.4 m l/min ..
temperature 40°C. Diluant A: 0.01 The autochrome an alyses that show colorimetric differen ces ind icate
M aqueous sol ut ion of' sodi um
that they actually con tain the same dyes. The variations in hues a re t herefore
perchlorate ;1djustcd to pH +5 with
phosphoric acid. Diluant 1 3 : 0.01 M clue e i ther to d i ffere nt proport ions of dyes or to agi ng phenomena, which we
sol ution or sod i u m perchlorate in w i l l address later.
acctonitrilc.

The St;arch M ixture and Coat;in.g t he Screen

After tinting the gra i n s b l u e, green , or reel , t hey were comb ined and m ixed
at length u n t i l a hom oge neous m ixture \Vas achieved . Regard less of how
carefu l ly this process i s carried out, gra ins of the same color have a ten­
dency to stay together; it is those cluste rs of grains that the eye perceives i n
a plate and that give autochromes that poi n t i l list appearance. A single layer
of starch was then spread over the plate. To accomplish this, the glass plates
were coated with a tacky, latex-based varnish. The starch m ixtu re was then
pou red o nto that su rface and the excess b rushed off, while the empty i n ter­
stices between the grains were fil led with powdered charcoal. The resu l tant
starch screen a bsorbs 90% of the light. One day, when Lou i s L u m i e re acci­
dentally scratched a starch scree n , he noticed that its transparency could
be fu rther en hanced. By c rush i n g the grains of starch their th ickness is
reduced, the i n terstices fi l led with carbon black are compressed, and light
d iffusion is l i m i ted, thereby decreasing the opacity. But how do you design
a press capable of applying pressure greater than five metric tons per square
centimeter to a glass plate? Trials using traditional presses fai led, s i nce glass
at the time was s l igh tly concave and any u n i form pressu re broke the plate.
 Reading 54 L 1\ V E D B I N E A N O G A N D O L F O

Accord ing to his writings, Louis Lum iere s ucceeded i n 1 905 "using a cyl i nder
1 . 5 mm i n d iameter i n the form of su ccessive tangent recti l i near stripes . "
Th is i n tentionally vague desc ript ion was not sufficient for us t o imagi ne the
structure of the press. M irac u lously, we fo und a specimen of that press i n
Lyon and h a d i t sh ipped to Paris, where it is being restored. W e ma naged to
have it classified as a scientific and ind ustrial heritage asset.
Despite the ravages of time, our study enabled us to understand how
i t worked. The p late that was to be lami nated was p l aced on a mobile steel
baseplate. The asse m b ly was slowly pu l led beneath a rotating metal rod that
swept over the su rface of the plate ( l i ke a wi ndshield Vlriper). This technique
made it possible to l i m it the contact surface to an area on the order of one
sq uare m i l l i meter, on which strong pressure was applied with no risk of
breaki ng the glass.
This press seem s to have been manufactu red from an industrial plane,
which goes to show the Lumiere brot hers' i ngen u ity. I n 1 907, eight s i m i lar
p resses were i n continuous operation at the factory.
Once laminated, the screens were covered with a dammar and cellu­
lose n i t rate varnish, a n d then with a l ight-sensitive si lver bromide emu lsion
su rface. The sensitivity of those plates is esti mated at ISO 0.25, or a sun
exposure time o n the order of one second. The plate was exposed, back to
the lens, so as to filter the i m age through the screen, and then developed l i ke
a black-and-white sl ide. I t was then protected wi th varnish and covered with
a glass plate.

S tabi l i ty of Autochrome Plates

Compared to more modern color photographs that have deteriorated after

about thirty years, a utochromes seem to have excellent s ta b i l i ty. However,
we have no refere nce a llowi ng us to assert that there is no slow deteriora­
tion. The changes often reported include delamination and i mage oxidation
problems. D u ring this study, we first foc used o n dyes and varnis hes.

Light Stability

\!\le used the various dyes analyzed i n the plates to tint sheets of Whatman
niter paper, which we then artificially aged with l ight u nder a xenon lamp at
50% RH and 30°C. This first experi ment revea led that the most u nstable dyes
are blue and purple dyes, while the most stable is tartrazi ne (ye l low color).
These res u l ts are not surprisi ng. The blue and p u rple dyes that were se lected
for preparing a u tochromes are i n the triphenylmethane fam i ly, whose poor
stabil ity to light has been known since the beginning of the cen tury.

519
Part VI T l-I E P H E S E R V c\ T I O N O F C O L O R P l l O T O G R /\ P l l Y

\Ne then repeated this ex'Periment with starches t i nted b l ue, orange, and
green, to be closer to the composition of the a u tochro mes. The b l u e starc hes
are the most fragile u nder l ight, si nce they conta i n the most sensitive b l u e
dye . W e monitored the p hotochemical degradation o f this b l u e dye u s i ng
ch romatography and mass spectrometry. Exposure to light causes demethyl­
ation of the n i t rogen groups and formation of d i phe nylated ketones.

The presence of these compounds in an au tochrome plate m ight

ind icate ph otochemical degradation, if they cou ld be characterized nonde­
structively. The dyes are not the only thi ngs that react to l ight . D u ri ng these
experiments, we noticed that the varni s h covering the starch layer crackled.
\Ne attri b u te this phenomenon to the prese nce of cellu lose nitra te, which
c ross-l i n ks d u ri ng i rradiation. This phenomenon, which is triggered by ligh t ,
m a y then progress i n the dark.

Thermal S tability

Most a utochromes are stored in the dark. Therefore, we wanted to determ ine
whether the colors could change u nder those conditions. Some of the dyes
we studied deteriorated when exposed to moist heat. The thermal stabi l i ty
is different from what we find with l ight expos u re. H owever, the flexo b l ue
8 1 0 dye is thermally the m ost fragile. The weakening of this dye in darkness
occ u rs t h ro ugh the formation of triphenylcarbi nol.

The early stages of that reaction fo llow first-order kinetics. By apply­

i ng Arrhenius' equation between 50 and 90°C (at 60% R H ) , we were able to
extrapolate the degradation at a m bient temperatu re . On cel l u lose, it seems
that the dye may deteriorate markedly after a few years. I f the same phenom­
enon occ u rs on plates, the blue grains turn purple, which wou l d ex'Plai n the
d i fferences in coloration between certain plates.

Conclusion

Th is study furthered our u n dersta nding of the au toc h rome. Agi ng tests using
heat and ligh t reveal a certai n fragil i ty and lead us to recommend controlled
conditions of storage and u t i l ization. Absent any references, admi ttedly it
is diffi c u l t to q u antify t hese transformations, which manifest as changes i n
tonal ity and, i n extreme cases, formation of a monoc hrome image . E xamples
of plates that have degraded i n this way have been fou n d i n collections.
This study i l l u strates the type of research encou ntered by heritage sci­
entists. U nderstanding how the materials age, preparing or finding reference

520
 Reading 54 L A V E D B l i\1 E A N D C J\ i\1 D O L F O

produ cts, a n d analyzing col lections are its i neluctable stages. These involve
lmowledge and research not only i n the physical sciences, b u t also in the
historical and technological arena.
Our c u l tu ral heri tage is enriched by m a n u factured objects and materi ­
als whose characteristics, composition, and many properties are well known
to manufactu rers. By contri buting to a better c haracterization and to the
choice of preservi ng and conserving such heritage, i ndustrial arch ives can
save scientists, conservators, and c u rators considerable time, on cond ition
that the archives themselves are preserved.

Acknowledgments

\Ne were able to conduct this study thanks to the su pport of Mesdames Beau­
soleil, Bove, Chemin-Doub l ier, Fl ieder, and Monad, and Messrs. Bonho m me,
C hardere, Demure, Genard, Seyewetz, Susbiel les, and Trarieux- Lu m iere.

Patents

1 900, November 27, 'lo. 30 5 .784, " U n nouveau genre de couleurs" [A new type of color]
1 903, December 17, No. 339.223, " Procede d e photographic en cou leurs" [ Color
photography proces s ]
1 904, January 13, N o . 3.89 1 , 1 st supplc111cnt
1 904 , November 9, 4290, 2nd supple111cnt
1 906, April 5, No. 7.230, 3rd supple111ent

References

Letters addressed to Louis Lu111iere concerning starch grains:

Amidonnerie et Fecu lerie Patin ( Patin Starch Factory), Paris, March 12, 1 905
A111 idon ncric ct Fecu lcric Patin ( Patin Starch Factory), Paris, March 14, 1905
A111 i don neric et Fecu lcric Patin ( Patin Starch Factory), Paris, M a rch 19, 1905
A111idonnerie e t Feculerie Patin ( Patin Starch Factory), Paris, March 23, 1 905
Ateliers de construction 111ecanique J. Schnepp (J . Schn c p p Mechanical Construction
Shop), Paris, M arch 3, 1 905
M i l lot, A., Zurich, Februa ry 22, 1905
M i l lot, A., Zurich, March 4 , 1 905
,
Bru eder & C i e Arches, Dccc111bcr 9, 1904
Capun, G . , D i rection de I' Agri c u l tu re ( B u reau of Agric u l t u re), Hanoi, J u ne 20, 1905
Carandas, C . , G ilocourt via Orrouy. Dcce111ber 9, 1904
D u four, J . , Epinal, Dece111ber 9, 1 904
Fabrique de fecule Lancelot Louis ( S tarch Factory, La ncelot Louis), La Flcche,
December 1 2, 1904
Fecu lerie Cotes & Ledieu ( S tarch Factory, Cotes & Lcd ieu ) , A 111 bc r t ,
Dcce111bcr 9, 1 904

)2 1
Part VI T l- I E P R E S E ll V A T I O N O F C O L O R P I- I O T O G ll 1\ P I- I Y

Fccu leric Feurs, N i gay Freres & C i e (Starch Factories of Fcurs, N igay Frercs & C ie),
Fcurs, December 1 2 , 1 904
Feculerie Feurs, Nigay Freres & Cie (Starch Factories of ' Fcurs, N igay Freres & C ie ) ,
Feurs, December 1 5, 1 904
Fecu lerie Feurs, N igay Freres & C ie (Starch Factories of Feurs, N igay F re re s & C ie ) ,
Feurs, December 23, 1 904
Fecu lcric Fcurs, N i gay Freres & Cie (Starch Factories of Feurs, N igay Frcres & Cie),
Feurs, J a n uary 3 , 1 905
Fecu lerie Feurs, N igay Freres & Cie (Starch Factories oF Feurs, N igay Freres & C ie),
Feurs, J u ne 29, 1 90 5
Fec u l e de M arsac ( Starch of M arsac), Lemoine J a rra i l lon, Marsac, not dated
Fecu leries de pommes de terre ( Potato Starch Factories), Poncct, Amplcpuis,
December 8, 1 904
Fecu lerie du Bourg-d'Arlanc (Starch Factory of Bou rg-d'Arl anc), Paul Portail Succ.,
Ariane, December 1 5, 1 904
Fecu lerie E. C hauvet & Cie (Starch Factory E. C hauvet &. Cic), Port-Salut,
December 1 0 , 1904
Fcculcries cl G l u coseries de To u rnus et Arg-les-Gray ( Starch and Sugar Factories oF
Tou rn u s and Arg-les-G ray) , Tou rn u s , December 1 4 , 1 904
Fecu lerie J . Denis ( S tarch Factory J . Denis), St Germa i n - Laval , J a n u a ry 1 1 , 1 906
Fecu leric J. Denis ( Starch Factory J. Denis), S t Germai n - Laval , J a nuary 25, 1 906
Fecu lerie J. Denis ( Starch Factory J. Denis), St Germai n - Lava l , J a nuary 29, 1 906
Feculerie J . Moraillon (Starch Factory J . M oraillon), St Forgeux- Lespinassc,
October 1 0, 1 904
Fecu lerie Rene C rappier Starch Factory, C hevrieres, not dated
Fecu les, Gommelines, Dextrines, Le'iogom mc (Starch, Gommefin, Dextrin, Starch G u m ) ,
Victor Louis, E p i n a l , December 9, 1 904
Foucret, Compiegne, October 9, 1 904
G. de Berchoux, Lyon, J un e 1 5, 1 905
G . G a l land, R e m i remont, Febru ary 20, 1 905
J . P. G u igues (?), Embru n , October 6, 1 905
Josef Sch i mek, Berli n , February 24, 1 905
L'Eplucheuse, Paris, March 1, 1 905
Laboratoire m u n ic i pal ( M u n icipal Laboratory), Lyo n , December 8, 1 903
La ParmentiCre, Paris, not dated
Lib l a i n & Cie, M arsei lle, May 8, 1 905
Louis Faucherre, N ice, M arch 3 , 1905
Lumiere N .A. Co. Ltd, London, February 1 5, 1 904
Lumierc N.A. Co. Ltd, London, January 1 8 , 1 904
Maison 1-1 . & G. Rose Freres, Poissy, not dated
M ateriel agricole et viticole Vermorel (Vermorel Agricultura l and Viticultura l Equipment),
Vil lefranche, January 28, 1 905
Materiel agricolc et viticole Vermorel (Vermorcl Agricultu ral and Viticu ltural "Equipment),
Vi l lefranche, February 6, 1 905
Moulin de G i boudet ( M i l l of G i boudet), P. Ossian-Henry, Paris, December 10, 1 905
Pautet, Lyon, April 6, 1 905
Pautct, Lyon, M a rc h 22, 1 905
Roux (?) Fr., Lausanne, J u ly 18, 1 907

5 22
 Reading 54 L 1\ V E. D B I N E A N D G A N D O L F O

Societe des Feculeris & G l u coserie (Starch and Sugar Factories), Tauperiot Fils,
Chalon-su r-Sa6ne, December 10, 1 904
Societe des Feculeris & G l u coserie (Starch and Sugar Factories), C ha lon-sur-Sa6ne,
December 9, 1 904
Victor Motrieux, La Fleche, October 9, 1904
Victor Motrieux, La Fleche, J a n uary 28, 1905
Vil morin-Andrieux, Paris, January 9, 1 904

B ibliography

" N otice sur !es titres et travaux de Lou is Lum icre" [ Note on the titles and works by Louis
L u m iere ] , Lyon, l mprimerie Leon Sezanne, 1 9 1 8.

Bellone H., Fellot L. "H istoire mondiale de la photographie e n cou leurs des origines it
nos jours" [ v\lorld h istory of color photography from its begi nnings to the present ] , Paris,
Hachette Heali tes, 198 1 .

Boulouch N ., "La photographic autochrome e n France ( 1 904-1931 ).·· These de doctoral

sous la d i rection de M m e Jose Vovelle [ Autochrome photography in France ( 1 904-193 1 ) .
Doctoral d issertation u nder t h e d i rection o f M s . Jose Vove l l e ] , U n i versite d e Paris I , 1994.

Ducos du H a uron L., Les coulcurs en p hotogra p h ie, solution d u probleme" r colors i n
p hotography, the solution t o the proble m ] , Paris, A . M arion, 1 869.

Lavedrine, B . , " Les autochromes: approche historique ct technologique du procede,

etude des problemes l i es a sa conservation" [ Au tochromes: h istorical and technical
approach of the process, analysis of the problems of their conservation ] , La conservation
des doc u ments gra p h iq ues et photogra p h iques, Travaux d u Centre de Hechcrche s u r la
Conservat ion des Doc u ments G raphiques. Paris, Archives nationales: La Doc u mentation
Fran�aise, 1 993, 29- 1 29.

Lavedrine 1 3 . , Gandolfo J . P., "Autochromcs: From the Pri n c i ple to the Prototype," Joumal
of l-Jisto1y of Photography, vol . 1 8, no. 2, S u m mer, 1994, 1 20-1 28.

Seyewetz A., "L'emploi des matiercs colorantes en p hotographies ct en c i ne matographie"

[The use of dyeing materials i n p hotography and c i nematography], Hevue generale des
matieres colorantes, aoOt 1 939, 1-4.
 P A R T V I I

Developing Criteria in the

Conservation of Photographs :
Collection Management
and Treatment
Early p hotograph conservation treatment techniques emerged in part from
the practices of photographers, who struggled to red uce d isfiguri ng stains
on and damages to their photograph i c prints and n egatives. N i neteenth- and
twentieth-century p u b lications are replete with recipes for chemical i n ter­
ve ntions of all kinds (see C rabtree, John T . , ''Stains on Negatives and Pri nts:
Their Cause, Prevention and Removal, " American Annual of Photography 3 5 ,
1 92 1 , as an excellent example of these popular publications). Over ti me, these

restorative approaches were modified and combined with variations to more

trad itional practices i n paper, pain t i ngs, and objects conservation; stre ngth­
ened with scientific research , h istory of technol ogy, and connoisseu rship
studies; i mproved by strong ethical standards; and broadened to reflect
changes in value, s igni ficance, access, and use. The readi ngs in Part V I I
i l lustrate the systematic development of treatment criteria and phi loso­
p hy, of the decision-making process, and of contemporary sensitivities and
approaches to p hotograph conservation practice, i n c l u d ing preven tive care.

J u l i a Margaret Cameron ( British, b o rn I nclia, 1 8 1 ;-1879), Tlie Wh isper of tlie M11se I Port-mil of G . F
\1\!atts (detail), 1865. Albumen silver print, 26 X 2 1 .4 cm { 1 01/.+ X Si/16 in.). Los Angeles, J . Paul Getty
M useum, S+xz. 1 86,96
 R e a d n g 55

L o u i s - A L P H O N S E D AVA N N E
AN D A I M E G I RA R D

Applied C hemistry-Note on the

C auses of Deterioration of Positive
Photographic Prints and on a
M eans of Restoring Them ( 1 8 5 5 )

Louis Alphonse Davanne ( 1 824-1 9 12 ) was a French. che m ist and photogra1?her
who experimented with a variety of photographic processes and equipment .
H e was a fou nding member of t h e Societe Franc;aise de Photographie. His
colleague Aime Gira rd ( 1 830-1898) was also a French chem ist and the third
president of th.e Societe Franc;aise de Chimie. The two authors collaborated
on other publicat;ions regarding t he stability of toned prints, and /;heir writ­
ings have been cited in twentieth-century conservat ion literature. I71is reading
provides an acco u nt of a nineteenth-century scientifi.c analysis of photographic
print rnat;erials aimed at providing a better underst;anding of their deteriora­
tion. It 1vas originally published in French an.cl has been translated into Eng­
lish for inch1sion in this p-ublication. I71e foc us of t his pa1?er is the analysis
of toned and u n t;oned print materials through dest ructive testing. Part VII
focuses not on the stability of image material (see Part I I ) b-ut, instead, on the
history and clevelop1nent of treatment; criteria for photographs. I71is reading
serves as a good introduction to a nineteenth-century "examinat ion " of photo­
graphic 1naterials as well as a s uggested che1nical treat ment approach to create
a "perfectly restored" print. As such, it provides some i nsight on early "treat­
men t " of photographs.

If there is somet h i ng that sti l l stands i n the way of the i m mense development
that serious photogra phy is destined for, it is assuredly the general instabil­
i ty of posit ive prints. I n deed, only few a re able to withstand several years of

L o u i s - A L P H O N S E 01\\1/\ N N E and A 1 � 1 E G mA H D , " C h i mic appliqucc-Note sur lcs causes qui

amenent J'aJteratiOll des epreuves photogra p h iqucs positives, Ct SUI' Li il lllO)'Cll d e Je revivi­
fier," B11/le1 i11 de / 'Acnde111ie des sciences ( Paris, 1 855) 666-69.
 R e a d i n g 55 DAVA N N E A N D G I RARD

contact with at111ospheric agents. H ere we i n tend to speak only of prin ts pre­
pared using the ord i nary hypos u l fite process, and not of prints whose prepa­
ration includes the use of go ld salts.
We know that the former of those p rocesses, which h i therto alone
e njoyed the favor of photographers, consists of first soaking the print, as
i t comes out of the printing fra 111e, in a sod i u 111 hyposu l fite bath, i n order
to dissolve the nondeco111posed s i lver ch loride. The print e merges from this
bath with a tawny-red tint that we try to replace with beau tiful p u rp lish-black
tones, obtained i n the so-ca l led toning baths. These are composed of sod i u111
hyposulfite with either acetic acid or si lver ch loride added. After such a bath,
the print is covered with beautifu l tones, b u t long experience has shown that
t hese afford no sol idity.
Heretofore, various hypotheses had been p u t forward about the fact of
this destruction, but no serious study had ever been u ndertake n. We have
atte111pted to fi l l this gap and shed light on this i nteresting q uestion th rough
chemical analysis. Reflecting on the earlier operations, everyth i n g led us to
suppose that a ftxed but nontoned red pri n t was formed by d ivided s ilver
111etal and not by si lver su bchloride, as is generally accepted, and that this
s ilver-in contact with the aforesaid bath s-was transformed i n to s u l fide,
which was then changed by at111ospheric e111anations. Experience demon­
strated the accuracy of this hypothesis.
To verify this hypot hesis analytical ly, we tried to determi n e 1 ) the state
of the s ilver on a fixed and nontoned positive sheet, also, i nc identally, l ook­
ing for any sod i u 111 hypos u l fite that may have remai ned i n the paper pulp;
and 2) the state of the si lver on a pos it ive print that had been toned with the
usual processes, i.e., u s i ng hyposulfites loaded with s ilver ch loride or acetic
acid from the baths that photographers call old hyposulfites.
The process we used for the analysis was very s i mple. I t consisted
of impregnating the sheet of paper with a saltpeter and sod i u m carbonate
solution, then burning it and ana lyzi ng the ashes. After calcination, the sil­
ver remained in an insol uble state, while the c hlorin e and the s ul fu r were
transformed i n to ch lorides and sulfates. We first verified the accuracy of this
process by b u rn ing a sheet impregnated with silver c hloride, measuring the
s ilver by the ch lorine and the ch lori ne by the silver i n the ashes and weigh­
i ng the two ch loride prec ipitates, which turned out to be identical. We also
u sed this method to determ ine the composition of the ashes of p hotographic
paper, in order to take it into account i n subsequent analyses.
To decide about the first q u estion, we exposed a sheet i mpregnated
with s ilver chloride to light until it was completely b l ackened. \Ve then
rinsed i t with new sod i u m hypos u lfite and then with distilled water and,
finally, we b u rned it. \Ve fo und no traces of s u l fate in the ashes. The quan­
tity of chlorine was 0 . 002 g and the quantity of s ilver was 0 . 1 24 g. Therefore,
Part VII D E V E L O P l \' G C ll l T E H I A

i t is obvious, fi rst ly, that the new sod i u m hyposu l fite left no trace of sulfu r.
Fu rthermore, the proportion of ch lorine was so small compared to the silver
that it could be cons idered an i m p u rity of the paper. The Ag2 C I form ula
would have req u i red ten t im es more, or 0 . 020 g. Repeated several t i mes, t h is
analys is constantly gave us the same results. B u t before drawi ng any conclu­
sions, we wanted to give i t a more palpable form . \Ne prepared a relatively
large quant ity of si lver ch loride. \1\fe placed i t i n a tray, sti rred it for one day
u n der sun l ight, and ri nsed it with hypos u l fite and then with distil led water.
The residue melted with p u re sod i u m carbonate gave a si lver metal sedi­
ment, but the flux contai ned no traces of ch lori ne. Furthermore, we should
add that the su rface of the p hotographic prints is perfectly sol u ble in n i tric
acid, whereas s u bchloride i s considered insoluble.
From such experi ments, we bel ieve we can conclude that the pos itive
photographic i mage is formed by silver metal and not by si lver s u bchloride,
as stated u nti I now.
S u bsequently, in order to determine the state of the silver on the toned
prints, we ana lyzed a n u m ber of them, on which we had produced the desi red
black tones using ord i na ry toning baths (sod i u m hyposulfite m ixed with ace­
tic acid or si lver salt) and we sti l l fou n d not only si lver but also su lfur, those
two agents occ u rring pretty much i n atomic quanti ties, as requ i red by the
AgS form u l a . These resu lts were constantly re prod uced and we concluded
that, i n the aforesaid toning baths, the si lver that covers the sheet is t rans­
formed into su l fide. Th is reaction is easy to u nderstand i f we remember that
hyposu l fites a re i m mediate ly b roken down by acetic acid and i f we know-as
the experiment showed u s-that these salts, when m ixed with a si lver nitrate
sol u t ion, al most instantly transform i t i n to su lfide.
Moving on to the study of the deteriora ted pri nts, we analyzed: prints
prepared severa l years ago whose black tones had tu rned i nto yellow tones;
prints that we processed ou rselves by abandoning them i n water for sev­
eral clays after toning; and others that we had sulfonated d i rectly as we will
expla in later. I n all of these, we fou n d sulfu r and si lver and, strangely, the
proport ions were more or less the same as in the black prints comi ng out of
the ton i ng baths.
Thus it was established that, i n t he Fixed prints, the analysis detected
on ly si lver, while i n the toned prints, whether black or yel low, there was
s u lfur and si lver, and those two agents only. It remai ned to be determ ined
whether that su lfu ration was rea l ly the cause of the destruction of the i mages.
To ascerta in this, we s ulfonated well-F1xed prints, either u s i ng photographic
processes or in hydrogen s u lfide baths, or else in a hydrogen s u lfide stream;
whenever these su lfonated pri nts were i n any way i n the presence of h u m id­
ity, their black tones rapi d ly disappeared and gave way to yel low tones, while
the simply fixed pri nts did not deteriorate in any way. 'vVe will not desc ribe
 R e ad i n g 55 D A V A N N E A N D G I H A R D

a l l of the tests we performed; two w i l l suffice. I n the first, a sheet was l eft
for a long time in a hyd rogen sulfide solutio n . I t rapidly went through all of
the ordin ary tones and, fi na lly, while it was still in the bath, retained the
yellow tone of the was hed-out prints. In the secon d , a print that was previ­
ously dried in an oven and then kept for twenty-four hours in a perfectly d ry
hydrogen su lfide stream, retained i ts black tones, b u t later q uickly yellowed
when it was p laced in contact with water.
By way of analogy, we bel ieve we can state that, i n ord i nary p hoto­
graphic processes, sulfu ration causes toning and, in the presence of h um i d­
i ty, bri ngs about destruction. The use of gold salts, which gives rise to entirely
d i fferent reactions, does not have such drawbacks.
I t re mains to be determ i ned why b lack silver s ulfide turns yellow in the
p resence of h u m id i ty. As there is no cha nge in the proporti o n of the compo­
nent i ngredients in either case, we are forced to recognize that there is either
hydration of the compound or an isomeric change simi la r to those of reel and
black mercuric sulfide.
I n conclusion, we will say that, when a print prepared in this way has
been destroyed by ti me, it is easy to bring i t back to black tones whose i n ten­
sity may be increased or decreased at wi l l . To do so, one need only i mmerse
the print for several hours, in darkness, i n a bath contain i n g 2 to 3 grams of
gold chloride per l i ter. A dual decomposition occ u rs, and the gold is depos­
ited in p lace of the silver. The si lver ch loride that form s is then removed
with a m i ld sod i u m hyposulfite solution, then the pri n t i s washed and i s now
perfectly restored.
 R e a d i n g 56

ALI C E SWAN

C onservation Treatments for

Photographs : A Review of Some
of the Problems, Literature and
Practices ( 1 978)

The follawing review ·was written lry Alice Swan (see also Readings 29 and 57)
in 1 978 when t he field of photograph consen1ation was in its i nfancy. Swan
was one of the earliest conservators to speC'ialize i.n the treatment of photo­
graphs and the second conservator to worh in the conservation laboratory
at the George Eastman I-louse (see Reading 5). S he proposes that photograph
conservators avoid following the long-practiced techniques iised by photogra­
phers to "restore " new prints. Slie directs conservators, c urators, and scientists
alihe to "review the origi.ns, efficacy, safety, applicability, and adequacy" of con­
temporary photograph conservation and restoration practice. Through Swan 's
encouragement and scientific research, the e1nerging fi.eld developed improved
procedures and nwre appropriate criteria for the proper treatnient and care of
historical photographs.

From the earl iest days of the med i u m , photographs have been recognized to
be i nherently fugitive compared to tradi tional art-on-paper and printing p ro­
cesses. A h u morous poem published in Punch in 1 847 sati rized the problem:

B u t , a h ! - thy portrait of thy l ove,

Is but a type, no doubt,
And serves its fickleness to prove,
For soon 'tis a l l wiped out. 1

From A LI C E SWAN, ''Conservation Treatments for Photogra phs: A Review of Some of the
Proble111s, Liternture and Practices," l inage 2 1 , no. 2 (J u n e 1 978): 24-31 (24 excerpted
here). © George Eastman Hou se, I n ternational M u se u 111 of Photography and F i l m.
Repri nted by per111 ission.
 Read ing 56

The Photographic Society, founded i n Lo ndon i n 1 853, cons idered the stabil­
ity of the new process such a n i mportant problem that in 1855 they appoi nted
a commi ttee to study "the question of the fad ing of posi tive photographic
pictures o n paper."2 At frequent i n terva ls throughout the photographic l i t­
erat ure of journals a nd man uals, from the begin n i ngs of the med i u m to the
present day, the problems of fad i ng, sta i n i ng, tarn i s h i ng and all the other
ills photographs are subject to, have been considered, and recommendations
for im proved origin a l processing proced u res as well as for "restorative" treat­
ments have been made. All of these recommendations were previously ai med
at the practici ng photographer and were primarily i n te nded to be appl ied to
his own relatively new material. Within the last Fifteen years however, as the
va l ue of origin a l photographs has steadily and d ra matically i ncreased, and as
comprehensive conservation progra ms have been set u p to trea t other med ia,
not only i n art collections, but also in hi storical collections, there has been
a n increas i ng demand from col lectors, curators of collections, admin istra­
tors of conservation progra ms and conservators for a set of con servat ion/
restoration treatments which can be appl ied to older original p hotogra phs.
To fill this need many articles, pamphlets, guides and even a Few books
have been recently p u b lished on the conservation and restoration of pho­
tographic collections . I n addition, photographic conservation experts have
appeared and are holding works hops, semi nars and sympos ia to advise c u ra­
tors and conservators o n what is to be clone. One u niversity program for the
tra i n i ng of art conservators currently inclu des the treatmen t of photographs
in its c u rricu l u m . At least one Regional Conservation Center has advert ised
t hat it is preparing to handle photographs, and many other conservation cen­
ters have actually started t reating photographs.
M ost of this activity is unq uestio nably beneficial: curators of col lec­
tions are more concerned t h a n ever before with the care of their origi nal p ho­
tographs; consequently the storage conditions of p hotographic collections
are being i mproved d ramatical ly, and many i nstitut ions' holdi ngs of origi nal
photographs are being cata logued For the first time. But when one consid­
ers the conservation and restoration treatments cu rrently recommended for
photographs and u n dou btedly in actual use, some very serious q u estions
arise. S i nce t h is is n ew and re lat ively untrodde n ground, perhaps it would be
wise to review the origi ns, efficacy, safety, applicability and fi nally adequacy
of some of these treatments, before we prepare for the mass ive treat ment of
p hotographic collections.

53 1
P a rt VII D E V E L O P l ." G C R I T E R l 1\

Notes

Punch, vol. 12, p. 143. The ent ire poem is reprinted in The H i story of
Photography by H e l m u t and A l i son Gernsheim ( London, 1 969), p. 1 76.
2 The first report of the Fad i ng Committee, p u b l i s hed i n The J o u rn a l of the
Photographic Society, no. 36 ( N ovember, 1 855), pp. 25 1-2, found t hat ''the
most ordinary cause of Fading, may be traced to the presence ol' sul phur,
the sou rce of which may be i n t rinsic From hyposul phitc lel't in the print, or
extrinsic from the atmosphere, and in e ither case the action is much more
rapid in the presence of' moist u re. " Carefu l washi ng, gold toni ng, storage
away from dampness, and the use of gelat i n rather than starch For mounting
because i t is less hygroscopic, were recommended to mini mize f'a di ng. The
recommendations of modern "fading committees" arc not dissimilar.

532
 R e a d n g 57

A L I C E S WA N

Problems in the C onservation

of Silver Gelatin Prints ( 1 98 1 )

This a rticle by Alice Swan (see also Readings 29 and 56) addresses with exce11-
t ional detail the challenges associat:ed with the conservation t reatment of the
h ighly CO'lnplex silver gelatin photograph . Here, Swan describes physical prob­
le·in,s relat i ng to the lam:inate st.ruct: u re of gelatin silver prints including dif­
ferential expansion and contrac tion, curl, and i n terlayer cleavage, as well as
j1. la·mentary silver morphology and degradation. Swan strongly recom.mends
t:hat c u rrent restoration techniq ues, routinely pract iced by phot:ographers to
111:inim·i=e stains and improve image q ·ualit:y, be reexa mined, reevaluated, and
reformulated before being applied to valuable 11hotographic prin ts. /-/ er writ:ing
warns t hat common preservat ion efforts to enhance image pennanence and
prevent long-term degradation-S'llch. as reprocessing using sodium. hyposulfi te
and hypo eliminator solu t ions-will more often than not fu rther erode and
oxicl-i:e i:mage silver, causing u nwarranted damage (see Reading 16). Swan was
a head of her time i n recognizing t: he aggressive nature of che·wl'ical reprocess­
ing treat ments and with this ·writing she demands and inspires t he pursuit: of
alternat ive preservation techniques, including i mproved st:orage and handling.
The techniques reviewed here, more CO'lnmonly practiced in t he 1970s an.cl 'Sos,
are now generally regarded as t.oo invasive and are therefore rarely practiced by
photogra71h conservators today.

The conservation of p hotographs is an extremely new field. I t is only in the

last twenty or thirty years that photographs h ave been recognized as i mpor­
tant objects of aesthetic and h istorical value and that their condition has

ALICE SWAN, " P roblems in the Conservation of S i lver Gelatin Prints," in Tlie Ca1·e a11d
Cu11serva1ion of Photogrnphic Material, re p r i n t ed by the C rafts Council, Autumn 198 1 ,
40-48.

533
P a rt V I I D E V E L O P I N G C H I T E H I A

become of concern to museums, arch ives and col lectors. Very little research
i n to the characterist ic deterioration processes has yet been clone-certa inly
not enough to ge nerate sound conservation t reatments; and t hose few treat­
m e n ts which have been publ ished in the past were deve loped for use on new
materials, and prove to be damagi ng when applied to i rreplacea ble and age­
weakenecl prints.
Compa red to the traditional artists' pri nt making materials, p hoto­
graphic p ri n t i ng materials are compl ex and u n stable, consisting of a reactive
i m age of fi nely d ivided silver part icles embedded in a fragile colloid layer,
bonded to a paper su pport which frequently exh ibits poor a rc h ival charac­
teristics. \i\ih i l e paper conservation provides a usefu l set of tec h n iques and
many restoration materials for worki ng with photographs, the conservation
problems of the paper constituent of photogra phs are freq uently mild, com­
pared to the problems o f the silver and colloid constituents. Each of the
th ree constituents sets l i m its o n the treatments that are possi ble for the
other two-t hus, for exa mple, bleachi ng, a common paper t reatment, can not
be applied to photographs because the si lver const ituent is easily oxidized.
I nt rod uced in the 1 870s, si lver gelatin printing paper has been the p re­
dominant photographic pri nting material s i nce the turn of the centu ry, and
therefore the great majority of prints i n many photographic collections a re
si lver ge latin pri n ts. I n the paper which fol lows I will describe the stru c t u re
and materials of si lver gelatin papers, concentrat ing on the lami nate struc­
t u re of the paper and the m ic rostructure of the silver i mage, and I will relate
these struct u res to c haracteristic deterioration processes and conservation
p roblems. F i n a l ly, I will d iscuss the u t i l i ty of one of the most common, c u r­
rent conservation trea t m e n ts .

I dentification

Of the many varieties of si lver ge latin papers which have been m a n u fac­
t u red, only the early papers p resen t d i ffic u lties in ide n t i fication. Such papers
freq uently replicate the appearance of contem porary albumen and collocl ion
papers. Gelatin em u lsions, however, can be readily iden t i fied by placi n g a
droplet of water on the print su rface and observi ng the rat e of absorption
and the amount of swelling u nder the m icroscope. Col loclion su rfaces are
i m permeable to water (though water may be a bsorbed i nto the su bstrate
through b reaks in the su rface), and albumen emu lsions swell very little.
Aged albumen coati ngs have a chara c te ristic network of small fissures and
c racks i n the laye r which provide s tra ightforward visual ident i fication u nder
the microscope. Destructive but spec i fic micro-chemical tests, such as the
hyclroxyprol i ne test , ' can be used to supplement visual identification as a
tra i n ing device, but a re seldom needed i n practice.

53 4
 Read ing 57 S \\I A :"Ii

Lami nate Structure of the Papers

The struct u re and thic kness of the layers compos ing a pri nting paper greatly
i n A uence its physical properties. S i lver gelatin papers ge nerally consist of
a paper base, a gelati n -bari um s u l fate u n der- layer, the si lver-gelat i n "em u l ­
sion , " a n d a protective ge latin su percoat .
T h e paper base of earlier gelatin papers was com posed of rag fi bers,
but presen t printing papers are generally made from wood pulps, su l fite
p u l ps bei ng the most freq uently u sed . The a cellu lose content should be
very h igh-G laFkides claims that less than 4% of the fiber content may be
hem ice II u loses. 2
The fi bers are usually h ighly beaten and very short . The pulp must be
very pure and free from metals, especially i ron and copper, as we l l as from
other photograph ically active materials, such as hal ides and red ucible su lfu r.
Photogra phic papers must be able to withsta n d long wet-ti mes and much
handling while wet, as well as exposure to bases (the p H of developers is
freq uently 1 1 or 12), and acids ( fixing solutions usually have a p l -I of about 4).
To provide such chemical and water res istance, the paper is ge nerally sized
with starch or gelatin, a l u m-ros i n , and melami ne-fo rmalde hyde, which are
added to t he pulp as i n ternal sizing. Dyes and kaol i n are Freq uen tly present
for color and opacity.
The thickness of the pa per bases va ries widely accord i n g to the appl ica­
tion, from the t h i n "docu ment" papers measuring about 0.064 m m (2.5 m i l ) ,
t o "dou ble-weight" card papers, measuring about 0 . 3 8 m m ( 1 5 m i l ) . Dimen­
sional stability has been considered very i mportan t si nce the space d istri bu­
tion of the i mage frequently represents '' real " space, and should not cha nge
sign ificantly as a result of processing or with h u m i di ty Fl uctuations. For most
photographic papers expa nsi bil ity is within 0.004 and 0 . 0 1 4 per cent size
cha nge per per cent change in re lat ive h u m i d i ty. The papers are all mac h i n e
made and have a pro n o u n ced gra i n .3
The paper base is first coated with a layer of gelat i n conta i n i ng finely
ground baryta ( bari u m s u l fate) to give an opaque, smoot h , white su rface
upon which the emulsion can be evenly coated with good adhesion . Si nce the
emul sion layer must be of a u n i form thickness to accu rately record the densi­
ties of the n egative, su rface mod i ficat ions designed to prod uce a matte, glossy
or em bossed su rface on the fin ished paper are made on the baryta layer. For
glossy su rfaces, very finely d ivided baryta pigmen t is used, several layers of
the coat ing are applied to b u i ld up th ickness, and the coated sheet is calen­
dered. For matte su rfaces, the baryta p igment i s coarse, the layer t h i n ner,
and the sheet u n cale ndered. The baryta layer also contains ge lat i n hardeners,
such as a l u m and formalde hyde, as well as dyes or optical brighteners. After
coati ng, the paper is usually aged to al low complete hardening of the layer.

53 5
Part VII D E V E L O P I N G C B I T E H I A

The l ight-sensitive layer of the lami nate, i ncorrectly but i mmutably

termed the "em u lsion, " is coated next. In ge nera l , s ilver gelatin e mulsions
for pri nting papers contai n less s i lver and are coated more t h i n ly than film
emu lsions; s i nce they will be viewed by reflected rather than transmitted
light, only half the optical density will produce about the same absorba nce.
They are also much "slower" emu lsions, since a much longer l ight exposure
i s desirable for printing than for negative making. The lower speed allows
them to be " fine grai n " emulsions; the size of the original si lver hal ide crys­
tals and the later, metal l i c silver part ic les is very muc h smaller than it is in
fi l ms , which m u st have larger crystals to obtai n i ncreased light sensitivity.
Paper emu lsions util ize s i lver c h loride and brom i de, e ither si ngly or mixed,
and, u n l ike fi l m emu lsions, generally do not conta i n silver iodide. Major cri­
teria for the formulation of paper emu lsions are i mage color and contrast
control, rather than speed and granularity, as is true of fi l ms . The range o[
colors producible i n a s i lver image by controlling the size and structure of
the si lver particles is quite large, extend ing from warm red-browns through
blu ish blacks. I n addition to the si lver hal ide crystals in the gelatin matrix,
the emu lsion contains gelatin hardeners and various additives to control its
shelf life and developabil ity.
vVhen the emulsion has been coated and a l lowed to set but not to dry,
a very t h i n final coat of ge latin with harde ners is applied to provide su rface
protection to the emulsion.
This is the most common structure of sil ver gelatin papers; however,
in the century that these papers have been manufactured there have been
many variants. Many papers do not contain a baryta layer, the emu lsion
being coated d i rectly over the paper base. Such papers, common at the turn
of the century, usually have matte su rfaces, and the pattern of the upper
fi bers of the paper can be seen in the surface of the emulsion. Abrasion of
these papers frequently removes si lver density in the pattern of the su per­
ficial fibers, and may even d i splace i n dividual fibers if the e m u lsion is very
t h i n . S upercoat layers have often been om itted, especially si nce their coating
presented techn ical diffi c u l ties. Freq uently a "matting agent'' consisting of
starch grains or colloidal sil ica has been added either to the emu lsion or to
the supercoat. The common recent variant, resi n coated paper, i ncl udes a
polyethylene coating over the back and front s urfaces of the paper base, and
the emulsion i s coated directly on the polyethylene. It should be noted that
these papers are not ti me-tested materials, and that some of the manufac­
t u rers have stated that resi n coated papers have not been recom mended for
archival applications.
 Reading 57 S \V r\ N

Conserva tion P r obl e ms Related to the La m i n a te S t ru c tu re

The expa nsion and contraction of the d i fferen t layers with changing h u rn i d­
ity is not identical: the ge latin e m u lsion expands rnuch more than the paper
base, and the baryta layer, with its large content of d i mensiona l ly stable mi n­
eral, proba bly lies between t h e two i n expansibil i ty. Even i n prints where
the dryi ng process has been idea l , prod ucing a flat print with rn i n i mal ten­
sions, the s heet will c u rl with fl uctuations in h u m i d i ty, with the ernu lsion
i n side the cu rve at low h u rnid ities and outside the c u rve at h igh h u rn idities.
S i nce drying is seldom ideal, or h u rn idity even , prints freq uently curl non­
u n iform ly, producing a variety of local cleforrnations which a re cons idered
u nacceptable in art collections, given the cu rrent aesthetic of ph otographic
su rfaces as "clean, " s moot h, rnac h i ne-made and flat. The arnount of c u rl i s
control led by the comparat ive th ickness o f the layers, the stiffness of t h e
support, the method of papermaki ng and drying of the coated sheet. the dry­
i ng met hod after processing and the conditions of storage. Recent and rni nor
local plane deforrnations can be flattened by h u m idifying the print and then
pressing it between photographic-grade blotters u nder a glass sheet, but the
print m u st afterwards be kept flat i n an environrnent of even hurnidity or
deformations wi ll rec u r. Storage fac i l i ties for photographs clearly req u i re
h u rn idity control, for the retention of flatness as wel l as for the sta b i l i ty of
the si lver irnage.
The prob lerns of curling have been freq uently dealt with by adhering a
pri n t to a rnore dirnensionally stable, rigid, cardboard mou nt, usually by cl ry­
rnounti ng-that is, adhering the print with a heat-set adhesive in a heated
press. Th is mounting method has exhibited several problems i ncluding the
great d i fficulty of later removing the p ri n t from the mou nt , the deleterious
materia ls which have been favored as mounts, and the i n herently damaging
effects of the heat and p ressure i ncu rred in the mounting proced ure. B u t
beyond these wel l known p roblems, dry mounting i ncreases t h e d i fferential
of expans ion and contraction between the front and back of t he laminate,
s i nce it acids another, less reactive layer at the less reactive side. This causes
greatly increased tensions in the emu lsion with h igh or low hu mid i ty or with
fl uctuations. I rece ntly exam i ned a s il ver gelatin print from the m icl- 1 96os
which had been mou nted to a rigid board. The pri n t had been stored at low
h u m idity, seasonally cyc led with more normal h u m i d ity, over a n urnber of
years, and the contractive forces on the ernu lsion had become so large that
the emu lsion had pu l led u p, taking with it the baryta layer and the top half
of the paper base which it had split i nto two layers, leaving the lower half
of the paper ad hered to the mount; the separation had occu rred along one
whole end of the mou nted print.

53 7
Part VII D E V E L 0 P I N G G 11 I T E R I ,\

The opposite situation is commonly seen i n dry mou nted pri nts
which have been stored at high h u m idity. Dry mounting usually attaches
a print and mount while both are at m i n i m u m expa nsion, especially if the
mounter has "pre-heated"' the print and mount before attachment "to pre­
vent curl i ng. " \Vhen such a l a m in ate is exposed to h igh h u m id i ty, the much
greater expansion of the print frequently separates the photograph from
the mount i n u neven waves and b ubbles. The ge latin layers must expa nd
or contract in response to h u m id i ty change, and the weakest bond between
expa nding and non -expandi ng layers wi l l fa il-usually at the dry mount
tissue/mount i nterface .
Because of it s layered structure, a ny bendi ng or Flexing of gelatin
prints puts great tensile and compressive stress on the exterior layers, crack­
in g emulsions and creasi ng and breaki ng paper layers. Th is structural lack
of Flexibility leads to m uc h da mage i n handling. lt seems necessary that the
housings and mats devised for gelatin prints always prov ide rigid su pport.
The emu lsion is frequently the most brittle layer of gelatin prints.
The group of photogra p hs in which I have seen the most em brittlement and
cracki ng is that of "ferreotyped" glossy pri nts from the 1 930s and '40s. Such
photographs req u i re special protection against flexing or bend i n g i n ha n­
d ling. It is l i kely t h at ferrreotyping (drying the we t pri nt with i t s emu lsion
molded against a smooth and usually heated su rface) i tself contri butes to the
brittleness of an emu lsion si nce it d ries the emu lsion i n a h ighly stretched
state, setting in much tension . Add i tional ly, si nce adequate harden i ng of the
emulsion is critical to preven t the print from sticking to the ferreotype plate,
overuse of hardeners may be i nvolved.
The l arger expansive and contractive forces of the e m ulsion i ncrease
the difficulty of mending a break in an emulsion at a tear, crack or loss. Such
a break tends to pull i tself further apart, even u nder conditions of small
h u midity change. The emulsion someti mes separates from the baryta u nder­
layer in areas of damage as wel l , again clue to the uneven contract ive stresses
between the layers acting on an i ni t i a l ly i nadequate bond .
One frequently sees evidence of poor bonding between the emulsion
and the baryta layer i n older gelatin prints. \Nheneve r edge damage to a pri nt
has caused c hips of e m u lsion to separate from the baryta layer, or when
there are signs of "fri l l i ng" (separation of the emulsion from the baryta layer
around the edges of a print during the original processing), I wou ld particu­
larly hesi tate to dampen or wet such a pri nt, si nce the increased tensions
on the bond, ca used by swe lli ng differences among the wetted layers, wi l l
encourage fu rther separation. Such separations are extremely diffi c u l t t o
reattac h , even when very small. Among other d i fficulties is t h a t of finding an
appropriate adhesive: water based adhesives swell the loose emu lsion out of
pos ition, but one can h ardly use a solvent based adhesive si nce, either in use
 Reading 57 S \\' A N

or remova l , i t is l i kely to penetrate the s u rro u nd i n g a rea, preventing it from

accept i n g water u n i formly and causing fu rther local diffe re nces in expansi­
bil ity. N eed less to say, the adhesive m u s t also be chem ically u nreactive with
si lver and ge lat i n .
Very litt le i s known about the optimal harde n i ng o f prints for maxi­
m u m usefu l life : the lo ng-term effects of the va rious hardeners have not
been i nvestigated. H a rdening has been dealt with on im mediate, practi c a l
grounds, a s a n ecessary step t o preven t emulsions from di ssolving when pro­
cessed at h igh temperatures or in chemical solutions which attack gel ati n ,
a n d has been meas u red b y s u c h gross physical tests a s the melting poi n t
tempera t u re o f the e mulsion, a n d t h e weight with which a stylus c a n b e
loaded before it punctures a w e t or d ry e m u l s i o n . I know of no experi mental
work o n the re lation of hardening to e m u lsion brittleness, though common
sense wou ld suggest that such a relation exi sts; and I know of no experi­
mental work disprovi ng the existence of a syn d rome that m ight be thought
of an '"overhardening. " It is known that formaldehyde, the hardener most
freq uent ly recomme nded for use in restoration treatments of ge latin pri n ts ,
shows a ma rked tendency towards "afterhardeni ng"-t hat is, the degree of
hardness in the treated e m u lsion conti n ues to increase long after the treat­
ment. U n t i l more is known about the long-term effects of harde n i ng, the use
of hardeners (pa rticularly the i rreversi b l e aldehyde hardeners) on i rreplace­
able prints seems u nwise.
N evert hel ess, when a n older gelatin print is wetted one faces a pos­
sible swe l l i ng problem, ca used by the frequently th icker e m u lsions and the
u n predictability of harde n i ng i n older pri nts. N ewe r prints do not presen t
the same difficu lty s i nce t h e i r generally th i n ner e m u lsions a re more l i kely
to have been hardened in man ufacture (the major harde ning for older
prints was introduced by photographers i n process i ng) and si nce they have
been less affected by u npredictab l e aging c ha nges. Some i n d ication of an
e m u lsion's swe l l i ng tendency is given by its response to a droplet of water
observed by ra king light. P r i n ts shou l d be wetted slowly and t reatments lim­
ited to cold or room temperature solutions to contro l swe l l i ng. Conservators
must also be aware of the complex effects of various chem ical treatments o n
a n emulsion's swelling be havior, both in the solution itself and afterwards i n
wash baths; solu tion p l-I , conce n trati o n a n d temperature , a s well a s spec ific
chem icals, have strong effects o n swe l l ing.
Drying ge latin prints is also a sensitive job s i nce, when wet, the emul­
sions are swol len, soft, and tend to stick and mold to other su rfaces. In this
state, extraneous materials are easily embedded i n the e m u lsions (i ndeed,
e m bedded fi bers often provide an easily used clue in the identification of
ge latin prints which are l i ke ly to swell excessively in wet treatment). Gelatin
e m u lsions must be dried n early to completion before any system of flatte n i ng

5 39
Part VII D E V E L O P I N G C R I T E B I A

i nvolvin g contact or weight can be used. The frequen tly recom mended method
of d ryin g pri n ts face down on fi berglass d rying screens causes s u rface dam­
age; prints should be dried face up after water droplets have been carefu l ly
wiped from their surfaces. I t is freq uently i mposs i b le to u t i lize a photogra­
pher's origi nal drying or fl attening method because of the i n herent damage or
risk i n volved i n the method : ferreotyp i ng is a good example of such an u n us­
able method, as are the use of heated "drum" d ryers and dry mou n t presses.
For some smooth-su rfaced, u n ferreotyped gelatin pri n ts, su rface d i rt
can be removed by l ight, ge ntle clea n i ng with soft, non-abrasive erasers. Th is
should be done under a m ic roscope with adeq uate magn i fication and raking
l i ght, si nce there are great d i ffere nces i n the ease with which gelatin su rfaces
can be scratc hed and abraded, depe n d i ng on s u rface smoothn ess, e m u l­
sion hardening, the possi ble presence of s urface "matting" agents and many
other conditions. Any eraser res idue left on the surface should be removed
by gently wiping the su rface with d ry, clean cotton wool. This cleaning step
is only suggested because of the p revale nce of extraordi nary d i rt layers on
photographic prints caused by their typically poor storage conditions. It can
abrade and wear the su rface and should be avoided for less d irty prints.
Pads of cotton wool just slightly dampened with a lcohol and other
organic solvents are very hel pful in cleaning print s urfaces, though one m ust
be carefu l not to use enough solve n t to penetrate the emulsion, thereby
spreading dissolved material wh ich had been pre\riously confined to the sur­
face. I avoid using water i n surface cleaning because of its swel l i ng effect,
because of the certa i n penetration of the d i rty water i nto the absorbent e m u l ­
s i o n , and because of t h e i nc reased physical fragil i ty o f wet emu lsions. Use
of the frequently suggested ammonia solutions for s u rface clean i ng seems
particularly disadvan tageou s : not only is the swe l l of the emu lsion and the
penetration of the d i rty solution maxim ized by the h igh p H , but ammonia
forms a stro n g complex with s i lver, and if any oxidized s ilver i s present i n the
emulsion (which is q u i te l i kely-as si lver ..ge lati n ate, " for i nstance) it will
be moved about local ly, prod ucing silver distri bution patterns u n rel ated to
the image, and causing non-i mage dens i ties upon reduction by l ight or other
reducing conditions. lt would seem only reasonable that any u se of ammonia
should take i nto account its solvent action o n silver salts, should take place
u n i formly ( i . e . , by i m mersion, not local application) a nd should be fo llowed
by a thorough washi ng.

The M icrostructure of the S i lver I mage

S i lver gelatin papers can be d ivided into two classes based on the printing
method used: "prin t i ng out paper " ( frequently termed "P.0. P . " i n the man­
ual l iteratu re) forms images solely by the act ion of l ight; whereas "deve lop-

5 -! 0
 Reading 57 S \V A N

i n g out paper ("D.O.P. ") req u i res a m uc h shorter light exposure which forms
o n ly very small meta llic s ilver specks on the s i lver hal ide c rystals, and these
specks then be have as catalysts in the reduction of the crystal i n develop­
ment. All modern papers (with the exception of the "stud io proof" types) are
developi ng papers, with the consequence that only developing papers have
been invest igated by modern tec h n iques.
Gelati n pri nti ng out papers, common from the 1 880s th rou gh the early
1 920s, have s i lver ch loride e mulsions prepared so as to give crystals of very
small particle size. The emulsion contains a ha loge n acceptor-usually
sod i u m citra te-to prevent the recombination of chlorine, prod uced i n the
l ight expos u re, with the newly formed silver i mage . The s i lver particles so
formed would be q u i te small and rounded. Printing out papers were always
toned-usually with gold , which modified the i mage color from red-browns
towards deeper, purp le-brown tones; though formu las for su lfu r and plat­
i n u m toning are common in the manuals of the ti me, and eve n u ra n i u m
ton ing is suggested. Gold toni ng had been standard processing procedu re
for albumen pri n ts s ince the early 1 860s and was known to provide greatly
i mproved i mage stabi lity. (Gold toning is still the treatment of choice for
prod ucing stable si lver images-i t i s the recom mended treat ment for micro­
fi l ms, for instance, wherever economically feasible.) Si nce they requi red
mass ive light exposures, these papers were always pri nted in d i rect con tact
with the negative . .It is frequentl y possible to identify photographs pri n ted by
con tact beca u se of the small size of the reprod uced negative gra i n .
Deve loping o u t papers , i ntroduced i n t h e 1 870s, but n o t widely used
until the 1 890s, were designed for both contact pri n t i n g and en largi ng. They
have most commonly been left u n toned, t hough ton i ng prod uces a wide
range of color vari ations and some types of toning convey added i mage sta­
b i l i ty. The most frequently u sed ton i n g materials a re su lfu r, sele n i u m a n d
gold. Sulfu r toning pro d uces colors from warm b rown o r sepia through
warm black and has been commo n ly and consistently used . Sele n i u m toning
produces warm black to red-pu rple-black tones a nd has been used in very
m i n i mal amou nts by F1 11e art photographers concerned about su btle ton a l
gradation a n d perma nence. Gold toning has been s o expens ive and cl ose ly
associated with pri n t i ng-ou t rather than developing out papers , that i ts use
for developed emuls ions has been largely confined to arch ival applications
s i nce the m id- 1 96os .
Developed prints can be divided i n to two types depe nd i ng on the
struct u re of the developed si lver. I mages produced by ''d i rect develop ment"
are formed by reduction of the s ilver of the s i lver hal ide c rystals at the s m a l l ,
ligh t-prod uced, catalytic s i lver specks, s u c h t h a t a fi ne filament or thread of
s i lver is extruded at each catalytic s i te by the developer. Depe n d i ng on the
s ize of the si lver halide crystal and the amou n t of l ight exposure, there are

5-f I
Part VII D E V E L O P I N G C R I T E B I A

freq uently several catalytic s ites on the same crystal. The res ult i s a ta ngled
mass of filaments, retai ned by the gela t i n matrix i n approximately the space
origi nally occ upied by the s i lver halide c rysta l . This type of struct u re i s pro­
duced by act ive developer solutions with little a b i l i ty to dissolve s i lver hal ide
crystals . Such a structure has a large " coveri ng power," that is, a re latively
small mass of s i lver gives a large optical density; and it exh i b i ts u n i form light
a bsorpt ion of all colors of visible light. Consequently the i mage appears
neu tral black and gray in color. Print developers are usually of the d i rect
development type .
The second type of i mage structure is produced by " i n d i rect" or "solu­
tion physical devel opment." l n this type of development the s i lve r hal ide
crystals are dissolved a n d metallic si lver is deposited out of the solu tion onto
the catalytic silver specks. Consequently the developed si lver particles are
approxi mately spherical . Th is struct u re is produced by less active developing
sol utions with h igh solvent a b il ity. This stru cture has relatively low cove ri ng
power-a la rge mass of s ilver gives re lat ively low optical dens ity; and the
cove ring power decreases as the dia meter of the particles i ncreases past a
certain t h reshold value. This stru cture s hows a maxi m u m l ight absorption
a t the blue encl of' the visible region of the spectru m, which produces a yel­
low or wa rm-toned i mage by reFl ectecl light.4 Solution physical development
has ge nerally been avoided in the des ign of paper developers because the
image col ors i t produces have been thought u n pleasant. It is descri bed here
because it forms an i mportant second silver particle structure.

Characteristic Types of Deterioration of t h e S i lver Constituent

Of the two s i lver particle structures, the ro u nded particles a re the more sta­
ble, and their stab i l i ty depends on part icle s ize. The filamenta ry structure,
which has a greatly i ncreased ratio of su rface area to mass, tends to recrys­
tall ize to the rou nded, solid form u n less the s u rface is sta b i l ized by the pres­
ence of' a stro ngly absorbed material such as s u l fide, iodide, or one of the
n u merous organic compounds termed ''bl ue-black agen ts " or "anti-pl u m m i ng
age nts " precisely because they promote t he cold-toned fi lamenta ry structure
and preve nt recrystallization lo the warm -toned, rou n ded struc t u re u nder
adverse conditions such as elevated temperatu res in process i n g or drying.
Among the rou nded parti c les, smaller part icles tend genera l ly to recrystallize
onto larger part icles, though this process is dependent on many factors.
In a study of the stab i l i ty of silver filaments, T. H . James5 t reated emul­
sions of filamentary s i lver by i n c u bation at high h u midity and by i m mer­
sion i n va rious salt solutions. He fou nd that u nstab i l ized fi laments became
shorter and thicker after a few clays of incubation at 20°C and 1 00% R H , a n d
recrystallized i n to rou n ded forms within a few m i n u tes w h e n i m mersed i n

5 ...p.
 Reading 57 S \\' A N

solutions of salts forming s i lver complexes, such as thiocya nate or chloride;

whereas filaments stabil ized with su lfide through normal thiosulfate fixing,
or with iodide, changed much more s lowly. Recrysta l l ization was accompa­
nied by red uced reflection density and by changes in image color by reflected
l ight. This a uthor also notes t hat exposure to hydrogen peroxide causes
recrysta l l ization of filamentary si lver. The structural cha nge from filamen­
tary to rou nded form and fro m ge nerally smaller to larger ro unded particles
is one very likely source of the density loss and color s h i ft towards yel low
which arc characteristica l ly seen in older photographs.
Oxidation of the s i lver image i s another major cause of density loss and
color change, which may occ u r even ly, locally (along edges fo r in stance), or
i n spots. Reviewing the oxidants which had rep rodu ced naturally occ u rring
microfi l m spots u nder laboratory conditions, Henn and \Viest" l ist atmo­
spheric oxygen a t raised h u m idities, the effect of which i s accelerated by
the presence of hydrogen su lfide, ammonia and s u l fu r dioxide; ozone and
its derivatives, i n c l uding the nitric oxides it generates in smog; and perox­
ides, which are commonly evolved from fresh paint, plastics, bleac hed wood
(as in frames or cabinets), oxidizing metals and oxid izi ng organic mate r­
ials, including paper. I ndeed, the microfi lm spots which had occasioned the
research were eventually att ributed to peroxides formed by the cardboard
contai ners i n which the fi l m s were stored . 7 McCamy and PopeH reprod uced
microfilm spots by exposing r il ms lo fu mes from various oil, t u rpenti ne and
powdered ros i n . Elevated humidity was found to be a n im portant Factor in
spot formation; peroxide f"o rmation by paper, for instance, va ries d i rectly
with h u m idi ty. Gelatin e m u l s ions easi l y absorb wate r-dissolved gases cl ue to
their hygroscopic n a t u re, and u n der conditions of humidity cyc l i ng, m ight
be expected to concentrate such su bstances. \Veyde poi nts also to the i nflu­
ence of the paper base, "'which h as an astonishing storing effect b y adsorp­
tion of oxidizing gases."9
I n the micro fi l m spots, peroxides, active as oxid izing and as reducing
agents, were thought responsible for both the oxidation and red uction of s i l­
ver in the spots. 10 The structure of the spots showed clearly that image si lver
had migrated through t he ge latin matrix; it was t hought to have migrated
in an oxid ized state and then to have been red uced at preferred nucleation
s i tes, or to have been incorporated in a stable compound such as si lver sul­
fldc. I mage s i lver was found Lo have formed a new structure of colloidal s i l­
ver part icles, appearing ye llow and red because of the part icle size, and often
positioned in a n nu la r ri ngs, someti mes arou nd a center; to have redeposited
on the origi nal fi lamentary silve r particles, rou nding and fragmenting their
structu re by recrysta l l ization; lo have formed h ighly reflective si lver deposits
on the su rface of the emu lsion (su rface m irrors); and to have formed com­
pou nds such as s ilver s u lr1clc, si lver gclatinate and s ilver ch loride. 1 1 Though

5-13
Part VII D E V E L O P I N G C B I T E H I A

the base materials, processi n g conditions and storage modes are differen t ,
t h e microfilm spot research offers an ext remely helpfu l consi deration o f the
mechanisms of the fad i ng, yel lowing a nd mi rror formation that so frequently
occur on p hotographic prints.
Both recrysta llization and oxidation of silver images can be m i n i m ized
by atmospheric control-espec ially the mai n tena nce of low, eve n humi di­
ties. The cu rre nt American National S ta ndard for microfilm storage (AN S I
P H 5-4-1 970) specifies that material for "perma nent" storage be kept a t a
relative h u m i d i ty not exceed ing 40 per cent. Expos u re to oxid izi ng materials,
such as peroxides and sou rces of peroxides, must also be avoided .
The transformation of t he si lver i mage to s i lver s ulfide is a nother major
source of density loss and tonal change in silver ge latin spri nts. S i lve r sul fide,
one of the most stable of the si lver salts, is fo rmed by any sou rce of sulfide or
red uci b le s ul fu r in the presence of ionic silver. I t is formed as a monomolec­
u la r layer o n the su rface of i mage si lver d u ri ng fixation (or very shortly after),
even with ideal processi ng, so reliably that the quantity present can be u sed
to esti mate the su rface area of filamenta ry si lver. 1 2 \Nhen a source of su lfu r
i s ava i lable (such a s residual thiosu lfate left i n a n i ncompletely washed print,
or the i nsoluble silver-th iosulfate complex left in a print by a n exhau sted fix­
i ng bath , or one of the common su lfu r gases in pol l u ted air) oxid ized silver
will combine with it to form si lver s u l fide. A s i lver image which has u nder­
go ne significant tra n s formation to si lver s u lfide by these naturally occ urring
reactions has a ''faded " range of gradations of light yellow-brown, which are
most obvious i n highl ight and midtone areas. Recrystallization of the i mage
particles and optical effects caused by changes in the surface of the s u l fidecl
particles are also i m porta nt factors i n the typica l l y much redu ced optical
den sity of the i mage. I ncreased s u l fiding is freq uently seen aro u n d the edges
of pri n ts if greater expos u re of t he print to s u lfur sou rces has occu rred at the
edges, as happens, for i nstance, i n the exposure of stacked pri nts or prints in
albums, to polluted air.
To m i n i mize the su lfiding of silver i mages, oxidation of the i mage must
be avoided, and the avai labi lity o[ s u lfu r from both i n trinsic ( residual chem­
istry) and extri nsic (air and storage materia ls) sources m ust be m i n i mized .
The problem of su lfu r from i ntrinsi c sources will be considered i n a later sec­
tion. As for extrinsic sources, sulfu r gases are commonly present in poll uted
c i ty air; air cond itioning systems for photogra phic a rchives need a filtering
step to remove them. U n fortu nately, some storage and restorat ion materials
conta i n active sources of su lfu r. I have found acid-free i nterleaving papers,
art papers, J apanese papers , and polyvi nyl acetate emu lsion ad hes ives which
contain active su lfur and cause silver su lfide formation in si lver images. The
use of such materials in repai ring and mat t i ng photographs causes d rastic
local fad i ng; I have recently seen two u ncon nected cases-one where the

5++
 Reading 57 S \V A N

active material was a su lfur-conta i n i ng J apanese h i nging paper, the other a

sulfur-conta i n i ng starch adhes ive-where the image of the h i nged pri nt had
faded from deep purple brown to pale ye llow tones wherever the damaging
h i nging material had contacted the back of the print. In each case the h inges
had been in place about two years when the fad i ng was d iscovered, and the
photogra ph had been stored u nder h u m id cond itions, al lowing migration
of the su lfur source through the paper support to the emulsion layer. All
materials to be used in the repa i r and storage of si lver p hotographs m u st
be tested, using a s i lver tarni s h i ng test. 1 3 Because trace q uantities of active
sulfur have a large effect, a n d because such quantities of su lfur are possibly
present as a contaminant rather than as a constituent of materials, it is wise
to test each separate batch or lot of materia ls.
Another very characteristic visual appearance of si lver i mage deteriora­
tion is the formation of reflective metallic su rface deposits in areas of maxi­
mum si lver content. This effect occurs more strongly in ge latin prints than
in other types of si lver prints, and so freq uently as al most to typify older
s i lver ge lat i n materials. Such deposits, p resent i n the microfilm spots, are
caused by oxi dation of i mage s i lver, followed by its m igration through the
ge latin and red uction at the su rface. When a su rface source is available,
the deposi ted si lver is fou n d i n combination with silver s u l fide. Such depos­
its are commonly referred to as "si lvering" and are someti mes also called
"dichroic fog" i n negative materials.

Problems with Restoration Treatments of the S i lver Constituent

As noted previously, the restoration proced u res for photographs that have
been p ro posed in the past were not developed for, and have not been m odi­
fied for appl ication to i rrep laceable and age-weakened pri nts; in deed, the
great majori ty of form ulas long a n tedate the present, i ncreased monetary
values now assigned to p hotographs, belonging to an era which perceived
p hotographic pri nts as rep laceable and their collection as somewhat eccen­
tric. 1 4 U t i l iz i ng powe rfu I oxidizing agents, ext remes of p H , i rreve rs ible and
i nadequately control led deposition of i mage metals, or the rei ntrod uction of
sign i ficantly unremovable contaminants, these restoration proced u res need
careful exa m i nation, eva l uation, reform ulation and testing for long-term
effects before being applied to valuable prints. The restoration l i terature
appears to be caught i n a basic confusion between replaceable and i rrep lace­
able pri nts; there are obvious major differe nces between appropriate treat­
ment of one's own new prints and of valuable older prints on the basis of
replaceab i lity as well as the differences in materials and condition.
I ndeed, the most common ly prac ticed and least controversial of sil­
ver treatment, "reprocessi ng, " p rovides a clear example of the d i ffic ulties

5-1 5
Part VII D E V E L O P I N G C H I T E H I A

encountered i n applying excellent routine proced ures for one 's own mod­
ern pri nts to irreplaceable older pri nts. " Reprocessi ng " refers to treatment
in a new fixing solution, fol lowing by ''hypo-c leari ng" and " hypo-el i m i nati ng"
baths, both t h i os u l fate removal treatments, followed by extended was hing
i n water. The procedure is identical to that routinely fol lowed for the archi­
val processing of new prints, and is recommended throughout the restora­
tion li terature For al l s i lver pri n ts which have been tested with two "easily
used" test solut ions and found to contain res idual chemicals, i .e. the si lver­
th iosu l fatc com plex and thiosulfate. I t is my i mpression that reprocessing is
currently pract iced Frequently and rout i nely.
Residual si lver-th iosu lfate colll plex and th iosulfate, left in a pri nt by
an exhausted or poorly designed t h iosu lFatc ba th and by i nadequate wash­
i ng, are known to produce severe i lllage fad i ng and sta i n ing. The presence
of these residual chemicals has long been ident ified as a particu lar prob­
lelll for gelatin pri nts, promoted by the design of ge latin pri n t i ng materials.
The lll ueh greater mass of absorbant, retent ive material per unit of i lllage
area allows much larger amounts of residual chc lllicals to be stored than
is the case with the older pri n t ing materia ls. Compari ng just the typical
paper bases of salt, a l b u men and gelatin pri nts, it is clear that the t h icker,
h ighly culll prcsscd ge latin paper stock, with its heavy, synthetic. watcr­
res istant sizi ng, al lows less water movement thro ugh it and is therefore
Jll uch JllOrc d i lT1e u l t to wash effectively. \Vhilc extended vigorous wash i ng
is required for all si lver pri nt ing materials which have been fixed in th iosu l­
fate, and al l of' thclll fade and stain i f washing is inadequate, gelatin paper
prints have a lll uch larger capac ity to store res idual chemistry, which u nder
h u lllid cond itions slowly d i ffuses t h rough the lllaterial, causing fad ing and
staining capable of cont i n u i ng over 111any years as it gradually reaches the
si lver i lllagc.
The restoration l iterature d irects one to test for the presence of these
res iduals with two tests, one for res idual si lver ( l(odak Si lver Test ST- 1 ) and
one for res idual t h iosulfate ( Kodak H ypo Test I IT-2), forlllu las for which
are found thro ughou t the restoration l iterature as wel l as i n Kodak gu ides to
black-and-white processing. However, there arc several major practical prob­
lcllls in the use oF these tests, which arc ent irely u naddressed in the restora­
tion li terat ure. First, the tests cannot be applied to prints of va lue si nce both
tests forlll u n rc111ova ble si lver s u l fide stains (and l'orlllation of the stain con­
stitutes the test), i n the case of the t h iosulf'a te test, by supplying free si lver,
and in the case of' the si lver test, by supplying f'ree sul fide. A margi n or other
white highl ight a1·ea must be used for the test so that the res u l t i ng stain can
be seen and cst i111ated adequately-but most older prints have no remai n i ng
margi ns, and so llle do not even have clear highl ights in their pictorial spaces.
M oreover, bot h test sol u tions are severe contalll i nants of si lver i lllages, such
 Reading 57 S \\I A N

that even if the test res u l ts are negative the print m u st still be extensively
treated to re move the test solut ion.
Further, the res u lts of' the tests may be m i sleading. Margi ns, for
in stance, a re more l i kely to have been adequately fixed and washed than the
cen ters of prints, s ince most process i ng and wash ing systems pass consider­
ably more solution over edges than cen ters of prints, and solution f low is
typically a l i m i t i ng factor in these d i ffusion-controlled processes. Moreover,
thiosulfate is retained more strongly in the emulsion in areas of increased
si lver content (the shadows of prin ts) than in highl ights or margins. I n a
study of thiosu lfate retention in m icroll lms, C . I . Pope found a nearly l inear
relat ion between t h i osulfate retention and si lver conce ntration. 1 5 Add i tion­
ally, u n eve n d istrib ution of residual silver a n d t h i os u lfate is characteristic
of extremely i n adequate processing, such that a test res ult in one area of
such a print wi l l not necessarily match the test result from another area.
Anyone who has worked with h istorical photograph ic collections has seen
prints where ye!lowi ng and density loss were extremely u neve n , with "air­
bell " shapes or corners or ends with greatly i ncreased or red u ced fad ing.
Fi nally, the tests do not i n d icate the presen ce of the res iduals in the baryta
and paper layers of the pri nt, though their absorption and rete ntion in these
layers is known to be a major part of the problem.
Even i f the tests could be appl ied without i n c u rri ng major damage to
pri nts, and even i f the test res u lts were u n iform and rel iable. there wo u ld
still be sign incant p roblems with the evalu ation of resu l ts si nce there has yet
been no attempt to establish acceptable stain levels for older pri nts or to cor­
relate stain levels with even tual fad i ng and sta i n i ng. For example, the resid­
ual silver test a lways l eaves some amount of yel low s ta i n ; a posit ive test resu l t
is described with u nhelpfu l vagu eness as more than a barely visi ble cream
tint. 1 6 S i nce a posi tive resu l t d i rects one to a non-reversible treatment in an
imperfectly removed, contaminating material (refixing), it would seem i mpor­
tant to be able to different iate more precisely between pos it ive and negative
results. Appropriate eva l uation of t he res idual hypo test is equally u ncerta i n .
W'hile varying levels of sta i n From t h e test (established b y visual comparison
to fou r yellow-brown patches of vary i ng density provided in the Kodak " Hypo
Esti mator") are listed as acceptable for various p hotographic materials i n
cu rrent com mercial use, the Hypo Esti mator i n structions i m ply that mate­
rials for arch ival u se must show zero stai n . \!\fh ile i t seems reasonable for
new, physically strong and replacea ble pri nts, it see ms u n necessarily severe
for older, a l ready stained, i rreplaceable prints-espec ially since these prints
can not usually withstand the long, 1rigorous, effective washes routi nely used
for new materials, and a re also da maged by the commonly recommended
a l kaline peroxide hypo-eli m i nator baths; t hese are the two methods by which
zero hypo test stains a re ach ieved. Add i t ional ly, i t is u nclear i n genera l terms

547
Part VII D E V E L O P I N G C H I T E H I ,\

how s ignificant the ach ievement of zero hypo content wil l actual ly prove to
be over long periods of time for prints where significant amounts of the s i l ­
ver i mage have already been transformed t o si lver su lfide. I t i s importan t that
one be able to weigh the actual benefits of reprocessing a n aged, somewhat
faded print with a rel atively small amount of un reacted residual chem istry,
against the physical damages risked in the treatment.
In sum, a positive res ult for e i ther test has meaning but d i sfigures a
print and does not necessari ly ind icate treatment, while a negative result may
n ot be believable but sti ll requi res treatment sufficient to remove the test
solution (wh i c h , i n the case at least of the hypo test, means reprocessi ng) .
I should e mp hasize that both tests are very usefu l for eva luating the
adequacy of one's own processing of new material s . Further, the residual
silver test has an extremely i mportant use in archives to identify prints which
have been p rocessed by ·'stabil ization, " a fast-access process i ng method
which chemically sta b i l izes non-i mage si lver salts against l ight reduction,
instead of removing the m . 1 7 A stabil ized print will give a dark stai n with
even a very small drop of the sodi um s u l fide si lver test reagent. Such a print
should be refLxed and thoroughly washed before being added to a pri nt col­
lection , and any materials it was packaged i n should be discarded. Both test
solutions are u nstable and must be mixed fresh periodically; a deteriorated
sodium s u l fide solution will give a fa lse negative test result-a solution more
than a week or so old should be tested against a print known to have been
processed by stabilization .
With or without the i nadequate tests, if one decides to reprocess an
older print, what resu l ts m ight be expected? To examine the possibilities, the
process of fixing must be reviewed. Si lve r gelatin pri n ts are fixed i n a thiosul­
fate [ ( S 2 oy-J solution (either sod i u m or ammonium thiosu l fate) to dissolve
and remove the unexposed and undeveloped silver h a lide crystals. Th is is
accompl ished by the formation of a series of s ilver t hiosul fate complexes. If
silver bromide were the s i lver halide i n i t i a lly present, for i n stance, the reac­
tion could be written:

AgB r + ( S 2 0 3 ) 2- � Ag(S 2 0 3 J- + Br-

Ag( S 2 0 3 ) - + ( S 2 0 3 ) 2- � Ag( S 2 0 3 ) /-
Ag(S 2 0 3 ) 2 3- + ( S 2 03 ) 2- � Ag( S 2 0 , ) 3 5-

The first s i lver thiosu lfate com plex [Ag(S 2 0J- J is readily formed, but re mains
adsorbed to the s i lver halide gra i n . I t is only sl ightly soluble in wate r and not
very stable, breaking clown i n the presence of silver to form s ilver su l fide. If
en ough thiosul fate ions are avai lable for equ i l i brium conditions to allow it,
a second complex [Ag( S 2 0 3 ) /- J forms, which is soluble i n water and more
stable, an d goes i nto sol ution, diffusing away from the silver halide crystal
 Reading 57 S \V A N

thro ugh t he gelatin matrix. I f enough t h iosu l fate ions are still available to
satisfy eq u i l ibri u m conditions, the t h ird complex forms, also soluble and of
i nc reased stabil ity. 18
I F a print is fixed i n a bath with insufficient t hiosul fate ava i lable, the
second and t h i rd complexes will fa i l to form i n significant quantity and the
insoluble in itial complex will re main i n the e m u lsion. Because the rela­
tive amounts of the comp lexes are governed by eq ui li bri u m conditions, the
fi rst comp lex is always present i n a u sed ftxjng solution and diffuses into
the baryta layer and paper base, where it i s strongly adsorbed. This com­
p l ex can not be adequately removed by water washi ng a n d it breaks clown
to form si lver s u l fide, with the effect of d iscoloring the i mage . l mages so
affected show u n iform yel lowing which is most visible i n the h ighl ights. Rec­
ogn ition of this problem has led to the rou t i ne use of two successive fixing
baths for the processing of new materials, an d has been common practice
among photographers concerned with permanence since the 1 95os . 1 9 The
residual si lver test is i ntended to indicate the p resence of this fixing prob­
l e m , which is remedied by refixing i n a fresh thiosu l fate solution; t hough,
of cou rse, this must be clone before a sign ificant portion of the complex
has decomposed.
I f the print is properly fixed in a fresh thiosu l fate solution such that all
the si lver halide is complexed and removed, the thiosulfate itself must sti l l
b e completely washed out, since it is u nstable i n t h e presence of si lver, even­
tually comb i n i ng with i mage si lver to form silver s u l fide. U n fortu nately, t h io­
s u l fate is strongly retained by the e m u lsion, baryta layer and paper base of
prints, and it is not possible to remove all of it b y wash ing, especially when
it has been i ntroduced i n the standard acid hardening fbdng baths, since the
acid condition of the solution, requ i red by the alum hardener, causes ionic
retention of thiosu lfate in the ge latin. Treatment in a n a l kaline solution will
help to remove thiosulfate, but also reduced emul sion hardening just when
it is most needed- i t is ge nerally d u ri ng wash i ng steps that ge latin e m u l ­
sions reach maxi m u m swel l a n d are most vul nerable t o p hysical damage a n d
fri l l ing. The commonly u sed "washing aids" ( Kodak Hypo Clearing Agent is
the best known) are sal t solutions-usually buffered sul fite solutions-and
d isplace thiosulfate i n the emu lsion, baryta l ayer and paper base by ion
excha nge. They requ i re long wash t i mes, considerably longer than manufac­
t u rers' recommendations, and are not completely effective in removing th io­
s u l fate, but they are much less demanding to gelatin silver prints than the
commonly recommended "hypo-el i m i nators," which are hydrogen peroxide­
ammon ia solutions. The hypo-el i m i nators fu nction by oxicl izi ng th iosu I fate
to sulfate; u nfortunately t hey oxid ize i mage s il ver as wel l , frequently causing
perceptible bleaching of h ighlight areas. Their elevated p H causes excessive
swel l i ng of the gelati n , encouraging frilling of e m u l s ion edges. Add itional ly,

549
Part VII D E V E L O P I N G G R I T E H I A

they have been found not completely successfu l i n destroying all th iosulfate,
and the short wash t i mes recommended after their use may be i nadequate. 2 0
Their use on va luable older prints shou ld be avo ided.
The rate of the breakdown of res idual th iosu lfate i nc reases with
i ncreased h u m idity and the reac tion conlinues u n t i l either the th iosu lfate
or the si lver is exhausted. A print which has been completely fixed but insuf­
ficiently washed typically shows clean wh ite h ighlights, but develops faded
and yellowed i m age tones. The res idual thios u l fate spot test is i n tended to
indicate this d i ffic u l ty, and it gives a positive reaction for all sources of action
sulfu r-the polythionate breakdown prod ucts of t h iosulfate as wel l as th io­
su l fate itself. For new prints, this process i ng fa i l ur e i s remedied by additional
wash ing, though for older prints the resloration l i terature seems to recom­
mend a complete reprocessing t reatmenl. Any treatment, of cou rse, must be
done before a sign i ficant amount of Lhe thios u l fate has broken down to si lver
s u l fi de, si nce si lver s u l fide is not affected by washing or reprocessing.
While some reprocessing t reatment is u ndoubtedly essential to the
long-term preservation of recent prints fil led with residual chemist ry, repro­
cessing as outli ned in the restora tion literature (treatment in an u nspecified
fi,xer-presu mably the standard, pre-mixed, acid harden ing foer-followed
by t reatment in a was h i ng aid, washi ng, treatment in a peroxide-ammonia
hypo-e l i m i nator, followed by a final wash ) may be u n necessarily da magi ng to
al l prints and of no benefit to many. Ref1xing and the subsequent treatments
req u i red to remove thiosulfate might be expected to fu rther erode the fragi le
si lver i mage already parti ally transformed to si lver sulfide, oxidizi ng, com­
plexing and re movi ng i mage silver in the acid fixing bath, and oxidizing si lver
signi ficantly in the hypo-el i minator bat h . 2 1 Further, since refixing removes
oxid ized i mage si lver, it wi l l obstruct the fu t ure use of any si lver red uction
treatment which m ight be developed. Therefore it is of real i mporta nce to be
able to identify prints which wi l l actually benefit from refix i ng.
There are t h u s two sets of questions needi ng answers before t he
appropriateness of reprocessing any spec i fi c print can be known: the first
would exa m i ne the levels of residual silver-t h iosu l fate complex and thiosu l­
fate present after its original processi ng, while the second woul d examine
the levels of u n reacted res iduals cu rrently present which w i l l i n the fut u re
break down, fading and sta i n ing the i mage, if left u n treated. The rates of
breakdown reactiDns are very dependent on h u m i d i ty and temperature and
can not be pred icted as one might hope. Further, the mob i l i ty of residuals
through the layers of prints is undoubtedly affected by the composition of
the specific paper bases and baryta layers, making prediction less possible.
The residual silver and hypo tests, which would supply some of the needed
information, are too damaging to use. And while close visual exa mi nation
will establish that residual chemistry. in itially present, has broken clown,
 Reading 57 S \·V A N

staining h ighlights or causing highlight and m i d tone fad ing, i t gives no i nd i ­

cation t h a t a process h a s gone t o completion, and i t cannot pred ict a process
which has not yet begu n .
My own experience has been largely w i t h "fine arts" photographs,
which were generally processed to the h ighest archival standards of their
day, a n d where the large artistic, historic and monetary value of a n i nd i ­
vidual prin t precludes the poss i b i l i ty o f testing t h e adequacy of its processing
with visua l ly and chemically damaging solutions. Here, one can only address
the problem with i mproved storage conditions, a n d fervently hope that bet­
ter methods for determ i n i ng res idual chemistry will soon be developed. Thi s
situation may b e considerably d i fferent i n other sorts o f collections, however.
In collections, for i nstance, where the b u l k of p hotograph i c prints are rela­
tively recent, of low i n dividual value as origi n a l objects, and have come from
a sou rce renowned for poor origi nal processing (e.g. , newspaper arch ives) , i t
m ight b e q u i te reasonable t o reprocess large n u m bers of print, i f o n e could
know that the treatment was necessary and effective. (Though, here also,
the treatment of first priority must be control of the e nvironment-lower
h u m i d i ty w i l l decrease s u l fiding of poorly processed prints as wel l as oxida­
tion of all prints.)
To obta i n some i nd ication of the exten t of residual chemistry i n com­
mercially processed prints and of the effectiveness of reprocessing i n its
removal, I recently tested sixty si lver-gelat i n s napshots processed by pho­
to-fi nis hers, all dated and evenly d ivided a mong the 1920s, 1930s and 1940s.
They were chosen to represent a range of materials, sources and conditions.
All had c lear margins on which the ST- 1 a n d HT-2 tests were performed
and eval uated . Each print was then cut i n to four strips which were given
different treatments, and each strip was retested and eva luated . All wash­
i ng was accompl i s hed i n a succession of room temperatu re tap water baths,
gently agitated, with the prints thoroughly d ra i ne d between baths, and the
baths c hanged every five m i n u tes for a n hour.22 Thi s was hing method was
j udged to be as vigorous as most older gela t i n prints could withstand with­
out damage. The fixing solution was a plain thiosulfa te bath of 1 00 g sod i u m
thiosulfate (pentahyd rate) per l i ter o f solution, divided i n to two successive
baths, thus s upplyi ng adequate fresh th iosulfate i o n without great excess,
and avo i d i ng the difficu l t ies of i ncreased reten tion caused by low p H , a n d
the additional complication of u n necessary h ardeners. T h e washing a i d
( Kodak Hypo C learing Agent) was u sed at the u s u a l d i l u t i o n , and t h e hypo­
e l i m i nating bath was the standard form ula specified through out the restora­
tion l i terature.
Few of the prints showed the presence of residual si lver; the prints
were spotted with the ST- 1 sol u tion, allowed to sit for two m i n u tes, blotted
and then washed to remove water soluble components of the sta i n , making i t

551
Part VII D E V E L O P I N G G H I T E H I A

easier to j udge the amount of insoluble si lver s u l fide formed. After d ryi ng, no
s i lver su l fide stain at all could be seen on thirty-six of the prints i n the sam­
ple; a barely perceptible stain was visible on seventee n ; and seven showed
obvious l ight yel low stains. When the positive-test i ng pri nts were refixed,
hypo-cleared and washed an d then tested again, no stain was formed. In this
group of prints the presence of silver from the si lver-thiosulfate complex was
sl ight and could have caused signi ficant sta i n i ng on only seven prints. J u dg­
i ng from the amount of highlight sta i n a l ready present i n many of the prints,
it [is] likely that the complex had a l ready broken clown fairly completely in
most of them. Refixing was effective i n re moving the remaining residual
si lver complex.
I n contrast, nearly all the prints showed significant amounts of residual
t h iosu l fate to be presen t (90 per cent) and some pri n ts stai ned very deeply
(patch #3 and h igher on the Kodak Hypo Estimator) . Strips of the pri nts
were treated and retested; wash i ng alone was very effective i n red ucing the
response of pri nts to the test (bringing su bseq uent HT-2 tests to below patch /t i
on the Hypo Esti mator) . Hypo-clearing followed by wash ing was about as
effect ive as washing alone. Relixing, hypo-clearing and washing was sl ightly
more effective than wash i ng alone for most pri n ts, but for some prints the
stain was i ncreased ( i .e . , new hypo had been i ntroduced and retained ) .
Refixi ng, hypo-cleari ng, hypo-el i m inating and washing was consistently the
most effective at reducing the sta i n level (though the actual d i fference in
stains was sl ight), but hypo-e l im i nation also bleached the i mage noticeably
i n h ighl ight areas of many prints, and swel led the gelatin as wel l , promoting
some fri ll ing and physical damage. These resu lts may provide some indica­
tion that re fixi ng may be less necessary than has been assu med, and washing
more effective, t hough certa i n ly the washing method employed is of great
i mporta nce. This is o n ly a small fi rst step-much work is needed to fit the
procedure to the needs of older prints, maxim izing the benefits and m i n i ­
m izing the da mages o f the treatment, a n d t o i mprove t h e testing methods,
before reprocessi ng-the simplest of the si lver treatments-can be recom­
mended for use i n collections.
The situation is si m i l ar or worse i n regard to other, less studied, more
complicated si lver t reatments. J ust as the '"easily used" test solutions and
the reprocessing procedu re, typically covered i n a mere sentence or two i n
the restoration l iterat u re as t hough they were unquestioned standard prac­
tice, become, on exa m i nation, vast abysses of u nce rtai nty into which cou nt­
less man-hours of research w i l l have to be placed before they can be actua l ly
used, so, too, i t is with the other s i lver treatments-bleach i ng and redevel­
opment, i mage i nte nsification, etc. H ere again, the restoration l iterature is,
at best na ive, hopefu l and u nc ritical ; and whatever the intentions may have
been, the result has been most misleadi ng.

55 2
 Read ing 57 S \•\I A N

I would l i ke to suggest that given the c u rrent state of photographic

conservation, and the long pre-existence and slowly advancing natu re of
most of the deterioration processes, conservators d i rect their attention to
i mproving the storage and handl i ng conditions of photographic collections,
to performing the practical research on speci fi c conditions and t reatments
that conservators need to do themselves, and to prodding, demanding,
encouraging and s u pport ing basic research i nto the materials, which must
be left to well-trai ned scientists working i n wel l -equ ipped laboratories; and
that until the combi ned resea rch effort has yielded solid, re l iable res u l ts,
t reatments be postponed and m i n i m ized as much as possi ble. Compared to
analogous prob lems i n paper co nservation, the materials of photography a re
more fragi le and sensitive, physically and c he m icall y, and the delayed conse­
q u ences of il l-advised treatment are more l i kely; less margi n for error exists;
and da mages and repairs are usually 111ore obvious-the 111aterials are less
forgiving, less easily manipu lated, less a 111enable to treatment. In other fields
of conservation a 111ore co111 plex tec h nology has genera l ly been needed to
conserve the products of a less co111 plex tec h nology. P hotographic prints are
a l ready the produc t of a h ighly co111plex tec h nology and it is not surprising
that it should req u i re t i 111e and sophisti cated, long-term scientific help to
develop a technol ogy to conserve the111 . What is u nc lear is from where and
when such help 111ay be forthco111 ing.

References

1 T. J. Collings and F. J . Young, " I m p rovements i n Some Tests and Tec h n iq u es

in P hotograph Con servat ion," Studies i11 Co11Sermtion 2 1 ( 2 ) , 1976 . p. 8 1 .
2 P . Gla!Kides. Pl1otogrnp/1ic Che111ist 1)', I<. i\ I . H ornsby, t ra n s . , Fountain Press.
London, 1 958, vol . I, p. -H I .
3 i\ l uc h i nformation o n paper bases and coating i s available i n Glaflides
( reference 2) and in /\leblette's /- lc 111.dl1ooh of Pliot.ograpliy and Reprograpl1y,
7th ed . , ] . IVI . Stu rge, ed., Van Nostrand Reinhold, N .Y., 1 977.
-I T. H. J a mes and L. J. Fort m i l l er, H Dependence of Covering Power a nd
Spectral Absorption or Deve loped S i lver on Temperature and Composition or
the Developer," Phutogrnp/1ic Scie11ce a11d Engineering, 5 ( 5 ) , 196 1 , pp. 297-30+
T. H . James, " The Stabil ity or S i lver Filaments," Pliot.ograp/1ic Scie11ce c111d
E11gi11eeri11g1 9(2), 1 965, pp. 1 2 1- 1 3 2 .
6 R . \II / . H e n n and D . G . Wiest, " M icroscopic Spots in Processed i\ l icrof i l m , "
P/10tograpl1ic Science r111CI E11gi11eeri11g, 7(5), 1 963, p . 257.
7 C . S. i\ l cCamy and C. I. Pope. " Redox Blem ishes-Their Cause and
Prevention," Jo11rnal of Microgrnp/1ics, 3(-1), 1 970, p . 1 65 .
8 C . S . McCamy a nd C . I . Pope, "C u rrent Research o n Preservation or Archival
Records on Si lver-Gelatin Type M ic rofilm in Roll Form," Journal of Resea1'Ci1 ,
69A( 5 ) , PP· 390-39 1 .
9 E . Weyde, " A Si mple Test to Identify Gases Which Destroy Si lver I mages,"
Photographic Scie11ce a11CI £11gi11eeri11g, 1 6( 4 ) , 1 972, p . 283.

553
P art VII D E V E L O P I N G C R I T E R I A

10 McCamy and Pope, ''C u rrent Researc h , " p . 389 .

11 M c Ca my and Pope, " Redox Blemishes," p. 1 67; " C u rre nt Research," p. 388.
12 G. \"1. W. Stevens and P . B lock, ''Estimation oF Speci fic S u rface oF Developed
S i lver by Th iosu l p h ate Adsorpt ion, " Journal of Photogra]Jhic Science, 7, 1 959,
pp. 1 1 1 - 1 19.
1 3 T. J . Colli ngs a n d F . J. Young, " I mprovements," p. 79. I prefer to modih'
the test as written, by substituting a 1 .0 molar solution of acetic acid for the
0 . 0 1 molar solution of hydroc h l oric acid, thereby avoiding the masking oF
small amounts of s i lver su lfide by s i lver c h loride i n evitably formed by the
hydroch loric acid u nder the oxidizing cond itions of' the test.
14 The fol l owing references, l i sted i n c h ronological order, provide both a good
sample oF the l i terature in t h e field and a h istorical look at its develop ments:
. J . I. Crabtree, "Stains on Negatives a n d Prints: Their Cause, Preve ntion and
Remova l , " A1nerican Annual of Photogrnphy, 35, 1 92 1 , pp. 204-240; St:a ins on
Negatives and Prints, Publication U - 1 8, Eastman Kodak Co., 1 952; G . L. Eaton,
" Preserva tion, Deterioration, Restoration of Photographic I mages," Libra1y
Quart.erly, 40( 1 ) , 1 970, pp. 85-98; Caring for Photographs, Li l'e Library of
Photography, Time-life Books, N .Y., 1 972; E. Ost roff, Conserving and Restoring
Phot.ograpli.ic Collections, American Association oF M u seums (revised repri n t ) ,
\�lashington, 1 976; H . A. Weinstein a n d L. Booth, Co/.lect.ion, Use and Care
of /-/ istoricnl Photograpl1s, American Association for State and Local H i story,
Nashvi l l e , 1 977; Presen;at.ion of Phot.og ra]Jhs, Publ ication F-30, Eastman Kodak
C o . , Rochester, 1 979.
15 C. I. Pope, ''Stabi l i ty of Res idual Thiosu lfate i n Processed M i crofilm," Journal
of Research, 67C( 1 ) , 1 963, p. 1 7.
1 6 Preservation of Photogrnphs, p. 1 6 .
1 7 A brieF, usefu l re\�ew of stabil ization chemistry is pro�ded i n L. F . A. t\ l ason,
Photographic Processing Chell'listry, 2 n d ed., Wi ley, N .Y., 1 975, pp. 1 95-8.
18 G. H aist, M od er n Photographic Processing, Wi ley, N . Y . , 1 979, vo l . I, pp. 56 1 -3 .
1 9 Ansel Adams ' book, The Print ( Basic Photo Series, Vo l . 1 1 1 . M organ
a n d Lester, N .Y., 1 948), was enormously i n F l uential among practicing
photographers, recommending m u l t i p l e fixing baths and sel e n i u m toning
among other reasonable processing procedu res, and should be given a major
part of the credit for the ge nerally i m p roved processing of prints which has
occu rred among art photographers s i nce the 1 950s.
20 C. I. Pope, "Sta b i l i ty," p . 2 1 .
21 There was a period, hopefu l ly now ended, when conservators were
reprocessing a l b u m e n prints "to clear the whites, " in the belief ' that the
apparent brighten i ng of highl ight areas was caused by the removal of residual
s i lver complexes by t h iosulfate. M y own experiments show this to be the effect
of the peroxide hypo e l i m i nator i nstead, which had oxidised i mage si lver to a
degree very apparent in the h ighl ights.
2 2 Tap water was used here only for the sake o F economy i n a n i n i tial experi ment.
For treatment o f pri nts, a c l eaner, more control lable water source is needed.

554
 R e a d i n g 5 8

KLA U S B . H E N D R I KS , B E N L . To M ,
C H R I S T O P H E R S E R G E A N T , C H R I S E VA N S ,
} AC K M E LN I C K , P I E R R E P O I T RAS ,
A N D D o u G N I S H I M U RA

Experiments on the Restoration

of Discoloured Black-and-White
Photographs in Chemical
Solutions ( I 984)

Th is reading reviews and ex71lores t Jie deterioration of silver images a nd the

chemical restoration of faded an.cl cliscolorecl gelatin. silver prints. Unlihe
t he prior reading, Hen.drib (see also Readings 9, 24, ancl 65) pro1not:es t he
value of chemical restoration procedures. I-Ienclrib ancl his coa u t.hors lhn-ited
t heir study to gelatin silver developed-out pri nt materials t hat: had undergone
accelerated aging, having confirmed t hat printed-ou t photogra11hs, including
albu men prints, were not suiJable for bleach and redevelo111nent techniques.
This worh and subsequent systematic research demonstrated t hat presoabng
in. a cherni.cal hardener was beneficial, if not mandatory, a nd t hat density
changes in c hemically treated prints were often inevitable. This meticulous
resea rch broadened our u nderst:anding of silver image morphology a nd deg­
radation mechanisms and confirmed t he general fragili.ty of t he gelaU.n silver
print bi nder layer as well as t he adverse effe c ts of these aqueous chemical t:reat­
'l'nents on degraded p hotographic w1.aterials. Chemical restoration t ec hniques
are rarely 11racticed today.

KLAUS 13. To � 1 , C1 1 n 1 sToP1 1 En S EBGEANT, C 1rn 1 s E VA NS , jACK M ELNICK,

l-I EN D B 1 Ks , BEN L.
and Douc N 1 s 1 1 1 �1 UHA, " Experiments on the Hestoration ol' Discoloured
P l E IH I E PolTBAS,
Black-ancl-\�lh i te Photographs in Chemical Solutions," / C OM Co111. 111. i /./.eefor Couser11a­
l iou, Seventh Triennial Meeling, Copeuhage11, 10-14 September 1 984, P1·epri11/s 2 ( Paris:
The I nternational Cou n c i l oF M useums i n association \\�th the J . Paul Getty Trust, 1 984),
34-37. Heprintecl by permission.
Part VII D E V E L O P I N G C B I T E R I A

The field of i n q u i ry concerned with the conservation of photographs is con­

ven iently d ivided into three groups of activities, each of which requires a
different eJqJertise:

1. The application of conventional and esta blished pri nts and drawing
conservation tech n iques to photographs.
2 . The dupl ication of negatives and transparencies, and the copying of
positive ref l ection prints.
3 . The che111 ical restoration i n aqueous solutions of faded or d iscoloured

blac k-and-wh ite negatives or pri nt s.

\i\!h i l e certai n conventional conservation treat 111ents are pe rfor111ecl regu­

larl y in practice, they are a l 111ost excl u s ively adopted fro111 skills developed
e lsewhere . Exa111ples are the clea n i ng of p hotographs in the d ry or wet state;
re111oval of a picture fro111 the su pport onto which i t is mou nted; the flatten­
ing of c urled-up films or prints; the laying down of photographs onto a new,
stable su pport; and so111eti111es retouching. Knowledge and ski lls i n these
areas have flowed general ly in one d i rection: fro111 prints and drawing con­
servation towards photograph conservation . H owever, the equation of photo­
graphic prints with graphic works of art on paper proves to be an i nadequate
premise when considering 111ore co111 plex treat111ents. The fu ndamental dis­
t i n ction here is one of structure: 111ost photogra phic materials consist of two
separate layers which react differently to changing environ111ental conditions,
especially to changes i n relative h u 111i dity. Consequen tly, certa i n restoration
tec h n iques are typical to photographic 111aterials. There is, for exa111ple, the
tran sfer of the i 111age layer fro111 a deteriorating su pport onto a new and stable
base. Requ iring considerable manual ski l l , it is usually clone with transpar­
ent 111aterials, i . e . , negatives on glass or p lastic fi l 111, 1 and also with colour
transparencies. 23
A c haracteristic property of a processed photographic negative or trans­
parency is i ts capabil ity of being d u p licated onto an identical 111aterial with
faithfu l retention of tonal range and deta i l . Li kewise, the copyi ng of a black­
a nd-white print, using a suitable fi l 111 i n a camera , can produce a negative
from which an exact copy print can be obtained . The successfu l execution
of such activities req u i res spec ial skills and u ndersta nding of sensitometry
as i t applies to the theory and practice of what is tech n ically known as tone
reproduction. They do not constitute a restoration procedu re , as the ter111
restoration should be used only for work on an origi nal i 111age. H owever, the
ability to faithfu l ly d u pl icate an original presents a si ngu lar opport un i ty to
preserve that origi nal .
The che111 ical t reat111ent of d iscoloured, or faded, black-and-white neg­
atives and prints is a type of restoration procedure u n iquely applicable to
photographic si lver i 111ages. \i\!h i l e the fad i ng of organic dyes in processed
 Reading 58 1- I E N D B I K S E T f\ L .

colour photographic materials, caused by hydrolysis or oxidation of dyes,

appears to be i rreversible, d isco louration in processed black-and-white mate­
rials is i n i tiated by an oxidation of elemental s ilver, which is generally fol ­
lowed b y o n e of t h ree su bsequent reactions:

(i) si lver i o n s c a n m igrate t h rough the binding med i u m , which has,

for example, been observed i n albumen prints and s i lver gelatin
materia ls;
(ii) silver ions can react with available anions to form stable s i lver
salts; or
(iii) si lver ions can be red u ced to a modification of elemental si lver
which appears orange-red in colour.

\Vh i le a lateral m igration of si lver ions i nside a gelatin layer can not be dem­
onstrated easi ly, the u pward m igration is s hown by the appearance of a blue
metallic s heen i n the h igh density, or shadow, areas of a print or negative.
It is easily noticed when letting the incident l ight reflect from an affected
a rea. The formation of a si lver su lfide t ransfer i m age i n the baryta layer of a
pri nt, i.e. below the i mage-bearing gelatin layer, which was first observed by
\Veyde, 4 can be interpreted as proof of a downward si lver ion migration away
from the su rface through the e m u lsion layer.
The blue metal l i c sheen l i kely consists of a thin layer of elemental sil­
ver formed aro u nd si lver su l fide nuclei. Procedures to remove it chemically
have been published by H en n , C rabtree and Russel l5 and by \Veyde.6 Strictly
speaking, such treatments are chemical restoration procedures, as wou l d
b e the clea n i ng o f tarnished daguerreotypes using acidic t h iourea solutions
or potass i u m cyanide. It is also possi bl e to selectively remove the orange­
coloured modification of elemental silver in c h emical solutions. All these
methods have in common that a certai n amount of elemental si lver, the
i mage-form i ng su bstance, is i rreversibly removed from the picture. Other
methods attempt to i ncrease, or to red u ce, the si lver density and to convert
u nwa nted si lver salts-products of deterioration reactions-back into black
elemental si lver. Such methods have been known in principle since the 1 9th
century. They are referred to as i ntensification or reduction, when applied
to negatives, and bleach and redevelopment with respect to paper prints.
This presentation proposes to outline systematic attempts to develop safe
and reprod ucible chem ical restoration t reatments of the latter kind. These
treatments a re di rected only towards the i mage si lver and must not affect the
binding med i u m or the su pport.
Our interest i n examining the possibility of restoring d i scoloured
black-and-white photographic prints was kindled a few years ago when
we i nvestigated the reaction of such prints towards compounds that are
commonly used i n prints and drawings conservation for the bleac h i ng of

557
P a rt V I I D E V E L O P I N G C R I T E R I A

J?aper.7 O f four d ifferent b leaching agents-calcium hypochlorite, chlo­

rine d ioxide, hydrogen peroxide and Ch lora mi ne-T-only the latter had
l ittle appreciable effect o n the s-ilver density of contemporary developed­
out prints ( D . 0 . P . ) , but a more d rastic red uction in density was observed
with pri n ted-out paper ( P . O . P . ) i mages, such as salt prints, albu men prints
and silver gelati n P.0. P . While calc i u m h ypoch lorite showed a devastatin g
effect o n al l si lver materials ( P . O . P . and 0 . 0 . P . ) a s well a s on t h e gelatin
layer of carbon pri n ts an d \i\/oodb u ry-types, the binding agent i n albumen
prints remained i ntact. I ts silver density, however, was reduced consider­
ably d u ring fou r bleaching experi ments of five, fifteen , t h irty and sixty m i n ­
u tes duration. C h lorine dioxide, d u ri ng reaction ti mes o f two, five, fifteen
and thi rty m i n u tes, had a density-reducing effect which was about equally
strong for printed-out and developed-out silver i mages. I t seemed obvious
to attempt conversion of the b leached si lver i mages back into black s ilver
using a photographic developer. \t\fh ile some test samples of contemporary
developed-out papers responded we l l to such treatment, the printed-out
papers, espec ially albumen prints, gave u nsatisfactory results. Th ree obser­
vations with regard to printed-out papers are relevant: densities after devel­
opment of a bleac hed i mage often exceeded the origin a l val ues; i mage tones
ranged from p i n k to brown to green ; and there was a noticea ble increase
in gra i n iness. Experiments performed in other projects confirmed to us
that printed-out photographs, espec ially a l b ume n prin ts, are n ot suitable
for t reatments which req u i re bleaching and redevelopment of the i mage
si lver.
The results from these experiments led us to a m ore systematic inves­
tigation of the possibility of restori ng d iscolou red black-and-wh ite p hoto­
graphic i mages in chemica l sol utions. Whi l e there is no lack of formulae i n
t h e published l iterature, there appears t o be l i ttle published experimental
data about which formula i s applicable for which type of d iscolouration on
which type of i m age. Wal l8 p u b l ished a critical resume of a l l known methods
of i n tensification and reduction of negatives in 1 927, with a few hun d red
references. Another c lassical text, publi shed in 1 920 by Stenger,9 reviewed
the restoration and copying of posi tive i mages. Here too, a large collec­
tion of formu lae can be fou n d , but no data are presented that wou ld show
their effectiveness. M ethods for the i ntensification and reduction of nega­
tives seem to have been studied more i n tensively than those for the restora­
tion of d iscoloured prints by bleach and redevelopment. Correction of the
negative, being a un ique object and therefore more valuable than a print,
has attracted more attention than the i mprovement of prints. C rabtree and
M ueh ler reviewed i n tensifying and reduc i ng solutions for motion picture
fi l m . 1 0 H eymer d iscussed the reduction of contrast i n small format nega-

558
 Reading 58 H E N D H I K S E T f\ L .

tives with s i m u l taneous i mprovement of gra i n iness. 1 1 An i n tensifier for very

weak n egatives which gives exceptional density i ncrease was proposed by
M uehler a n d Crabtree. 1 2 T t was recently used to i mprove i mage characteris­
tics in aeria l p hotographic negatives of low density and contrast. 1 3 The effect
'of several reducers and i ntensifiers on the resolvin g power of photographic
emulsions was studied by Perrin and Altma n . 1 4 The chemical reactions that
take place in various procedures are rather complex. Photographic reduc­
ers gen erally convert i mage s i lver partially i n to soluble salts, such as si lver
chloride (soluble i n a t hiosu lfate solution ) , si lver sulfate or si lver ferrocya­
n ide, which are subsequently removed from the image. During i ntensifica­
tion reactions, elemen tary s ilver may be added to the origi nal i mage silver; or
dark-coloured s ilver complexes with other metals or with organ ic compounds
may be formed; or the structure and size of the s i lver gra i ns may be al tered
so as to produce an i n c rease in density.
By contrast, the principle of a chemical restoration treatment for dis­
coloured p hotographic pri nts i s simple: all i mage si lver i n wh ichever modi­
fication , and all s i lver compounds i n whatever form they may be present as
products of deterioration, are u n i formly converted into a s i lver hal ide which
i s then chemically red uced to black elemental si lver. This is sum marized in
the fol l owing schema:

J . silver and s i lver salts b leach plus hal ide sou rce ) si lver halide
2. s ilver h a l i de developer ) elemental s i lver

There is neither add i tional si lver prec ipitation from an external source,
removal of s ilver, nor the formation of complex si lver compounds.
The most commonly described bleachin g agents are :

-potassium dich romate;

-potassiu m permanganate;
-potassi u m ferricyan i de;
-mercuric c h loride;
-cupric chloride; a n d
-cupric bromide.

The first three require the addition of a hali de source, for example, sodi u m
c hloride, or potassi u m b romide. Other b leaching age nts have al so been used,
such as potassi u m cya n i de, or mercuric cyan ide.
B e i ng straightforward in theory, there are a number of pitfalls to avo i d
w h e n applyin g s u c h treatment i n practice t o photographic pri nts. Wh ile it is
the objective of such experiments to change the density range, and therefore

559
Part VII D E V E L O P I N G C B I T E H I A

the contrast, of a faded, or d iscoloured print, the fol l owing aspects must also
be considered:

1. The essential properties of the original i mage must be m a intained:

-grai n structure;
-resolution;
-image tone, or hue;
-su rface properties;
-highlight deta i l ; and
-physical i n tegrity.
2. The permanence of the res u l tant i mage m ust be ma intained or
e nhanced.
3. Stain formation, caused by the c he mical used in the treatment, m u st
not occur.
4. The treatment must not be damaging to the binding agent or the
support.

I mage stab i l i ty tests permit us to satisfy one of these conditions. The

occu rrence of stain formation is wel l docume nted i n the l i teratu re and rela­
tively easy to ascerta i n . However, contro l l i ng the essential i mage c haracter­
istics and the stability of the binding agent p roved to be a strong challenge.
I n consequence of the results of experiments described earlier, four
differen t contemporary black-and-white prin ts were toned i n commer­
cially available toni ng solu tions so as to produce s ilver sulfide i mages. 1 5
They were then treated by five different procedures published by Pope, 16
N eblette 1 7 and Pollakowski . 1 8 The first two u sed potassium permangan­
ate, where Polla kowski suggested potassi u m dichromate and hydroc h loric
acid in three d i fferen t ratios. The potassi u m permanganate for m ulae both
worked wel l , however, a highly acidic concentrated potassi u m dichromate
solu tion was requ i red to achieve the bleac h i ng of sepia-toned prints. In the
cou rse of these experi ments, one of the fou r prin t materials suffered from
the formation of blisters in the emu lsion and subsequent destruction of the
i mage layer . Thi s was a surprising observation, as the pri n t samples were
conte mporary materials p repared for the experiments. Further experi ments
with heavil y d iscoloured photofi n i sh i ng prints dati ng from 1 93 5 , which were
both poorly fixed 1 9 and i ncompletely washed, using a potass i u m permangan­
ate bleacher suggested by Sandys,20 showed a weake n i ng of the gelat i n layer
during the fi n al washing after the redeveloping step. Occasionally, the i mage
layer was completely destroyed, leaving a fai n t transfer i mage vi sible on the
remaining baryta l ayer. The large difference in pH between the b leac h i ng
solution and the highly alkaline developer was suspected to be respons ible
for the destruction of the ge latin.
 Reading 58 H E N D R I K S ET A L .

These observations led to a study of the p roperties of coated gel atin

layers i n c hemical solutions and experimental methods to eva luate and mon­
i tor its stability. 2 1 There appears to be a relationship between the swel ling
of gelatin layers and their corresponding stab i l i ty: excessive swelling i ndi­
cates a wea kening of the gel at i n . Using a swe l lmeter described by Green and
Levenson, 2 2 the swelling and deswelling of gelatin layers on photograph s was
recorded as they passed through variou s restoration cycles. The resu l ting
swell curves show c learly the effect of various p re-hardeners on the behav­
iour of gelatin layers. They also demonstrate that the final development
s tep must be followed either b y treatment i n a hardening fixer, or at least
by an acidic stop bath. \Vashing in water all ows the developer-soaked gela­
tin to swell excessively, probably caused by an osmotic effect, and to break
up completely. Thu s the key steps in c hemical restorati o n treatments, with
respect to the stabil i ty of the gelatin layer, are the first two-pre-soak and
prehardener-and the last step fol lowing the redevelopment; if the swelling
of the gelati n beyond a threshold value can be avoi ded, it wil l s urvive the
cycle. That the gelatin does not suffer a loss i n i ts strength can be demon­
strated by comparin g i ts melting point23 before and after treatment, as well
as its res istance to abrasion in the wet state.2 4 Both tests i ndicate that the
gelatin i s not affected adversely by c hemical restoration cycles; those prop­
erties of gelatin that are measured by these tests are reversi ble, as long as
complete destruction is avoided.
In order to assess the permanence of a silver i mage, that has u n der­
gone c hemical restoration treatments, photographic prints were subjected to
accelerated aging conditions specified by the American National Standards
Institute (AN S I ) . Specifications A N S I P H 1 . 28-198125 and P H i .4 1-198126 sug­
gest that i n cu bation for 30 days at 6o°C ± 2°C and 70% ± 2% relative h umid­
i ty be u sed as an image stability test for processed black-and-white safety
films. A N S I PH4.32-1 98027 proposes to eva l u ate the processing of contem­
porary b lack-and-white prints by e:-.'Posing them for one, ten or t hirty days
at 38°C ± 1 °C and 94% ± 4.0% relative h u mi di ty. In all cases, samples are
examined by visual inspection and density changes are measured using a
densitometer.
In p u rsuing the kin d of experimen tal work described here, care was
taken to identify the prin t materials to be treated as being made by the devel­
oping-out process . As there are no p u bl is he d test proced ures for the stability
of coated collodion and albumen layers, a l l materials used in this work were
silver gelatin prints which a llowed us to monitor the properties of the binding
agent. After pre-soaking i n water, a hardener of the formaldehyde type con­
tain i ng sod i u m carbo nate (for example, the Special Hardener S H - 1 by East­
man Kodak) was shown to be most benefic ial for the stability of the gelatin.
Another hardener similarly effective in contro l ling the swel ling of the gelatin
Part VII D E V E L O P I N G C H I T E R l tl

is of the potassi u m chrome a l u m type. As an example, we used the formula

S B-4 by Eastman Kodak. Towards the end of the treatment cycle, the re­
developed print must be treated i n a harde n i ng fixer, such as Eastman
Kodak's F-5 type, or the above-mentioned SB-4. Res u l ts were eval uated by
measuring density val ues before a n d after treatments. M i nor density cha nges
i nvariably occur. Aside from fluctuations caused by the densitometer, density
losses can occur becau se s ilver h a lide can be dissolved by sod i u m s u l fite i n
the developer, before it h a s been redu ced t o elemental si lver. Loss o f densi ty
in prints can also be observed as a consequence of the destruction of su rface
gloss .28 Yet another reason for density l oss a re changes in the fi ne struc­
t u re of the i mage silver caused by the d ryi ng of the prints. 2930 It is virtually
i mpossible to s u bject a sample print to any kind of treatment in chemical
solutions without observing minor densi ty changes. The nu merous variables
in a normal treatment sequence will be d iscu ssed and recom mendations will
be given for specific choices.
Treatments in chemical solutions are more difficult to con trol when
wo rking with photographic prints than with negatives. The former are gen­
erally more del icate because of their fine grain, particu lar i mage tone, and
their fragi le su rface properties. Of the criteria that m u st be observed when
treati ng photographs in chemical solutions, the permanence of the resultant
i mage, the avoidance of stain formation a n d the ma intenance of the stabi l i ty
of ge latin, can be met. M a i n taining the characteristics of the origi nal i mage
is by far the most i mportan t req u i rement. These properties a re essentially
determined by the s ize, structure and distribution of the i mage si lver. I ts fine
structu re can be studied-and poss i b ly controlled-with the aid of an elec­
tron microscope. Future efforts w i l l be d irected in this laboratory towards an
u nderstanding of the effect of b leach and redevelopment procedu res on the
morphology of i m age silver and the correspond i ng i m age properties.

The authors wish to express t he i r thanks to K. F. Foster, D i rector General

of the Conservation and Technical Services B ranch at the Public Arch ives
of Canada, for h is continued i nterest and s upport; and to Diane H opkins, of
this laboratory, for her help w i th the references and in proofreadi ng.

References

1 Gear, James L., iVlacC laren, Robert 1-J. and Mc Kiel, M a ry . " F i l m Recovery
oF Some Deteriorated B l ack and \,Yhite Negatives" American. Archivist,, 40(3) :
363-368; 1 977 J u ly.
2 Recd, Vil i<1 L. " E m u lsion S trippi ng" l<odah Data Helease. F-8 : 1 ; 1 979.
3 Thompson, Barton H. " Kodachrome Transfer'' jo·urnal of the Society of Motion
Pict111'e Engineers. 43(2):9)-96; 1944.
 Reading 58 H E N D B I KS ET A L .

4 \"leyde, E d i t h . · · Das Copyrapid-VerFahren der AG FA" (The Rapidcopy

Procedure of Agfa ) Meneilti n.gen a11S den Forsclningslaboratorien der Ag.fa
( Leverku sen-M uenchen ) . 1 :262-266; 1 955.
H e n n , R.\V., Crabtree, J . 1 . and Russell, H . D . "An Ammon i u m Hypo Reducer"
Plwtogrnph.ic Society of A rne1·ica Journal, Section B. 1 1 0--1 1 3 ; 1 95 1 November.
( Kodak Research Laboratories, Co m m u n ication No. 1423).
,
6 Weyde, E d i t h . ; A S i mple Test to l dentifv Gases Which Destroy S i lver I mages"
Pl'IOtographic Science aad Engineering. 1 6 ( 4 ) : 283-286; 1 972 J u ly-August.
7 Sergea n t , C h ristopher. Paper Bleacliing of Photographic Prints. Ottawa: Public
Arch ives of Canada, Picture Conservation Division, 1 978 S u m mer. 74 p.
( i n ternal working paper).
8 Wal l , E .J . lntensificat.ion and Reduction: A Critical Resume of All Known
M ethods. Bosto n , M ass.: American Photographic P u blishing Co., 1 927. 40 p.
9 Stenger, Erich. Wiecl.erherst.ellung al.t.er ph.otograpisch.er B ilder uncl
Reprocluhtion derselben. in-t urspruenglichen uncl ii-n neuzeitlich.en \!e1fah. ren .
(The Restoration of Old Photographic Pictures a nd the Reprod uction of Same
i n Old and New Ways) Halle (Saale): Verlag von Wilhelm Knapp, 1 920. 62 p .
( E nzyklopaedie der Photographic , H e ft 9 7 ) .
10 Crabtree, J . 1 . and M ue h ler, L . E . " Reducing a n d I ntensi fying S o l u t i o n s for
M otion Picture F i l m" Journal of the Society of Motion Pic t u re E ngineers. 1 0 0 1 -
1 052; 1 9 3 1 December. ( Kodak Research Laboratories, Commu n i cation No. 473 ) .
11 Heymer, Gerd. "Abschwacc h u ng u n d Kornverfeinerung van Kleinbild ncgativen
d u rch Wiederen twickl ung mil Paraphenylendiamin" ( Reduction and
Achievement of Fine Grain i n Small Format Negatives by Redevelopment with
Paraphenyl enedia m i nc ) \leroe}fent. Lichungen des wissenschaft:Lichen Zen t ral­
Laboratoriwns der photogmphischen Abteilung-Agfa . 4 : 1 98-200; 1 935.
12 M uehler, L . E . and Crabtree, J . 1 . "A S i ngle-So l u t i o n l ntensiner For Very \Neak
Negatives'" Plwtographic Society of A- 111. erica Journal. 8 1-85, 1 1 9- 1 22 : 1 945
February, M arc h .
13 Eastes, John 'vV. l 111age Enl1c111ce111ent by Cliemical lnte11sificatio11. Fort
Belvoir, VA. : U . S . Army E ngineer Topograp h i c Laboratories, 1 975 i\ l ay. 1 5 p .
( ETL-0 0 1 4 ) .
14 Perri n , Fred H . and Altman, J . H . '"Studies i n the Hesoh�ng Power ol'
Photographic E m u l s ions. V. The E ffect of Reduction and l n tensincation"
Jou rnal of t.he Optical Society of Ain.aica. 42(7):462-467; 1 952 J u ly. ( Kodak
Research Laboratories, Commu n i cation No. 1482 ) .
1 5 Tom, B e n L. Permanence of 131.ach-an.d-\Vhite Materials a n d Ch.e1J1.ical
Restorat.ion of SH!jidecl l111ages. Ottawa: Public Archives of Canada, Picture
Conservation Division, 1 978 September. 1 57 p. ( i n ternal working paper).
16 Pope, C . I . ;'Stab i l i ty of' Residual Thiosu l f'ate in Processed M icrof il m " Journal
of Hesearcli of I.he Nat:ional /311 rea11 of St.andards-C. Engineering and
Instrumentation .. 67C( 1 ) : 1 5-24; 1 963 J a n u a ry-March.
17 Neblette, C . 1 3 . l-lc111clbooh of P/101.ogrcl'phy. 2nd ed. New York: Van Nostra n d
R e i n hold, 1 930 p . 4-B ·
18 Pollakowski, Goetz. a E i nige chcmische Aspekte b e i der Arc h ivieru ng van
Kinenlm" (Some C hemical Aspects Covering the Archival Treatment of'
M otion Picture F i l m s ) Bile/. ·1md Ton. . 1 9 ( 2 ) : 52-57; 1 966.
19 After a successful restoration cycle, the yel l ow p ic t u re margi n-wh ich
should have been white i f the photograph had been suff-lciently nxed-had
P art VII D E V E L O P I N G C ll l T E ll l fl

t u rned lightly grey, caused by the Formation of elemental silve r from resid ual
si lver salts.
20 Sandys, Leslie G . "Convert i ng Sepia Pri nts to Black'' Bril.ish Journal of
Pliot.ography. 385-386; 1 930 J u n e 27.
21 Hendriks , Kla u s 13 . , Lesser, Brian, Stewart, Jon, and N i s h i m u ra , Doug.
" P roperties and Stability of Gelatin Layers i n Photographic M aterials "
A . J.C. Preprints. \�lashi ngton, D . C . : American I nstitute For Conservation of
H i storic and Artistic \\forks, 1 984. ( 1 2t h a n n u a l meeti ng, Los Angeles, CA,
M ay 1 5-20. 1 984).
22 G reen, A. and Levenson, G . l . P . "A Practical Swe l l meter" journal of
Photographic Science. 20-205; 1 972.
23 American National Standards I n stitute. Detennining the Melting Point
of a Nonsupport. Layer of Filws, Plates and Papers. New York: A N S I , 1964
December 2 . (ANSI P l-14. 1 1 - 1 964; reaffirmed 1 9 8 1 ) 7 p.
24 American National Standards I n stitute. Methods for Determining tlie
Resistance of Photograpliic Fil111s to Abrasion D11ring Processing. New York:
A N S I , 1 972 October 1 7 . (ANSI P J-14 .35- 1972) 7 p.
25 American National Standards I nstitute . Specifical ions for Photogrnphic Fil 111.
for Archival Records, Silver Gelatin Type, on CellHlose Ester Base. New York:
A N S I , 1 98 1 Febru a ry 24. (AN S I P H 1 .28- 198 1 ) ; 16 p.
26 American 'fational Standards I nstitute . Specifications for Phot.ographic Fi/.111.
for Archival Records, Silver Gelatin Type, on Polyester Base. New York: A N S I ,
1 9 8 1 February 24. (A N S I P H 1 .4 1 - 1 98 1 ) : 1 6 p .
2 7 American National Standards I nstitute. !Vletliod for Evalual.ing I. h e Processing
of Blach-and-White Photogmphic Papers wit h Respect lo 1.he Stability of t he
Resulta111 I mage. New York: A N S I , 1 980 August 1 5 . ( A N S I P H 4 . 3 2 - 1 980) 6 p .
2 8 Todd , H ollis N . a n d Zakia, Richard D . Photograpliic Se11silo111etry: The St udy
of Tone Reprod11ction. H astings-on-H udson, N . Y . : Morgan & Morga n ,
1 969. 3 1 2 P·
29 Blake, R . l<. and Meerkemper, 13. " Developed I m age Structure" Jo1mwl of
Pl101.ograpl1 ic Science. 9: 14-2 5 ; 1 955 .
30 Zwicky, 1-1 . " U e ber den U ntersc h ied der Schwae1-LLingswerte photogra phischer
Schichten i n trockenem u nd nassem Zust and " (On the Di fference in
Densities of Photographic Layers in Dry and \Net States) Zeitscli rift fuer
wissenschaftliche Photographic, Pliotopli)sih, H nd Photochemie. 50: 4 1 5-424;
1 955·
 R e a d i n g 59

C HAR L E S T . I SAAC S

Statement from the C ommittee

on Intensification ( 1 98 5 )

The following 1 985 state·ment. of t he Association of International Photography

A rt Dealers, Inc. (A T PAD) responds lo the contemporary 1nact ice of chemical
intensification offaded 11hotog1·aphic fi ne-a rt 11rints. This pu bli.c 1nocla m.at ion
by A /PAD ex11ressed i ts mem.bers ' collect ive concern and C01'mnit rnent to ethi­
cal conservat ion codes. A l PA D 's st:rong opposition t;o any and all intensification
techniques influenced consavation p ract ice and furthered discussions anwng
dealers, collectors, curat:ors, and conservators on p ressing topics ra nging from
appropriate t reat ment criteria to c 11.1 t henticity studies, materials characteri=a­
tion, and connoisseurship.

C ha rles T. I saacs, a representative of the Committee on I n tensification of

the f\ . l . P.A. D . , attended the Winter Meeting of the A! C/PM G and made a
presen tation which outli ned the concerns of the A. l . P.A . D . These concerns
were later drafted into the statement which appears below.
h m/6/85

The board of d i rectors of the Association of I nternational Photography

Art Dealers is opposed to the use or commission of any i n tensi fication tech­
n iques by conservators, dealers, col lectors, or c urators. A l PAD is resolved
t ha t its members w i l l not commission the use of these methods nor know­
i ngly sell any prints which have been i ntensified.

C1 1ARLES T. I SAACS, "Statement l'rom the C o m m ittee on I n tensification'' ( u n publ ished

conrercncc memo), Associat ion or International Photography Art Dealers, I nc . . J u ne 1 985.
Heprinted by perm ission oF the Associat ion or I ntcrnational Photography Art Dealers.
Part VII D E V E L O P I N G C R I T E B I A

The c u rrently accepted pri nciples of good conservation practice are

embodied i n the code of ethics of the American I nstitute for Conservation.
A l PAD endorses this code.
Despite A I PA D's strong opposition to any use of intensification tech­
niques at all, anyone who does i ntensify a photograph for any reason, such
as resea rch , should i ndelibly mark the su rface of the pri n t so that these
photographs may be eas ily and un iversally identi fied in the fu ture as having
been i ntensified.

566
 R e a d i n g 60

]AM E S M . R E I L LY

Preserving Photograph Collections

in Research Libraries :
A Perspective ( 1 99 1 )

Both this reading by Ja mes Reilly (see also Readings 7, 1 9 , a nd 36) and Read­
ing 61 by Debra /-Jess Norris (see also Reading 64) address early efforts to develop
systematic and cost-effec tive sl rategies for the m.cmagem.ent, preservation, a nd
access of large research library collections. These pubU.cations were based on
a series of ·meetings i nvolving conservators, scholars, and research librarians
organized by th.e Research. Libraries G roup at SJ;anford University and focused
on preserva t io n prioritization for photographic holdings.

Exh ibitions and celebrations marked photography's 1 5 o t h birthday in 1 9 8 9 ,

provid i ng a fresh opportun ity to reAect on the state of preservation of the
vast acc u m u lation of still and movi ng pictures prod uced since its d iscovery.
Many of these i mages ( no one knows precisely how many) have foun d their
way i nto research l ibrary col lections.
Th is resource, which i n c l udes daguerreotypes, cinema, microfi l m ,
pri nts, negat ives, sl ides, a n d a host o f lesser-known processes, is mu st larger
(and much richer) than people i magi ne. I ronical ly, it is mostly i nvisible even
to those who work with it every day. The photographs are h idden away, doz­
ens or h u n d reds to a box, much more anonymous than books on a shelf.
M any collections exist entirely in the form of negat ives, virt ua l ly u n known to
the staff and u n usable for research.

jA1\ IES i\ I . REI LLY. " Preservi ng Photograph Collect ions i n Research Libraries: A Perspec­
tive," in Plw1ugrapli Presen>alio11 a11d lhe Research Lihra1y, ed. J e n n i fer Porro ( i\ lountain
View, CA: The Research Libraries C roup, I nc . , 1 99 1 ) , 7-17. © 1 991 O C LC Online Com­
p u ter Library Center, I nc. Used with OC LC's permission.
P art VII D E V E L O P I N G C H I T E H I A

The Nature of Photographic Col lections

The starting poi nt for p reservation of photogra phs in research l ibraries m u st

be the nature of the objects themselves and how t hey are used within the
i nstitution. Some bas ic tru ths about photographs, sl ides, and movies m ust
fi rst be acknowledged : they are hard to catalog, awkward and i nefficient to
use, and expensive to store.
Cataloging diffi c u l ti es derive from two si mple facts: visual i nforma­
tion is fundamentally d i fferent from the written word, and there are h u ge
n u m bers of pictures which await cataloging. Neither the traditi onal bibl io­
graphic cataloging model of libraries nor the arra ngement and description
methods of arc hives fit wel l with the needs of photograph collections. A pic­
ture is worth a thousand words, or at least a t housand catalog entries; one
researcher may seek for meaning i n the face of Lincoln a t Antietam, while
another tries to identify the spec ies of tree in the background. The same
catalog entry is u n l i kely to satisfy bot h .
Computers make the mechanics of cataloging easier, b u t t hey don't
help with the basic problem of translating, condensi ng, and orga n izing visual
commun ication i nto written la nguage-t hat m u st be clone by people who
have a sense of how the collection will be used and by whom. The sheer
magnitude of the task i s also daunti ng. The Li brary of Congress has been
a world leader in the technique of cataloging visual materials, but LC itse l f
h as a 20-year backlog i n cataloging its photography collection.
In fact, most photographs in i nstitu tional collections a re tota l ly
uncatalogued and u nseen-buried, l i ke the treasure of a p i rate who has m is­
placed his map.

Problems i n U sing Photographs

Yet for those photographs which a re cata logued (or at least accessible i n
some way), there are problems i n actually using them for researc h . I mages
m ust be physically strong enough to withstand handl ing and be armored
with a suitable enclosure. Every photograph (the term includes all the kinds
of objects mentioned above) needs its own i ndividual enclosure to protect
from handling damage, dust, and enviro n mental po l l utants. Without protec­
tion, photographs are quickl y dest royed. For example, a good housing for an
u n mounted paper pri nt provides a rigid bac king to avoid Aexing and has a
t ransparent cover to p rotect the print su rface.
Poor-qual ity enclosures and adhesives ( for example, old brown kraft
envelopes, mounting boards, etc . ) are often the very source of cle terioration­
causing contami nants, so both chem ical i nertness and functional design a re
 Reading 60 BE I L LY

critical. I n practice, a good deal of the institutional fu nds and staff time
spent on photograph preservation goes toward providing appropriate enclo­
s u res for storage and use.
At the moment of use, looking at photographs may be informative and
pleasu rable, but i t is a slow, i nefficient process when care is take n . Storage
retrieval and replace ment take time and effort. Each time that a photograph
is used, it is handled; often pictur e s are repeatedly handled in the process of
searching for some other i m age.
Some collections permi t researchers access only to d isposable copies
(or su rrogates), an approach that allows for a much lowe r leve l of pro tective
packagi ng and vigi lance d u ring handling. B u t this strategy is too costly for
most l i braries, aga in because of the n u m bers i nvolved and the h igh costs
of photographic copies. Though access to origi nal photographs is i mportant
o n ly to relatively few researchers, i n most cases u n ique origi nals are p ro­
vided to them because no other alternative exists.

C o l lection S ize and S e l ectivity

Those u nfa m ilia r with photographic collections may have in mi n d the model
of a fine a rt collection, perhaps the prints and d rawi ngs department of a
great museu m-orderly boxes of a few h ighly prized objects selectively p u r­
c hased or bestowed by gen erous connoisseurs. For some photography collec­
tions (typically not in l ibraries) , this is an accu rate percept ion, but in reality
o n ly a tiny fraction of i nstitutional coll ections fit i nto this context .
M ost photographs were originally prod uced to be a part of a system­
atic documentation project for i n dustry or government, were a publ ication
in themselves or were i ncidental to a p u b l ication ( for exa mple, a newspaper
·'morgu e"), or were made for direct sale (portrait and commercial photogra­
phy). Large projects and enterprises tend to p roduce large acc u m u l ations
of photographs. \l\fhe n their originators die, go o u t of busi ness, or s imply
want to be rid of the photographs for one reason or another, these accu­
m u lations fi nd the ir way i nto i nstitutional col lections, often without their
cata logs and indexes, and very often as a huge file of negatives, lacking
positive pri nts.
The key point is the size of these collections, their sheer bulk, and the
d i ffic u l ty of dea l i ng with i mages i ndividually when they n u m ber in hundreds
of thousands, even m u lt i p le m i l l ions. More than a few la rge i nstitutions do
not know to the nearest m i l l ion how many photographs they own . Not only
a re col lections already large, additional photographs are easy to acquire .
Like kittens and gerbils, photograph collections are offered regu larly to a n y
fai n tly responsible institution that seems wi l l i ng to accept them.
P art VII D E V E L O P I N G C R I T E R I A

Of course, the most obvious steps to Lake a re to become select ive

about what is accepted and weed out what is u n i m portant fro m collections
a l ready acq u i red. The first obstacle to weedi ng is simple size-the enormity
of the task of examining and deciding on the rate of. say, one m i l l ions i mages
one at a time.
The rea l ly difficult part about selectively discarding (or preservi ng)
photograph collections is the dec ision process itself. Concepts l i ke va l ue,
qual ity, appropriateness to the col lect ion, and uniqueness come to mi n d ;
all of these t h i ngs, together wi t h the constra i nts dictated b y i n stitutional
resou rces, should be taken i nto account.
\11/e can i magi ne (or at least hope) that there is someone i n an institu­
tion who possesses the knowledge and judgment Lo weigh a l l the factors and
make a balanced judgment on behalf of bot h the i nstitution and the cul ­
t u re at large. T h i s ideally would be someone wh o recognizes t h at a lthough
no identifiable landmarks of !\ l a i n Street are visible i n it, a given print is a
bea u t i fu l landscape photograph, superbly composed. gorgeously printed, and
we l l preserved . This person wou ld also understand, on the other hand, that
repetitive and aesthetically u n i nteresting images can possess great scient i fic
or hi storical va lue, perhaps fo r reasons t h at have nothing to do wi t h their
origi nal pu rpose.

Obj e c t vs . I mage

These a re the paradoxes and the great power of visual com m u n ication, and
the situation is always complicated by the Fact that photographs are phys ical
objects as well as i mages. Artifact va lue can not be overlooked-original pho­
tographs h ave h igher i mage quality than any subseq uent copy and are often
bea u t i ful or i nstructive objects in themselves. A vigorous col lectors' market
exists for photographs, and the dollar va lue of some i mages is surprisi ngly
h igh. Thus, both institu tional priorities and a rt i factual considerations bear
on the process of dec i d i ng what to keep (and also on how to al locate fu nds
for preservation). Sometimes the decision wi l l be to preserve the origi nal
object, sometimes only i ts i m age content, and someti mes neither.
In the encl , we can i magine that our hypothetical person of good j udg­
ment actually exists, b u t not that he or she has the time to consider 500,000
images. Discouragement-and even profess ional bu rnout-over the task of
managing a photograph collection is a rea l-life problem for collection staff in
l ibraries and archives.
 Reading 60 B E I LLY

Taking Action

At present, the first order of busi ness i n preserving photograph ic collec­

tions in research l i b raries is to better assess their size, natu re, and sign i fi­
cance (both art ifactual and intellectual). To some degree, we have to have
faith that photograp hic collections are worth the effort to overcome the
d iffic ulties that their s ize and their advancing deterioration (disc ussed
below) present.
In the past, photograph collections have merited only a low level of
i nstitutional priority because of their i nvisibility and inaccessibil ity, but new
technology will make i mages vastly easier to get at than ever before. E lec­
tro ni c imagi ng tech nology will not only sweep away the e nc u m b rances of
fin d i ng and using i mages, it will in the long run shift lea rn i ng patterns even
more toward visual commu nication and elevate t remendously the cultural
value of origi nal photographs.
We can only hope that by the time photographs become easy to access
electronica l ly (and therefore better known and appreciated ) , deterioration
and u nwise weeding will not have rob bed us of the best of p hotography's
heritage. Meanwh i le, as these tech nological cha nges u n fold, it is essential
to keep clearly i n mind the differe nce between actions take n to ensure the
long-term preserva tion of an image and actions taken to m a ke i t more acces­
si ble for research.
The most long-l ived i maging media are sti l l traditional forms of pho­
tography; magnetic and optical media simply do not last long enough to
be considered suitable for long-term s u rviva l . The issue is a complex one
because digital imaging syste111s offer the pro111 ise of perpet u a l copying and
trans111 ission without quality loss. Thus, it m ight be argued, when hardware
becomes obsolete or a disk is in clanger of deteriorating, one s i mply transfers
the fi les to the next ava i lable technology. This is certa i n ly a form of i mage
preservation.
The problems with this approach are not theoretical b u t practical.
Libraries do not have the money to keep up with every hardware and soft­
ware format change or the in-depth technical expertise it takes to actually
do the transfer from one operating syste 111 , or i mage-encodi ng scheme, to
another. A pri111e exa111ple of this has been NASA-even it, with all i ts own
computer expertise, has i 111 111ense problems recovering computer data fro111
the last 20 years of the space progra111. This short period i ncorporates about
a dozen i nco111 patible 111agnetic-tape formats.
Added together, the d i fficu lties of scarce and obsolescen t hardware,
missing software and/or docu mentation, deteriorating magnetic tape, and
poor record keep ing 111ake electro n ic i magi ng a very problematic way to ensure

57 1
Part VII D E V E L O P I N G C H I T E H I A

l ong-term su rvival of i mages. Qu ite apart from the Financial and techn ical
d ifficulties of periodic transfer, each t ransfer represents a selection process,
requiring a l l the breadth of j udgme n t necessary to weed a col lection i n the
ord i nary keep-it-or-toss-it way.

Deterioration and S torage

As if there weren't enough to think about for l i brary photographic col lections,
there is the fact of deterioration, which is l i nked i nsepara bly to the question
of the storage environment. Deterioration can be slow or fast, depending on
the environment and the kind of p hotographic objects i n the collection. The
easiest way to approach the subject is by considering photographs from a
materials point of view.
Most p hotographs have three generic components: i mage, bi nder, and
support. The i m age i n every photograph is phys ically com posed of some
substance, such as metal l i c silver (as i n black-and-white photography) or
organic dyes (as i n color photography). Image fad i ng is largely a matter of
what chemical reactions m ight occ u r to si lver or dyes so that they no longer
absorb l ight.
S i lver images have an u njustified reputation for stabi l ity. Th is is due
mostly to the fact that deterioration is often overlooked by untrai ned observ­
ers and also because color photographs are so much less stable by com­
parison . B u t the rea l i ty is that si lver is extremely sensitive to moisture and
contaminants from either the general atmosphere or from storage materials
and ad hesives.
S i lver fades by a p rocess known as oxidation, in which both chemical
and physical cha nges occur to the m in u te i mage particles. Once oxid ized,
the si lver begi ns to migrate and may be redeposi ted in a new location within
the binder or support. This is why many faded si lver i mages also have a blu­
ish meta l l ic sheen i n the dark parts of the picture, a p henomenon known as
silver m irroring . \l\fhen m igrating si lver is preferentially depos i ted at the very
u p permost su rface of the gelatin layer, m i rroring res u l ts.
The most common manifestations of oxidation in si lver i mages a re
fad i ng and d iscoloration. As oxidation proceeds, the image gradually gets
l ighter, especially in the highl ights; at the same time, its color changes fro m
black to b rown. These symptoms res u l t from the withering away and physi­
cal breakup of i m age particles. Si lver i mages made up of very small particles
are ora ngish or b rown because such small particles can no longer absorb
l ight u n iformly across all colors of the spectru m . (To ach ieve a neutral black
color, the i mage parti cles m u st absorb all wavelengths equally we l l . ) The
smaller and more spread apart the particles become, the yel lower and lighter
the i mage appears.

5 72
 Reading 60 ll E I L L Y

R H , Te m p e ra t u re and Airborne C ontami nants

,

The storage environment governs the rate of si lver-image oxidation. \Nater

is an essential reactant i n the process, and thus the overal l rate of i mage
fading is determined principal ly by the relative h u m idity ( R H ) of the ambi­
ent environment. Temperature also plays a role, b u t i n the deterioration of
black-and-white materials it is a m i nor one compared to R H .
Thinking in the preservation field about the ideal R H for photographic
storage has c hanged recent ly, tending toward lower levels than previously
recom mended. Not only si lver i mages benefit from low RH; fad ing of color
dyes and espec ially the chemical deterioration of plastic fi l m bases ( n i t rate
and acetate) a re slowed by low R I-1 .
The I m age Permanence I nstitute has proposed to A N S I (American
National Standa rds I nstitute) and to I SO ( I nternational Sta ndards Orga n iza­
tion) that the recommended RH range for fil m storage be 20% to 30% instead
of the broader 1 5% to 50% Ii I-I range specified in c u rrent standards. Photo­
graphic glass plates may have a problem of e m u lsion delam i nation at very
low R I-l s, so when prese nt in a collection, it is prudent to keep glass plates at
an RH of 30% or 35%.
In addition to RH and temperature, atmospheric conta m i nants can be
a factor in si lver-i mage degradation. General air pollutants (ozone, n i t rogen
oxides, etc . ) or localized conta m i nants from within a box, room, or bu i lding
can cause oxidation. Someti mes occurrences of conta mination can be acute
and qu ickly destru ctive, as, for example, \1·hen oil-base paints a re used near
photograph storage areas ( hydrogen peroxide, a strong oxidant, i s produced
when oi l-base paints c u re ) .
Though t h e destruct ive effects o f various oxid izi ng, s u l fi d ing, a n d acidic
gases are known, speci fic maxi m u m concentrations for them have not yet been
establ ished. Protection agai nst i mage attack by atmospheri c conta m i nants
can be provided to si lver im ages by t reating t h em with gold or polys u l fide.
For color photographs, cya n , yel low, and magenta organic dyes are the
substances that actually make up the i mage. Though they differ somewhat
from prod uct to product and fro m one manufacturer to another, color photo­
graphs in general share two great environ mental sensitivities: heat and light.
Fading of color images is primarily controlled by the storage temperature
and, to a lesser but still significant degree, by R H . The basic facts to know
in stori ng color photographs arc that they req u i re storage wel l below room
tempe rature in order to ach ieve a long l i fe an d that they are rat her qu ickly
rui ned by exposure to l ight.
A n u m ber of instit utions t hat have committed to keeping color c i n ­
ema a n d still photographs have i nstalled c o l d vau l ts o r o t h e r arrangements
for low-temperature storagc. The colder the tempe rature, the longer the

5 73
P art VII D E V E L O P I N G C H I T E H I A

expected l i fe . Light damage while on display is dependent on the nature ,

inte nsity, and d u ration o f i ll u m i nation that fal l s on the photograph.
Systematic studies of the effects of po l l utants on color photographs
and nonsi lver m i crofi l m materials (as well as si lver i mages) are now u nder­
way at the I mage Permanence I nst it ute, with fu nds from the National
E ndowment for the H u ma n i t ies' Office of Preservat ion and the Andrew W.
Mel lon Foundation.

Deterioration of C e l l u losic Plastics

U n t i l this poi nt, the d iscussion of deteriorat ion has considered only th e
image o f the photogra ph, b u t i ts ot h e r components ( b i nder and su pport) also
have their problems.
Gelatin i s t he most common binder material (the e mulsion layer which
holds the i mage) and i s relatively free of deterioration un less stored at h igh
h u m i d i ty, whereupon fungus growth becomes possible. The only effect ive
strategy to cope with mold growth is to prevent it before it happens.
Perhaps the most serious type of deteriora t ion of a l l occ u rs to the plas­
tic su pports of films. This kind of degradation renders the photograph tota l ly
useless-u npri ntable, u nprojectable, u nusable i n any way. I t can happen to
�1ny object made of a cellulosic plastic (cellulose n i t rate or cellu lose acetate) .
This includes virtually al l movies, st il l negat ives, and tra n sparencies made
from the 1 890s to the 1 960s. I n rece n t t imes a nonce l l u losic plast ic (polyes­
ter) has come to be used in many applications of photography, but movies
and amateur rol l films (color negat ives and sl ides) a re still being produced
on cel l u lose acetate .
M a ny people are aware that older films made of cellu lose n i t rate
are highly A a m mable and also subject to a slow but catastrophic chemical
decompos ition . Previously it was thought that so-called safety films (made
of cellu lose acetate) were not only safe from the danger of fire but also
not l ike ly to chemically decompose as n i trate does. Recent expe rience and
research have conc l usively shown that this is not the case.
All of the cellu losic plastics-acetate as wel l as n i t rate-share the same
u n derlyi ng deterioration mechanism and will degrade at more or less the
same rate i f stored improperly. There are some d i ffe rences in the sym ptoms
of n itrate and acetate degradation ( n it ra te fi l m becomes brittle, shru n ke n,
sticky, and terribly faded, while acetate becomes b ritt le , shrunke n, covered
with crystals, and the e m u lsion buckles ) , but the end res u l t is total loss i n
bot h cases. O n e d i ffe rence is that c u rators often have more t i m e t o 1·eact to
the fi rst signs of degradation in nit rate, wh i le with acetate the signs are more
su btle and the end can come more precipitately.

57-1
 Reading 60 ll E I L L \'

Researc h has been clone on the problem by the Eastman Kodak Com­
pany, by the Center for Polymer Stability at iV l a nchester Polytechnic i n the
U . K., and by the I m age Permanence I nstitute at Rochester In stitute of Tech­
nology. ln a large research project fun ded by NEH, the National H istorical
P u blications & Records Commission ( N H PRC), and Eastman Kodak Com­
p any, the I mage Permanence I nstit u te has shown clearly that a l l types of
cel lu losic films have essentially the same behavior ( n i t rate and cliacetate a re
not in herently better or worse than triacetate, etc. ) and, most i mportan t ly,
has q uantified the benefits of low Rl-1 and low temperature in preventing
fil m-base deterioration.
Lowering the R I- I From 50% to 20% can p rovide a fou rfold improvement
in expected film li fe. This is because water is a n essential component i n the
deterioration reactions and denying this reaction the moisture it needs will
greatly retard (though not completely stop) its progress. The reaction is also
temperature dependent: if the RH is kept at 50%, lowering the storage tem­
pera t u re from 20°C (68° F ) to 3°C (37° F) wil l m ultiply the expected l i fespan
of fi l m by ten ti mes.
The preservation field has come to grips with the slow decomposition
of n i trate film by formu lating a policy of "segregate and duplicate. " Though
we have come nowhere near to the goal of d u plicating a l l nitrate fi l m, at
l east concept ually it seems possible.
With the knowledge that o u r past and presen t experience with n i t rate
is l i kely to foretell the fut u re of acetate, a much l a rger p roblem is loom­
ing. Already, nearly every sizable collection of film has at least some acetate
deterioration. Expos u re to h igh h u m id i ty and temperat ure causes a rapid
advance of the decompos i tion process, so collections in hot and h u m i d areas
have experienced the h ighest incidence of loss.
The problem so fa r has been worse with sheet-film col lections (that
is, film in cut sizes l i ke 411 X 5 1 1 , 811 X 1 011, etc . ) than cinema col lections for
severa l reasons. 'vVhole gro u ps of fi l m i n s heet - fi l m col lections tend to be lost
at once-for example, nearly all of the negatives doc u menting the con struc­
tion of N ew York's Tri borough Bridge i n the 1 930s have degraded . The 1 930s
and 1 940s a re part icu larly a ffected decades in sheet-fi l m collections beca use
t hey represent the oldest acetate materials in this format.
I t is difficult to get a n overal l f-igure for how much acetate fil m has
degraded so far i n still photography col lections, but an educated guess wo uld
be 3% to 5% of the total existing fi l m . In cinema col lections less fil m has
degraded beyond usa b i l i ty, but perhaps 1% to 2% of the total holdings have
the acetic acid (vi negar) odor that is evidence of advan c i ng deterioration.
M icrofi l m col lections a re similar to ci nema collections, and concern for
older acetate microfi lms is growing.

575
Part VII D E V E L O P I N G C H I T E H I A

Al the moment, there a re no good ways to assess the condition of col­

lect ions with respect to acetate deterioration. A technique that relies on
smelling the fi l m not only lacks prec i sion but i s u npleasant and a health risk
( t h roat and nasal passages qu ickly become irritated ) . Research shows that
acidity level s in film are the earliest and best overall indication of its con­
d it ion. Objective methods using p H measurements or other tech niques to
measure b u i ld u p of acetic acid i n the film support have not yet been devel­
oped to t he poi nt of practical ity.
Certa inly it is safe to say that large amou nts of fi l m wi l l be degrad­
ing over the nexl decade beca use of a long previous history of i mproper
storage . The s i tuation with acetate wi l l come to resemble the present status
of nitrate: much film a l ready destroyed, but a l so a good deal of i t still in
exce llent shape.
The key poi nt is that changes i n storage conditions are the only realis­
tic solution to the long-term prob lem of cel l u losic plastic fi l m preservation.
We know now t hat the key elements of such an enviro n ment are low R H and
low to moderate temperat u re.
For fi l m that i s a l ready on the brink of degradation (assuming we can
find a way to reliably identify it), only very efficient, automated copying proj­
ects have a hope of saving collections before they a re lost. After the l ibrary
com m u n i ty finds out how much cellu losic plastic fi l m it has-and dec ides in
a general way how much i n tel lectual value should be attached to it-then it
is l i kely that preserving degra d ing acetate material wi l l natura l l y emerge as
a top priority. Large-scale duplication wil l beco me an i nc reasi ngly essential
tool to save photography's heritage, especially t he still negatives of the 1 930s,
1 940s, and 1 9 50s.
The R esearch Libraries G roup i s in an ideal position to coord i nate bot h
the physical and intellectual assessment of photographs i n research l ibraries
and, when t he t i me comes, to coord i nate or i n itiate a pilot project to show off
the potential for a new approach to preservation of cellulosic fi l m materials.

Future Strategy

The problems of photograph preservation a re complex. One outsta nding

need is for al l concerned to become more aware of the tech nical and mana­
gerial issues that photograph ic collections present.
As we look to the fut ure, at least the outli nes of a stra tegy are clear:
the goals will be to make the i n tellectual case for having such collections,
to priorit ize collections accord i ng to significance and state of health, and
then to choose an appropriate mix of preservation and access measures with­
out losing s ight of which actions guarantee i mage survival and which merely
make them easier lo view-for now.
 R e a d i n g 61

D E B RA H E S S N O R R I S

Preservation Planning for Diverse

Photographic H oldings ( 1 99 1 )

This reading h)' Debra I-Jess Norris (see also Reading 64) co1nple111ents Lhe
previ01.1s reading b)' James NI . Reilly (see also Readings 7, 1 9 , and 36). Lihe
Reilly's, t h is reading e1nphasi=es t he pressing need to evaluate collection sig­
nificance, value, fut: u re access, conclilion, and si=e, while also h ighlighting t he
i mport:cmce and value of 11revent ive conservation.

P hotographic i mages can be found in m useums, arc h ives, historical societies,

libraries, and private collections i n a bewildering variety of types and sizes.
They a re complex objects created by a m u ltitude of techniques. M ost com­
monly t hey occ u r as la m i nate stru ctures consisti n g of a primary su pport and
a t ransparent bi nder l ayer i n which the final-i mage material is su spended.
The most i mportant and pro m i nent final-image material foun d i n
n i neteenth- and twentieth-century photographic materials is meta llic si lver,
although plati num, i ron complexes, pigments, and organic dyes have been
used throughout photographic history. The most common binder materials
a re albumen, made from the whites of hens' eggs; collodion, a form of cel­
l u lose ni trate; and gelatin, a h ighly pu rified, commercially prepared protei n .
Primary su pports i n c lude paper, silver-plated copper, japa nned iron, glass,
and fi l m .
Because photographic collections are often large a n d d iversified, their
long-term preservation can prove prob lemat i c . Those faced with caring for
those collections are tru ly challenged .

DEBH/\ H ESS NoHHIS, " Preservation Pla n n i ng !'or Diverse Photographic Hold ings " in Pho­
tograpli Preservat ion and the Research Librn1y, ed. J e n n i fer Porro (Mountain View, Cf\:
The Research Libraries C roup, I nc., 199 1 ), 1 9-27. © 1 99 1 OC LC Online C ompute r Library
Center. I nc. Used with OC LC's perm ission.

577
Part VII DEVELOPING C H ITEBIA

To assess t heir condition, photographic col lections should be s u rveyed

by a conservator. II types of items in the collection should be carefu l ly
exa m ined, including glass-plate and f i l m-base negatives, early photographic
items (such as daguerreotypes, am brotypes, and t i n types) , prints, albums,
scrapbooks, and newer items such as microforms and color negat ives, trans­
parencies, and prints. Owing Lo quant ity, it is often d i fficult, i f not i mpos­
s i ble, to examine all photographic art i facts in a collection; however, boxes
and groups of items can be ra ndomly sampled and assessed For storage,
t reatment, handl ing, and exh ibition need s. I n doing so, the conservator may
make a checklist for tracking and quantifying genera l cond i tion and deterio­
ration problems associated with va rious photographic items.
The fol lowing discussion out l ines a general, long- ra nge preservation
strategy for d iversi fied photographic col lection s. The ten-point plan proceeds
from most-critical to least-critical need.

1. Env i ronmenta l Assessment and Con trol

All photographic materials arc adversely affected and i rreversi bly damaged
by exposure to certain enviro n mental cond itions. The conservator, therefore,
m u st first su rvey the fac i l ity and the photographic hold ings for evidence of
i mproper and potentially damagi ng environmental condi tions. Once identi­
fied these problems should be addressed .
I deal ly, most photographic materials should be housed al a relative
hu mid ity ( H I-I ) oF 20% to 40% (20% to 30% is preferred for film-base stor­
age ) . Low-temperat u re storage of 40° F or below i s preferred for most color
and fil m-base negat ive collections. Levels ol' gaseous pollutants l ike nitrogen
d ioxide, s u l fu r d ioxide, hydrogen s u l fide, and OLone should be carefu lly mon­
itored. They and many particulates in the air (such as greasy d i rt and dust)
can be con tro l led through air fi ltration.

2 . H a nd l i ng Procedure s a n d Di saster Plans

OF utmost i m portance is the establishment of hand l i ng and preservation

proced u res geared toward stabilizing the condition of the entire collection.
Adherence lo these procedures ensures that the level of preservation i s con­
sistent throughout a collection.
Handling and preservation procedures may vary i n terms of their com­
plexity and the level of efforl req u i red. They should i n c l ude instructions
for processing newly acq u i red and donated materials, specifications for the
t reatment of works t hat are exh ibited or lent ( for example, what l ight levels
L hey may be exposed Lo, how long Lhey may be exh i b ited, what temperature
and h u m idity they should be stored at), and recom mendations for the use of
collect ions by researchers (for example, gloves should be worn, only pencils
 Reading 61 ll E S S N O l ! l! I S

should be allowed in the viewi ng room, the type of protective enclosu res
items should be hou sed i n ) .
Disaster plans and procedu res i n t he case of fire, earthquake, o r nood­
i ng should also be outli ned . In particu lar, work p u blished by the National
Arc hives of Canada on the sa lvage of water-damaged photographic materials
should be cons u l ted . 1

3. I nspection of F i l m - Base Negatives

One press i ng and diffic u l t problem is the active and rapid deterioration of
fil m-base negative collections. Because many i mages exi st only as negat ives,
their prese rvation must be given h ighest priority.
Fil m-base collections-espec ially those on cellu lose n itra t e or cel lu­
lose acetate-based fi lm-must be routinely i nspected and eval uated for dete­
rioration. As t hese materials are exam i ned, d u p li cation programs, hand l i ng
guideli nes, and archival storage procedu res must be establi shed . Temporary
storage of u n stable fil m-base materials in a low- R H and low-temperature
environ ment-a cold-storage vault or frost-free refrigerator-may retard
their deteriorat ion and thus preven t furt her loss.
The chem ical and physical deterioration and extreme f·la mmability
of ce l l u lose n itrate film ( used from 1 889 to circa 1 940) have been well
documented, and many i nstitutions have isolated these negatives while
awaiting t heir du plication onto more stable fi l m . At the very least, cel l ul ose
nitrate films must be identified and isolated and fire regu lations consc ien­
ti ously followed.
From 1 930 to 1 950 most origi nal still-camera negatives were prod uced
on film with a cel l ul ose diacetate or m ixed cell ulose ester base. Alt hough not
flammable, these acetate-based films deteriorate through solvent loss and
hydrolysis, resu lting i n a severely embrittled and shrunken fi l m base. The
deterioration is exacerbated by h igh RH levels. D uring the last Few years,
la rge quanti ties of acetate-based m icrofi l ms, motion p ictures, and s t i l l pho­
tographs that have been exposed to i mproper enviro n mental cond it ions or
have experienced water da mage have suffered severe loss.

4. D u p l ication of Deteriorated Negatives

The conservator may choose to dup l icate film-base negat ives before dete­
rioration advances. For maximum quality in dupl ication, the production of
an in termediate fil m posit ive (called an -interpositive) that is made From the
original negative by contact pri nting is often preferred. A laterally correct ,
dupl icate negative can be made from the i nterposi tive as needed, and the
interposit ive is retained as the arch ival master.

579
Part VII D E V E L O P I N G C R I T E R I A

Another procedure u ses direct-reversal fi l m to produce a d i rect but lat­

erally reversed dupl icate negative. The resol ution of d i rect-dupl icating fi l m
is very good, al t hough , owing t o i t s fine-grai ned nature, it is prone t o oxida­
t ive attack i f not properly p rocessed and toned .
Another option to consider is the use of long-rol l camera fil m for effi­
c ient and cost-effective duplication of large col lections. Th is method uses
less film and can be au tomated, and, although it prod uces reduced-size
dupl icates, the qual ity of the dupl icates is not comprom ised if the duplica­
tion is carried o u t properly.
As a final resort, an i n stitution may choose simply to make copy prints
from the original negative and then to rephotograph one of the copy pri nts to
make a new negative. The i mage, however, loses resolution i n the process.
vVhen faced with massive deteriorati ng film holdings, collection man­
agers and conservators m u st carefu l ly eval uate the available d u plication
options. Factors to consider incl ude the number of items i n a collection,
the informati onal and intrinsic value of these items, their condit ion and pro­
jected use, and the financial resources of the i nstitution.
The least chemically stable items should be dupl icated first, followed
by the most signi ficant and va luable i tems. (Contrary to popular opinion,
cellulose n itrate fi l m is not necessari ly less chemically stable than acetate­
based f i l m . In fact, recent research from the I m age Permanence I nstitute
i nd icates that cellulose n i trate fi l m and acetate-based f i l m , when stored
under the same conditions, deteriorate at the sa me rate. However, the flam­
mability of cel l ulose n i trate fi l m makes it a special hazard to store . )
Today, many i nstitutions systematically destroy film, especially n itrate
f i l m , fol lowing dupl ication. This practice may prove d isastrous i f the dupli­
cates are not of the h ighest optical and a rchiva l quality.

5. Rehousing of Photograph i c Prints

Photographic prints may need to be rehou sed to prevent chemical deterio­

ration and damage . H armful and i rreversible chemical and physical i nter­
actions between photographic materials and their enclosures can cause
final-image deterioration such as fad i ng and mi rrori ng, binder-layer sta in­
ing, and su rface modi fications. Many of these problems can be avoided by
rehousing in acceptable plastic or paper-based materials.
The cu rrent ANSI Standard 1T9 .2 ( 1 988) req u i res that all enclosure
materials be chemically stable and free of acids and peroxides. They must
pass an accelerated aging test known as the Photographic Activity Test that
empirical ly determines whether harmfu l chemical or physical i n teractions
between a photograph and an enclosure material wi l l result over the storage
l i fetime. Produ cts chosen for rehousing operations should meet the requ i re-

5 80
 Reading 61 H E S S ,\I O B B I S

ments of this AN S I standard, and manu facturers of enclosu re materials

should be encouraged to have their produ cts thoroughly tested and eva l uated.

Plastic Enclosu res

P lastic materials considered s u i table for ph otographic storage i nclude

uncoated polyester, polyethylene, polypropylene, an d cel l ulose triacetate
(although the chemical stabi l i ty of cellu lose triacetate is b e i ng q uestioned
and continues to be evaluated ) .
These transparen t materials, avai lable i n n umerous s leeve and folder
formats, a l low an image to be viewed without removing it from the enclo­
s u re, thereby greatly reducing the possibility of h a nd l i ng damage. When
u s i ng plastic enclosures, however, special concern should be given to h u m id­
i ty because it can cause photographic emulsions to sti c k to the slick surface
of these materials and it can cause ferrotypi n g (shiny spots to appear on
the e m u lsion). The comparative expe nse of plastic, often three times that of
paper, should also be taken into account.

Pa1nr Enclosu res

Paper enclosures should have an alpha c el l ul ose content greater than 87%
and conta in no l ignin, ground wood , or a l u m rosi n sizing. Both b uffered
(alkali ne) and u n b u ffered papers are acceptable, although u nder certa i n con­
ditions one may be preferred over the other. For example, i nh erently acidic
photograph i c materials, such as plat i n u m prints or cellulose n itrate a n d
acetate fil m , benefit from storage i n b uffered enclosures. Presen t research
i ndicates that salted paper, albu men, gelatin, or collodion p hotographi c
items c a n b e safely housed i n buffered enclos u res i f proper h u midity levels
a re maintained.
A N S I IT9.2 expl icitly recommends that contemporary black-and­
white photographic materials be housed i n paper enclosures with a pH of
7.2 to 9 . 5 . In comparison, this standard recomm e n ds that contemporary
color photographic materials be housed i n paper enclosures having a p H
between 7 . 0 a n d 7.5.
Paper enclosures are available in several formats, including envelopes,
seamless enclosures, and folders. Four-flap seamless enclosures are h i gh ly
recommended because they have no adhesive seam to attract m oisture and
thereby contribute to i mage deterioration .
There a re advantages and d isadvantages to u si ng paper enclosures.
They are easy to write on, genera l ly Jess ex'Pensive than plastic materials, and
opaque, thereby protecting photographs from light. But they also requi re the
removal of each photograph from its enclosure each tim e it i s exa m i ned,
greatly i nc reasing the possi b i l i ty of han d l i ng damage.
Part VII D E V E L O P I N G C R I T E B I A

All enclosures, plastic or paper, should be standard i n size and able

to fit eas ily i n acid-free fi l e folders or boxes. Paper and board stock used to
construct boxes may have an a lka line reserve. Flat storage in acid-free boxes
is particularly recommended for fragil e p hotographs and those adhering to
brittle mounts. Upright storage in boxes of acid-free hanging file fo lders is
acceptable for photographs 811 X t011 or smaller.

6. Evaluation for Conservation and Preservation

Du ring rehousi ng, photographic items should be exa mi ned and eval uated
to assess the need for fu rther preservation treatment. Custodians of pho­
tographic materials should learn to identify those deterioration problems
req u i ring i m mediate conservation treatment.
For example, the p resence of active mold growth is a critical prob­
lem that must be addressed i mmed iately. Spore removal (via aspiration)
coupled with stringent environmental control should preve nt continued
biodeterioration.
Photogra p h ic materials exhib i t i ng actively flaking binder layers, the
presence of p ressure-sensitive and rubber-cement adhesives, and severely
deteriorated and embrittled p ri mary and secondary su pports should be iden­
t i fied for conservation treatment.

7. Rehousing of Glass-Plate Negatives

G lass-plate negatives, comprising collodion wet-plate negatives and the

more com mon gelat i n dry-pl ate negatives, should be rehoused and stabili zed
as necessary.
A four-fl ap paper enclosure i s recommended for the vertical storage
of glass-plate negatives i n good condition. D u ri ng reh ousi ng, it may be nec­
essary to clean the nonemulsi on side of the glass negative with a sl ightly
dampened cloth.
G lass-plate n egatives exhi biting actively flaking or deteriorated
b i nder layers or cracked or broken pri mary supports shou ld be housed flat in
a sink mount constructed of arch ival box board and paper. Rag-board shims
can be used to separate glass fragments, thus p reventing abrasion along
broken i nterfaces.

8 . Rehousing of Photographic Albums and Scrapbooks

If poss ible, a l l photographic albums and scrapbooks should be boxed to

ensure adequ ate protection from d i rt, dust, and gaseous poll utants. Once
boxed, they should be stored flat. M i c roforms or d u p l icate prints should be
used for research and reference purposes in place of origi nals.
 Reading 61 H E S S N O H H I S

Photographic albums should be interleaved as necessary, particularly i n the

fo llowi ng si tuations:

• The presence of plat i n u m or platin um-toned photographs. Plat i n u m

is a catalyst f o r cellu lose deterioration; therefore, photograp hic pri nts
housed i n direct contact with plati n u m i mage material w i l l be i rrevers­
ibly stained.
• The presence of bronze powders. These decorative powders, which
were often u sed for gilt borders and ornamentation, are composed of
copper and zinc and will select ively oxidize and fade (in a spotted pat­
tern) silver p hotographic images.
• T he presence of glossy photographs wi t h highly reflective su rfaces.
These items are more easi ly abraded i n an a l b u m format owi ng to the
weight of the text block and potential handling p roblems.
• The presence of e mbrittled, acidic. deteriorated, or h ighly colored
album pages. They should be i n terl eaved for further protection.
• The presence of i mproperly processed materials (such as t hose
found in a newspaper morgue). I m properly processed m aterials may
i nc l u de p hotographs that were not properly fixed or washed d u ri ng
manufacture. Their res idual che m icals may i nteract to cause i mage
deterioration.

The abrad i ng potential of i n terleaving materials shou ld be considered. The

materials most commonly used today for i n terleaving i nc lude po lyester
fi l m (selected for its transparency) and acid-free u n buffe red and l ight­
weight rag papers.

9. Rehousing Daguerreotypes, Ambrotypes, and Tintypes

These objects are frequently fou n d housed in their origi nal decorative Folding
cases, which were often constructed of wood covered with embossed leather
or paper. The p hotograph i c i mages are protected by a lacqu ered brass mat
and a cover glass, u su al ly bou nd together with paper tape and further cov­
ered with decorative brass fo i l .
The combination o f t h e cover glass, mat, and the folding case pro­
motes glass corrosi on on the i nside su rface of the cover glass. The type of
corrosion and i ts severity appear to depend on the chemical composition of
i nd ividual cover glasses.
Actively deteriorating cover glasses should be identified and, as t i me
and money permit, replaced with contemporary high-grade glass. U ncasing
and resea l i ng operations should be su pervised by a tra ined conservator.
Part VII D E V E LO P I N G C H I T E H I A

Ambrotypes and tintypes with flaking collodion binder layers should be

identified and housed flat to await conservation t reatment. Often the flaking
col lodion on a t i n type is caused by the active corrosion of its japa n ned i ron
su pport; this can be controlled by storage in a low- h umidi ty environment.
Photographic cased objects can be housed i n acid-free fol d i ng boxes.
These boxes, made of a heavy-weight acid-free board, wi l l protect these
objects from further breakage and abrasion.
Daguerreotypes, ambrotypes, a n d t intypes that are no longer in their
p rotective cases are susceptible to corrosion as we l l as abrasion. They should
be housed in acid-free paper enclosures of appropriate s ize and construction.

10. Preservation o f Color M aterials

Conte mporary color prints, negatives, and transparencies have become an

i ntegral part of most photographic holdings. Ch e mically produced color
i mages are made of organic dyes (usually cyan, yellow, and magenta) that
vary dramatically i n their stabi l ity over time: temperature, h u mi d ity, l ight,
original manufacture, and subsequent process i ng all affect the longevity of
color p hotographic materials. I mage deteriorat ion can i nc lude a loss of h igh­
l ight detai l with reduced overall density and con trast, a shift i n color balance
as the organic dye layers fade at u nequal rates, and stain formation in the
highl ight or m i n i m u m-density regions. The only cu rrently avai lable means
for preserving most color materials is dark storage at low temperatu res (4o° F
or lower) and low relative-hu midity levels (40% R H or lower) .
Collections of color negatives, transparencies, and prints, depend­
ing on their size, should be housed in a frost-free commercially available
refrigerator/freezer. ( I n doing so, a frost-free refrigerator with low- h u mid ity
refrigeration should be used.) These u n its must be careful ly selected and
constantly monitored for temperature and h u m idity levels.
Access to t h e materials stored within these un i ts sh oul d be l i m i ted,
and all staff should be trai ned in the special procedu res of retrieving items
from the refrigerator (special warm-up times are req u i red) and returni ng
them to refrigeration. I n addition, color prints and negatives should be boxed
and bagged i n polyethylene before refrigeration to fu rther protect them from
moisture damage in case of mechanical fa i lu re . Color transparencies may be
housed in either acid-free boxes or h igh-qual ity polypropylene or polyethyl­
ene slide pages.
Large cold-storage va u lts, such as those c u rrently maintained at NASA
(o°F and 25% R H ) and The John F . Ke n nedy Li brary (o°F and 30% R H ) , may
be most u sefu l for very large collections.
Refrigeration or cold storage is the only method to stop i rreversi ble
deterioration of color photographic materials.
 Reading 61 H E S S N O R R I S

I n Conclusion

The preservation plan outli ned in this paper addresses some of the many
problems associated with large and diversi fied p hotograph ic holdings. M y
a i m h a s been t o present practical an d general guidelines that c a n b e adapted
to the needs of many types of photographic collections.

Notes

Klaus B . H endriks and Brian Lesser, "' D isaster Preparedness and Recovery:
Photographic Materials. " Arnerican A1-cliivist 46, no. 1 (Winte r 1 983), 52-68.
 R e a d n g 62

J o s E 0RRACA

Developing Treatment
Criteria in the Conservation
of Photograp hs ( 1 99 1 )

De111anding greater collaboration with the fields of paper, pain,t;ings, 111et­

als, and textile conservation, as well as ·in.creased attenti.on to photograph
cormoisseursh.i:p-process, tonality, sw:face character, presentation., and a rt ist
intent-Jose Orraca (see also Heading 4) defines t he essential qualit ies of a
photograph conservator. Not i ng th.at "t reat. rnent is at the core of our profes­
sion., " Orraca shares his observat ions relat;ing t.o t he challenges, opport unit.ies,
and 1nivileges of professional conservation practice. Orraca 's elegant and heart ­
felt ideals a re relevant to all presen1at ion disciplines and are an i11spiration for
current and f11 l 1 1 re conservators.

The conservation of photographs, as a professional endeavor, had its begi n­

n i ngs in the mid 1 97o's at the Art Conservation Department of the U n iver­
sity of Delaware. But from the begi nnings of photography, photographers
have had a keen i nterest in the stabil ity and pe rmanence of the photographic
i mage. ln Fact, many i m provements i n the photographic process, such as go ld
toning and carbon prints, came about as a response to prob lems of deteriora­
tion in photographic i mages. Gernsheim's 1 969 edition chapter 28 is usefu l
in u nderstanding the concerns that were prevalent i n the 1 9th century and
which continue today as we pursue the preservation of our photographic heri­
tage. v\/ith the advent of the twentieth century the newly emerging ind ustrial
barons of photography real ized the com mercial val ue of marketi ng photo-

.
Jost 0RBACA. " Developing Treatment Critcri<1 i n the Conscn«1tion oF Photographs, Top­ .

ics i11 Pliotograpliic Presermtio11 4 (\1\las h i ngton, DC: f\111crican I nstitute for Conservation,
Photographic i\ latcrials C roup, 1 99 1 ) . 1 5 1-55. Hcpri nied by perm ission of Jose Orraca,
Conservator of Photographs.

)86
 Reading 62 0 H H J\ C ii

graphic materials with a certain degree of permanence. Kodak, in particular,

has to a great extent attempted to address the problems of i mpermanence and
deterioration fou nd in paper supports, em u lsion layers and processi ng chem­
istry. While it must be real ized thal industry's u l t i mate goal is profit, in the
process of making money the photographic industry has exh ibited a consider­
able degree of responsibi l i Ly in making photographic materials more last i ng.
It is in color materials that Lhis degree of responsibi l i ty begi ns to d i m i n i s h .
Through t h e 1 96o's there h a d been indi viduals i n terested in the pres­
ervat ion of photographic i mages. S ignificant among these has been Eugene
Oslroff, C u ra tor of Photographs at the S m ithsoni an, whose ea rly wri tings i n
Nl useu:m News did much to elevale Lhe general i n terest in these issues. What
was needed in the 1 97o's, however, was an approach to photographic conser­
vation that was rooted in Lhe already i mportant field of Art Conserval ion and
away From the pervading i n f l uence of the photographic indust ry as evidenced
in material standards of the period and i n the fact t hat preservation came to
be defi ned in the th i rd quarter of L h i s century as s imply copying. The photo­
grap hic industry can provide us wilh usefu l i nformation and i nsighls, but it
can never define the para meters of the practice of conservation, for its sci­
entists can seldom u nderstand how a conservator thi nks and whal criteria he
or she must apply to their work. Th is is not meant as a criticism, but merely
to state that theirs is a d i fferent Frame of m i n d when discussing the preserva­
tion of photographic i mages.
Today the conservation of photographs i s defined within th e larger
context of a rt conservation, in terms of t rai ni ng, ethics and pract ice. In fact,
we make a grave m istake when we as photographic conservators isolate our­
selves from the larger profession and when we are ignorant of issues and
answers fou nd in the fields of paper, paintings, metals, and textiles conserva­
tion. If there a re any regrets in my starting the movement toward specia lty
groups [one] is that it tends to polarize us and to move us away from i mpor­
tant i n formation foun d i n other areas of specialization.
S i nce that begi nning in Delaware, other conservation programs have
become involved in the conservation of photographs. Extremely useful infor­
mation has also come out of R I T and Ottawa. Also, after my early years
teaching in Delaware, apprent ices h i ps have proven i n my pract ice to be an
excellent avenue for t ra i n i ng if the right student can be fou n d . But in the
encl, I bel ieve that conservators are not made at gradu ate programs, or i n
apprenticesh ips, or si mply beca use one wants to be on e . Essential i n forma­
tion is gained in graduate progra ms and appre nticeships, but Conservators,
in the fu ll sense that term implies, are made through an ongoi ng, u nstint­
ing and practical relationship with objects. Thi s is i n fact the pri nciple
under which the graduate progra ms were fou n ded. \Ve still have the need
P a rt V I I D E V E L O P I N G C H I T E H I A

for more knowledge, for better tech n iques, and for a more mature practice
of conservation.
By now you are wondering what a l l of this has to do with " developing
treatment criteria in the conservation of photographs,'' which is the title of
my talk. Let me b l u ntly state that it has everyth i ng to do with it . A conser­
vation treat ment, after al l , begins with the conservator i n whose hands l ie
the object, and the commitment, knowledge and skills that he or she bri ngs
to that object. No dou bt, the cliche is true, it is the object that makes its
own demands on the conservator. But to recognize and meet these demands
req u i res of the conservator the fol lowing qual it ies.
First, a conservator m u st have love and respect for the work of art. It
is much more than a "challenging object" or the possi b i lity of a " neat t reat­
ment," or a good research p roject. A photograph is after all a work of art,
an object of h istorical i mportance or of sentimental attachment. In spite of
all the photographs that l have handled, I stand i n awe at the photographic
i mage and the process that c reated it . I t is still amazing to me that such a
t h i n layer contains so much i n formation , so many disti nct areas of light and
shade, and that i n those areas is so clearly expressed the i n tent of the pho­
tographer who created it, and the period of history i n which it was created .
I t is still possib le for me to j u mp with private joy at the beauty of the work of
art which has been entru sted to my hands.
Second, a responsible conservator m u st have in-depth knowledge of a l l
aspects of the work of art. Recognizing t h a t what is before y ou is an albumen
print, as i mportant as that is, is but a small part of what you ul t i mately need
to know. You need to know the artistic temperament and h istoric environ­
ment i n which this photograph was c reated . You need to know the technical
elements that brought it about, its chemistry, and the materials that were
u sed in the photographic system. You need to know the manner and style i n
wh ic h photographs of t h is period were presented. And y ou will constantly
need to be in formed of how these photographs deteriorate . Tha nks to J i m
Reilly and Klaus Hendriks, w e are begi n n ing t o do that.
Th ird, to u nderstand all aspects of the work of art you need to do more
than read, you need to see. Studying one albumen print, or even ten, does
not tell you everything you need to know. I consider myself l uc ky to have
worked with two major collections in my ea rly years, The Libra ry of Congress
and the George Eastman H ouse. These extremely varied and rich collections
were the stage set on which everyt hing that I have done in p hotography had
its begi nni ngs. New York's many fine and comprehensive collections added
what I lacked i n depth . At every opport u n i ty my i n tention was, and still is, to
observe and to d iscern by the simple act of seeing. \i\ lhen studying a photo­
graph you need to keep in mind what are the succi nct qualities that deserve
c l ose exam i nation: process, tonal ity, su rface character, presentation and the

588
 Reading 62 O R R A C A

relationship of one photograph to the magn itude of a photographer's work

or to the breadth of the accomplishments of a period of h i story. All of these
qualities will give you i mportant c l ues as you decide on what treatment, if
any, the object req u ires.
The s u m total of what I have said adds u p to that body of i n forma­
tion that is absolutely necessary for you as a conservator to have before you
i ntervene in a photograph, or for that matter in any other artistic or h istoric
work-connoisse urship.
Now that we have fi n al ly arrived at treatment p lease al low me to ma ke
some points that will help c larify what I need to say later.

1 . Treatment is at the core of our profession. There are other fields;

archivists, conservation scientists, collections management, researchers, and
c u rators. They each play their i mportan t and u nique role i n the world of a rt
and h istory. Bu t it is entrusted to the Professional Conservator the privilege
and responsibility to i ntervene, or not to i ntervene, in the phys ical wel l being
of the objec t .
2 . In t h e conservation o f artistic a n d h istoric works, n o t every treat­

ment that is wanted is possible, not every treatment that is possi ble is neces­
sary, and not every treatment that is necessary is advisable.
3. The term "mass conservation" is, to say the least, a diffi c u l t term. It
conj ures u p i mages of survival rates, or casualties from "friendly fire ." Truly,
d i ffere nt col lections have d i fferent req u i rements. Archival col lections, clue
to their nature and size, requ i re d i fferent approaches. But the treatment cri­
teria for objects that come i n such quantities should be no less informed,
no less respectfu l , and no less ethical than the criteria we apply to a single
object of va lue. vVhen we p lace conservation concerns on the same level as
q uantity and money then we prostitute our profession and we place at risk
the objects entrusted to our care.
4 . I take my work very seriously, but I do not take myself very seri­

ously. I ncl ivicluals that place such i mportance on what they can do for the
object seldom consider the appropriateness of a treatment. The decisions
that I make for an object are an i n fi n i tesimal part of its total history. What I
wa nt to assure is that at another poi n t in h istory another conservator may be
able to intervene without being h i ndered by what I have clone.

As a conservator, many tasks are asked of you . They come i n different

forms, written orders, verbal commands, and actual threats. These requests
can provide you with an excel lent opport u nity to educate you r c u rator
or client. You can share with them you r knowledge of the object, the i ntrin ­
sic characteristics th at are i mportan t t o preserve, and you ca n e l icit from
them useful i n formation. You can also discuss with your c l ient your know!-
Part VII D E V E L 0 P I 'I G C 11 I T E H I ,\

edge of that type of treatment being requested. I t is i mporta n t that you also
consu l t with other con servators in the field. But when i t comes to a decision
as to what treatment, i f a ny, should be carried out, then the responsibi l i ty is
strictly i n your hands. It is you who m ust be true to you r sense of ethics. J ust
because an object is brought to a conservator for t reatment is not in itself
sufficient reason to do the t reat ment. The Nuremberg excuse that you were
fol lowi ng orders is not sufficient to the responsi ble conservator. He or she
has the responsibility to i n form, to d iscuss, to pursue possible avenues, but
also he or she has the respons ibility to say no when their treatment cri teria
m ight be violated . This is not to say that I pe rsonally experience a l i ly white
practice. I have somet i mes succ umbed to the l u re of an exc i ting t reatment
or to the press u re of an overzea lous client, and i n retrospect I wish I had
not carried out some treatments. But the pa i n t hat these have cau sed me
strengthens my determi nation to re main true to my treatment criteria.
Developing criteria for the co nservation of photographs is a difficu lt
task. I t assumes that I have the expe rtise to do it, and that it can be clone.
The d iffic u l ty of establ ishing t reat ment standards for the profession has
always been that: 1 . As l have said previou sly, every object has its own chemi­
cal and physical makeup, its own enviro n mental history, and its own needs.
Success with one sal ted print does not guarantee success with another salted
print, even by the same maker. 2. \1Ve as conservators are a stu bborn and
opinionated lot. When the A I C Board lasl year presented a revised code of
eth ics to the membersh i p, they could hardly expect the fury that t h i s engen­
dered. Often our ju dgment is formed through d iversi ty of tra i n i ng, variety
of t reatment experiences, and just sheer w i l l . Seldom can we genera l ize
prod uct ively.
And now, to rei n force some of the crucial issues I 've ra ised, perhaps
it is best i f l present you with some of the objects that have come into my
studio, state what condition brought t hem to me, explain to you what I could
deci pher or already knew about the object, and what was my decision as to
t reatment. I do not hope that you will agree with each of my choices, nor
am I foo lish enough to t h i n k you wi l l . What I hope is to start you clown the
road of analytical t h i n ki ng that will lead you to develop you r own treatment
criteria i n the conservation of photographs. After all, it i s not as i mportant
what I say as what you do.
 R e a d i n g 63

MARK H . M c C o R M I C K- G o o n HART

The Allowable Temperature

and Relative Humidity Range
for the S afe Use and Storage of
Photographic Materials ( I 996)

This essay by Marh J-1 . McCorm.ich-Goodhart (see also Heading 40) defines
environ n1.ental standards for the long-term care of 11hotographic materials.
As illustrated in Part JI (Si.lver Image Structure and Stability), the negative
effects of h igh ten1.perature and relative h umidity on photographic ·materials
have been recognized since the nineteenth century. However, i.t was the essen­
ticil research in the late twentieth century at institutions such as the Image
Permanence Institute, the National B u reau of Standards, the Public Arc hives
of Canada, and the Smithsonian Institution that led to a c learer understanding
of the effects of adverse environmental conditions on photographic materials
and to the establishment of appropriate preservation standards. McCormich­
Goodhart 's careful consideration of chemical and physical stability issues and
his attention to the practical effects of time-out-of- (cold) storage are es11ecially
notable. Jn this reading, McConniclz-Goodhart accentuates the importance of
a sensible preservation plan for photographic collections and the need to cou­
ple the benefits of cold storage with careful planning for exhibition, handling,
and scholarly use.

Introduction

Conventional photographic materials typically make use of a gelatin b i n der

in one or more coating layers. Although the fi n al i mage may be formed by
s ilver particles, organic dyes, or o ther i norganic components, gelatin has

NIABK H . M c C0111v1 1 c 1<-GooD HAHT, "The Allowable Temperature a n d Helative H u m id i ty

R ange for the Safe Use a n d S torage of' Photographic Materials," Journal ()f the Society of
A1·chivisls 1 7, no. 1 ( 1 996): 7-2 1 . © 1 996 Society of Arc hivists. Reprin ted by permission of
t he publisher, Taylor & F rancis Ltd, http://www. i n formaworld.com.

591
Part VII D E V E L O P I N G C H I T E H I A

been the material of choice for more than a century to serve as the i mage
b inder. Additional gelatin layers are also frequently presen t . They fu nction ,
for exa mple, as anti-curl layers or overcoat layers which improve abrasi o n
resistance and/or alter su rface textu re. The gel a t i n layers are adhered to
a common support layer, and substrates made of acetate, polyester, glass,
paper, or polyethylene resi n coated paper have fou n d widespread u sage. The
p hysical structure of the majority of twentieth centu ry photographic fi l m s
and prints c a n b e u n derstood b y considering combinations o f these basic
m aterial components. The enviro nmental guidelines for safe use and stor­
age of photographic m aterials presented in this paper are applicable to and
inclusive of t hese comm o n varieties of fil ms and papers.
Temperature and relative h u m i d ity recommendations for p hotograph i c
materials should b e cited wit h two purposes i n m i nd-safe storage and safe
use. Room temperature and moderate h u m i di ty ranges are more suited to
the requ i rements of frequent access and comfortable use and d isplay while
low temperature storage is i mportant, i ndeed necessary i n most cases, to
m eet long-term preservation objectives. O n ly temperature and h u m i di ty
levels that reasonably g uarantee both chemical and p hysical safety can be
al lowed, and the materials m u st not be harmed by cycl ical conditions which
occur as they move between storage and use.
Chem ical stability is often determined by accelerated aging tests,
and natura l aging has confirmed how photographic m aterials degrade over
time. The physical stab i l i ty of photographic i mages has been more diffic ul t
t o quantify. Anecdotal evidence c learly i n dicates t h a t wide e nvironmental
cycles, notably changes i n relative h u m i d ity, cause p hysical damage to p ho­
tographs. The d amage appears as cracks, Raki ng, and permanent warpage
or curl. J ust as chemica l stabi l ity data i ndicate an allowable range, p hysi­
cal stabi l i ty m ust also be ensured by l i m iting the cha nges i n temperature
and relative h u m i di ty to a n al lowable range. A t h reshold u nder which m i n i ­
m a l phys ical damage t o m useum objects wil l occur has previously been sug­
gested but not determi ned. 1 Cautious experts h ave t herefore advised aga inst
repetitive temperature and relative h u m i d ity cycles of any magnitude. Most
p hotographic storage spec i ficat ions have l i kewise been establ ished with very
tight tolerances for environ mental cyc l ing; modern HVAC systems can be
speci fied to control within ± 1 °C and ± 2% R H .
U n fortunately, spec i fications with narrow tolerances are d i fficult to
m ai ntain and make the frequency of access versus the p hysical well-being of
the collection a problematic issue. One cannot freel y move items to and from
storage and display without violati ng tight environmental tolerances unless
the storage and user e nvironments are perfectly matched. Th is is very often
not the case, particu larly when cool and cold storage cli mates are used. The
situation leads to u ncertainty for the collection manager. How many t i mes a

592
 Reading 63 M C C O R M I C K - G O O D H A R T

clay, a month, or a year can one violate the temperature and h u m idity toler­
ances? How many large environ mental fluctuations equate to more frequent
b u t smaller fl uctuations? I ronically, what if a safe threshold rea lly does exist
under which no physical damage occurs in response to cha nges in tempera­
ture and relative h u m i di ty? These questions req u i red new research and a
scientific method for their resolution. 2

The Yie l d Point as a C r i terion for Physical Damage

M aterials do i ndeed have a threshold for damage as we l l as a reversible

range of elasticity. As long as the materials are not subjected to environ­
mental cycles which cause them to exceed their true yield point, the m ateri­
als behave elastically. The materials will expand and contra c t in response
to temperature and RH f luctuations i n a completely reversi ble manner. N o
permanent plastic deformation or fracture occurs. P lastic deformation leads
to micro defects such as d islocations and voids which u ltimately cause
cracks, and clelamination of composite l ayers. M any materials tolerate exten­
s ive amou n ts of plastic deformation before actu ally breaking. H owever,
very brittle materials have little ability to plastically deform before fracture
occurs. Total physical safety for a l l material components can t herefore only
be guaran teed when all materials remain elastic and are not taken beyond
their yield point.
M a ny tests have been conducted i n our laboratory i n order t o deter­
mine the true yield poin t of a wide variety of cultu ral materials. The yield
point may be viewed as the change in length which must be exceeded i n
order t o cause a permanent change in length o f t h e material. The yield
point therefore defines the l i m i ts of ex'Pansion or contraction which are
ful ly reversible. The test m aterials h ave included gelat i n , polyester, cellu­
lose, cel l ulose acetate, cellu lose n itrate, hide glues, oil, a l kyd and acrylic
paints, natura l and synthetic varnishes, metals, woods, hair, epoxies, and
many others old and new. A surpri s i ng result was that the true yield point is
very consistent. M aterials yield at approximately 0.4% elongation (or sl ightly
greater if they have experienced strain hardeni ng). By using the conserva­
tive val ue of o-4% elongation for yield and with knowledge of thermal and
h umidi ty coefficients of expansion, the temperature and R H changes nec­
essary to reach the yield poin t can be conservatively esti mated . The worst
case resulting from environmental changes occurs when a materials is fully
restrained from movement in a u n i axial direction . Physical restraint occurs
by con fining materials i n frames or other fixtures and also arises when one
material is bonded to other materials which possess different coefficients of
expansion. The composite layers of a p hotograph are an excellent example
of the latter case. A gelatin emulsion adhered to glass, for example, will try

59 3
Part VII D E V E L O P I N G C ll l T E ll l tl

to shri n k i n response to a decrease in relative h u m idity, b u t i t is prevented

from doing so by the glass su bstrate which remains rigid and u nresponsive
to the c hange in h u m id i ty. Thus, restra i n i ng a layer so that i t is not free to
shrink or expand in response to environ mental changes induces stresses that
are just l i ke mechanically applied stresses.3 [ n other words, stresses cau sed
by changes in temperature and relat ive h u midity have the same effect on
a n object as mechanical stresses C�lllsed by physical han d l i ng (e.g., bend­
ing, stretching, etc . ) . With this knowledge, rational l i m i ts for temperature
an d rel ative h u m i dity can be calcu lated i n order to ensure the total physical
safety of the p hotograp hic materials.
The material properties research has also shown that old "embrittled "
materials have the same or even greater degree of e lasti c i ty as new materi­
als (due to stra i n harden ing effects). H owever, they often Jose the ability
to plastically deform compared to new materials, so breakage occurs more
readily. Hence, we perceive old materials as more delicate to handle safely,
and this is true because any deviati on outside the elastic regi me more eas­
i l y causes breakage. Nonethel ess, the allowable environmental cycle which
keeps the aged and em brittled material within the elastic regime is the same
as or greater than when the material was new. To s u mmarize, emrironmen­
tal fluctuations that do not cause the materials to exceed their yield po int,
whether they occur seasonally, daily, or hourly, will induce only expansions
and contractions that are tota lly reversible, and p hysical stab i l i ty is ens u red .
Photographic films or papers will respond to the environmenta l cyc le by
changing dimension and degree of curl, but in a reversible fashion that does
not cause permanent deformation or fracture.

C hemical and Physical Stabi l i ty

From the preceding discussion, it is clear that allowable ranges of temper­

ature and relative h u mi dity must i ncorporate knowledge of both chemical
stability an d p hysical stab i l i ty. Because the p hotographic m aterials consid­
ered i n this paper contain ge latin and very often other hygroscopic materials
as well , the relationship between moisture content withi n the photographic
materi a l and the material's physical and chemical sta b i lity is very i mporta nt.

The Moisture Content Eqwilibriw1n State in Photographic Materials

P hotographic materials are very hygroscopic i n nature. Even when fi lms and
papers are "dry" t hey hold significant quantities of water absorbed withi n the
molecular structure. The moisture content of the gelatin layers are of partic­
u lar s ignificance. For example, at 22°C and 50% R H , gelatin contains nea rly
1 4% by weight of water. At 22°C and 80% RH (above Tg) the gelatin contains

594
 R e a d i n g 63 M C C O R M I C K - G O O D H A R T

approx imately 20% by weight of water. M o isture content i s a vital parameter

relating to the chemical and physical stabi lity of p hotographic materials, but
i t is not conveniently measurable, and rel ative h um id ity has l argely come to
be viewed as a n equally mea n i ngfu l i ndicator. Whi l e the moisture content of
gelatin and other hygroscopic materials l ike paper or triacetate fi l m base is
i ndeed related to re lative h u m id i ty u nder enviro n menta l equ ilibrium condi­
tions, the equ i libri u m state is also i n fluenced by temperature a n d pressure as
well . General ly, pressure can be treated as a constant val u e (standard atmo­
spheric pressure), but the i n fl uence of temperature cannot be overlooked
if enviro n mental guidelines for storage and use a llow large exc ursions from
ordi nary room temperature. The relationship between temperature, relative
h u m idi ty, and moist u re content in photographic gelatin at standard atmo­
spheric pressure has recently been i n vestigated." I t is not a simple u nvarying
relationship, but a usefu l general izati o n can be made. I n order to mainta i n
a constant level of moisture content wi t h i n the gelatin e m ulsi on t h e rela­
tive h u m id i ty must be red uced 3-4% for every 1 0°C drop in temperature. It
fol l ows that maintaining a constan t relative h u m i d i ty set point as tempera­
ture is lowered will lead to additional water absorption wit h i n the gel atin
layers. Other hygroscopic polymers such as c el l ulosic materi a ls and acetate
fi l m supports display similar behaviour. This p hysical behaviou r has i mpor­
tant i mplications for cold storage of photographic m aterials which wi l l be
addressed in more detail later in this paper. However, proper compensation
for the effect is achieved by i ncorporating gradually decreasing RH level s
i nto t h e environmental guidelines as t h e temperature level at w h i c h t h e pho­
tographic materials are kept is reduced.

T71e Importance of t he Glass Transit ion Temperature of Gelatin

The glass transition of gelatin is essential to the very existence of modern

p hotography and is also oF great significance to the p reservation of photo­
graphs. M aterial scientists define the glass transition temperature of a m ate­
rial as a d iscontinu ity in the rate of c hange of specific vol u me with respect
to the change in temperature. ln practical terms, gelatin's glass transition is
eas i ly recognized by changes in phys ical handling characteristics. Below a
critica l glass transition temperature (T) , gelatin i s a hard, tough polymer.
Above T�, gelatin becomes "soft and rubber- l i ke" to the touc h . The gel atin
changes from a sol id state to a gel state. This distin ctive change in material
properties is not as s harply defined as the melting point of a crystal (e.g.,
ice to water) but i s d iscreet enough for a speci fi c temperature value to be
assigned to the transition. H ygroscopic polymers l i ke gelatin have an i n ter­
esting and very im portan t additional feature, i .e., Tg changes sign i ficantly
with moisture content. The higher the moisture content of the gelatin the

595
P a rt VII D E V E L O P I N G C R I T E ll l A

lower the temperatu re needed to make the gel a t i n c hange from the solid
to the gel state. Th is behaviour is what makes gelatin u n i quely suited to
photography. When water is used to wet the gelatin emulsion the moisture
content i nc reases dra m atically, and the glass transition i s now crossed at a
temperatu re value below ordinary room temperature. Photogra phic process­
i ng then becomes possible. Above Tg the gelatin is h ighly permeable and
a l lows chemical agents to rapidly d i ffuse through the gelatin and reach the
s ilver hal ide c rystals.
U n fortu nately, gelatin does not have to be ful ly wet by liquid contact
in order to reach the gel state at room temperature. Very dry gelatin has a
Tg val ue above 200°C, but Tg drops to room temperature (22°C) when the
gelatin has equilibrated to a relative h u m id ity condition of approximately 70
to 75% R H . At 30°C, gelatin needs on ly to be i n equilibrium at approximately
65% R H . The hard, d ry, protective properties of the gelatin coat i ng d isappear
and are replaced by the h ighly permeable gel state properties. Th us, photo­
graphic e m ulsion l ayers are very sensitive to environmental conditions which
often occur i n the rea l world. The low glass transition temperatu re of gelatin
at h igh RH is a fu ndamental reason why high h u m i d ity i s so detrimental to
p hotographs. E m u lsions which stick together and to other objects, changes
i n emu lsion su rface appeara nce (ferrotyping), and serious mou ld damage are
d i rect consequences of gelatin stored above i ts glass transition temperature.
The oxidation-reduction process on si lver image particles which ca uses the
appearance of "si lver m i rrori ng" is also promoted by gelatin in the gel state.
S i lver ions can diffuse away from the origi nal si lver site more readily because
the diffusion rate is m u c h h igher when the gelatin b i n der layer is function­
i ng i n the gel state rather than i n the solid state. \Vith regard to proper e nvi­
ronmental storage after a photograph has been properly processed and d ried,
it is extremely i mportant to avoid environmental conditions that will cause
the ge latin to cross its glass transition and revert to the gel state.

The Dom inant Role of Temperat u re i n Chem ical Stability

H igh relat ive hu midity is clearly a critical para meter when i t cau ses the gela­
tin to exceed Tg under normal use or storage conditions. Additionally, h igh­
to-low relative h u m i d ity cycles lead to h igh mechanical stresses that cause
permanent plastic deformation, and eventua l ly cracki ng or delamination of
the coati ng layers. Thus, for reasons of both chemical and physical safety
the practical range of relative h u m id i ty at ord i nary room temperature lev­
els must be confi ned to within moderate l i m its, approximately 35-60% R H .
C hanges i n R H withi n this h umi d ity range can affect the chemical stabi l i ty
of photographs by a factor of two or three . S i m il arly, l i mi ts for temperature
can be establ ished . Conventional photograph ic materials are physically tol-

596
 R e a d i n g 63 �1 C C 0 H �1 1 C K -G 0 0 D H A H T

erant of wide temperature cha nges, so the l im i ts primarily reflect consid­

erations of chemical stability. Temperatures above 25°C can be ruled out
si mply because chemical stability is com pro mised too much. Temperatures
lower than -25°C are not u sefu l because further ga ins in chemical stabi l i ty
cannot be real ized i n practice. The time a photograph spends out of cold
storage and i n use at room temperature ulti mately l i mits the overa ll level of
chemical stability, no matter how stable the materials are i n storage .5 The
i n f l uence of " time out of storage" will be addressed in a fol lowi ng section
of this paper.
\Vithin the temperature range from 25°C to -25°C reduct ions in tem­
perature can slow aging rates more than 1 00-fold. Si nce many photographic
materials wil l suffer serious levels of deterioration i n less than a century
u nder room temperature keeping conditions, the dramatic i mprovement i n
chemical stability afforded by low temperatu re storage is esse n t ial for the
long-term preservation of photographic materials. Although low temperature
storage i mposes practical constraints i n terms of access to the collection,
the i m portance of preservation m u st outweigh the restrictions on i m mediate
use for photographic collections of permanent h i storical va lue.

The Al lowable Range of Temperature a n d R e lative H u mid i ty

Based on the preced i ng discussion of chemical and physical stab i l i ty, the
a l l owable combinations of temperature and relative h u m idity can be plotted
graphically as shown i n Figu re 1 . Region 111 s hown in Figure 1 represents the
combinations of temperature and relative h u m idity which are both chemi­
cally and physically safe for conventional photograph ic materials (i.e., fi l ms,
plates, and papers with gelatin e m ulsions). Points A, B, C, and D delineate
the boundary conditions for region # 1 , and as long as the photographic mate­
rials rem a in in equ i libri u m anywhere within this region, a n in herent degree
of physical and chem ical safety is ensured. Region #1 also compe nsates for
the re lationship between gelatin's moisture content and relat ive h u m idity
as temperature is decreased . Moreover, any combination of relat ive hu mid­
ity and temperature located with i n region # 1 can be i nvoked at any time.
There are no l i m itations on the frequency or magn itude of the environmen­
tal cha nge as long as the change does not fal l outside region # 1 . In order to
remain within region # 1 cold objects must be warmed with care, otherwise
temporary deviations cau sed by temperature-induced moist u re gradients
and dewpo i n t conditions may occur. Often , a simple vapour barrier provides
adeq uate protection from d i rect condensation. Also, it is i mportant to note
that cold materials can lose a significant amount of their abi l i ty to plasti­
cally deform, so any add itional mechan ical stresses appl ied to them over
and above the a l lowed environ mental stresses may cause cracks or breakage.

597
 P a rt V I I D E \ I E L O P l i\ G C H I T E H l tl

30 30

\rg
20 20

.'!_ 10 ° .'!_ 10
Q)
A=25 C, 35% R H
�
� �
:s
2 ° 2
"' B=25 C, 60% R H
0
Tg \
0 °
Q) Q)
C= - 25 C , 40% R H
0. ° 0.
E D= - 25 C , 20% R H

� - 10 �
I-"'-
- 10

Tg ':
- 20 - 20
D

- 30 L---'--'-''-'--����__,__� - 30 ���'-'---'--����__,__��
0 1 0 20 30 40 50 60 70 80 90 1 00 0 1 0 20 30 40 60 70 80 90 1 00
Relative humidity (%) Relative humidity (%)

Figure 1 Figure 2
Hegion // 1 : chemically and physically saf'c. Hcgion /12: h igh Hcgi o n s //3 and //4: chemically safe but not physicrilly safe.
risk because gclalin crosses T;: .

Carefu l hand l i ng and packagi ng which prevents di rect bendi ng and Aexing
of the photographic materials is therefore h ighly recommended when work­
i ng with photographic materials in cold temperatu re storage.
Environ mental Fl uctuations within region # 1 are physically safe because
they only cause expansions or con tractions of the photographic materials that
are elastic and reversible. For exa mple, photographs which have contracted
or curled slightly due to a change in temperature and RH from 20°C/55%
R H to 5°C/30% RH can be reversibly expanded ( u n c ur led) si mply by return­
i ng once agai n to 20°C/55% R H . These elastic d i mensional changes may be
j udged by some people to have subtle aesthetic implications, but the changes
are not permanent. The perceived differences in appearance are a matter of
preference, not risk. Region #2 i ndicates the combi nations of temperatu res
and relative h u m idity that wi l l cause ge latin to exceed its glass transit ion tem­
perature. Photographic materials will not reta i n high quality very long u nder
these conditions. The clashed l i ne representing the threshold for Tg in Figure 1
has been plotted u si ng data for glass transition ava ilable at this t i me.6 Some
small refi nements may be u sefu l i n the futu re as Tg is probably affected to
some degree by chemical hardeners, hu mectants, and other add it ives that
might i n A uence moisture content of the gelatin. H owever, the temperature
and relative h u m idity combinations identified as region #2 should serve as a
reasonable approxi mation for most photographic emu lsions.
Regions #3 and #4 have been added to the gra ph in Figure 2 . These
regions rep resent combinations of temperature and relative hu mid ity that
are actually safe for photographic materials with regard to chemical stab i l i ty,
but not totally safe with respect to physical safety. I n particular, region #3
 R e a d i n g 63 ,\ J C C 0 H � I I C J( - C 0 0 D I I t\ Jl T

leads to a level of chemical safety that is h igher overall than region 11 1 , the
primary reco mmendation. Unfort u nately, i n order to move i nto regions //3
and //4 and then retu rn at later ti mes to environments within region # 1 , pho­
tographic materials may experience a fu ll environmental cycle that causes
some plastic deformation to occu r. Plastic deformation may be u navoidable
at t imes because rigorously stayi ng wi t h i n the bou ndaries of region // 1 may
not always be possible. H owever, it is i mportant to real ize that an environ­
mental gu ideline which seeks to avoid any plastic deformation (by staying
within region # 1 ) i s very conservat ive. Plastic deformation often docs not
cause visually detectable problems, and ph otographs are man ufact u red to
withstand considerable amounts of such treatment. For example, the act of
wet process ing causes one cycle of plastic deformation s i nce the wet e mul ­
sion must pass th rough extremes i n region /12 before it reaches an equ i l i b­
rium d ry state preferably within region // 1 . Print Flatten i ng by heat and/or
pressu re is another example of deliberate plastic deformation. Th us, photo­
graphic materials can generally tolerate a significant amount of this kind of
physical cyc l i ng, but their in herent physical stab i l i ty cannot be guaranteed .
H e nce, exc u rsions outside region # 1 are to be avoided. Such exc u rsions may
lead to physical damage sooner or later depending on the type and age of the
materials and the frequency and magnitude of the exc ursions.
Because chemical stability increases as temperature and re lative
hu m idity are decreased, some conditions within region // 1 render more
chemical sta bility than others even though region # 1 was selected to pro­
vide at least a m i n i m u m l evel of chem ical sta b i l i ty and the ful l measure of
physical stability. As i ndicated i n Figu re 3 , the c hem ical stabil ity i n region #1
increases as the c hosen environment is shifted from poi nt 8 (least c hemically
stable) to point D (most chemically stable). The relat ive chemical stabi l i ty
factor correspondi ng to each conto u r line was calcu lated from Arrhenius test
data on the dark fading characteristics of typical c hromogen ic colour dyes.7
The relative stability has been normalized i n Figure 3 to a va lue equal to 1 .0
for a standardized m u seu m envi ronment at 2 1 °C/50% R H . Although these
contour li nes were derived from c h romogenic dye s tability data, they serve
as a general guide to i l l u st rate how d i fferent combinations of tempera t ure
and relative h u m idity affect the chem ical stabi l i ty of photographic materi­
als. The trend holds true because the act ivation energy for the dark fad i ng
of ch romogenic dyes and their response to R H is s i m i lar to other i mporta nt
aging mechanisms i n photography, notably acetate base degradation. As an
example, the coordinates 5°C and 45% R H fa l l c lose to the contour line with
a va lue equal to 1 0. A photograph stored at 5°C/45% Rl-1 is about 10 ti mes
more chem ically stable than when it is in use at 2 1 °C/50% R H . Although
the contour li nes a re approximations, the t rend c learly demonstrates how
cool and cold storage i m proves the lo ngevity of photogra phic materia ls.

599
Part VII D E V E L O P l 'I G C R I T E H I A

H owever, the practical va lue of a spec ific combination of R H and tempera­

t u re values depends on a n u mber or cons idera t ions besides c hem ical stabil­
ity. These considerations i nclude ease of access, h u ma n comfort d uring use
of the collection materials, and the cost or constructing and maintaining a
part icular environment. The collections manager ·s decision i s fu rt her com­
pl icated by operating costs that are not a simple Fu nction of eit her tem pera­
ture or h u m i d ity.
To s u m marize, all combinations of tc111perat u re and relative hu mid ity
located within region #1 have sign ificant va lue to photograph i c conservation.
The logic beh in d region #1 is to provide a range of conditions that can be
used i n terchangeably to enha nce chc111 ical sta bility, provide convenient use
or d isplay conditions, and simultaneously protect the materials fro111 physical
da mage. C learly. the best way to balance preservation and exhi bition needs
is by mainta i n i ng two d i stinct but physically safe c l imates, one to i mpart
su perior chemical stabi l i ty in storage, t he other to ensure a reasonable level
of che111 ical stability during use.
Once aga i n , consider what happens to cold-stored objects that are to
be used at roo111 te111 perature. They can 111ove safely i n the reco111 111ended
zone as often as is des i red. There arc no l i mits to the frequency and magn i­
tude of the environmental cha nges within this allowable zone. 1-l owever, fa i l­
ure to keep a vapour barrier in place or to ra ise the temperature slowly can
cause excessive h u 111 idity, even wa ter condensation, on a collection object
that is in itially in cold storage and then re111oved to a war111er user environ­
ment. The 111icroc l i 111ate at the su rface of the object then deviates from the
boundary conditions set by region ti 1 even if the new d isplay enviro n 111ent to
which the object has been tran sferred is i n Fu II compliance with region /1 1 .
Care must therefore be taken not t o ra ise temperatu res too rapidly. Thermal
shock is not the issue. Photographic materials can not be h eated or frozen
fast enough u nder any ord i nary c i rcu mstances to cause p hysical damage
which can be attributed to thermal shock. The prob l e m of rewarm i ng a cold
object is strictly one of making sure t hat a temperature gradient does not
cause 111oisture migration and condensation. Co111 mon sense should prevail
when re moving photograph i c 111atcrials Fro m cold storage in order to guara n­
tee that the m icrocl i mate at the su rface of the photograph i c material is not
deviating from the allowable hu mid i ty range.

JV /icrocli11wle £.ffe ct:s in. Sealed Paclu1ges

Ca refu l inspection of Figure 1 reveals that the allowable R H range For cold
te111perature storage (e.g., l i ne CD) is sl ighliy narrower and s h i fts to the left
compared to the h u m id i ty tolerances at roo111 temperature (e.g. , line A B ) .
A s d iscussed previously, a lower R H level must b e established at low tern-

600
 R e a d i n g 63 M C C O H M I C K - G O O D l l 1\ H T

peratu res 1 11 order to retai n the same moisture content level which exists
in ge latin at room temperature. Th is is a natural consequence of the way
the gelatin equilibri u m moisture content changes i n response to changes i n
temperature a nd relative h u m id ity. Th e narrowing of the RH ra nge is due
to convergence a s the R H val u e d raws closer to its l im iting value of zero .
A h u m id i ty control led cold storage vau l t complies with the al lowable tem­
perature and RH range i n a stra ightforward way. For example, the relative
h u m idity at -25°C can be fixed or al l owed to fluct uate anywhere between 20%
RH and 40% R H . Objects so stored may be safely returned to room tempera­
t u re, up to 25°C for example, and their moistu re content is then in eq u i l i b­
rium with a specific R H va lue somewhere withi n the 35% to 60% Ii i-I range
denoted by line AB. Because it is assu med that photographic materials which
a re kept i n h um idity-control led roo ms can "breathe " and thus equ i l i brate to
the surrou nding RH leve l, any changes i n moisture content will be safe ly l i m­
i ted to the environmental boundaries of region llr provided that storage and
user environ ments comply with the temperature and h u m idity val ues estab­
l ished by region # 1 . But what about sealed or quasi-sealed packages that do
not a l low the object to eas i ly equ i l ibrate to the surrou n d i ng environ ment?
Very few p hotographic materials are actually stored as individual items on
a shelf. Most photographic malcrials are hou sed in envelopes or packages
and fu rther packed with other items in larger boxes or contai ners. Practi­
cally speaking, very few photographs are truly allowed to "breathe . " The con­
tainer or package that houses them isolates the c l i mate i nside the box from
the conditions of the su rrou nding environment. An important m icroc l i mate
is thus established i nside the box for extended periods of time before mois­
t u re equili bration with the surrounding environment can occu r. \i\lhile tem­
perature eq u i l i briu m may be reached in hours, moisture content equ i l ibrium
may take days, months or even years to be reached, especially at cold tem­
peratures where diffusion rates of water vapou r are significa n tly lower. The
typical package of photographic materials is usually moderately or densely
packed with photographic items. Consequently, l ittle free a i r vol u me exists
compared to the amount of materials inside the package, and the microc l i ­
mate i nside t h e package is actually "over buffered" by t h e moisture absorp­
tion capacity of the photographic materials.8 Because the moistu re content
i nside the package remains essent i a l ly constant for long periods of t i me, the
R H in side the sealed package au tomatical ly sh i fts within a matter of hours
in order to mainta i n the natural equ i l ibrium state which m u st exist between
moisture content, relative h u m idity, and temperature. Thi s behaviour is i l l us­
t rated in Figure 4 by the poi nts 1-1 and I . A box of p hotograph ic prints sealed
at 23°C/58% RH (point 1-1) will fol low the environmental path ma rked by the
a rrow i nside region fl 1, and at - 1 8°C the microclimate inside the package wi 1 1
stabil ize a t approxi mately 40% R H (point T ) . U pon retu rn to a steady slate
 Part VII D E V E L O P I N G C H I T E H I A

30 30

K
Above
20 20
Above Tg

/5 10
Tg
G 10 °
H=23 C , 58% R H
E:' E:' 2
I= - 2o c , 40% R H
'
::> ::>
li1 0
' li1 0 '
J= - 2o c, 65% R H
Q) Q)
Q_ Q_ °
E E - 10
K=23 C , 78% R H

� �
- 10

- 20 - 20 J
- - - - - - - - -' F '.
- 30 ������� - 30 �����
0 1 0 20 30 40 50 60 70 80 90 1 00 0 1 0 20 30 40 50 60 70 80 90 1 00
Relative humidity (%) Relative humidity (%)

Figure 3 Figure 4
Contour lines ol' equ ivalent chemical stability. i\ l icroclimalc response or confined photographic films and papers.

condition at 23°C the package will aga i n have an i n ternal relative humid ity
of 58% R H (point H ) . The correlation of decreasi ng RH with decreasing tem­
perature is counter-intuitive to many people because t hey are often fam i l iar
with psychometric charts which show that RH will i ncrease i n a vol u me of a i r
as t h e temperature is decreased. Psyc hometric charts identify t h e moisture­
holcling propert ies of air and do not take i n to account the moisture-buffering
pro perties of hygroscopic materials l i ke gelatin, paper, and acetate film base.
A poten tial risk also ari ses from the microclimate charac teristics of
packaged photographs. I f a sealed package slowly e qui librates over time to
a s urrounding enviro n ment outside of region II I , it drifts out of compliance
with the recommended range. Consider l i ne J K i n Figure 4 . At point J , the
- 1 8° C/65% RH level is an environ ment typical of conventional freezers. I f a
h igh moisture barrier package was stored i n a conventional freezer with an
i n itial microcli mate at poin t I , b ut the package leaked slowly over time, it
wou l d eventually come to equilibri u m at point ] . This new microc li mate is
stil l very safe for the object in terms of chemical stability as can be inferred
from the contour l i nes in F igure 3. H owever, upon warming to room tem­
perature the packagi ng material keeps the extra moisture trapped i nside,
and the package warms to point K (approxi mately 23°C/78% R H ) . Once the
glass transit ion temperature is exceeded, the ge latin's abil i ty to over bu ffer
the package disappears. I t now behaves more l ike a saturated salt sol ution
attempting to properly buffer the environment. I-Je nee, the path denoted by
the arrow connecting points J and K takes a sl ight bend as the glass transi­
tion is crossed. The fi nal equi l i bri u m R H will depend, of course, on the pro­
port ion of ge latin to t h e proport ion of other hygroscopic materials located i n
the package, b u t the general trend i l l u strated by the path between poi n ts J

602
 R e a d i n g 63 1\1 c c 0 n 1\ I I c I ( -c 0 0 I ) 1-1 A n T

and K is va l i d . The room temperature condition at po int K is risky for both

mould damage and emu lsion blocking because i t is above Tg . This risk can
be removed by ve ntilating the materials as soon as possible after warm-up.
Nevertheless, one plastic deformation cycle has now happened, and it is bet­
ter to avoid this type of exc u rsion altogether.

Ti me Ou.I: of Stomge

The contour l ines in Figu re 3 show the remarkable i n f l uence of te mperature

on the l i fe of photographic materials u nder steady-state conditions. 1 -J owever,
the practical benefits of cold storage environ ments are ul t i mately l i mited by
the com bi n ee! effects of storage a n d use. \Vhen photographs are removed
from cool or cold enviro n m e nts and then used at ordi nary room te mperature,
the agi ng rate returns to the rate established by the temperature and relative
h u m i dity levels in the user enviro n ment.9 The chemical kinetics of the stor­
age and user e nvi ronments must be proportionately weighted to acco u n t for
the amount of time that a photograph spends i n each environment. A precise
i n tegration wou ld sum up the effects over discreet [sic] time i nterva ls a t every
temperature and H H va lue enco u n tered. A si mpler but very instructive eval­
uation can be made by assuming just two steady-state environme nts, one for
the user condition and one for the storage area. This eval uation is reported i n
Table 1 . The values listed i n Ta ble 1 i n d i cate t h e effect ive chem ical stability
that can be real ized after the stability in storage has been compensated for
the t i me that an object is o u t of storage and i n use. Table 1 assu mes that the
re lative stab i l ity is equal to 1 .0 when the object is i n use. f\s i n the contour
l i nes in Figure 3 , a relative stability val u e equal to 1 .0 is obtai ned at 2 1 °C/50%
HI-I or other comparable enviro n ment. 'Ti me out of storage'' is t reated as
a n amortized amount of time. i . e . , an average n u m ber of days per year that
a n object is out of the storage vau l t and i n use. For example, a colour pri nt
t hat h a s been exh i bited for six months at room tem perature after spe nd ing
20 years i n cold storage has spe n t approxi mately g days per yea r out of stor­
age. Table 1 demonstrates that as the chemical stabil ity in the storage area
i m proves, the t i me out of storage becomes i n c reasi ngly more i n fl u ential. For
exa mple, i n Table 1, row 2, t he chemical sta b i l i ty of the storage environment
is identical to t he user environment, so the t i m e out of storage has no effect.
I n row 1 , t he s torage environment is worse than the user environment so
the re lative chemical stabi l i ty actually i n c reases as the materia ls spend more
and more time i n the user environment. A very stable storage emriro n ment
is shown i n row 8. The materials are 500 times more sta ble i n storage than
on d isplay. However, small amounts of time o u t of storage now d ramatically
affect the overa ll level of chemical stability that can be ach ieved i n practice.
If a photograph is removed from this exceedingly stable storage enviro n ment

60..,
_,
 Part VII D E V E L O P I N G C R I T E B I A

Table 1
Relat ive chemical stabil ity va l u es compensated for "t i me out of' storage. "

Time Out of Storage ( Days per Year)

Relat ive Chem ical
Sta b i l i ty in S torage 0 2 5 10 30 60 1 80 36 5

0.5 0.5 0.5 0. 5 0.5 0.5 0. 5 0.5 0. 7 1 .0

1 .0 1 .0 1.0 1 .0 1 .0 1 .0 1 .0 1.0 1 .0 1.0

2.0 2.0 2.0 2.0 2.0 1 .9 1.8 1 .7 1 .3 1.0

+o 4.0 +o 3· 9 3.8 3-7 3. 2 2. 7 1 .6 1 .0

10 10 10 10 9 8 6 4 2

30 30 28 26 21 17 9 2

1 00 100 79 65 42 27 II 6 2

500 500 211 1 34 64 34 12 6 2

IOOO 1000 268 1 54 68 35 12 6 2

Note: Relative chemical sta b i l ity of' display environment normc_il ized to 1 .0.

Table 2
Combi ned effects of' temperatu re, relative h u m i dity, a n d " t i me out oF storage" on chemical stability.

Time Out of Storage ( Days per Year)

Storage Temp RH 0 2 5 10 30

m u seum standard 21 50 1 .0 1 .0 1 .0 1.0 1 .0

cool, h igh RH 15 56 1 .9 1 .9 1 .9 1.8 1 .8

cool, low RH 15 32 +1 4.0 3· 9 3.8 3·3

cold, h igh R H 52 9 8 8 7
cold, low R H 28 18 16 15 12 8

Freezer, high R H -20 42 3 80 I 2..� 61 33 12

freezer, lo\\' R 1-1 20 21 6 90 145 66 35 12

Note: Relat ive chemical stability o f displa�· environment normal itl'd t o 1 .0.

and retu rned to room temperature use at 2 1 °C/50% RH for 1 , 2, 5, 1 0, or

30 clays per year out of storage, the re lative chemical stab i l i ty d rops to 2 1 1 ,
1 34, 64, 34, and 1 2, respectively.
Table 2 illustrates the contrasting nature of the R H and the time-out­
of-storage parameters. At tem perature levels close to ordinary room tem­
perature the relative h u m idity in the storage area is i mporta nt while the
ti me-ou t-of-storage parameter is i nsign i ficant. For example, cool storage at
1 5°C and 56% R H approxi mately doubles the chemical stability compared
to the museum standard condition of 2 1 °C/50% R H . Redu c i ng the RH in
the storage area to 32%, the lowest al lowable, increases the relative stability
even fu rt her to a \'alue of 4 . Under these cond itions, Table 2 shows that up
 Reading 63 M C C O R M I C K - C O O D ll A B T

to 30 clays per years o u t of storage does not seriously a lter the effectiveness
of the cool, low RH storage environment. On the other hand, at low storage
tem pera tu res the ti me-out-of-storage parameter is more i mportant than R H .
Consider the h ighest and lowest al lowable R H values i n freezer storage. Five
clays per year out of -20°Ch 1 % R H storage yields an effective re lative stabil­
i ty va lue of 66 while the same time out of -20°C/42% R I-I storage yields a
va l ue of 6 1 . For low temperature storage, the ti me-out-of-storage para meter
domi nates. R I-I has now become i rrelevan t with respect to chem ical stabi l i ty
and is essential only for physical stability.
Although it is perhaps s u rpri s i ng to see how much stabi lity i s given
u p with even small amounts of time out of storage, low tempera ture stor­
age is still far more effective in preserving a photographic col lection than
room temperature storage at low RH. The col lection manager must ca refu l l y
choose h o w much t i m e materials spend outside o f t h e storage va u lts. I f a n
object is always out o f c o l d storage, no chemical stability benefit c a n accrue.
On the other hand, i f an object is never al lowed to leave cold storage, any
useful purpose for the col lection seems u n l i kely. Cold storage i s a vital pres­
ervat ion strategy, b u t it m u s t be complemented by careful plann i ng for exhi­
bition, handl i ng, and schol arly use.

Summary and Conc l u s i o n s

Several concepts have been discussed 1 11 this paper w h i c h are i nterrelated

and con tribute to the overal l physical and chemical stability of conventional
photograph i c materials. An u nderstanding of these concepts led to the a l low­
able range of temperature and relative h u m i d ity which i s s hown in Figure 1 .
The recom mendations and the u nderlying concepts are i ncorporated i n
Figure 1 a n d they also reflect a basic col lect ion management strategy. Th i s
strategy can be s ummari zed as fo l lows.

1 ) Lower temperatures and to a lesser extent lower relat ive hu mid­

i ty levels i nc rease chemical stability. M axi m u m chemical stabil i ty i s
achieved a t su b-zero temperatures (-20 t o -25°C ) .
2) Low temperatu re storage is essential for t h e long-term preservation
of photographic col lections because most photographic materials do
not possess enough i nherent chemical stability to survive i n good con­
d i t io n for decades at ord i nary room temperature.
3) The opti m u m way to preserve photographic materials i s to mainta i n
two distinct but physically safe c l i mates, one t o i mpart superior chemi­
cal stab i li ty i n storage, the other to ensure a reasonable level of chemi­
cal stabil i ty d u ri ng use or exh ibition. Carefu l management of the time
spent on exh i bit ion versus time in storage i s crucial to this approach .

605
Part VII D E V E L O P I N G C R I T E 11 1 A

4 ) The safe upper l i m i t for use and display of photographic material s

is approxi mately 25°C at 60% R I-I . P hysical safety is ensured between
35% and 60% at 25°C .
5) Keep processed p hotographic materials below the glass transition
temperature of gelatin at all t i mes.
6) As temperature i s reclucecl, the relative h u m idity set poi nt in the
storage area should be adjusted downward to compensate for the
moisture absorption capacity of the gelatin ( i .e ., by red ucing the R I- I
approxi mately 3-4% R H per 1 0°C d rop in temperature ). The relative
h u m idity within sealed packages adjusts au tomatica lly cl ue to the
moisture buffering propert ies of the photographic materials i nside t he
package provi ded that the package does n ot contain excessive free air
vol u me.
7) Cold p hotographic materials should be warmed slowly and mois­
ture vapou r barriers u sed i f necessary i n order to avoid transient h igh
h u m idity conditions and water condensation prob lems at the photo­
graphic em ulsion's su rface.
8) Cold stored film s , papers, and p lates must be handled with great
care because any m echa nical forces that exceed the elastic l i mits a re
more l i kely to cause brittle Fracture.

The temperat u re and relative humid ity recom mendations in t h i s paper con­
sider both chem ical and p hysical stabil ity to safely exh i bit and store photo­
graphic materials. Conservative scientific protocols were used to establish
l imits of physical safety. The great majority of conventional photographic
films and papers use gelatin as the i mage binder layer coated on a l i m ited
va riety of base materials, i . e . , glass, polyester, paper, res i n-coated paper, and
cel l u lose acetate su pports. For t hese photographic media, all set points and
environmental A u ctuations that occ ur within the ranges defined by region
1/1 i n Figu re 1 arc permissible. The Frequency and magnitude of the cha nges
within this region do not contri bute to any p hysical damage. Thus, the rec­
om mendations are Aexible, particularly i n regard Lo m ixed media col lect ions.
Two basic environments are necessary, one for storage and one for use. The
desired chemical stabi li ty is established by select ing and managi ng these two
enviro n ments. Lower tempera t ure in the storage environment is critical for
preservation pu rposes because the chem ical stabil ity benefits derived from
low temperatu res cannot be obtai ned d u ri ng room temperature use or exh i ­
bition. A su itable storage environ ment c a n b e determ i ned b y estimating t h e
l i kely a m o u n t of t i m e out of storage, selecting the des i red level of effect ive
chemical stability from Table 1, and identifying t he corresponding storage
parameters requ i red to meet the goal from Figu re 3. Ch oosi ng the appropri­
ate level of chemical stability clearly depends on other issues as wel l . These

606
 R e a d i n g 63 M C C O R M I C K - G O O D H A R T

i nc lude but are probably not l i mi ted to ease of access, type and existing con­
d i t ions of the collection materials, and the costs of constructing and operat­
ing the n ecessary storage an d d isplay environ ments.
Most existing s torage standards published to date recommend con­
ditions that typically fal l somewhere within the allowa ble ra nge show n i n
region /1 1 . Some sta ndards have exploited part o f region ft3 . Region 11 3 i s
chemically very safe b u t may lead t o physical problems over time caused by
accu m u lated damage from p lastic deformation as objects move to and from
conditions of storage and n ormal use.
The al lowable environmental range and A uctuations give the collection
manager latitude to develop a sensible preservation plan for photographic
collections. Nonetheless, the recom me nded range i s not s u fficiently wide
enough to e l i m i nate the n eed for h u m idity and temperature control. With­
out some type of mechanica l controls, many regions of the world will not be
able to achieve fu l l comp l iance for a safe exh ibition environment, and the
tremendous advantages of low temperature storage wi l l be mi ssed.

Aclmowledgments

The author thanks Dr. Marion F. M ecklenburg, Dr. C ha rles S. Tu mosa, and
Dr. David Erhardt for c lose collaboration with the author on the chemical
and physical properties of cultura l materials. The research and recommen­
dations presented i n this paper wou l d not have been possible without their
assistance.

N otes a n d References

1 Carry Thomso n , The M11se11111 Environlll. e nt ( B u t terworths, London, 1978).

2 M. F. Meckle n b u rg and C. S . Tumosa, "The relationship or externally
appl ied stresses to environmentally induced stresses," Fiba Composites i n
l nfraslruc/. u re, Proceedings of t he First. lnl.ernat.ional Conference in. Cmnposit. es
in l nfrastruct 111·e (Tucson, Arizona, 1996, pp. 956-71 ) ; M. F. M ecklenburg,
C. S. Tumosa and M ark H. M cCormick-Goodhart, "A General Model Relating
Externally Applied Forces to E nvironmentally I nduced Stresses i n M aterials,"
Materials Issues in Art and Archaeology 1 \1, vol . 352 ( 1 995), pp. 285-92; M. F.
i\l l ecklenberg, C . S . Tumosa and M ark H. i\l l cCormick-Cood hart, "A general
method for determ i n i n g the mechan ical properties needed for t he computer
analysis or polymeric structures subjec1ed lo c hanges in tempera t u re and
relative h u m id ity," Materials Issues in. Art. and Archaeology I l l , vol . 267 ( 1 992) ,
pp. 337-58; David E rhardt, M . F. Mecklen b u rg, C. S . Tumosa and Mark 1 - 1 .
McCormick-Goodhart, "The determi nation of allowable R H f l u ctuations,"
\Vest.em Association for A rt Come111at io11 News/et.fer, vol . 1 7, no. 1 ( 1 995),
pp. 1 9-2 3 ; M . F. Mecklenburg, Mark H . M cCormick-Good hart and C. S.
Tumosa, " l nvcsl igation into t he deterioration of pain tings and photographs
Part VII D E V E L O P I N G C H I T E H I A

using computerised model l i ng ol' stress development," Journal of 1 l1 e Au1erica1l

/11Sl i l u / e of Collserva l io n , vol. 55, no. 2 ( 1 994) pp. 1 53-70: M . F . i\ l ecldenburg
and C. S. Tumosa, · · computer mode l l ing ol' the effects of temperature and
relative h u midity on stresses in the layers ol' c u ltural materials,"' Proceedings of
Ifie A l l1ericr111 Che111ical Society, Polyu1eric /\ laterials Sciellce aml Ellg i1 1eerillg,
vol . 68 ( 1 993). pp. 226-28; David Erhardt and i\ 1 . F. J\ l ecklen b u rg, "' Helat ive
h u midity re-exa m i ned." Preve1 1f il'e Co11serFalio 1 1: Practice, Theo1y w1d Rese(lrch
(prepri nts ol' the contributions to the Ottawa Congress, 1 2- 1 6 SepL. 1 994, The
I nternational I nstilute for Conservation ol' 1 1 istoric and Artistic v\lorks),
pp. 32-38; 1\ 1 . F. i\ l ecklenburg, C. S. Tumosa and David Erhardt , "'St ruct u ra l
response o f wood panel paintings t o changes i n ambient relative h u m idity,"
i n Proceedillgs of t he Pai11tecl \!\loocl Syu1posi1111l ( 1 995, in press): 1\ 1 . F.
i\ l ecldenbu rg. C. S . Tumosa and J . D . E rlcbachcr, "'i\ l echan ical behaviou r
ol' artists' acrylic pai nts under equ i l i brium conditions,"' Poly111er Prepril l ts :
Poly111ers ill M 1 1se111lls Sy111pos i 1 1 1 1 l, vol . 35, no. 2 ( 1 992), pp. 297-98; i\ 1 . F .
i\ l ccklcnburg, "'Some mechanical and physical properties of gi lding gesso,"' i n
D. Bigelow. E . Cornu, G . J . Landrey a n d C . V a n H orne (eds.). G ile/eel Wood
Collsen•atio11 nllcl HistOIJ' ( Sound Vic\\' Press . Conn . . 1 99 1 ) . pp. 1 63-70:
1\ 1 . F. 1\ l ecklenburg . "'Applied mechan ics ol' materials i n conservation
..
research . i n P. 13. Vandi,·er . J . Dru1.ik <llld G . S . Wheeler (eds. ) . /\laterials
lsrnes ill Art all(/ Archaeology 11 ( 1\ l aterials Hesearch Society, Sympos i u m
Proceedi ngs, vol . 1 85, Pittsburgh, 1 99 1 ) . p p . 105-22: 1\ 1 . F. i\ l ecklcnburg a n d
C. S . Tumosa, ''Appl ied mechanics i n pai n t i ng conservation," in PreprilllS of
I he 1 9 9 1 Alb11c/ 11erq·11e Collfere11ce of' 1 /1e A u1erica11. I nsl.itute for Consen1a/ irm;
M. F . Mecklenburg, "The effects ol' at mospheric moisture on the mechanirnl
properties or col lagen u nder eq u i l ibrium conditions,"' Preprinls, Si.Ylee1 l l f1
A 1 1 1 1 1 1al J\!leet i11g. 'T'he A 111ericr111 I 11sl ii 11le .fur tl1e Co11servat-ion of Historic a11d
A rl islic \ \ 101·hs (Was h i ngton . D.C . . 1 988), pp. 23 1-4+ \\/. S . Hong. J. Wang.
1\ I . F . 1\ l ccklcn b u rg and P. Albrec h t . "'Effect of" moisture on tensile behaviour
..
of" adhesives . l 1 1tematio11al S ) 111posi11111 Oil tldl1esit'ely Bo11ded J o iIlls; Tes li llg,
A 11alysis a11d Desig11 ( AST1\ 1, 1 986): 1\ I . F. i\ l ecklen b u rg and P. A l b recht,
"' Effect of" h u m i d i ty on behaviour ol' polymeric materials, "' Poly111er prepri 111s.
Divisioll of Poly111er Che111isl1y, A111erica11 Cl1e1l1ical Society, vol . 26, no. 2
( 1 985), pp. 247-58.
3 IV I . F . M ecklenburg and C. S. Tumosa, "The relationship oF externally
applied stresses to environ mentally ind uced st resses," i n Fiber Co111posiles
i11 lllfrasl rn c / 1 1 re ( N S F and t h e U n iversity ol' Arizo n a , 1 996, in press); i\ I . F .
1\ l ecklenburg. C . S . Tumosa and i\ lark I I. r-. lcCormick-Goodhart. "'A general
model relat i ng externally appl ied forces lo environmentally induced stresses i n
materials, J'v lale rials lss11es in A ri a11d A rchaeology JV. vol . 352 ( 1 995).
..

pp. 285-92.
4 J\ l ark 1-1. i\ l cCormick-Goodhart . "'i\ l oi s t u re content iso l i nes of gelat i n and t h e
i m p l ications for accelerated a g i n g tests and l o n g term storage o l ' photographic
..
materials . }011mal of l uwgi11g Scie11ce wul Tecl1 11ology. vol . 39 . no. 2 ( 1 995) .
pp. 1 57-62.
i\ l ark 1-1. r-. l cCorm ick-Goodhart and 1\ I . F . i\ l ecklcnburg, "'Cold storage
enviro n ments for photogra p h i c malerials,"' I. S . & T. Final Pmgra111 aml
Ad1,c111ce Pri l l l i11g of Paper S 11 111 111aries, I. S . & T. ,j.61.h Annual Co11fere11ce (The
Society !'or I magi ng Science and Tec h nology, Spri ngfield, VA, 1 993).

608
 R e ad i n g 63 M C C O R M I C K - G O O D H A R T

6 M a rk H . :V l cCorm ick-Gooclhart, "' Moisture content isol i n es and the glass

transition of photographic gelat i n ; t heir signi ficance to cold storage and
accelerated aging" Hesea,.ch. Tech. n.iques i n Photogrnphic Conservatio n ,
Proceedings from the Copenhagen Co11feren.ce (The Hoyal Danish Academy of"
Fine Arts. School of Conservation, M ay 1 995), pp. 65-70: P . I. Hose, '"Gelatin,"
in T. H . James (eel . ) , The Tl1eory of Photographic Process (4th eel . , M ac m i l l a n ,
1 977), c hapter 2 .
7 G. T. Eaton, The Co11se111atio11. of Phot.ogrnphs ( Pu b l ications no. F-40, Eastman
Kodak Co., Hochester, New York, 1 985).
8 M ark H. McCormick-Goodhart, '"Moisture content isoli nes of ge latin and the
impl ications for accelerated aging tests and long term storage of photographic
materials," Jonl"nal of I 111agi11.g Science c m d Technology, vo l . 39, no. 2 ( 1995),
pp. 1 57-62.
9 M ark H . McCorm ick-Goodhart a n d M. F. M ecklenburg, '"Cold storage
environ ments for photographic materials," I. S. & T. Final Progra JJJ and
Advance Pri n t i ng of Paper S 11 JJl lJJ(J ries, I . @. & T 46tlt Aniwa/ Con.fere11ce (The
Society for I maging Science and Technology, Spri ngfield, VA, 1 993).
 R e a d n g 64

DEBRA H E S S NORR I S

Surface C leaning of Damaged

Photographic Materials : C urren t
Practice a n d C oncerns ( 1 999)

Debra Hess Norris (see also Reading 6 1 ) has t;aught and mentored graduat;e
st udents in photograph conservat ion at; the Wi n terthu r!University of Dela­
ware Progra 1n in Art Conservation since 1 982. Conservation is a 1?rofessi.onal
fi.elcl wi.th a rich oral tradition. wherein. in.clivicluals are trained to t reat objects
t h rough ap1?renticesh.ips, i. nternsh:ips, a nd int;ense graduate-level st udies
foc used on. h.an.cls-on experiences u nder t he gu idance of profession.al conserva­
tors. For t;his reason i t is often. diffi c ult to fi.ncl formal ·wri t ings that clocmn.en. t.
t he most ro·iitin.e an.cl basic forms of conservat ion. t reat ment. In. this reading,
Norris p rovides a thorough i.n.troduction. t;o J?erhaps the most comnwn. t reat­
ment tech n ique for all conservation disciplines: su 1face cleaning. /-/ere, she
evaluates several conventi.onal siuface cleaning methods, addressing their rishs
and benefits. J n doing so, Torris p resen ts nu merous factors a nd ethical prin­
ciples that m ust be considered prior to conservation. treat ment.

M any photograph ic print and negative materia ls are routinely su rface

c leaned in fine art, historical, and a rch ival collections throughout the
world . 1 In doing so, the conservation professional must first thorough ly eva l­
u ate these material s for the possibil ity of physical or chemical damage, as
we l l as pe rmane n t a lteration i n su rface re f l ectanc e or gloss. Severe struc­
tural damage to a bi nder layer and the propensity for abrasion may pro h ibit
d i rt remova l . C racked, c ra zed , and f laking bi nder layers, h ighly ferrotyped

D E B H/\ H ESS No 1 rn 1 s, .. S u rface C leaning or Damaged Photograph i c Materials: C u rrent Prac­

tice and Concerns," in Care of Photogrnp/1ic Movi 11g / 111age & So1mcl Collections, ed. S u sie
Clark ( Leh igh, v\lorcestershire, U K: The I nstit ute of Paper Conservation, 1 999), 96-1 0 1 .
Reprinted by permission o f the I nstitute o r Conser\'ation, London, U . K. , www.icon.org.uk.
 Reading 64 H E S S N O H R I S

surfaces,2 additional coating layers, original retouching, i mage deterioration

(especially silver mirroring) and mould damage pose particular challenges.
These attributes increase the l i kelihood of damage during cleani ng. Dam­
aged and deteriorated secondary supports may Further complicate cleaning.
S i milarly, u n mounted print materials m ay be adversely affected by aqueous
methods. M a ny conservators are greatly concerned about the s hort-term and
long-term effects of residual su rface c lean ing materials that may remain on a
photograph's surface including eraser particu lates and solvents.
M a ny conservators concl ude that the risks associated with su rface
c leaning general ly outweigh the benefits. The removal of an original vei l of
grime from a photograph's su rface may reveal severe stai n i ng previously h id­
den by dirt. Striking a balance between reducing grime and m i n i m izing stain
may prove challenging.
S urface c leaning tec h n iques are intrusive treatme n ts, and conserva­
tion professionals must proceed with caution. Conservators genera l ly agree
that some photographic materials, i n cluding degraded salted and plat i n u m
prints, severely cracked, Aaki ng, and mou ld-damaged materials, and many
contemporary colour processes, cannot be safely c leaned. Furthermore,
many note that evenly dispersed layers of dirt and grime are often not ter­
ribly disfigu ri ng.
The decision to surface clean a photograph is frequently based on the
des i re to i mprove visi b i l i ty of the i mage or enhance image quality and i n for­
mation. Reduction of surface soil can reveal subtle detai ls in a print as well
as i ncrease i mage contrast, tonal ra nge, and su rface reAectance. Conserva­
tion professionals may surface c lean photographic m aterials in an attempt to
i mprove their s hort-term and long-term stab i l i ty, red u c i ng the potential for
damage by removing extraneous materials that may be abrasive, hygroscopic,
or otherwise (chemical ly) degradative. Particulates and accretions may p hysi­
cally weaken bi nder layers and paper supports. Pollutants may contain reac­
tive sulph ides and c h lorides that wi l l oxidize metal l i c i mage particles. Fi nger
oils are in herently acidic and can etch binder layers over time.3 Surface
c leaning may also prevent redeposition of soi l ing materials onto adjacent col­
lection materials. Wel l-cared-for col l ections demonstrate committed stew­
ardsh ip and can compel patrons and staff to observe handling guidel i nes.
Consc ientious working methods and sound judgment m ust guide treat­
ment activities. At a ll ti mes, techn iques and materials that will have the least
adverse effect m ust be employed . Treatment procedu res are often d ictated
by the type and condition of the photograph. The training and background
of i ndividual conservators will also d i rectly i nAuence treatment choice. 4
This survey revea ls that many photograph conservators commence
treatment, regardless of process, with soft brushes.5 After that point, con-

61 1
Part VII D E V E L O P I N G C R I T E H I A

servation t reatment tech ni ques and protocols vary widely but typically con­
sist of the use of su l p h u r-free vi nyl erasers (block or crumb led, with strong
opin ions favouring each type of eraser), and/or solutions and admixtures of
distilled water, ethanol, and acetone as wel l as, to a lesser extent, chemi­
cal sponges, sal iva, and commercial cleaning prod ucts including ch lorinated
hydrocarbons and solutions of ethyl acetate.6 Su ccessive campa igns using
combinations of these m aterials, carefu l ly monitored u nder h igh magni fi ca­
tion, are often u sed .
Photograph conservators use cotton swabs, pads, or balls to del iver
solvent m ixtures to d irty p hotographic su rfaces. Preferences vary greatly,
although many argue that the use of cotton ba l l s or pads prevents su rface
abrasion. Cotton swabs, in contrast, provide the conservator with greater
contro l . Some conservators selectively clean damaged su rfaces, rem oving
d i rt from the h ighlights only. Such approaches may alter the original tonal
balance and adversely affect the photograph's long-term stability.
Where present, secondary supports may also requ i re su rface clean i ng.i
In doing so, photograph conservators must ensure that the extent of clea n i ng
for both su rfaces ( t he p hotograph and its mount) is simi lar and that a n aes­
thetic "balance" is estab li s hed. Clean i ng of a d i rty mount only, for example,
may cause the photograph to appear more grey or discoloured i n comparison.
\l\ihi le the quality of the treatment must not be governed by the qual­
ity or va lue of the object, a photograph collection's size and condition will
most definitely affect the final t reatment methodology. J n these situations,
skil led and carefu l ly supervised conservation tec h n icians may be trai ned to
assist i n clea n i ng collections. In doing so, protocols and procedu res must be
establ ished by the photograph conservator. The use of tech n i cians is con­
sidered most desirable when collections are large and somewhat homoge­
neous. At al l ti mes, it m ust be clearly u nderstood that surface cleani ng is not
routine.

Specific Methodology and Current Practice

As noted above, many p hotograph conservators employ varied su rface clean­

i ng tech niques dependent upon a photogra ph's type and condition. Ques­
t ionnaire responses repeatedly emphasized the vital i mporta nce of repeated
testing. Decisions regarding surface clean i ng m u st be preceded by close
exam ination (3oX is often requ i red) and spot testi ng, as necessary. Spot test­
i ng must be clone in both the low-de nsity and h igh-density i mage areas to
provide reasonable comparison.
Anticipated problems, ge neral observat ions and approaches, and treat­
ment practices used by respondents for selected processes are s u m marized
below.8 l nnovative or u nique treatment approaches a re also i n cl uded where

612
 Reading 64 ll E S S N O H H I S

appl icable. All photographs, regardless of type, req ui re carefu l exami nation,
analys is, and testing prior to treatment.

Salted Paper and Platinum Prints

1. The binder, which typ ica l ly affords some protection against abra sion
although it can itself be quite sensitive, is not present in these pro­
cesses: the image particles are embedded i n the uppermost layers of
the photograph's paper su pport, and su rfaces are exceed ingly delicate.
The abrasive nature of cotton swabs and other dry clean i ng methods
may make them u n s u i table for su rface cleani ng, parti cularly in i mage
areas. The risk of losing plat i n u m or s i lver i m age material and al tering
the paper/image s urface is s ignificant.
2. Al though the plati n u m i mage i s extremely stable (i t does not tarnish
or Fade), the paper su pport i s often em brittled and deteriorated owing
to the presence of residual i ron salts and acids as wel l as the catalytic
deteriorative effect of plati n u m metal on cellulosic fibres. Care must
be taken not to place u n necessary stress on a potentially brittle paper
support; the local i sed pressure of block erasers may be dangerous.
3. Some photograph conservators vary their treatment approach to plati­
num and sal ted paper prints, noti ng the finely d ivided and highly reac­
t ive nature of the salted paper's photolytic s i lver i mage. The short-term
and long-term effect of eraser residues m u st be considered .

Su111.ma ry of Treat ments Used by Responclen.ts

Vac u u m aspiration (for localised accretions) and soft bru shes arc most com­
monly used to remove su rface grime. Some conservators note that these
vul nerable materials cannot be safely cleaned . Erasers are used with great
caution and as a last resort, taking care not to d isturb image particles and
paper fibres. Conservators most frequently choose erasers made of polyvi nyl
chloride ( PVC) in the belief that the ageing an d chem ically reactive proper­
ties of' PVC are better than those of ru bber or vulcan ized vegetable oil fou n d
i n other erasers.
Owing to the fragi l i ty of these matte s u rfaces, se lective cleaning ( non­
i mage areas only) is often em ployed. G rated vinyl erasers are preferred owing
to their controllabi lity, alt hough some photograph conservators use tailored
vi nyl erasers locally. ( I n doing so, erasers are sculpted to fine points, and d i rt
and accretions are removed local l y by a tamping rather than rol l i ng action.)
Some conservators avoid su rface dry clean i ng tec hn iques for these vul ner­
able materia ls entirely, recommending bat h i ng in aq ueous sol utions as the
safest method to effectively remove embedded dirt, grime, and sta i n i ng.
Part VII D E V E L O P I N G C R I T E R I A

I n novative or Unique Approaches

Con servators generally agree on treatment approaches to these si ngle-layered

materials. No in novat ive or u n ique approaches were c u l led for these materi­
als from this su rvey. Treatment opt ions are lim ited.

Albumen Prints

1 . Albumen prints typically exhibit cracked and crazed su rfaces which

may trap d i rt and grime and/or be h ighly vul nerable. Aqueous meth­
ods may em bed dirt i nto cracks, making them appear darker and more
prominent, most especially i n non-image areas. The addition of etha­
nol to aqueous solutions i ncreases penetration and the probability of
dirt m igration. Once em bedded, dirt and gri me are virtually i mpossible
to remove. Research un dertaken by Messier and Vitale has demon­
stra ted that aqueous tec hniques of any kind may initia te and/or propa­
gate cracking in a l b u me n binder layers.9 Dry methods, which are often
abrasive in nature, can physically i nj ure a brittle su rface such as albu­
men, espec ially i f the cracks are severe. In addition, block erasers can
cause local burnishi ng (resul t i ng i n increased gloss) or stress crack­
i ng. Cracked and crazed bi nder layers are more l i kely to hold resid­
ual eraser part icu lates after t reatment providing a possible source for
future chemical attack i f the eraser is react ive.
2. The a l b u men binder and paper support are characteristically t h i n ,
a n d aqueous methods, especially those conta i n i ng ethanol, c a n i n i t i ­
ate sta i n i ng from discoloured and h ighly coloured mou n ted materials.
Ethanol-sol uble dyes or water-sol u ble decomposition prod ucts may be
leached o u t of the mounts and i n to the albu men print's paper support.
3. Aqueous methods may cause planar distort ion i n unmounted albu men
pri nt materials.

S u m mary of Treat ments Used by Respondents

Approaches lo the su rface cleaning treatment of t hese materia l s vary consid­

erably, although most conservators prefer soft brushes fol lowed by sulphur­
free vinyl erasers (cru m bs or block) and very sl ightly dampened swabs (water
or sal iva ) for severe d i rt and local ized cleani ng. 1 ° For damaged and cracked
su rfaces, many conservators prefer d ry methods such as d ry cotton swabs,
soft brushes, or carefu l ly manipulated tai lored erasers. (Conservators note
that a n u tmeg grater can be used effect ively to shape and clean block era­
s u re edges). In these i nstances, many conservators avoid ethanol solutions
 R e a d i n g 64 ll E S S � O H B I S

entirely, and others si 111 p ly do not clean severely cracked and crazed albu-
111en binder su rfaces.
Pre l i 111 i nary research u ndertaken at the \,\/intert h ur/U n iversity of Dela­
ware Progra111 in Art Conservation i nd icates that M agic Hub by Faber Cas­
tell and M ars Plastic by S taecltler effect ively remove dirt from the su rface
of albu men prints (thereby increasing gloss) but do not cause appreciable
physical da mage. Erasers 111ust be u sed judiciously and may be an i nappro­
priate choice when the su rface is severely clegraclecl . 1 1
I t should be noted that re111oval of d i rt from t hese su rfaces 111ay result
i n a su bstantive i nc rease i n gloss and reflectance. This change i n su rface
character should not be 111 isinterpretecl as damage caused by t reat111ent.

In novat ive or UniqHe Ap11roaches

So111e conservators note that su rface cleaning crazed albu111en su rfaces with
very d i l u te methyl cellulose solutions (applied with a soft brush or large
cotton swab) s uccessfully and control lably re111oves d irt while at the same
t i 111e "consol i clating" the cl isru pteel su rface and improving gloss. It may be
assu 111ecl that with th i s technique a t h i n layer of 111ethyl cellu lose is being
depos ited on the photograph.
Vulcan ized rubber sponges arc u t i l ized by a mi nority of conservators
to remove e111beclclecl d i rt fro111 al b u 111en su rfaces. 1 2 Conservators attest to
their controlla bility and ease of use. S u rfaces are cleaned evenly, without
abrasion or damage. These sponges are also used to clean secondary sup­
ports. Sponges can be cut into smal ler pieces, but cru mbs a re not eas i ly
for111ecl . Previous research performed by the Canadian Conservation I nsti­
t u te has shown that these sponges are 111ost co111111 o nly co111posecl of vulca­
n ized cis- 1 ,4-polyisoprene with calc i u 111 carbonate fi l lers. They also contain
trace a111ounts of oil, probably fro111 the 111 an u facturing process, and trace
elements (S , Al, S i, Fe, Zn , and Na) . u Photograph conservators 111ay be
concerned about the potential react ivity of t race s u l ph u r left behind i f the
eraser cru111bles during use and particu lates are not re111ovecl completely. 1 4
Likewise, oil residues and residual calcium carbonate may i n i tiate localised
degradation, increase the rate of d irt absorption over ti me, and i n h i b i t fut ure
conservation treatments.

C o l lodion C h loride Prints

1. The collodion b inder is pote ntially sol u ble in ethanol and a l most cer­
tainly soluble in acetone. These organic solvents should not be used
in the treatme n t of col loclion c h loride pri n t materials, matte or glossy.
Part VII D E V E L O P I N G C R I T E R I A

2. Collodion is very eas i ly abraded . Matte collodion surfaces are especially

sensitive. The u se of cotton swabs and dry cleaning methods that can be
abras ive in nature mu st be employed with great caution. H igh-density
areas are vul nerable. B lock vinyl erasers may local ly burnish the surface.
3. The baryta layer may swe l l or soften i n water. Hairline cracks i n the
collodion bi nder may absorb water preferentially when water i s applied
by swab or i m mersion . In this case, the cracks may appear darker,
and small (and often permanent) tidelines at the boun daries of these
cracks can result.

Summa ry of Treat1nents Used by Respondents

Aware of the fragile and v u lnerable nature of t hese pri n t materials, many
photograph conservators l i m i t their treatment to soft brushes, d ry cotton,
vinyl eraser cru mbs (or block in some cases) , and dampened swabs on ly
where necessary. Some conservators comment that they are more l ike ly to
u se moist swabs with glossy surfaces, which are typically considered to be
less prone to abrasion when compared with matte-surfaced prin ts.

I nnovative or Unique Approaches

Some conservators note preference for art gu m rat her than vinyl eraser when
cleaning col lod ion su rfaces. These erasers are sold in b lock form and com­
posed of vulcan ized vegetable oil ( factice) as wel l as chlorine, sulph ur, and
other additive s . "

S i lver G e latine Photographs

1 . The ge latine bi nder layer may swell, soften, or be sol u b i lized u pon expo­
sure to aq ueous solu t ions. Softe n i ng of the b inder l ayer m ay res u l t i n
a cha nge i n su rface reflectance. Carefu l a n d deliberate spot test ing is
requ i red. B i nder sensitivity to aqueous solutions must be ascertained.
Mou ld-damaged and l ight-da maged gelatine s urfaces are very sensit ive
to moist u re. Ferrotyped su rfaces (a relatively common p roblem from 1 9 1 0
t o 1 940) are also vul nerable t o aqueous a n d organic solve n t solu t ions.
2. Many si lver gelatine prints will exhibit s ilver m irroring (tarnish) i n

their dense i mage areas. S ilver mirroring (prim arily elemental si lver
and s i lver salts on the surface of the photograph) may be u n i ntention­
al ly red u ced by both wet and dry su rface cleaning methods.
3 . U n mounted gelatine-based materials may deform and exhibit a per­
manent increase in c u rl (owing to a hysteresis effect) upon exposure
to moisture.
 R e a d i n g 64 H E S S N O B R I S

Suinrnary of Trea t11ients Used by Respondents

For matte-surfaced photographs in good condition, photograph conservators

u t i l ize a wide range of materials and techniques. Approaches include the use
of soft brushes, vinyl erasers (both block and powdered) , vu lca n ized rubber
sponges, and swabs da mpened i n saliva, water, and mixt u res of water and
ethanol . 1 6 Ethanol is added in percentages of u p to 50% i n an attempt to con­
trol swe l l i ng of the gelatine binder layer. M any conservators agree, however,
that admixtures of d istilled water and ethanol do not clean as e fficiently as
d istilled water alone. In addition, some conservators are concerned that eth­
anol may dehydrate ge latine bi nders . Ethanol/water or sol u t ions of c hlori­
nated hydrocarbons (such as Kodak Fi l m C lea ner) may be used with caution
for the localised removal of greasy d i rt .
For ferrotyped su rfaces, m an y photograph conservators spot test rigor­
ously and l i m it their options to brushes, block erasers, or ethanol or acetone/
distilled water solutions (85: 1 5) . Con servators acknowledge that t hese high­
gloss su rfaces are exceedingly problematic and extremely react ive to conser­
vation treatment of any kind.
S i lver-m irrored su rfaces pose a considerable challenge, and many
conservators strictly l i m it t reatment to non-image, non-m irrored areas.
Conservators note that mirrored su rfaces may be eas i ly abraded and i rrevers­
ibly da maged. Many agree that these i mages should not be su rface c leaned
u n less reduct ion of mirroring is a speci fic treatment goal . In this case, water
and d i l u te solu tions of ammonium hydroxide may be u t i l ized (see d iscussion
of ammon i u m hydroxide below) .

T n novat i.ve or Unique Approaches

Some photograph conservators u t i l ize d i lute ammoni u m hydroxide solutions

( 0 . 1 % , pH 10) for clea n i ng gelatine su rfaces. These alka l i n e solutions may
da ngerously swell protein binder layers; such techn iques req ui re extreme
caution and care. Ammonia can com plex with and sol ubil ize si lver salts,
resulting in a decrease i n i mage density.

C ontemporary Colour Print M ateria l s

1. Contemporary colour print processes vary tremendously. Photograph

conservators must accurately identify photograph type, specific con­
struction, and condition such as chromogenic, si lver dye-bleach , dye
d i ffu sion-transfer, or dye- i mbibition prior to treatment.
2 . The presence/absence and/or reactivity of a gelatine su percoat may
d irectly i nfluence treatment options. I lfochrome (silver dye-bleach)
Part VII D E V E L O P I N G C H I T E il I A

prin t materials do not have a su percoat and they are the refore more
vulnerable to da mage from contact with cleaning solutions. The gel­
atine su percoat on some dye-di ffusion processes is very reactive to
moisture.
3. In al l cases, ext reme care must be taken that cleaning sol u tion s do
not penetrate t he gelatine b in der layers causi ng d i lution of the i mage
dyes. In c h romogen ic processes, alcohols, esters, ketones, and ethers
may swel l and penet rate ge latine binders, d isru pting the dye layers.
Azo dyes (silver dye-bleach processes) a re not adversely affected by
alcoho l . 1 7

Su1n 111ary of Treatments Used by Respondents

Many photograph conservators acknowledge that their experience with t hese

materials is l i mited. Loca l treatments ( re moval of fi ngerpri nts, etc . ) include
the u se of ethanol-dampened and water-dampened swabs, although, for the
most part, conservation professionals agree that the use of aqueous solutions
may be dangero u s. 1 8 Treatment protocols are genera l ly l i mi ted to dry cotton
swabs, s i l k squares (gently bu ffed on the surface), and prop rietary prod ucts.
In many i nstances, even these tec h n i q ues carefu l ly applied can resul t in a
fine pattern of li near scratches.

Gelatine Dry P late Negatives

1. With t hese materials, the most d i fficul t chal lenge is often a function
of quantity and not tec hnique. G lass plate collections are typically
large, req u i ring safe and efficient cleani ng techniques and procedures.
These collections are often cleaned by conservation tec h n i c ians and
vol u n teers who are c losely supervised by photogra ph conservators.
2. G lass plates must be exa m i ned carefu l ly for type and bi nder layer
condition (extreme care may be req u i red, and treatment options
wi l l be severely l i m i ted with mould-damaged materials) and glass
decomposition. Actively deteriorating glass su pports should not be
cleaned with aqueous sol utions. Care should be taken that adhesion
between t he bi nder layer and substrate is stro ng. Plates with flaking
emu lsions ( most com mon at the outer edges) must be handled with
extreme care.
3. Some gelatine d ry plates were varnis hed ( loca l ly or overa l l ) . This
coating may be adversely affected by aqueous and non-aqu eous sol u­
t i o n s. Carefu l spot testing is req u i red before emuls ion-va rnished or
emulsion-lacquered su rfaces are cleaned.
 R e a d i n g 64 II E S S N 0 H H I S

S-u 1n mai1' of Treatments Used l1y liespondents

Photograph conservators util ize d i ffe rent procedu res for clea n i ng the glass
side vers us emulsi o n side. Approaches also vary widely dependent upon con­
dition, and many conservators clean the glass side only. The glass side may
be clea ned with l ightly da mpened cotton swabs or balls. M ixt ures of distilled
water and ethanol (to faci l itate d ryi ng) are typically used.
Gelatine emulsions in good condition are clea ned first with soft
brushes to remove loose dirt and debris, sometimes fol lowed by proprietary
prod ucts or similar solven ts such as trichl oroethane. 1 9 These solutions do
not swell e mulsions and will effect ively remove greasy d i rt layers. Such sol u­
t i o ns ma y a ls o dissolve varnishes and coatings , resulting i n the formation
of a white haze on the negative's e m u lsion su rface. Spot testing is ma nda­
tory. After careful testi ng, some conservators will c lean ge lat ine em ulsion
su rfaces with distil led water/ethanol solutions. In doing so, bot h swabs a nd
cotton b a lls are used.
Mould-damaged surfaces are c leaned only with soft brushes and dry
cotton . The vast m ajority of conservators use only dry met hods when clean­
in g these types of materials.

Conc lusions

Photograph conservators strongly agree that s urface cleani ng research i s a

high priority. Cited research needs include b u t are not l i mi ted to the effect
of orga nic solvents on contem pora ry dye i m ages and stabil ity issues associ­
ated with the use of vulcan ized ru bber sponges, d i lute ammonia sol utions,
su rfactants, and sulphur-free PVC erasers. In addition, some conservators
Feel that new and practical approaches for addressing the treatment needs of
la rge collections mus t be developed .
J n novative approaches in which clea n i n g systems are designed spe­
c i fica lly for gelatin e or albumen layers merit further investigation. Carefu lly
prepared emulsions may al low the conservator to u se a n aqueous clea n i ng
system i n a more con trolled manner. Such e mulsions can be e ngi neered spe­
c i fically for differen t clea n i ng problems and s urfaces. The p l -I , ionic stre ngth,
percent water, and i n c lu s ion of a c he lator m ay be designed i nto the emul­
sion to opt i mize cleaning. 20
S u rface cleaning must be considered within a con t i n u u m of treat­
ment practice and preservation activities. Once cleaned, collections must
be housed i n good-q uality inert enclosures and be wel l protected from the
in trusion of dirt, dust, and pol l utants.
P a rt V I I D E V E L O P I N G C ll l T E ll l A

Acknowledgments

Special thanks to all photograph conservators who participa ted in t h is s u r­

vey and to past and presen t p hotograph conservation Fellows in the Winter­
t h u r/Un iversi ty of Delaware Program in Art Conservation for their i mportant
work and research on t h i s subject.

References a n d Endnotes

In this context, su rface clea n i ng may be dellncd as a mechanical or solvent­

based technique used to reduce soi l , dust, gri me, i nsect droppings, accretions,
or other s u rface deposits. S u rface cleaning may be used as a s i ngular
treatment tec h n i q u e , as one step i n a more comprehensive treatment protocol,
or as a p relude to other treatments (such as h u m i d i fication a n d/or aqueous
i m mersio n ) that may cause d i rt to set i rreversibly i n a photograph's b i nder
layer or s u pport.
2 Ferrotyping is a term com monly used in America to describe the permanent
a l teration in s u rface c haracteristics produced i n a softened h u m id gelatine
e m u lsion when it is pressed against a smooth su rface; usually plastic or glass.
Sometimes the e m u lsion will a l so partial l)' adhere to the adjacent s u rface.
3 K. H endriks and R u diger Kra l l , " F ingerprints on Photographs,'' Topics in
Pliot.ogra)'liic Preservation: American I nstil 111.e fo1· Co11sen•ation Photographic
Mcaerials Gro11p 5, ( 1 993): 8- 1 3 .
4 Review of t h e q u estionnaires reveals, f o r exa m ple, t h a t some conservators who
trained in E u rope u t i l ize solvent-based systems (such as trich loroethane) for
the removal of e m bedded d i rt and grime f'rom water-sensit ive s u rfaces. The
use of c h lorinated hydrocarbons i s severely restricted in the U n i ted States,
and therefore conservators trained in the U n i ted States rely more heavily on
d i s t i l led water/ethanol sol u tions and dry clea n i ng tec h n iques.
Although soft brushes are used rou t i nely, many photograph conservators
readily acknowledge that they do not effectively remove embedded d i rt and
gri me.
6 Com mercial products i nclude P E C - 1 2, Edwal Film C l eaner, and Kodak F i l m
Cleaner. Micro-FTI R a n a lysis of P E C - 1 2, manufactured b y Photographic
Solutions, I nc . , i n dicates that t h i s clea n i ng solution is primarily n-bu tyl acetate
with small amou nts of ot her acetates. Th is ana lyt ical work was conducted
a t the v\li n tert h u r Analytical Laboratory i n 1 992. I n formation a bo u t t h i s
commercial product i s proprietary, and it is l i kely t hat t he composition h a s been
a l tered over t i me. According to the M a terial Safety Data Sheet (revised 1 993)
f'or Edwal Anti-Static Color Film Cleaner (manu l'ac t u red by Edwal Scientifi c
Prod ucts), t h i s commercial c l e a n e r contains 1 , 1 , 1 -trichloret ha n e as we l l a s
s o m e non hazardous ingredients. According lo t he M S DS sheet ( prepared
1 989), Kodak Photographic F i l m C leaner contains 69% 1 , 1 ,2,trichloro- 1 ,2.2
t ri f l u o rethanc ( F reon 1 1 3 ) and 3 0-3 5 % n-hepla nc. Other commercially avai lable
clea ners contain admixtures oF chlori nated hydrocarbons.
7 This paper docs not address cu rrent practice as it relates to the removal of
d i rt and grime from secondary s u pport s . i\ l any commonly used tec h n iq ues

620
 Reading 64 H E S S N O H H I S

arc based d i rectly o n paper conserva l ion rnethods-the use o F soft brushes,
crurnbled and block eraser, a n d d i l ute sol utions oF rnet hyl cellu lose-and
are addressed in the p reservation l i terature. Clea n i ng tests perforrncd on
the rnount rnay provide t he photograph conservator with a rnore acc u rate
i n d i cation or the arnount of' d i rt present on the photograph's su rface. For t h i s
reaso n , 1nany p hotograph conservators commence s u rface clean i ng trc<.1tmcnts
with the rnou n t .
8 T h e question naire , d i stribu ted i n October 1 998, requested i n forrnation re lat ing
to the rnethods and mate rials most cornrnonly employed for the safe and
efficient removal oF d i rt a n d grime from a variety of photographic processes
such as salted paper, Fcrrotyped s i lver gelatine, or a severely deteriorated
a l b u rn c n print. Responde nts were also asked to address general benefits and
risks, i n novative treatment approaches, research needs. a n d phi losophical
concerns. Response rate: 80%.
9 P. Messier and T. Vitale, " E ffect of Aqueous Trcatrnent on A l b u rnen
Photographs," Jou rnal of tlie A111ericc111 I nstit11te for Conservat.io11 33:3 ( 1 994):
278-300.
10 1-1 u man sal iva is a complex m ixture of organic and i n organic substances,
i n c l u d i ng: 98% to 99.5% water; salts of calc i u rn , sod i u rn , potassi u rn and
c h lorine; u rea, u ric acid, lactic acid, phenols and a l b u m i n s and prote i n s i n t he
forrn of enzymes and rn u c i n . Sal iva has been u sed for cleaning by conservators
in a l l discipli nes. It is viscous and control lable and appears to s u spend or
ernu lsify d i rt part i cles. Con servators who use saliva typically "clear" cleaned
areas with d isti lled water.
11 B. Bern ier, "The Study o r Polyvinyl C h loride Erasers U sed i n the S u rface
C leaning of Photographs. " Topics i 1 1 Pliotograpliic Preservation: A111ericm1
/ 11stit11tefor Consen1atio11 Pl10togmpliic J\laterials Cro11p 7 ( 1 997): 10-1 9 .
C learly more research is req u i red, part icularl y as i t relates to plastic izer
depos ition and long-term effects on both albumen and silver gelatine
rnatcrials.
12 These sponges (also referred to as d ry-chcrn sponges) are sold by a nurnbc r
or suppl iers and rnorc corn monly rel'crrcd to by their brand n a rn c s i n c l u d i ng
Absorbe11e Dirt Eraser and the Co1i=o Wonder Sponge.
13 E . M offat, "Analysis of Chemical Sponges Used by the Com rnercial Fire
Cleaning I nd u stry to Rernove Soot from Various S u rfaces " Tech nical Notes,
8·111/et. i n /IC-CC 1 7 : 3 ( 1 992): 9- 1 0 .
14 Prc l i rn i nary research u ndertaken by J oanne Hackett, v\l i n te rt h u r/U n ivcrsity
of Delaware Program i n Art Conservation Fel low, i n d icates that particu late
residues are not left behind o n text i les. This work. which incl u d ed S E M
ana lysis of treated a n d u n t reated cotton rn u s l i n , wi l l b e p u b lished i n t he
A 111erican lnstit11tefo1· Co11senmtio11 Textile Specialty Cwup Postprints, 1 998.
Sec "Observation on Soot Hernoval rro111 Textiles." C l early foc u sed research
i nvestigating the effects o r these vu lcan ized ru bber sponges Oil photographic
n1atcrials is necessary.
15 Sec the American I 11stit11te for Co11sermt ion Boo ft and Peiper Catalogue, S11 1face
Cleaning For i n -depth i n formation re lating to eraser materials, including
block (polyvinyl c h l oride-, racticc-, and rubber-based materials) and powdered
erasers. A n u m ber o r excellent art icles arc also publis hed on the topic or eraser
treatments and should be consulted.
P a rt V I I D E V E L O P I N G C H I T E H I A

16 P . Knipe, 'The Evaluat ion of Four Aqueous and Non-aqueous S u rface

C l ea n i ng Tec h n i q u e s on Si lver Gelatin Photographs," Topics in Pliotograpliic
Preservatiori : A merican l nstit.u.tefor Conservat ion Photographic Materials G .-oup
7 ( 1 997): 1 9-28 for p re l i m i nary research on the use of water a n d water/ethanol
m i x t u res i n the s u rface clea n i n g of s i lver ge latine print materials.
1 7 As reported i n a conversation ( 7 J u ly 1 998) with tec h n i cal representatives from
l l f'ord Photo Corporation. Note that water 111ay be proble111atic a n d that old
l l fochromes 111ay have a very brittle su rface and t hese mate rials are espec i a l ly
vul nerable.
18 Peter Krause, photographic consultant, notes that Fi ngerprints may b e safely
re111oved Fro111 l l fochro111e 111aterials with c h lori nated hydrocarbon s , toluene.
or lacquer t h i n ner.
19 C h l orin ated hydrocarbons are toxic and pose very specific and dangerous
heal t h hazards. These 111aterials 111ust be hand led using a chem ical fume-hood
with appropriate personal protection . Their use i s severely restricted in the
U n i ted States and Canada.
20 These tho ughts are based on discussion and work with Professor R i chard
Wolbers oF the U n iversity of Delaware, a leader in the development of safe
and practical clean i ng solutions for da 111aged and deteriorated cu l t u ra l
property.
 R e a d n g 65

KLA U S B . H E N D R I KS

The Evaluation of C onservation

Treatments ( 1 995)

J n Part Vfl we stray from the convention of organizing t he readings clironolog­

ically to concl ude with the reflections of I<la,us Hendrihs (see also Readings 9,
24, a nd 58) on the challenge of consen;ation treatment, With shilled brevity
a nd ast;ou nding insight, f-lenclrihs evaluates the ,merits and com11lexities of 1nany
f;opics addressed by other authors in this part, including rest;oration techniques,
proper environinental conditions for housing photographic '11'/,aterials, clu11lica­
tion, and ethical standards, Jn doing so, Herulri}'lS promotes the needfor "fresh ancl
original tkinldng" to advance photograph conservation treatment practice, Treat­
ment lrnowledge and research has progressed significantly since the publication
of this a rticle owing in pai-t to the i nfluential writings and research of Henclrihs,

I ntroduction

Jn many of our activities, whatever their nature may be, a goal is defin ed
first, which outlines what is to be clo n e and i n which order, materials and
tools a re chosen, and estimates for cost and needed time a re prepared, The
work is then performed as planned, \i\That next? An eval uation of the results
may be ca rried out for q u ite fun damental reasons: to see whether the goal
that had been set was i ndeed achieved . Was the work done as planned, was i t
done wel l , was i t clone effectively? Could it have been clone d i fferently, using

KLAUS 8 , H ENDRIKS, "The Eval uation o f Conservati o n Treatments," Research Tec/1-

niques i n P/101ographic Conservation, Proceedings of the conference held at the National
M useum of Denmark, Copenhagen, M ay 1 2- 1 6 , 1995, post-prints (Copenhage n : Royal
Danishy Academy of Fine f\rts, 1 996), 47-50. Repri nted by permission of the Hoval Danish
f\cademy of Fine Arts, School of Conservation,
Part VII D E V E L O P I N G C R I T E ll l A

other, or additional materials? Could i t have been done faster? Should i t

h ave been done slower, to leave more time for reAection a n d evaluation d ur­
i ng the execution? This i s not un l ike quality control, a term used m ore often
in the m anufacturing world. One of its pu rposes is to learn from a given
process how it could be i mproved should si mi lar work be clone aga i n . From
an administrative poi n t of view, one may want to know whether parameters
such as time frame and cost factors have been adhered to.
All this is q u ite normal for any work that consists of a combination of
i ntellectual and manual efforts. What makes the subject of eva luation of con­
servat ion t reatments of c u lt u ral property so sensi t ive i s the recognition that
conservators have to deal with objects from another era whi c h was character­
ized by i ts own spirit. Not o n ly is it necessary to develop an u nderstanding for
the i ntentions of the creator of an art object, but also an u n derstanding that
each work of art is a ch i l d of i ts t i me with its own spirit . That spirit must be
grasped and taken i nto consi deration when an object is treated.
Cri teria for the success of conservation treatments for p hotographic
i mages have not been developed, as far as the a uthor i s aware . This makes
the discussion of this subject a del icate one. The t i tle of this essay suggests
that i t may be i nterpreted to mea n two separate u ndertakings. On the one
hand, i t could indicate the need for a discussion of methods to eval ua te
fai rly, perhaps even to ran k, conservation treatments. That wou l d be a usefu l
task indeed. I nstead of referri n g to eth ics and the "highest standards" (which
are they?) of the profession, relying on the assu mption that their application
makes an evaluation of a fin ished treatment u n necessary, objective criteria
could be formulated by which to measure the val u e and merit of a conserva­
tion treatment. Such criteria wou ld not have to be applied after each i nd i ­
v i d u al treatment, but could be used to eval uate a type, or class, or category
of treatment. I t will be u sefu l to ach ieve some agreement among experts on
any such criteria. l n the absence of standards for the execution of conserva­
tion treatments, or certification of members of professional associations and
of l icencing of practitioners, this becomes a formidable task.
On the other hand, the title may be i nterpreted to mean an actual
eval uation of various conservation treatments, an attempt to place a value, a
merit on actual treatments, with the res u l t that some may be d iscredited, and
others be recommended. But who could claim to be fam il i ar with all exist i ng
treatments i n a field that is steadi ly developi ng? Sometimes the resu lts of a
treatment can be inspected, b u t the deta i l s of its execu tion rem a i n un lmown .
M et hods not revealed cannot be eva l uated. Properly described treatments
are open to easy criticism.
These introductory remarks demonst rate the d i le m ma that is i nherent
in the discussion of the eval uation of conservation treatments. When using
the term treatment, I i ncl u de three broad areas:
 Reading 65 ll E N D H I K S

1 . Preservation through storage and housi ng.

2. D u pl ication of n egatives and copyi ng reflection pri n ts.
3. Conservation treatments o n a n origi nal photograph, such as clean­

i ng. S uch treatments are best d ivided i n to those carried out in the d ry
state, and those carried out i n water or aqueous solutions.

Storage

Good storage is the main tool of preventive conservation. Fortu nately, i n

t h e field o f photographs, there are standards for t h e storage of plates, f i l 111s
and prin ts written by the American National Standards I nstitute (AN S I ) ,
which h ave also been adopted b y the I n ternational Orga nization for Stan­
dard ization ( I S0) . 1 ·2 ·3 In the past i t has been easy to recommend these stan­
dard practices, since they were the result of deliberations by experts from
the photographic i n dustry and u ser groups from cultural i nstitutions. B u t
i n recom me n d i ng these standards, there remai n ed always an u ncomfortable
fee l i ng, not about the levels of te111perature and relative h u 111icl ity, but about
the strict tolerances. It is d ifficult to j ustify, for exa111ple, to a bu ilding e ngi­
neer why a tolerance of ± 2°C is needed for a storage area. Consequently,
it is not surprising that the recommended levels for te 111 perature and rela­
t ive h um i dity ( RH ) have recently u ndergone a critical review. T. Padfield
and J. Johnsen of the National M u seum of Denmark have questioned the
strict standard recom111enclations with reference to both the proposed l evels
and the allowed fl uctuation. They postulate that the recommended storage
conditions do not necessari ly con tri bute to the preservation of photographs
that are i n herently u n stable. Such photographs are l i kely to degrade fu rther
even when kept at standard conditions. Conversely, the authors suggest, wel l
processed photographs 111ade fro111 stable materials wi l l b e able t o survive for
a long time even if kept in conditions that do not 111eet those proposed by the
standards. S i nce the rea l c l imatic conditions which are prevalent on all cor­
ners of this planet deviate considerably from standard conditions, atte111pts
are made by the authors to align the two closer together in a co111prom ise
which suggests relaxin g the standard conditions sl ightly towards more rea l i s­
tic and cost-saving levels. 4
The narrow tolerances of ± 2°C or ± 2% R I-I have also been questioned
recently by researchers from the Conservation Analytical Laboratory ( CAL)
of the S m ithsonian I nstitution i n Wash i ngton, D.C. Changes i n te111pera­
ture and variations in RH can cause p hysica l expansion and contraction of
fil m and paper supports. A si111 i lar ex'Pansion, called stra i n or elongation,
takes place if a force (stress) acts on a 111aterial, for example a strip of paper.
Thi s is clone in an i nstrument b u i l t speci fical ly for the pu rpose which a l lows
the measu rement of the behavior of materials u nder stress. I t is possible to
Part VII D E V E L O P I N G C R I T E H I /\

determ ine how far a materi al can stretch before it breaks. I f a force is acting
upon a strip of paper of speci fied d i mensions, the paper will at first stretch
elastical ly, i . e . , l i ke a rubber band, which contracts to its origi nal length after
the force has been released. I n the case of a 20 cm long paper strip, the e las­
tic el ongation is in the order of magn itude of one to two m i l l imeters . In a
plot that shows the elo ngation as a res u l t of the applied load, the elongat ion
rises in the elastic range l inearly with the increase i n the load . Then a poi nt
is reached where the elon gation becomes i rreversible, i.e., the paper does
not contract to its origin al d i mensions after the stress has been re leased. I t
contin ues t o stretch u ntil i t b reaks. S u c h plots, which demonstrate t h e con­
nection between st ress and e longat ion, describe i mportant mechan ical prop­
erties for n u merous materials that a re found in objects of cultural properties.
M. F. M ecklenburg, M. H. McCormick-G oodhart and C. S. Tumosa, of the
CAL, have observed that even at h igher tolerances for tempera t ure and H I-I ,
for example a t :±: 1 0- 1 5°C and :±: 1 0- 1 5% H 1-1 , expansion and contraction of
film and paper su pports occu r on the elastic part of the stress-stra i n c urve;
in other words they are reversib le . 5 They conclude that higher tolerances arc
acceptable than those recommended 1 n the c urrent standards, without the
expectation of adverse consequences.
These recent deve lopments a re a flne example of the kind of fresh
and origi nal thinking that i s necessary to advance knowledge i n an area
of expertise.

Duplicating and Copying

An i n tegral part of the conservation of photographs, these preservation

measu res-not actual treatments-are nevertheless rarely performed by
photo conservators, but are in many count ries left to photogra phers. It has
been shown that a correctly prepared dupl icate negative possesses a l l i mage
qual it ies of the original, i n a published article that reviews va rious proce­
d u res and provides experimental res ults fro m sensitometrically controlled
duplicating proced u res. 6 Prints made from dupl icate negatives a re i nd istin­
guishable from those made from the origi nal, even a t extreme magn i fications.
The com plex task of copying reAection pri nts has also been d i scussed in the
l iterature and therefore needs no further exploration here. 7 In that they serve
pu rposes of ei ther preservation or access. the significance of dupl ication and
copying work is u ndisp u ted.
In restricting the use of the term restoration to work on a n origi nal
photograph, two copying proced u res should be mentioned, which have at
ti mes been labeled as restoration. The first, which was proposed several
ti mes d u ri ng the past three decades, uses rad ioactive i mage-forming sub­
sta nce (si lver or si lver salts, the prod ucts of fad i ng), or an i mage toned with

626
 Reading 65 ll E N D H I K S

rad ioactive sulfur, to prod uce a copy by close contact with a radiographic
fi l m . The method does not appear to have fo und widespread application. By
contrast the second method enjoys great populari ty, quite l itera l ly because
of the increased availability of sophi sticated software and its ease of use:
the manipu lation, i n c l u d i n g reconstitu tion of scan ned i mages by a com­
pu ter. Th i s method is so new that critical voices have not yet been heard;
suffice to emphasize that the origi nal i mage is i n no way affected by this
manipulation.

Restoration Treatments

First some i ntrodu ctory remarks. Perhaps this paper could be the begin n i ng
of a discussion on the merits-or the lack of them-of conservation treat­
ments for p hotographs. Such deliberations have taken place in many other
fields of conservation of cultural property, notably in the field of conserva­
tion of paintings. Paintings have been in existence for hu ndreds of years,
and each century has added many more to those i n existence, with artistic
perceptions and styles changing, as wel l as the materials used by a rtists. So it
is not surprising to learn that oil painti ngs have been restored for centuries:
cleaned, restored and overpainted by artists the mselves. Well known is the
so-cal led cleani ng controversy which was triggered by an exh ibition, in 1 946,
on the cleaning of paintings at the National G al l ery i n London. This con­
troversy lasted i nto the 1 960s. The question, whether oil painti ngs should be
cleaned and retouched, and if so, to which degree, has spawned d i scussions
which nil vol u mes.
S i m i lar discussions have not become common place i n the conserva­
tion of photographs, a you ng field which awaits eval uation of existing resto­
ration tech n iq ues and the development of n ew ones. Two i m porta nt eve nts
will gu ide u s i n our deli berations. One is the Code of Ethics of the American
I nstitute for Conservation (AIC). The second is a d raft of the Photo Conser­
vation Treatment Catalog on the subject of retouchi ng. I t l i sts the nume rous
details which m us t be considered in the development of restoration meth­
ods. While this catalog of materials that may be used in the i n pa inting of
photographs-using tech n i q ues su itable for and appropriately chosen for
each of these materials-does neither recommend nor endorse a given mate­
rial or treatment method, the sheer n u mber of factors to be considered is
staggering: covering power of retouching dyes; the use of an isola ting layer;
choice of the i npai n t i ng med i u m from a wide range of products; the manu­
facturer of retouch i ng colors; tec h n iques of app l ication; color matc hing with
the photograph to be retouched ; l ightfastness of the dye/watercolor; perma­
ne nce of the retouching dye; its compatibil ity with the i mage-form i ng sub­
stance, i.e., elementary s ilver or dye and the maintenance of glossy su rfaces.
P art VII D E V E L O P I N G C B I T E B I A

This part of the catalog is a l ready, as a d raft on ly, 25 pages long. S i m i lar
reviews will be put together for other treatments that can be done, and are
carried out i n practice or ex1Jerimentally. The d raft on retouching is a fine
example of what to expect from the development of conservation treatments
for photographs; much of the eva l uation is done beforehand, in the stage
of planning and pondering the advantages and possible disadvantages of an
i n tervention.
\Nhat is the pu rpose of a conservation treatment' M ore spec ifical ly,
what is the pu rpose of restoration? A c u rrent exh i bition in Germany has the
title: "To restore does not mean to make something new aga i n . " One critic
asked promptly and consistently: But what does i t mean? If we i nclude the
provision of correct storage conditions, i ncluding housing, and d u plication
and copying u nder conservation treatments, the question about their pu rpose
is answered readi ly; to prevent objects from deteriorati ng, to protect them
from damage , to increase their longevity. As for restoration work, a second
mot ive exists and that is to i mprove the object's appearance, to let it appear
wholesome. Restoration has two main pu rposes: to strengthen the object, or
to i ncrease its stabi l i ty; and cosmetic i mprovements. I t is the latter goal with
which the public identifies best, witness the description of restoration efforts
i n the popu lar press as, for example, "refreshi ng" a painting. J ust as people
may refresh the mselves at the encl of a hard clay, by putting on a l i ttle fresh
make-u p . . . \Nh i le the emphasis between the two goals may shift from one
to the other dependi n g upon the wishes of the owner or of the person payi ng
for the service, the pu rpose of i ncreasing the stab i l i ty should be foremost
in all restoration efforts. (Sometimes a decrease in the rate of degradation
replaces the desired treatment to i ncrease stabi l i ty, when that option is the
only one avai lable. The best example is the storage of color photographs at
low temperature and controlled h u m id i ty.) Restoration is i n contrast to repair
work, i n which a basic com mod ity must Fu nction after it has been treated.
A repaired and fresh ly painted door will also close aga i n ; a tractor, not only
looks nice and clean agai n , it also runs aga i n . I ndividual p hotographs do not
have such a spec i fic u ser fu nction. They are viewed, studied c losely, exhib­
i ted or publ i shed, all of which can be done without putting stress on them.
But a motion picture film that is torn in two pieces is repaired so that it can
be shown in the projector; or a bro ken glass plate is repaired so that a print
can be made from it. So the requirement to meet a specific user fu nction is a
th i rd pu rpose of physical repair or restoration work.
The pu rpose of conservation treatment is to keep an object in a usable
condition (cf. storage; copyi ng) or to make it useable aga i n (cf. clea n i ng,
repair, retou chi ng, fi l l i n g in losses). The survival of an object is also the
foremost priority specified by the A J C Code of Ethics. This pu rpose infor­
mally justifies the n u mero u s mechanical restoration treatments that can be
 R eading 65 ll E N D H I K S

applied to photographs. Many of these have been adopted, a l be i t often i n

modified form, from established tec h niques for prints and drawi ngs. While
the principle of reversi b i lity is not accepted as u n iversally applicable to a l l
treatments by the AIC E t h i c s G u idelines, they do requi re t h a t compensation
for loss should be made reversible.
The foregoing has foc used on treatments carried out i n the d ry state,
with the possi b le exception of c l ea n i ng a photograph or glass plate i n water.
The controversial restoration treatments are those which seek lo restore
a faded or discolored b lack-and-white photograph in chemical sol u t ions.
With few exceptions, they make u se of redevelopment of the i mage, after
the i mage si lver and its degradation prod ucts ( i . e ., silver salts) have been
converted i n to s ilver hal ides. One notable exception is the removal of a blue
metal l i c sheen, often referred to as si lver m irror, from si lver gelat i n glass
plate negatives ("dry plates") u si ng a solution of iodine in dry ( ! ) alcohol. I t
was s uggested by Edith Weyde i n 1 972.8 I ts elegance l ies i n the suggestion to
u se absolute a lcohol which does not penetrate into the hydroph i l i c gelat i n
layer: the iod i ne can react o n l y with t h e silver t h at ha s migrated to the sur­
face of the e m u lsion layer. I t does so with formation of si lver iodide which is
then removed u sing a common solvent for si lver hal ides.
S u c h treatments are controversial not only i n the m inds of c u rators
and photo h istorians, but surprisi ngly enough with photo conservators as
wel l . The term photo conservator as it is used i n North America ( U .S.A. and
Canada) does not i mply that restoration work m ust necessarily be clone. The
German translation is photo restorer, al tho ugh restoration of photographs
is not practiced widely in that cou ntry. Restoration treatments i n c he mi ­
cal solutions suffer t h e sam e fate as t h e duplication of negatives: alt hough
they ought to be an i ntegral part of a photo conservator's practice, they are
largely shu nned by practitioners. The reasons for this conservative attitude
are not easily u nderstood. Both types of work constitute an exciting intellec­
tual c hal lenge. Both have been d isc ussed i n tec h nical detail i n the li terature
for everybody to study.8 •9· 1 0 Such treatments meet a l l the requi rements out­
l ined above with respect to the pu rpose of restoration: a restored glassplate
whose pu rpose it is to yield a good print meets that pu rpose and is i m mu ne
towards fu rther degradation by virtue of a ton i ng treatment.9 A treated pri nt
d isplays the original black-and-white tonal range, and obtains increased sta­
bility through toni ng. 1 0 L i mi tations and possible pitfal l s are presented clearly
in those publications, pitfa l l s that can be guarded aga i nst i n advance.
\,Yhile restoration t reatments for photographs in the d ry state, often
adopted from long-practiced treatments of works of art on paper, are the
ma instream of c u rrent photo conservation practice, i t is i n the area of res­
toration of faded black-and-wh ite photographs in chemical solutions where
refi nements will be developed and new t reatments will be proposed . Such
P a rt V I I D E V E L O P I N G C B I T E B I A

work req u i res a curious and inquisitive m i n d and a complete u n derstand­

i ng of both the photographic process and the mechanism of degradation of
i mage si lver. A fine example of the latter is iV l . \!\fare's recent study of the
deterioration of printed-out-si lver in early 1 9th century photographs. Chemi­
cal reactions run their course Fol lowing wel l known natura l laws. Therefore,
the success of such treatments can be est i mated with more certa i n ty than
that of manual restora tion treatments.

E n dnotes

The A I C Code of Ethics has determi ned that the su rvival of the object is the
foremost priority in guiding the work of a conservator. I t also happens to be
the main pu rpose of any conservation treatment. Disclosu re to the owner/
client of materials used and of details of the actu al treatment performed is
another requ i rement of the Ethics G u idelines. This wou l d a l low the treat­
ment to be eval u ated independently. Photograph conservation is a field i n
which nearly a l l treatments cu rrently u ndergo critical review, with the excep­
tion of methods of d up l ication and copying. This makes for a healthy devel­
opment of n ew tech n iques and methods which are u rge n t ly needed. Keepi ng
i n mind the purpose of a conservation treatment and gu ided by accepted
E thics G u idelines, the conservator has the tools to make i n formed decisions
on i n tended conservation treatments. M any of t hese can be eva l u ated o n ly
after more experience has been accu m u lated.
I wish to thank Debbie Hess Norris and Andrew Robb for their help i n
obtai n i n g pert i nent i n formation.

Literature

1 American National Standards I nstitute. IT 9 . 1 8. Practice For Storage of

Processed Photographic Plates. New York, A N S I 1 995.
2American National Standards I ns t i t u te. IT 9.20. Practice For Storage of
Photographic Prints. New York, A N S I 1995.
3 American National Stancbrds I ns t i t u te. IT 9. 1 1 . Practice For S torage of
Processed Safety Photographic Film. New York, A N S I 1993.
4 Jesper S . Joh nsen in: Preven tive Conserva t i o n . Practice, Theory and Resea rch .
Prcp1·i nts of Contri b u t ions t o t h e Ottawa Congress; September 1 2-16, 1994,
p. 202-206. Sec a lso T. Padfleld's contribution in this vol u me [ referring to:
Hesearch Tec/1 11iq11es in P/ioiograp/1ic Consen1a/ion J .
Marion F . Mecklenburg, l\llark M cCormick-Goodhart, and C harles S . Tumosa.
" l nvc�L igation inlo the Deterioration oF Pai n t i ngs and Photographs U si ng
Computerized Model i ng of Stress Development. " Tlie jo1mwl of t l1e American
I nsl il.ule for Conserval ion. 33, (2), p. 1 53-1 70 (September 1 994).
 R eading 65 H E N D H I K S

6 Klaus B. Hendriks, Douglas R. l\l lad eley , Fred Toll and Brian Thurgood. "The
Dupl ication of H istorical Black-and-vVh ite N ega t i ves . " Journal of Inrngi.ng
Tech nology. 1 2 , (4), p. 185-1 99 ( A u g u s t 1 986).
7 R . G . R udd. "Copying the Black-and-Wh ite Pri n t . " Photograpliic Science and
Technique, Section B of PSA Journal 16 B , p. 30-38 Qune 1 950).
8 E d i t h Weyde . "A S i m ple Test to I de n tify Gases w h i c h Destroy S i l ve r I mages."
Photographic Science and Engineering. 16, (4), p. 283-286 ( 1972 ) .
9 Jesper S. J o h n s e n . " I mage Q u a l i ty of C h e m i c a l l y Restored Black a nd W h i te
N ega t i ve s . " Journal of hnaging Science and Technology. 36 ( 1 ), p. 46-55, ( 1 992).
1 0 Klaus B . H e ndi-iks. " U ber d ie chemische Restaurierung des S i l berbildes
verg i l b t er oder verforbtcr Photographien." In: Wiener Berichte i.i ber
Natu rwissencha l't i n dcr Kunst. Vol . 4/5, p. 372-389 ( 1 987/88) .
 P A R T V I I I

Exhibition Practice

The i ncreasing market valu e and popu larity of art p hotograph s has resu l ted
in a much greater demand for blockbuster shows, traveling exhibitions, and
i mmediate access. "Safe" i l l u m i n ation levels, packin g and shipping protocols,
proper mounting methods, and environmental conditions h ave been dis­
cussed and debated over a h undred years, and sign ificant changes i n i mage
density and stain ing following prolonged exh i bition have been observed and
measured. Photographic m aterials are vulnerable to irrevers i b le deterioration
when displayed , and originals must be protected from excessive display. Part
V II I addresses the central challenge of all conservation discip lines: how can
we best preserve c u l tu ral property for education a n d enrichment of future
generations while also providing safe and appropriate public access?

Hippolyte Bayard (French, 1801-1887), Arrangement of Specimens (detail ) , ca. 1842. Cyanotype
(direct negative), 27.7 X 2 1 . 6 cm ( 1 0 1 Y1• X BY. in.). Los Angeles, J. Paul Getty Museum, 84.xo.968.5
 R e a d i n g 66

P H O T O G R A P H I C S O C I E TY O F L O N D O N

Preparing Photographs
for Exhibition ( 1 892)

Our understancl :i ng of 11hotographic clegraclation. has been inform.eel by research

an.cl observation-often by scientific technical commit tees an.cl other scholarly
gatherings. In this reading from 1 892, members of t he Photographic Society of
Lon.don. address aest het ically appro11riate mount i ng, framing, an.cl display of
photographic 11ri.n.ts as well as their displeasure with fugitive print materials. In
many ways, we continue to gra11ple with these challenges today

Tuesday, 22n.cl Novernber, 1 98 2 .

Mr. A. Cowan, i n the Chair.

TH E HoN. S E C H ETAHY asked whether the time had not arrived when p ri n ts
that were not permanent should be exc lu ded from exhi b itions? When one
saw prin ts actually fad ing d u ri ng the six weeks of an exhibition he thought
i t was necessary to take such a course. It wou l d be a d i fficult matter to draw
the bou ndary l i ne.
M R . D E B E N HAM thought p hotographs ought not to be exc l uded on the
ground mentioned by the Hon . Secretary; exclude them from collections
i n tended to be preserved, by all means. I f a man t h i n ks he can get the m ost
beauty, even though it be a Aeeting beauty, by a certain process, let h i m do
it. If necessary let the process be mentioned, so that those i n c l i ned to under­
val u e the work beca use i t is not what they consider permanent may do so
i f they p lease. He knew some raised objections to stating methods and p ro­
cesses con nected with t h ings sent to exh i bitions, but such objections seemed

F ro m PHOTOGHJ\Pl l l C SOC I ETY OF LONDON, " Preparing Photographs for Exh i bi t ion," The
Pho!.ograpliic Journal. ( December 1 892): 78-8 1 (79-80 excerpted here).
 Reading 66 P H O T O G R A P H I C S O C I E T Y O F L O NDON

to h i m most u n reasonable. I f an exhi bi t ion was i ntended to serve a n educa­

tional p u rpose the general or spec i fic means of prod uction should certainly
be stated as far as possible except where such were eviden tly i ndicated by
the work i tself. He did n o t know what the objection could be, u nless it was a
petty jealousy that some one else should do the same thing. He could not see
why any rational m a n could object to state means of production except i n
the case of processes a s t o which patents were pending. O n ordi nary artistic
or photographic gro unds he could see no reason for objection.
THE CHAIRMAN : Then you would l ike i t stated on the prel i m ina ry c i rcu­
lar that the process should be m en tioned?
MR. DEBENHAM said no, h e wou l d not call for it, beca use i t cou ld gen­
erally be seen a t onc e by wh at process a p ri n t was produced; but where there
was a nythi n g which was not evident he wou l d l i ke i t stated. The name m ight,
of course, be put to a lot of p l a t in u m prints or albumen pri n ts or gelatine
prints, but t here was general ly i n those i nstances n o necessi ty to do so, they
could be told a t once, b u t where the means of production was not evident i n
the face o f the photograph he thought i t shoul d be stated, and the objection
to doing so seemed to h i m to be u tterly futile.
THE HoN. SECRETARY said i f, then, they were to do nothing to excl ude
what was so very fugitive, i t might perhaps be made compulsory for an exh i b­
itor to say i n what way h i s prin ts were p roduced, and that a picture should
be excl uded i f the process was not stated. H e woul d even go further than
that, and d i rect the j u dges not to award medals for pictures that were not
certainly permanent .
Several members dissented from t h i s suggestion, a n d i t was pointed
out that artistic effect should be considered before permanency-the nega­
tive rem a ined when the print had faded.
 R e a d i n g 67

H E N RY WI L H E LM

Monitoring the Fading and S taining

of C olor Photographic Prints ( 1 98 1 )

Henry Wilhelm (see also Reading 50) has led the field in the study of the per­
manence of color and digital i mage p rocesses. This reading o utlines basic tech­
niques for nionitoring the fading and staining of color photographic 1nints
in both light an.cl dark conditions using a photographic color densi.tom.eter.
Wilhel m 's research and subsequent p u blications raised aware ness regarding
acceptable Umil:s for print deterioration and the use of proper dis11lay and sl:or­
age i1l111nination to best preserve color photographic materials.

I ntroduction

People often want to d isplay origina l color photograph ic prints in a museu m,

gal lery, or arch ive; u nfortu nately, h owever, such d isplay exposes the prints
to l i ght which will cause gradual i m age deterioration in the form of fad­
i ng and changes in overal l color balance. In addition, many types of color
prints are subject to sta i n formatio n . Such stains are most readily visible in
the l ighter areas of a prin t and are usu a l ly yel l ow; with a n u m ber of com­
mon color print mate rials, sta i n formation over a period of time may be the
most obvious type of i mage deterioration. Compared with most other types
of artistic media, color photographs ge nerally fade a nd/or stai n fai rl y rapidly
when d isplayed, and many types of color pri n ts are q u i te u nstable even when
kept in the dark.

H ENBY \�l1 L J- I E L � I , " M o n i toring the Fading a n d Staining of Color Photographic Prints, "
Ju11mal of tl1e f\1J1erican I nstit11te .for Conseniat.ion 2 1 , no. 1 ( 1 9 8 1 ): 49-6+ © 1 982 by Henr y
\Ni l helm. Text a n d images reprinted by permission of the a u t hor.
 Reading 67 II' I L J-1 E L ,\ J

C hanges wh ich take place in dark storage can usually be arrested only
by plac i ng the photographs i n low-temperature and low- h u m id i ty storage.
At n ormal room tempera t u res, dark storage changes (often referred to as
darh-faclin.g) 1 will contin u e whether or not a pri n t is on display. Th us, when
a prin t is displayed , the total cha nge that takes p lace is some combination of
clark-facli ng/stai n i ng and I ight-facli ng/stai n ing.
Light-fading is caused by both visible l ight and u l traviolet radiation.
For most types of color pri n ts displayed i n normal museum d isplay condi­
tions, image deterioration caused by u ltraviolet radiation is m uc h less signi fi­
cant than changes caused by visib le l ight and storage a t room temperature.
M u seum display conditions for color photographs vary widely fro m
one museum to another and even wi t h i n a given institution. Typically, color
prints are i l l u mi nated with tu ngsten lamps of abou t 2,800-3,200° 1<.; i n ten­
s i ty on the pri n t surface is about 1 30-325 lux ( 1 2-30 footcandles) for about
1 0 hours per clay. The l ight is normally fi l tered by the glass sheet used i n
fra m i ng the pri nts. Low i l l u m i nation levels o f about 50 l u x ( s footcanclles)
have been suggested for d isp lay of color photographs; however, the a uthor
believes that this level is too low for proper viewing of most color p hotographs.
S horter d isplay ti mes at h igher i l l u m i nation i n tensities are preferable. \Nith
many common types of color p hotographs, such as Kodah Ehtacolor 7 4 RC
c h romogen i c2 prints (often incorrectly referred to as "Type C" prints), dark­
storage reactions may predom inate when the prints are displayed u n der low­
level t u ngsten l ight; the use of extremely low-level tungsten i l l u m i nation on
the order of 50 l ux () footcanclles) may res ult i n l i ttle if any gai n i n print l i fe .
H igh-intensity accelerated l ight-fading tests often produce data which
do not give a n acc u rate i n d icat ion of actual long-term fad i ng and stain i ng
characteristics, 3 and long-term da rk-storage data are not presently ava i lable
for the wide variety of existing color pri n t materials or for the wide range of
dark-storage and d isplay conditions in museums and galleries. I t is t here­
fore d i fficu l t to predict with any certa inty the rate at which changes may
take place for a given pri n t material. C u rren tly available color print materi­
als man ifest a wide range of differen ces in display and dark-storage fading
c haracteristics. 4
To determine the cha nges that take place i n a color pri nt over a period
of months or years, it is necessary to measure periodically the color and
optical density of a pri n t d i rectly. Alternatively, the changes can be mea­
sured indirectly with a "fad i ng monitor" made of the same type of color pri n t
materials as t h e photograph i n question a n d subjected t o t h e same l ight,
tempera t u re, and re lat ive h u midity conditions as the color p hotograph. Mea­
surements are made with an accurate electron ic color densitometer designed
for photographic use. The quant itative data thus obtai ned i n dicate at which
poi n t in time s l ight-but visually sign i ficant-changes have taken place so
P a rt V I I I E X ll l B I T I O N P l1 t\ C T I C E

that the user knows when to ret ire the origi nal print to cold storage i n the
dark, substituting copy prints for study and d isp lay pu rposes. Table 1 [ not
reproduced here J shows the quantitat ive l i m its of acceptable c hange sug­
gested by the aut hor.
Because the relationsh ip between dark-fadi ng/staining and l ight-fadi ng/
staining oF Lhe dye sets used in the many types of color photographic materi ­
a l s is complex, and for a variety of other reasons, meas urement o f the total
l ight exposu re received by a print using the British Wool Standards, N B S
Fading Papers, integrating photometers, and s o forth w i l l genera l ly not i ndi­
cate accu rately the degree of deteriora t ion of a color photograph d u ri ng
long-term d isplay and/or dark storage.
The color print mon itoring procedures described below can also be
used to measu re changes i n monoc h rome photographs such as si lver-gelatin
and si lver-albumen prints.5 Likewise, yel lowing and other forms of deterio­
ration i n works of art on paper and i n other paper objects can be moni­
tored d u ri ng long-term d isplay and storage. The measurement techn iques
described here are also applicable i n documenting c hanges i n objects after
conservation treatments. Changes in watercolors and pai n ti ngs can be mea­
su red using si m ilar procedures, but beca use of the wide variety of colorants
u sed in pa ints, a spect rophotometer may have to be employed 6 i n add ition
to, or in place of, a color ph otographic densitometer to ensure acc uracy.
Color photographic images are com posed of cyan, magenta, and yel low
colors which have spectral absorption peaks within a fai rly narrow ra nge;
photographic densitometers a re des igned to measure colors with these spec­
tral characteristics. While the concept of predetermined l im its of change is
d i rectly applicable to paper objects, watercolors, paintings, and so forth , the
l i m its selected will probably d iffer from those suggested here for color pho­
tographs. S t i l l , il is i m portant to measure and record the visual c haracteris­
tics of all objects of t hese types quantitat ively so that any changes i n fu t u re
years can be determined with reasonable accu racy.
Basic to any monitoring syste m is an i nstrument ca libration proced ure
which ass u res the cont i nued acc uracy and comparability of measurements
even after old equipment has been replaced by new i nstru ments of different
design . Mai ntai n i ng system accu racy for hundreds or thousands of years i n
t h e future will req u i re carefu l planning a s wel l as the very long-term pres­
ervat ion of color photographic cali bration standards in an u n c hanged state
t h rough the use of h u midity-controlled cold storage. Preserved color pho­
tographic calibration standards are thought l i kely to provide more acc urate
densilometer cal ibration than woul d be possible using porcelain plaques or
stable pigment standards, which have spectral characteri stics different from
those of the cyan, magenta, and yel low dyes used in color photographs.
 Reading 67 IV I L 1-1 E L 1\ I

Direct Moni toring of Color Prints

Of the two methods described i n this article for monitoring the fading and
sta i n i ng of color prin ts, most i nstitu tions will c hoose to measure i mage
changes d i rectly on the prints. Separate "fading m o ni tors" are usefu l chiefly
for research i n cases where the fad i n g monitor's u nique ability to distinguish
between l ight-induced changes and dark-storage deterioration can p rovide
i mportan t information in the design of better storage and display conditions.
The diffic ulties i nvolved in preparing and u si ng fading monitors, as well as
the fact that monitors cann o t be made for p ri n t m aterials which are no lon­
ger comme rcia l l y ava i lable, will l i mit their routine institutional use. I n some
cases it may even be i mpossible to identify precisely the type of color mate­
rial that was used to make a print, so that it will not be possible to use a
fad i ng m o n itor with that print. There m ay also be u ncerta i n ty as to whether
or not a n origina l pri n t has been correctly processed and washed; to be accu­
rate, a separate fadi n g monitor must be made with materials processed and
washed exactly as was the print bein g monitored. These and other req u i re­
ments w ill gen e rally l i m it the use of monitors to contemporary color prints,
where the monitor color patches can be made at the same time as the print.
ln most situations, a color print should be moni tored d i rectly even when a
separate fadin g monitor is being used.
S u i table color reflecti o n densitometers for prin t monitoring are ava il ­
able from a number o f companies.7 Kodah \!\!ratten fil ter n u m be rs 9 2 (reel),
93 (green), 94 (blue), and Visual 1 06 are recommended for this application i n

p reference to Kodah Certified Status A filter sets because the Kodah Sta t us A
fi l ters are more likely to become obsolete i n fut u re years than a re the tradi­
tional Wratten filters; the Status A fi l ters were designed pri mari ly for Kodak
chromogenic materials a n d may not be welJ matched to the dye sets used i n
other types of color photograph s. H owever, some high-quality p hotographic
densitometers are n ow being suppl ied only with the Status A fi l ters, and
these fi l ters should be used i f the Wratten fi lters can not be readily i nstalled.
Densitometer fi l ters shou ld be replaced by the i nstru ment's manufacture r
every 3 or 4 years.8 T o ensure maxim u m l i fe of the i nstru me nt, t h e densitom­
e te r should not be used for other museum applications such as p hotographic
process control . In general, read i ngs are taken with the red-green-blue fil­
ters; use of the Visua l 1 06 fi lter is not necessary during the m o n itoring of
most t)1Jes of color prints, although i t should be used in addition to the color
fi lters for the monitoring of monochrome pri n ts. Densi ty data should a lways
be recorded i n t he standard red-green-blue sequence to avoid confusion.
It is not possible to measure i mage density accu rately when a print
is fram e d with glass, so the print should be removed from the frame when
Part VIII EX JI I ll I T I 0 N I ' 11 A C T I C E

density readi ngs are to be made. To avoid direct contact of the densitometer
head with the su rface of the pri nt, and to provide a n exact record of the
densitometer reading locations on the print, a thin matte-surface polyester
overlay sheet9 must be prepared for each print (ce l l u lose acetate or polyvinyl
c hloride sheets are not satisfactory because c u rl i n g and dimensional stabi lity
are potential problems), with the prin t i mage locations marked on the sheet
so that the densitometer head may be registered accu rately on the i mage
d u ring each series of readi n g (Figure 1 ) . The matte su rface of the polyester
sheet accepts i n k and pencil l i nes readi ly; ord i nary clear polyester should not
be u sed, as i n k will not firmly adhere to the su rface a nd may smear or wear
off. The au thor has fou n d that polyester sheets with one matte side and one
glossy side are more satisfactory for this application than sheets both sides of
which are matte. The sheet should be cut about 5 cm (2 i nches) larger than
the pri n t in both dimensions; space on the edges can be used to write identi­
fication data, elate of preparation, and other i n formation. The polyester sheet
material should be 3 m i l or 4 m i l ( .003 or .004 i nc h ) in t hickness for gen­
eral appl icat ions; t h i n ner material may be used for prints 20 X 25 cm (8 X
1 0 i nches) a nd smal ler.
Densitometer head locations must be precisely marked on the overlay
sheet using a tech nical pen with a medium poi n t and a suitable stable black
i n k. 1 0 The glossy side of the polyester sheet is placed clown, against the sur­
face of the photograph. The matte side of the sheet is on top, and a l l i n k
markings a nd notations should b e on t h e matte side of t h e sheet. Great care
should be taken to keep i n k away from the photograph. It is usually satisfac­
tory to mark the dens itometer head locations by traci ng the outer edges of
the densitometer base plate ( Figure 2). After the densitometer head locations
have been determined and marked, the polyester sheet should be removed
and a hole about 1 .5 cm ( V2 inch) in size should be cut at each densitom­
eter head readi ng locatio n . ' ' All ink marki ngs on the overlay sheet should be
completed before cutting the holes; otherwise, the pen poi n t m ight acciden­
tally slip thro ugh a hole and depos it ink on the photograph . To avoid confu­
si o n , the overlay sheet sh o u l d be marked (e.g. , "Top," " Bottom") to indicate
its position. The sheet should bear a seria l nu mber that identifies the print,
a nd densitometer cali bration data should be recorded i n a notebook made
of reasonably stable paper. The overlay sheet m ust rema i n i n exact regis­
tration with the print d u ri ng all read i ngs; smooth-su rfaced weights placed
o n the sheets will help keep them in positio n . Because of local ized density
variations i n most color prints, subsequent read ings must be take n at pre­
cisely the same locations as the original readi ngs if the meas u re ments are
to be m ea n i ngfu l . 'v\lhen densitometer heads are changed, a method must
be cle,risecl for position i ng the new head using the old tracings. The i mpor­
tance of taki ng fut u re read ings at the exact locations used for the original
 Reading 67 IV I I . 1 1 E L 1\I

Figure 1
Print and matte polyester overlay
,. sheet marked wil h densitometer
1 •
head reading locations. The
photograph (original is a Kodak
Dye Transfer color print) has
.
: . a n image size of 25 X 25 c m
( 1 0 X 1 0 i nc hes ) and is of the
John F. Kennedy l'amily; it
was taken August -I· 1 963, by
Cecil Stoughton. The original
color negative is part of d1c John r:.
Kennedy Library Collccrion.

' •.

.,

Figure 2
Densitometer head located in the
reading position by a n i nk tracing
of the base of the head on the
polyester overlay sheet .

read i ngs can not be overemp hasized : accurate data can not otherwise be
obtained. The person taking the read ings should test h i s or her technique by
seei ng whether readi ngs taken by a second person prod uce the same results.
Work areas should be clean, and to avoid putting fi ngerpri nts on
the photographs, cotton gloves should be worn by the operator. A sheet of
bright white matte board or opaqu e white glass should be placed on the work
table and prints placed on this white su rface while densitometer readi ngs
are made. As most print su pport materials transmit a sign i ficant a mount of
l ight, the reAectance of the su rface beneath a prin t may have a sign i ficant
effect on densitometer read i ngs made i n low-density areas of a photogra p h .
F o r example, readings taken o n a dark work su rface w i l l usually indicate
P a rt VIII E X ll l B I T I O N l' B J\ C T I C E

somewhat higher densities than readings taken on a white work su rface;

such discrepanc ies may be quite l arge with albumen prints and other types
of p hotographs made on thin paper supports . The same type of work s ur­
face shou Id be u sed for making all read ings, and densitometer readings of
the work surface i tself shou Id be recorded each time the work surface is
cleaned or changed.
Density readings through the reel, green , and blue densitometer Fil­
ters should be taken at m i n i m um -density locations, low-density locations of
about 0.35, and maxim um-density locations. Normally, readings in each den­
sity range should be taken in at l east three locations (for a total of at least
nine reading l ocations), and the readings should i nc l u de near-neutral colors
if possible. Some of the readi ngs should be taken near the top of the print,
where the i ntensity of i l l u m i nation d uring d isplay is usually somewhat h igher
than it is in the lower areas. Fairly large areas of u n i form tones should be
selected i f possible for readi ng locations. H owever, in many photograph i c
i mages such areas m ay n o t b e ava i lable, so a large n u mber of readings wi ll
be requ ired for accu rate representation. After readings have b e e n taken, the
polyester overlay sheets should be stored .flat in a protective polyester sleeve 1 2
o r i n a h igh-qual i ty paper envelope.
When pri n ts are displayed and are subject to l i ght fad i ng, it is par­
ticularly i mportant that m i n i mu m -density and low-density (approxi mately
0.35) areas be carefully monitored, as dye losses in the low-density areas will
be m u ch greater proportion a l ly than dye losses i n high-density areas. Th is
relationship between dye loss and density is typical of ma ny types of color
print materials; however, some types of prints, such as Polaroid SX-70 prints,
m ay develop stains which alter m in i m u m density behavior. In dark-fading,
dye losses tend to be proportional t hroughout the density range of the color
i m age. Prints wh ich have faded i n dark storage do not suffer from the type of
h ighligh t detail loss that is characteristic of prints which have faded because
of exposure to l ight.

Color Print Fad i ng M o n i tor

Use of a color print fad i ng mon i tor a llows one to measure i n d i rectly the
changes which take place in a color photograph . All of the colors and tones
of a color photograph are obtained by varying the concentrations of cyan ,
magenta, an d yellow i mage dyes or pigments i n t h e e m u lsion layers which
are coated in three or m ore layers on the s urface of the support m ateria l.
A few types o f color prints, such as Fresson. Quadri.chron'!.ie pigment prints,
m ake use of black as a fourth color; the black p igment is normally present
o n ly in h igh-density (dark) areas of the image. The same three (or four) col­
ors are u sed to form all the colors in a color print, and a neutra l gray patch
 Reading 67 \\I I L 11 E L 1\ I

consists of nearly equal concentrations of the three (or fou r) i mage dyes or
p igments. The m i n i m u m-density patch contains l ittle or no dye or pigment .
It is possible to measu re c hanges i n neutral gray patches of m i n i m u m den­
sity, low density, and maxi m u m density and thereby to obtain a reasonably
accurate in dication of changes occurrin g i n any area of a color pri nt if the
three patches are made of the same print material and are processed in the
same way as the original print. A si n gle fad i n g moni tor should be used with
o n ly one color pri nt, and the monitor shoul d be permanently assigned to
that pri nt with a serial n u mber.
Potential disadvantages of fad i n g monitors i n clude possible d iffer­
ences i n print and monitor fading/staining rates which may be caused by d i f­
ferences i n materials, processi ng, or use conditions. Furthermore, as noted
above, monitors can be prepared o n ly from prin t materials and processes
which are avai lable in the marketplace: monitors therefore can not be pre­
pared for most, if not all, older color print materials in a collection. Most
i nstitutions will find i t more practical and accu rate to monitor most of their
color pri n ts directly and to reserve the use of fadi n g monitors for spec ial
situations; for example, in some cases i t may be u ndesi rable to remove a
pri n t from its frame repeatedly for d i rect measurements.

Preparation of a Fading Mon itor

Three patches, each about 1 . 3 cm X 3 . 3 cm ( 1/2 X 1 1/4 i n c hes), should be

prepared u s i ng prin t material , processing chemicals, and processi ng proce­
d u res identical to those used with the origi nal print. Any variation from the
processing chem icals or procedu res used with the origi nal prin t may affect
the fading characteristics of the mon i tor and may red uce i ts acc uracy. One
patch should be m i n i m u m dens ity (white); one patch should be a neutral
gray of about 0 . 3 5 density; one patch should be m axi m u m density (black).
Ideally the patches should be prin ted on the border <lrea of each original
print when i t is made. However, it is u n l i kely that this will become com­
mon practice, and the patches will usually have to be optically pri nted in
the proper size on a si ngle sheet of prin t material. As an a lternative, entire
sheets of material can be printed to the desi red density and the sheets c u t
i nto t h e proper s ize after processi ng.
The three patches should be moun ted o n the same type of board used
to mount the photograph being monitored a n d should be attached with the
same type of ad hesive or mounting system. When it is used, the monitor
should be covered with a matte made of the same type of board as that used
to overmatte and support the original pri nt. The overmatte should have an
ope n i ng in the center, and only one-half of each patch shou ld be exposed to
l ight, so that the l ight-fad i n g and dark-fading fu nctions of the monitor are
Part VIII E X ll l B I T I O N P H ,\ C T I C E

separated (the overmatte must be esse ntially opaq ue to l ight if the monitor
is to give an accurate i ndication of dark-fadi ng). The monitor should then be
placed i n a small fra m e 1 3 u s i ng the same type of glass or plastic covering and
backing materials that were used with the original prin t to which the moni­
tor has been assigned .

Use of the Fad ing M o n i tor

At all ti mes the mon i tor should be kept in the same temperature and rela­
t ive humid ity conditions as the pri nt to which it has been assigned . When the
pri nt is o n display, the mon itor should be exposed to the same i n tensity of
l ight of the same spectral distribution for exactly the same l ength of time. The
monitor can be ex1Josecl to l ight in a room separate from the d isplay area only
if a l l conditions are identical. The l ight level on the monitor can be adju sted
by varying the d istance of the mon itor from the l ight source; the level chosen
should be equal to the l ight i ntensity on the 1nost brightly illu mi nated portion
of the pri n t . Most ga l lery and museum d isplay areas do not provide completely
u n i form i l l u m i nation on the entire su rface of a pri nt . If daylight is present in
t he d isplay areas, it will probably be necessary to place the monitor on the
wa l l adjace nt to the pri nt, as it is d i fficu l t to obtain identical l ight ing condi­
tions at all ti mes of the clay i n a d i ffe rent location. When the pri nt is shipped
to another location ( for example, when it is loaned to a nother i nstitution), the
mon itor m u st accompany the pri nt d uri ng transit and storage; the monitor
and the original pri n t must be kept together at all t i mes. The borrowing i nsti­
t u t ion m u st be i nstructed as to the proper use of the monitor.
I n itially, the fad i n g m o ni tor densities should be measu red at least once
a year to see how much change has taken place; ex 1Jerience with each type of
print material and with the dark storage and d isplay conditions to which the
prints are subjected will i n d icate whether the mon itor should be measu red
more or less freq uen tly.

M a i ntai n i ng Long-Term Acc uracy of Print Monitoring Systems

The most d i ffic u l t aspect of a mon itoring program is maintai n i ng long-term

system cali bration; the u l t i mate usefu l ness of a mon itoring program will be
determ i ned by the degree of accuracy of i ni tial and future instru ment cali­
brations. In fine art applications, one must be able to measure accu rately
very small changes i n the visual characteristics of color prints.
The cali bration syste m must not be affected by c ha nges i n color densi­
tometers or i n other measuring equipment. I t is obvious that present equ ip­
ment and fi lters will become obsolete and will be replaced many ti mes d u ring
the next several h u n d red years with new optical dens ity measu rement i nstru-
 Reading 67 IV I L 1-1 E L 1\ l

ments. As two differen t color densitometers may give sign i ficantly d i fferent
readings from the same print samples, the data obtai ned with one piece of
equ ipment will have to be translated accurately to permit comparison with
readi ngs taken with the other instruments.
A specific densitometer should be set aside for use i n the mon itoring
progra m , and it s houl d not be u sed for an y other appl ication. Th e densi­
tometer should be used in an envi ro n ment with constant temperature and
consta n t relat ive h u midity and should be allowed to warm up until cali bra­
tion read i ngs stabil ize (depe nding on the type of densitometer, an adequate
warm-up period may range from 30 m i nutes to about 1 2 hours ) . Before den­
sity readi ngs a re made of each print (or each fading moni tor), the densitom­
eter should be carefu l ly calibrated using the fired porcelain enamel plaque
s u ppl ied by the manufactu rer of the i nstru ment. I n addition, before each
measu rement session, or at least o nce each day the densitometer is used,
the accu racy of the densitometer should be checked with a Kodah Reflection
Densitometer Chech Plaque; 14 this plaque wi l l i n d icate cha nges in spectral
response of the densitometer that resu l t from fading of the filters or from
other causes. The Kodak plaque should be permanently assigned to the den­
sitometer and should be stored carefu lly between uses.
I n add ition, measu red gray scales and color scales made of each type of
color photographic material in the collection should be kept in cold storage
at -18°C (o°F) or lower and at 30% relative h u m idity; very low-temperature
storage w ill reduce changes i n t hese photograph ic calibration stan dards to a
n egligible amount duri n g the next 1 ,000 or more years, accord i ng to current
esti mates based on accelerated test data . 1 5
A Macbeth ColorChecher16 i s recommended a s a suitable original gray
scale and color patch i mage for u se i n preparin g the photographic mate­
rial cali bration standards; the standards should be printed in a s ize of about
7.8 X 1 2.7 cm (3 X 5 i nches), i ncluding a border of at least 1 cm (3/s inch) to
protect the i mage area. All of the color patches, i nc l udi ng those with low­
satu ration colors, should be read and the data recorded. While the porcelain
calibration plaques will generally be adequate for the contin u ed calibration
of a spec i fic densitometer, their u se w i l l not necessari ly prod uce acc u rate
read ings after an instrument has been repaired or if the fi l ters have faded or
have been replaced; i nstru ment respon se may also change if the l ight sensor
has been replaced. Each dye of each type of color photographic print has a
disti nct set of spectral absorption characteristics; for t h is reason , any change
in the spectral response of a densitometer w i l l produce differen t readi ngs
from a given photographic sample even if the i nstru ment has been cali brated
with a porce la i n plaque.
When the color photograph i c calibration standards are needed, they
should be removed from cold storage and the packages conta i n i ng the stan-
P a rt V I I I E X H I B I T ION P R A C T I CE

da rds should be allowed to reach room temperat ure before they a re ope ned.
The densitometer should be calibrated with the porce lain plaque, and read­
ing should then be take n , with the color photographic calibration standards
and nu merical conversions determ i ned for each gray scale density and color
patch of each materi a l ; use of these conversions wi ll a l low continued acc u­
racy of the overal l system d uri ng the l i fetimes of t he color prints. In fut ur e
years, most i nstitutions w i l l have computer-based catalogin g a n d data stor­
age system s; the densitometer can be i nterfaced directly with the computer,
and a program can be devised for automatic conversion of curre nt data to a
form that can be compared directly with t he i n itial and subsequent densito­
metric readi n gs for an original print or fad i ng mon itor.
\Vh i le other long-term cal ibration proced u res may be devised in the
future, the author bel ieves that at present, lo ng-term system accuracy can
be maintai ned only by the use of preserved photographic calibration stan­
da rds for each type of material in a collection. It is presu med that in the
near fut u re most i nstitutions with significa nt color photographic col lec­
tions wi l l i nstall h u m i d i ty-controlled cold-storage facilities for the preser­
vation of their color collections; 17 the cal i bration standards can be kept i n
these cold-storage areas. I f h u midity-con trol l ed cold storage i s not avai lable,
the photographic calibration standards should be sealed in suitable vapor­
proof packages 1 8 and should be placed in a normal - 1 8°C (o° F) household­
type freezer.

Cau tions

Wh i le the use of a fadi n g moni tor or the direct mon itoring of an original
color prin t w i l l give an accurate i nd ication of dye fad i ng and sta i n formation,
i t may or may not i n d icate the physical deterioration which can occur i n a
color print. Examples of p hys ical deterioration i nclude cracking of the top
polyethylene a n d emu lsion layers of resin -coated ( R C ) prints, cracking of
e mulsions on fiber-base pri nts, and i n ternal i mage-receiving layer cracking
or the formation of small " snowflakes'" in Polaroid SX-70 prints. Retouching
and corrective "dust spott in g" may produce irregular fading or stain i n g such
as the orange d iscolorations sometimes seen on I<odah Ehtacolor R C prints.
All prints should be carefu lly exa mined on a regu lar basis so that any physi­
cal defects or other i rregularities can be documented and photographed for
future reference. 1 9

Recommended L i m i ts of Color Print I mage Deterioration

Exami nation of a large n um ber of deteriorated color prints-including sam­

ples which were faded i n accelerated l i ght-fading and dark-storage tests and
 Reading 67 \\' I L 1-1 E L 1\ I

prints which slowly faded during long-term d i sp lay and dark storage u nder
normal condition s-has led the author to propose the set of l im its for color
prin t i mage deterioration shown in Table 1 [ not reprod uced here J . This set
of four groups of data describes all of the significant visual cha nges that
can take place when a color print deteriorates i n dark storage and/or dur­
i n g exposure to light and/or ultraviolet rad iation. Such cha nges i nclude stain
formation, density and contrast cha nges, color balance shifts, and the vari­
ous common com bi nations of t hese changes. A color prin t may be consid­
ered to have passed the acceptable l i m i t of deterioration when any one of the
numerically expressed criteria has been reached. With any given color print
materials, the particular c ha nge in volved depends on the particu lar concli­
tions of display or dark storage. For example, wi t h Polaroid SX-70 prints kept
in the dark, the " m i n i m u m -density stain formation" l i m i t will al most always
be reached first. With Kodah Dye Transfer pri n ts ( made with the dye set com­
merc i a l ly ava ilable i n the 1 965-1 980 period) on d isplay, the "red-green-blue
density loss i mbalances" l i m it will probably come first, because of the l ight­
fad i ng i nstabil i ty of the Koclah Yellow Dye Transfer Dye . This more complex
a nalysis of color i mage deterioration correl ates m uc h better with visually
observed changes than does the criterion "o. r density loss of one or more
dyes at an i nitial density of 1 . 0 , " which has sometimes been used i n the tech­
n ical l iterature of the manufacturers .20 The "0. 1 density loss" criterion also
ignores sta i n formation, which is often the principal factor i n color i mage
deterioration i n materials l i ke Polaroid SX-70.
The author suggests, of course, that the limit of color i mage deteriora­
tion should not be reached duri ng any s i ngle exhibition period and that color
prints should not normally be placed on conti n uous d isplay u n t i l the l i m i t
has been reached . S o m e types of chromogen i c color pri n ts, s u c h a s Koclah
Ehtacolor 74 RC pri nts, wi l l pass the suggested l im i ts of deterioration i n less
than 10 years, even when kept in the dark at room temperature, because of
their poor dark-storage stabil i ty; t h is can be preven ted o n ly by placing the
prints i n low-temperat u re storage. The curator wi!J have to decide how much
of the usefu l l i fe of a print he or she will al low to be consumed d u ri n g a
particular exh i bit, or d u ring the cu rator's ten u re, and how m uch wil l be left
for future cura tors. For example, given this set of deterioration criteria, and
knowing the stability c haracteristics of Koclalz Ehtacolor 74 R C prints, one
could conclude that u nder moderate-level tungsten i l l u m i nation (200 l ux/
20 footca ndles) and room -temperature con d i tions of 24°C (75° F) and 55%
relative h u m id i ty, the pri n t wi l l have a usefu l display l i fe of about 6 years;
this wou l d a l l ow 24 t hree-month exhi b i t ions i f the print was kept i n cold
storage between display period s . If the pri n t was not; kept in cold storage,
and i nstead was kept at room temperature, the usefu l l i fe would probably
be less than 8 years even if i t was never exhi bited. If the print was kept i n

6.17
P art VIII E X 11 I ll I TI 0 N I' 11 A C T I C le

cold storage between exh ibitions, and was exh i bited for a si ngle three-month
period each 5 years, the final exh ibition of the print could take place about
1 20 years after the first exh ibition. Other pri n t materials (such as many of
the early color processes) a re much less stable than J<oclah Ehtacolor 7 4 RC
pri n ts and could tolerate only a fraction of this total d isplay time.
Grant Romer, t he conservator of photographs at George Eastman
House i n Rochester, N ew York, working i n conju nction with the author and
Ron E merson , c u rator at George East man House, and John Upton, guest
curator at the museu m, will be using the basic color print monitoring pro­
cedu res descri bed here for "Color as Form: A H istory of Color Photogra­
phy," an exh ibition which will open at the Corcoran Gal lery in Wash i ngton,
D . C . , on Apri l 9, 1 982 and at George Eastman H ouse on Jul y 2, 1 982. To the
author's knowledge, this w i l l be the first exhi b ition of color p hotographs to
be monitored densitometrically d uring t he exh i b ition period. Some of the
photographs chosen for the exh i bition will not be shown i n their original
form beca u se of physical problems and/or the extreme i nstab i l i ty of their
color images; i nstead, color copy prints or transparencies will be d i splayed .
Any of the origi nal color photographs on d isplay that change beyond prede­
termi ned l i m its will be replaced with copy prints d uring the 6-month period
of the exh i bition.

Acknowledgme nts

The author expresses apprec iation to Carol Brower and Marcia Brubeck for
their thoughtfu l assistance with the preparation of this article.

Additiona l Fad i n g M o n i tor I n formation

on S pecific Color Pri nt M aterials

Fadi ng mon itors for i nstant materials, such as Polaroid 600, SX-70, Pola­
color 2, t<odah I nsta n l: Color Filrn PR 1 0 , f<oda 1nati.c fnstan/: Color Fil1n, and
Fuji lnslanl Color Film Fl-10, should be prepared by optically pri nting the
t h ree density patches in the center of the [Hints. Si nce cutting or trimming
such prints will alter their sta b i l i ty characteristics, the prints should remain
i ntact for use as monitors. Kodah Ehtafiex P C T i nstant darkroom color mate­
rials can be treated in the same manner as convent ional color print materi­
als, though great care should be taken i n cutting £htc(f/,ex patches to size.
Both Kodak and Polaroid have been making changes i n their i nstant color
materials on a fairly frequent bas is, and some of these changes alter stability
characteristics. One should therefore ascerta i n that a monitor for an i nstant
color pri nt is made on the same material used for that print. The manufac­
turer can be consulted for advice on t h i s point, but i f there is any doubt,
 Reading 67 II' I L I I E L ,\ I

the pri n t should be monitored d i rectly and, i f possible, i n combi nation with
the use of a print mon itor. Polaroid 600, S X- 70 , Polacolor 2 , a nd Polacolor
ER pri nts i n particular may have exceeded the suggested low-density stai n
formation l i m its before t hey arrive i n a museum collection. I n such cases,
the pri n ts should be measu red d i rectly in low-density areas, and t hese
readings should be com pared with data obtained from identical materials
shortly after they were processed ( readings should generally be made about
24 hours after the processing of an i nsta n t print). As i nstant color prints
usually have higher i n itial m i n i m u m density than other pri nts, low-density
readings should be taken from areas of about O A 5 instead of 0.35 as sug­
gested for other prints. The origi nal Polaroid Polacolor fi l m ( now referred to
as Polaco/or 1 ) introduced in 1 963 is no longer avai lable, so pri nts made from
this film must be monitored d i rect ly; these prin ts characteristically exhibit
very good da rk-storage stability and do not have the m i n i m um-density stain
problems associated with the later Polaco/or 2 and Polacolor E R pri nts. Sev­
eral other types of color pri nts, including Kodah Dye Transfer, Fi1ji Dyecolor,
Cibaclnome, Fresson Qi1adricli ro1nie, and tricolor carbon/carbro appear to
have very good dark-storage stability and freedom from sta i n formation;
however, they are subject to l ight-fadi ng. While these pri nts seem to have
good roo m-temperature da rk-storage properties, they should nevertheless be
monitored for dark-storage changes that m ight eventually necessitate plac­
ing them in cold storage . J<oclah Dye Transfer and pigment color pri nts are
made with a variety of color layer seque nces; if possible, t he fad i ng moni­
tor should have the same layer sequence as that which was used to make
the pri n t being moni tored. I n the preparation of fad ing moni tors for the
chromogen ic materia ls, such as Eht.acolor RC papers, every e ffort must be
made Lo fo llow the identical processing procedu res (chemical process, the
use or nonuse of Kodah Ehtaprin.t Stabili:er-Process EP-3 , wash time , wash
water temperature, and p H ) u sed to make the original pri n t . The pH of the
final wash water may have a sign i ficant effect o n the dark-storage stabil ity of
the cya n dye and m i n i m u m-density sta i n formation in l<oclah Ehtacolor 78,
74 RC, a nd 37 RC papers. If the origi nal processing cond itions are u n known
or uncertai n , the original print should be monitored directly as wel l as by a
separate Fadin g monitor. Color transparencies, such as L wniere Autoch rome
plates, can be mon i tored using the same general proced ures outli ned for
d i rect mon itoring of pri nts; however, a transm ission densitometer will be
req uired for taking density readi ngs.

References and N otes

1 Dark-fad ing is used as a genera l term to describe t h e kinds of color l'a di ng a n d

stai n i ng w h i c h take place w h e n l ight is not presen t ; the rates o l ' t he c h e m ical

649
Part VIII l: X l l l B I I I O N l' H A C "l I C E

reactions i nvolved i n dark-\'a d i ng arc governed by tcm peralLirc a n d , t o a lesser

ext e n t , by relative h u 111id i ty. The h igher the tc111 pera t u re and the h igher t h e
re lat ive h u m i d i ty. t h e \"aster t he rate o\" dark-\"a d i ng. \•V i t h 111any types o f " color
prints. d a rk-fa d i n g rates approxi111atcly double \"or each 6°C ( 1 1 ° F) i ncrease i n
te 111perature. f\s l ight i s not i nvolved i n dark-\"adi ng, t hese c he 111ical reactions
continue i n essent i a l l y t h e same f"nr111 when a print i s exposed t o l ight o n
d isplav. L ight-f"ad i ng i s t h e res u l t o f " photoche111 ical reactions. When a pri n t i s
o n d i spl ay, l ight-fa d i ng and dark-\"ading occ u r s i m u lta neously.
Chro 111ogcnic color prints, which arc t h e rnost COilllllOn t\1Je o r color prints,
contain n o dyes prior t o processi ng. The i mage dyes arc sy nthes ized i n the t h i n
gelat i n e m u lsion layers b y a process cal led d1 m111oge11ic de1dop111e11 t . Exposed
l ight-se n s i t ive s i lver h a l i d e ( s i lver ch loride. s i lver bro11 1 ide, or s i l ve r iodide)
is developed i n a color developing age n t ( u s u a l ly a phe nylencd ia111 i nc) "·h i c h
produces 111e t a l l i c i 111age s i lver a n d oxidized deve lo p i n g age n t . T h e oxid ized
dc\'cloping age n t reacts w i t h orga n i c molecules kno\\ n as color cou plers
(\\' h i c h arc normally p u t i n t o t he c111 u l s i o n layers d u r i n g 111an uf'act u re. or.
as in the case o\" the Kodach ro111c Process. t he couplers arc d issolved in t he
color developers) Lo produce cyan ( us u : d lv a i n d oa n i l i n e clvc). 111agc nta. a n d
ycl lo\\' ( u su,dly a1.0111 c t h i n c dyes ) . T h e 111cta l l i c si lver produced i n t h e course
oJ" dcve\op111ent is chcmica\Jy rCnHl\'Cd by the end of" processi ng; the color
i mage consists only o f the t h ree o rga n i c dyes. For a detailed d i scussion ol'
c h ronrngcnic development, sec C : rant \ l <1ist . t\ludem Photogmphic Processi11g,
Vol. 2 ( N ew York: J o h n \Vi Icy and Sons, 1979). \Vh i lc 111any types o\" colorants
\"adc o n prolo nged exposure t o l ight, the chro n wgc n i c dyes used with color
photographs arc d i s t i nguished by the \"act t hat 111:111y o r t hese dyes f'adc fa i rly
ra pidly d u ri n g dark storage.
3 H enry \Vi l hc l 111 . " Light Fad i ng C h a racterist ics ol" H e l l ection Color Print
1\ l a terials." presented at the 3 1 s t r\ n n u a l Con l"cre ncc of" t h e Society of"
Photographic Scientists and E ngi neers, Was h i ngt o n , D.C .. t\ l av 1 . 1 978. Some
of" the i n l"o rma t i n n prese nted i n the t a l k has been pu b l ished: H e nr�' W i l h e l m .
" C o l o r P r i n t I n sta b i l i ty."" t\ loclern Pl10togm l 'I') . vol . -13 · no. 2 ( February 1 979 ) .
pp. 92-93. 1 1 8 . 1 20- 1 2 1 . 1 24. 1 _) 4, 1 .)8 . 1 40 . 142. 1 76.
Possible reciprocity effects \\Cre 111entioned hr Hobert J . Tui te. ·· 1 111age
Stabi l i t y in Color Photography: · presented at the 3 1 st t\n n u a l Con \"e rencc o\"
The Society o r Photogra phic Scientists a ml E ngineers, Was h i ngton , D . C . ,
IV l ay 1 . 1978. Tu itc's t a l k was l:Jter p u b l i s hed as " I mage S t a b i l i t y i n Color
Photogra p hy," Journal of A / lplied Plwtogm/l/1ic E11gi11eeri11g, vol . 5 , n o . -! ( Fa l l
1 979). p p . 200-207.
-! f\n acco u n t or rec i procity effects in accelerated l ight -fad i ng tests was given
in H e nry W i l h e l m . " H cciprocity Effects i n the L i g h t Fadi ng o r Hcncction
Color Prints. " prese n ted at the 33rd A n n u al C o n ference of" Thc Society o\"
Phot ogru phic Scientists a n d E ngi neers. i\ l i n ncapo l i s . i\ l i n ncsota, i\ l ay 5, 1 980.
So111c o\" t he i n l"ormation i n 1he talk has been p 1 1 b l i s hcd : Bob Schwa I berg,
"Color Preservation U pdate. " Po/111/11r Plwtogm/1/1; . vo l . 89, no. 1 (January
1 982). p p . 8 1 -85, 1 3 1 .
Two a rt i c les o\" i n terest conce rn i n g h igh-intensi ty l ight Fad i ng tests o F color
photogru phs ( poss i b l e rec i p roc ity effects were not i nvestigated):
C . 1 1 . C i lcs, S. D . Forrester. H. I lash1m, a n d H . I lorn. " Light Fast ness
Eva l uation o\" Colour Phot ogra phs. " Tlie jo11n11il of Photographic Scie11ce.

650
 Reading 67 II' I L I I E L ,\I

vol . 2 1 ( 1 973). pp. 1 9-23. (The l ight l'ad i ng sta b i l i t ies or cert a i n u n iden t i f ied
color photogra p h i c 111aterials were eval uated using t he B . S . I. B l ue Wool
Standards as a 111cans of' co111 parison ) :
1 1 . G . Rogers. i\ I . l delso n . R . F. W. Cicc i uc h . a n d S . i\ I . 13100111. " Light
Stabi l i ty of' New Pol<1roid Colour Prints." Tl1e )011nwl of P/10togmp/1ic Science,
vo l . 22 ( 1 97-1 ). pp. 1 38- 1.p. (The authors were "·ith the Research Laboratories.
Polaroid Corporat i o n . Ca111bridgc 1\ l assach u sett s . )
J\ project to monitor <1lbumen prints w a s started a l George E a s t m a n H ouse
in Hochester. New York. i n 1 979 by Ja mes Reil Iv, Doug Severson, and G ra n t
Romer. B o t h 1 9t h -ce n t u ry a n d freshly m a d e a l bu 111en prints ( i n t h e f'orm
or gray scales) were i ncl uded in t he project in a n e ffort to ga i n a belier
understan d i n g or t h e stability charact eristics of this t)'pe of' print. The project
i s s l i l l u n der way Hl t he L i me ol' t h i s wri t i ng.
David Kolody, a priv<1lc conservator rrom Boston, 1\ l assach u setts. has adapted
t h e method or d i rect monitoring of' prints described in this art icle Lo the
rou t i n e m o n i tori ng o r black-a nd-white p hotographs, l i t hographs. watercolors.
and etchi ngs. Kolody prepared a polyester overlav sheet marked w i t h a grid
consisti n g of' n u m bered l i nes drawn 2 c m (·l4 i nc h ) apart and with holes cul
al the i n tersect ions or eac h l i n e . Density readings can be qu ickly taken al l i ne
int ersection points on the grid w h i c h correspond Lo high-d e n s i tv, med i u m ­
densi ty. a n d low-densi ty parts or t he i mage; t h e l i ne coord i n ates a n d density
data are recorded i n " notebook. Only one overlay sheet need b e prepared u s i n g
t h i s procedure; t h e s a m e sheet is u s e d f'or a l l o f ' t h e p r i n t s bei ng monit ored.
W h i l e the pre-drawn grid overlay sheet does n 't orFer the f l ex i b i l i ty or bei ng able
to locate t h e densit ometer head al any desired point on a p r i n t . l<olodv believes
t hat t h e 111elhod is adequate f'or rou t i ne 111 o n itoring oF \\'Ork before and arter
conservation t reat men Ls; he slartcd u s i n g t he system in early 1 982.
6 In 1 966, Garry Thomson. sc i e n t i fic adviser Lo the National G a l lerv in
London, started a n i nvestigation o r methods to record changes in pai n t i ngs
and arranged f'or a specially designed s pectrophotometer to be b u i l t f'or t h e
p u rpose; c c r L a i n pa i n t i ngs a r c n o w being meas u red o n c e every rive years. Sec
Linda B u l lock, " Renecta nce Spectrophotometrv for i\ leasure m e n t or Colour
C h a nge." Nat irmal Ga/lei)' Tecl111ical / 3 1 1 llet i 1 1 , vol . 2 ( 1 978), pp. 49-56. Also
sec R . i\ I . J o h nson a n d H . L. Feller, "The Use of D i ffere n t i a l Spectra l C u re
f\ nalvsis in t h e Study ol' i\ l useurn Objects,"' Dyest.11Jfs, vol. 4 4 , no. 9 ( 1 963).
p p . 1 - 1 0, a n d H . L. Fell er, " Problc111s i n Spectrophotometry," i n G . Tho111 son.
(ed.). 1 976 Lo11do11 Co11 /ere11ce 011 M 11se11 111 Cli111atology, I I C . 2 n d ed . ( London.
1 968). pp. 1 96- 1 97.
7 The companies i n c l u d e t h e 1Hac/Je1/1 Division of the Ko l l morgen Corporation.
L i t t le Brita i n Hrrnd. P.O. Drawer 950. Newburgh, New York 1 2 550, phone:
9 1 4 -56 1 -7300, a n d E/eclrn11ic Syste111s E11gi11eeri11g Co111pr111y, East A i rport Road,
C u s h i ng. Oklahoma 74023. phone: 9 1 8-255- 1 266. Heflect ion densi tometers
or good qualitv cost bel\\'eCn $ 1 .500 a n d S3.500, depe n d i n g on t h e 111od e l .
T o m o n i tor c o l o r t ran sparenc ies. such as A 1 1 l oc h ro111e plates or Eh1acl1ro111e
t ra nsparencies. a combi nat ion t ra n s m ission/reflection dens itometer should
be obtained: bot h of' the above companies supply separate a n d combination
mode l s .
8 Telephone d i scussion with J oseph P. Cassc les, Service Specia l i s t . MacbeJ/1
Dil'ision of the Ko l l mnq.(en Corpora t ion. Newburgh. New York (January. 1 982).
P art VIII E X ll l B I T I O N P H t\ C T I C E

9 i\ lalle su rf'ace polyester (such as D u Pont .\ /ylar or Cro11a.-) sheets ol' a s u itable
type can be obtai ned From stores that sell dral't i ng a n d engi neeri ng drawing
s u p p l ies.
10 Densitomete r head locations can be marked with a tec h n ical pen (such as a
/(o/i- 1-Noor Rapidograpli ) \\"i l h a N o . 1 point ( m ed i u m ) a n d a suitable stable
black ink (such as Higgins Professio1wl / 1ulia /11hfor Fi/111 No. ++65 Blach.
t<oli - 1 - Noo r Rapiclograph " Unil 'ersa/" Waterproof Blach Drml'i11g /11h No.
3080-P, or Ko/i-/-Noor Rapiclo11n1t Blach /1il< No. 3074-F).
11 H o les i n the polyester overlay sheet arc best c u l by placing t h e sheet o n a l a rge
piece of' glass a n d c u t t i ng o u t a c i rcle with an X-ACTO Craft S1l'itd lfoife No.
32. p . As an alte rnative to rou nd holes, square holes may be c u l u s i n g a stn1ight­
bladc kni l'c. Be certai n that t h e k n i fe b lade i s very sharp and c u l the holes
carcl'u l l y to avoid rough edges which m ight scratch the su rface ol' a pri n t .
T h e author gratefu ll y acknowledges t h e suggestion b y G ra n t Homer, con ser­
vator al George Eastman H ouse in Hochcslcr, New York, t hat holes be c u l i n
t he polyester overlav sheet. E l i m i n a t i ng t he polyester l'rom t he dens itometer
optical path i m p roves t h e long-term acc u racy ol' t h is system: i t also perm its
t h e use ol' mat te-s u rface polyester, which has i n k adhesion Far better t ha n
t hat ol' t he n o r m a l h igh-gloss polyester surface. I n t he originnl version of'
the moni tori n g system proposed bv t he author in 1 978. readi ngs were made
t h rough a clear polyester overlay sheet.
12 S u i table polyester ( D u Pont My lar-D) sleeves which open along o n e edge, l i ke
t he pages of' a book, so t hat it is not necessary to slide a print or l l l m in and
out ( t h u s m i n i m i z i n g risk or scratching the print su rface). arc ava i lable l'rom
TALAS, 1 30 Fi f'th Ave n u e , New York, N ew York 1 00 1 1 . phone: 2 1 2-675-07 1 8 .
13 I nexpensive metal frames of' t h e appropriate s ize can b e obtai ned a l
m a n y variety stores a n d , for l a rge q u a n t i t �1 p u rchases. o n e c a n contact a
m a n u facture r such as l ntercraf't I nd u st ries Corp., C h icago. I l l i no i s 606 1 4 .
Backing materials s u pp l ied w i t h such frames s h o u l d be d iscarded a n d replaced
with high-q u a l i ty matte board.
14 t<odah Hejlect ion Demito111eter Clrech Plaq11e. Kodak Catalog No. 1 40-5026: l'or
use with ref lection densitometers. For t ra n s m ission densi tometers. obtain a
Koc/ah Tra11s111issio11 Densito111eter Clrech Plaq11e. I odak Catalog No. 1 70- 1 986.
Eastman Kodak C o m pa ny, 343 State S t reet, Hochcslcr. New York 1 4650.
15 Eastman Kodak Company, Eva/11ating Dye Stability of Koc/ah Color Products,
C u rre n t l nf'ormation S u m mary ( C I S ) , i\J o . 50, J a n uary. 1 98 1 . C I S No. 50 series
sta b i l i t y i n format i o n sheets are ava i l a b l e f'or each Kodak s t i l l color f i l m and
print material ; data are given for fad i ng rates at normal room tcn1pcra t u rcs
and f'or refrigerated storage. Contact Sheldon P h i l l i ps , Consumcr/Prol'essional
and F i n ishing Markets, East man Kodak Company. 343 Stale S t reet, Hochester,
New York 1 4650. Also sec Storage rurcl CMe ()( Koc/ah Color J\llataials. Kodak
Pamphlet \fo. E-30 ( 1 2 - 1 980 revi s i o n ) , and Charleton C. Bard, George W.
Larso n. H owell H a m mond. and C l a rence Packard. " Predicting Long-Term
Dark S torage Dye Stabi l i ty Characteristics or Color Photographic Products
l'rom S hort-Term Tests." Jo11rna/ of Applied Plrotogmplric E11gi11eeri11g, vol . 6,
no. 2 (April 1 980), pp . .p-4 5.
16 The J\llacbetlr ColorChecher can be obtai ned l'rom photographic suppl iers or
l'rom t h e J\ / Division oF t he Kollmorgen Corpora t i o n , Little Britain Hoacl. P.O.
Box 950. Newburgh, New York 1 2550, phone: 9 1 4- 56 1 -7300.
 Reading 67 II' I L 1 1 E L � I

17 The firsl arl i n s t i l u l ion to have a humidity-controlled cold-storage Faci l ity

will be the An I nslilule of C h icago. The Fac i l i ty, u nder construction at
the l i me of t h i s writi ng, w i l l be capable of' mainta i n ing a temperature of'
- 1 8°C (o°F) al 40% relative h u m i ditv: i l is scheduled to be [ readv for use ] in
April . 1 982. Al t h is writi ng, George East man H ouse in Rochester, Ne\\' York
does not yet have cold storage f'a c i l ities for i ts extensive collection of' color
s t i l l p hotographs and color motion pictures. Other collecting i n st itutions
which have low-temperature cold-storage f'aci l ities are the J o h n F. Ken n edy
Presidential Lib rary in Boston, M assachusetts ( - 1 8°C [o° F] , 30% R H , opened
i n 1 979). National Aeronau tics and Space Adm i n istration ( NASA) i n Houston,
Texas (-1 5°C [ 5° F J , 25% RH, opened i n 1 982, replacing a fac i l ity which
operated al 1 3°C [ 55° F [ , 50% R H , opened i n 1 963), and Time, I nc . , Rockcl'cllcr
Center, New York (-18°C [o°F [ , 30% RH, to be operat ional i n early 1982).
I nstitutions with modcralc-tempcralurc cold-storage Fac i lities i nclude the
Peabody M useum at Harvard U n iversity (3°C [37° F ] , 30% R H , opened i n
1 979); the Library of' Congress, Landover, M aryla n d (2°C [35°F ] , 35% R H ,
opened i n 1978); H u man Studies F i l m Arc h ive, S mi thson ian l nstitution .
v\lashi ngton, D.C. (4°C [40° F [ , 50% H H , opened i n 1975) ; Lyndon B. J oh nson
Presidential Library, Aus t i n , Texas ( 1 0°C [50° F ] , 45% R H , opened i n 1 97 1 ) ;
Gerald R . Ford Presidential Library, A n n Arbor, M i c h igan (4°C [40° F [ , 40%
R H , opened in 1 98 1 ) . A rental cold-storage fac i l ity for the storage of color
photographs and motion pictures (- 1 8°C [o°F] , 30% R H ) w i l l open in Los
f\ ngelcs, Califo rn ia, in late 1 982: Jack B. Cold man, President, Advanced i\ l cd i a
Archive, I nc . , 9 6 H a rvard Avenue, B rookl i ne, Massach usetts 0 2 1 46, phone:
6 1 7-277-52 1 4 .
18 Kodah Storage E11ve/opesfor Processed Fi/111, Kodak Catalog N o . q 8 6398
(size 4 X 5 i nches), and Catalog No. 149 0028 (size 8 X 10 i nches). These
hcat-sealablc envelopes arc made with an a l u m i n u m foil barrier; ordi nary
plastic bags readily t ransmit water vapor and are not su itable for the storage
of photographs in uncontrolled h u m idity conditions. The Kodak storage
envelopes arc ava i lable from photographic suppliers or From the Eastman
Kodak Company, 3-13 State S t reet, Rochester, New York 1 4650.
19 Documentation photography is most effectively done w i t h color reversal f i l m s
(such a s l<oclah Ehtachro me 5 0 Professional Fil m ) . After processi ng, the color
transparencies can be preserved by placing them in cold storage. The <l ulhor
bel ieves t hat i n most cases, color f i l ms stored u nder the proper conditions
( - 1 8°C jo°FJ, 30% RH) will greatly outlast archivally processed black-and-wh ite
films stored u nder typical room tempera t u re conditions. I t is assumed here
that a n i nstitution engaged in a n1on itori ng program wi ll have access to cold
storage faci l i t ies for ils collections, densitometer photographic cali bration
sta ndards, and color doc u mentation photographs.
20 See for example Robert J . Tuite, ' ' I mage Stability in Color Photography,"
Jou rnal of Applied Photographic Engineering, vol . 5, no. 4 ( F a l l 1 979), pp. 200-
207, and Eva/11ati11g Dye Stability of l<oclah Color Products, Kodak Publ ication
C I S-50, J a n uary, 1 98 1 , Eastman Kodak Compa ny. 343 State S t reet, Rochester.
New York 1 4650.
 R e a d i n g 68

D O U G LAS G . S EVE R S O N

The Effects of Exhibition

on Photographs ( 1 986)

Douglas Severson. has served as 7?hot:ogra7?!1 conservator for the A rt I nstitute

of Ch icago since 1 9 8 1 . /-le has been a leading proponent of cold storage an.cl
proper exl1 ibit ion J?mct:ice an.cl 1 1 1 1der h is guidance t he A1-t Inst i t u te of Chi­
cago 11ins the fi rst a rt inst itution. to establish a l1 11111 idit)'-COntrolled cold-storage
facilit . J . The fi ndings s11 rn. 111ari=ed in. t h is art icle clearly de111onst rate that: pris­
t ine prints can change even when 111.011 nt:ed and exh ibited to the h ighest stcm­
darcls. As such, t:h.e worh i.nfl11encecl exhibition practice for years a nd became
a bench. m.arh for t.he cr11.cial i.111portan.ce of 111onitoring exhibited ph.otographic
materi.als usi ng the tech n:iq11.es described by Wilheln1 in Reading 67.

\!\!hat happens to photographs when they are exh i bited i n ga l lery conditions?
Th is subject has prod uced much speculat ion and some laboratory testing,
but very l i ttle actual measurement of change in real exh i bition situations.
The photography col lection at the Art I nstitute of C h icago has a very
act ive exhibition progra m . Frequent decisions m ust be made about whether a
certain photograph can safely be exh ibited, either i n the m u seu m's own ga l­
leries or on loan to another i nstitution. In a n effort to base these decisions on
rea l data rather than specu lation, a program was begu n to monitor cha nges
in prints by making reFlection density readi ngs before and after exh ibition.
The mon itoring method used was descri bed i n an article in the fa ll 1 98 1
issue o f th e jou rn.al of t h. e A I C ca lled '' Mon itori ng t h e Fad ing a n d Staining of
Color Photographic Prints" by H e nry \!Vi l helm. This article provided detailed

D O U G LAS C. S E V E l1 S O i\' , "The E llccts ol' Exhibition on Photographs," Topics in P"1010-

gmpliic Prese 1w1/io11 ' (V\lashi nglo n . DC : A m erican l n s t i l u l e /'or Conservat i o n , 1 986),
38-.p. © 1 986 Art I ns t i t u t e o/' C h i cago a n d Douglas G . Severson. Hcpri n tecl by perm i ssion.
 Reading 68 S E V E H S O N

working in stru ct ions which shal l not be duplicated here. The 111clhod shall
instead be briefly o u t l i ned to provide a bas is for u ndersta n d i ng the aclual
results presented.
To monitor a given print, an overlay was prepared usi ng 3-mil polyester
with one side matte. The slightly oversize sheet was placed over L hc pri n t
w i l h the matte side up, a n d L he edges a n d a few details o f t he image were
sketched in to ensure that the overlay could be returned to exactly the same
position on the print. S ix to twelve areas on the p hotograph were chosen to
be read, i nc luding h igh. 111 iddle, and low densities, and any suspect areas
such as a stai n . These locat ions were marked on the overlay, then Lhc sheet
was re111ovecl and turned over. A hole was pu nched at each 111arking with a 116
leather punch. (The sheet was inverted for punching so the edges of the hole
would l i ft away from the print rather than toward it, to prevent scratc h i ng. )
Reflection density read ings were then 111ade using a MacBeth TR524
Densito111eter with VVratten filters. The instru 111ent was regu larl y cali brated
with the Mac Beth porcelain check plaque and a set of color photographic
calibration standards, all of which were kept in h u 111 idity-controlled cold
storage when not i n use. All readi ngs were made with t he sa111e i nslru111ent
and the same filters i n the same location. Two different opera t ors were used,
but frequent cross-checks were 111ade to verify readings and no d iscrepancies
were fou n d . Reliability of the readi ngs was estimated q u ite conservat ively,
with a 111argin of error of :±: .02-Lh us, only cha nges greater than .04 were
considered significant.
For si mplicity and brevity, the resu lts presented here constitute a case
study of one particular exh ibition. This show i nc l u ded 1 80 photographs fro111
the Art I n stitute Photography Collection, representing a broad cross-sect ion
of photographic h istory and tech n ique, with prints dating fro111 1 842 to 1 982.
Thirty eight of these prints, including 1 3 different processes and 24 d i ffere nt
artists, were monitored before leaving C h icago and again after their ret u rn .
T h e prin ts were away Fro m the Art I nstitute for a total of 1 2 weeks,
with the actual exhi b i t ion last ing for 9 weeks. Duri ng that period the gal­
lery te111peratu re ranged from 56-77° F and relative h u111 idity ranged from
39-66% . The gal lery l igh t i ng was a l l t u ngsten ( no daylight or fluorescent),
with leve ls specified only as " less than 30 footcandles." l nfor111ation about a i r
qual i ty in t h e gal lery could nol b e obtai ned. The p hotographs were a l l t rans­
ported and exhibited in ragboard mats and in fra111es conta i n i ng Acrylite
O P-2 u ltraviolet-fi lteri ng acryl ic sheeti ng.
\Nh ile not idea l , these exh ibiLion conditions are nol atypical of what
111ost 111u seums and gal l eries actually ach ieve (as opposed to whaL is st riven
for or promised) . I n fact, t hese cond it ions may be somewhat beller Lhan aver­
age, si nce the l argest deviation Fro111 nor111al requi re111ents is in the d i rection
or lower temperature, which is general ly beneficial to photographs.
P a rt V I I I E X ll l B I T I O N P B A C T I C E

There <i re, however, two un known environmental factors which may
have contributed heavil y to the changes that took place i n some of the
prints. First, the air quality may have been poor. While no measurements of
pol l u t ion levels were ava ilable for t h i s particular t ime and place, the damag­
i ng e ffect on photographs of va rious common oxidants i n the at mosphere is
wel l -known .
Second ly, the photographs may have been exposed to excessive or rap­
idly A uctuating temperatures and h u m id i t ies in t ransit. It has been shown
that the baggage compartment of an airplane can be as cold as -40°F, while
that of a t ruck on a hot clay can reach as h igh as 1 20°F. Uncontrol led hu mid­
ity can be even more damagin g, and it is known that the crates in t h i s exhibit
experienced at least one major ra i n fa l l i n the course of their jou rney. Condi­
tions in tra nsit are al ways one of the most cli fncult aspects of any t raveling
exh ibition to control and measu re, but they may be a more l i kely cause of
damage than any other event i n the ful l cou rse of the exhibit.
The actual changes fou nd i n the 38 photographs monitored for this exh i­
bition are presented i n Table 1 [not reproduced here ] . Changes a re reported
as percentage of i nitial density in whichever color cha nged most-ge nera l ly
blue. While this does not ful ly describe the changes in a print, it does pro­
vide a si mple but meaningful i ndex of relat ive amounts of change.
I n order to determ i n e i f the cha nges fou nd were i n deed re lated to exhi­
bition and wou l d not also have occu rred i n storage, another set of density
readi ngs were made on all prints after an eq u ivalent 1 2 weeks i n dark storage
in the Art l nstit u te's temperature and h u m icli ty-con tro l lecl va u lts. No fu rther
changes from the previous readi ngs were fou n d .
The figu res presen ted i n Table 1 [ not reprod uced here] a re somewhat
erratic and clear patterns are difficult to d iscern . However, several results
are quite notable, and certai n tentative concl usions can be drawn pend i ng
fu rther i nvestigation.
Overa l l , of the 38 prints monitored, 17 did not cha nge, 15 changed 1 0%
or less, and 6 cha nged more than 1 0% . Of the 1 3 d i fferent processes moni­
tored, only 5 were i m m u ne to cha nge and 4 of these were rather u nusual or
hybrid materials (silver gelatin bei ng the only common process to remain
uncha nged) .
\l\fith regard t o albumen pri nts, t h e most common type of ni neteent h
centu ry photographic material, several poi n ts can be noted . S upport can
be f'o uncl here for the notion that the rate of i mage deterioration in these
materials is closely related to their condition. v\/ithout exception, t he prints
in better cond ition showed m ore density cha nge than those in poor cond i ­
tion. F o r instance, t h e most stained and faded albu men pri n t i n the exh i bit
( /!7 by Baldus) was unchanged, while that with the richest tonalit ies ( # 1 4 by
Jackson ) stained considerably. Also, the pattern of results in pri nts /1 1 0- 1 3
 Reading 68 � L V E H S O N

would ind icate that s ta i n i ng appears llrst in the shadows, where it is the least
detectable by the h u man eye.
Perhaps the most su rprising res ult to be found here is the change that
occu rred in photograph /'2 1 by St iegl itz. Plat i n u m and palladi u m pri nts have
a reputation for extreme stab i l i ty, but this i mage yellowed considerably i n
the m idtones a nd s hadows. One m ight assume the cha nge is a yel lowing of
the paper base du e to the acidic nature of the process, but the absence of
h ighlight yel lowi ng tends to contradict that notion. There may be other dete­
rioration mechanisms at work here.
The color p hotographs, on the other hand, may have changed less than
one would anticipate, given their reputation for instabil ity. One might a l so note
the i nverse relationship of age to deterioration with t he llvc Eliot Porter dye
transfer pri nts-the newest print changed most while the oldest was stable.
Patterns such as those mentioned above are of interest but must awa it
confirmation by other measurements. One must also consider that density
change is j ust one aspect of the deterioration that photographs undergo. No
attempt was made with these pri nts to measure the sorts of physical change
that may also have occu rred (e.g. su rface cracking or embrittleme n t ) .
H owever, one principal conclus ion see ms inescapa ble- na me ly, that
some photographs do i ndeed cha nge when exh ibited, sometimes i n ways that
are d i fficult to u nderstand or pred ict, and sometimes more than one wo uld
ever anticipate.
The question of how much, i f any, change should be deemed accept­
able is a large and controversial topic which shall not be addressed here.
S u ffice it to say that accord i ng to the " Recom mended Limits of (Color) Print
I mage Deterioration" stated in the aforementioned \Vi l helm article, 2 1 of
t hese 38 monitored prints wou ld have exceeded those l i mits in this one exhi­
bition period.
Th is method of prin t monitoring can be a very t i me-co nsu ming and
exacting activity . B u t for those i n a position to make decisions or give advice
about exhibiting photogra phs, t he i n formation it provides can be ext remely
u seful and importa n t .
 R e a d i n g 69

GRANT B . ROMER

C an We Afford to Exhibit Our

Valued Photographs? ( 1 986)

This reading was writt:en as a di rec/, response l o Severson 's alarm i ng report (see
Reading 68) on the dramatic changes in print density recorded ova the course
of one ni ne-weelc exh ibi,t;ion as well as to the general proliferation of photo­
graphic exhibitions, /-/ere, Romer u rged photographic h istorians, collec/:ors,
c u rators, dealers, and conservators to responsibly define safe exh ibition and
st:o rage conditions for photographic nwt:erials, G rant Ron'Ler (see also Headings
14 a nd 3 1 ) calls for /:he reevaluat:ion of cu rren/: exh ibition and display 11ractices
and the i -r nplementat ion of intensive 1ni nt monitoring programs to eliniinate
t he systematic degradation of our mos/; valued and i mport:anl' photographs,
T1iis effec tive "call to anns" sti m u lated decades of research and rigorous photo­
graphic print mon itoring progrc l// 1s and inspired greater caution,

Douglas Severson's report, 'The Effects of Exhibition on P hotographs,"

brings i nto the open an obsc u red issue of great i mportance to the preserva­
tion of our most prec ious origi nal photographs, Severson's fi nd i ngs con firm
a fact that has long been suspected a nd d readed, that is, that the exhibition
of photographs is incommensurate with their preservation , If it is not pos­
sible to predict the individual behaviour of all exh i bited photographs, if the
environments encou ntered in display and t ransit can not be com prehensively
mon itored and regu lated, if the entirety of the photographic artifact can­
not be constantly observed to record deleterious changes, then we are i rre­
sponsibly subject ing photographs to condi t ions which assuredly wi l l result

C HANT 1 3 , Hm1rn, "Can W e Alford t o Exhibit O u r Valued Photographs?'' Topics i 1 1 Pho­

logrnphic Presen•at io11 1 (v\lash ington, DC: American I nstitute for Conservat ion, 1 986),
23-30, Heprin ted by perm ission,
 Reading 69 11 0 � I E H

i n their degradation. Perhaps this is not a significant issue for photographs

which can eas i ly be replaced or are of l ittle artifactual or aesthetic val u e . B u t
for those images which are irreplaceable i t is extremely significant.
In recent years the exh ibition of such material has prol i ferated. A
review of the exhibitions l isted in Pictu rescope wi l l give only an inkling of
the thousands of va lu able photographs of all types and vin tages which are
c u rrently on exh ibition in the world today. These exh ibitions a re mounted by
a wide va riety of organizers with a corresponding wide variety of knowledge,
ski l ls and resources. The best of them give considerable care to protecting
the photographs d u ring display and transit, while the worst give no care a t
a l l , t he vast majority of exh i b itors fal l ing between the two extremes.
The exhibition Severson monitored was moun ted at the h ighest level
of practice and was of relatively short d u ration, yet dra matic changes were
recorded . The few other monitoring projects which have been conducted
show similar resu lts. I F one contemplates the p robable effects upon the
majority of photographs displayed for longer periods, under l ess controlled
conditions without monitoring systems, the i mp l ications a re sobering.
I ndeed, there is every reason to believe that the c u rrent exhibi tion vogue will
continue to grow in ternationally, with the result that more and more photo­
graphs will experience accelerated deterioration, which, because it is usually
too subtle to visually detect, w il l go u nobserved and u n c hecked. G iven the
i nadequ acy of the best of curre nt protection methods, the lack of general
awareness of the extent of the problem and the complexity of the issue, we
must accept the conclusion that we are squandering the largely u n renewable
resources of our photographic heritage in an ignorant fash ion. It is sadly
iro n ic that this is being done u nder the banner of promoting the apprecia­
tion of photographs.
If c u rrent exh ibit ion practice accelerates the degradation of p hoto­
graphs, new standards, p h i losoph ies and habits m u st be rapidly evolved and
implemented by those responsible for setting the trends i n using photogra­
phy. In fact, it is an obl igation for t hose i n fl uential entities to do so. H ow­
ever, there is good reason to doubt that this w i l l happen rapidly or effectively
si nce the prestigious and i n f l uential i nstit u t ions which mou nt the most
i mportant exh ibitions have too much vested i n terest in maintain i n g things as
t hey are now. Exhibitions are the means by which careers are establ ished and
Fu rthered , reve nues generated, costs recovered and publicity gai ned. H ence,
suggestions that exh ibitions should be curtailled are met with considerable
coldness. Practical inabilities. financial realit ies, and other obl igations wi l l
keep many institutions from changing their established modes of behaviour.
The only ent i ties which have the fl exib i l i ty to change are those that do not
have an established policy for exh ibiting photographs.
Part VIII E X H I B I T I O N P H ,\ C T I C E

Certai nly, t he responsi ble caretakers of i mportant col lections have

made compromises and have gra dua l ly employed more rest rictive and cau­
tious po l ic ies i n regards to exhibiting and lendi ng. H owever, the nature of
the problem m i tigates aga inst the compromises being anything more than
conscience-soothing i l lusions of effective response. The bottom line is that
photographs must pay with their cond ition for the m istakes i n judge ment
made by their caretakers. There are plenty of photographs that show gross
exh ibition da mage, there are more that a re da maged, just as deleteriously,
but i n ways too subtle for those without proper, but basic, conservation
knowledge to notice and appreciate.
It is only fai rly recently that certa i n photographs have acq u i red sig­
n i ficant art market va l u e, thus warra n ti ng the type of conservation attent ion
trad itionally reserved for Fine art objects. The current appearance of h igh
soph istication in regards to the apprec iation, u se and care of photographs is
ga ined re lat ive to the abysmal sta te of t h i ngs i n the not far distant past. Pho­
tographic h istorians, col lec tors, dealers, curators and conservators have bor­
rowed heavily from the established methods developed for the traditional Fine
arts. Many of t hose methods have not proven entirely appl i cable to the spe­
c ial needs of photography. At best, these borrowings have served as efficient
places to start evolving the appropriate methods requ i red for photographs.
At worst, they have given the appearance of sophistication and legitimacy to
pri m itive and disreputable p ractices.
The discipline of photographic conservation is i n a very nascent state
of development. The few specialists i n the Field would be the First to admit
t hat t hey are merely students of a h ighly complex su bject. If anyt h ing, the
experience that has been gai n ed i n the brief period of h igh level foc us on the
issues of photograph ic preservation has contributed to a greater appreciation
f'or t he i m mensity of the problems being faced, rather than the generation
of solutions to those problems. P hotographic conservators and preservation­
ists have found themselves del ivering more bad news than good . Th us, it
has been in their i n terest to keep their voices low. Those serving the needs
of collections being heavily used for exhi b i tions face a serious di lemma. On
one hand, they are chronicall ing [sic l , a i ding and abetting i n the system­
atic dest ruction of the photographs they are charged to protect by su pport­
i ng reprehensible exh i bition pract i ces. On the other hand, they largely owe
their existence to t hose very exh i b ition progra ms. Si nce their knowledge is
so i ncomplete and t h eir methods of protection so l i m i ted, they cannot rea­
son effectively against exhibiting with c u rators and others responsible for
organizing exh ibi tions. They have had to content themse lves with slowing
the probable degradation of the photographs by regu lating l ight levels and
l i m i t ing exposure time. (\i\lh i ch Severson's Fin di ngs demonstrate are i nsuf-

660
 Reading 69 11 0 � I E H

ficient systems of protection.) Often conservators are very confused about

which p hotographs should receive special p rotection . Frequently, prints i n
very poor condition are given special care while others, potentially more
vu lnerable, a lthough i n excellent condition, are given less attention. It must
be remembered that most photographic exh ibition cannot boast the vigilance
of even a confused conservator.
M ost of those responsible for the caretakersh i p of photographs do not
have a perception of the preservation problems of photographs beyond know­
ing that p hotograph s fade and that l ight can be a major factor in their deteri­
oration. Very few have the ability to perceive or differentiate between density
l oss, density accru a l , color sh ift and the whole h ost of other deterioration
manifestations l i kely to be encountered. Fewer still can adequately e.>qJlain
the causes of those manifestations. Thus, how can we expect a change i n
exh ibition practices t o occu r rapidly, i f the problem cannot be easi ly per­
ceived or u nderstood?
Although many institutions have adopted more cautious policies for
displaying and travell ing their valued p hotographs, none can claim to be
m eeting the preservation obligations, s imply because it cannot be clone. In a
few notable i nstances, organizations with the tech n ical and financial means
have generated high q uality facsim i les and reproductions to serve their exhi ­
b ition needs. Most exhibiting entities d o not have s u c h means at the i r dis­
posa l. Thus, the only al ternative i s not to exhi bi t valued p hotographs i n the
n u m bers and for the d u rations common today.
M a ny of the p urposes of today's exh ibitions can be well met by pub­
l i cation programs. M odern photo-mechanical technology makes the repro­
duction of original print quality very viable. Certainly it is abs urd to advocate
the destruction of those qual ities i n the process of glorifying them. There are
those who will argue that p hotographs are goi ng to deteriorate a nyway, so
why not exhibi t them while we can. To those I wou ld a nswer that properly
s tored p hotographs wi ll m ai ntain their condition well. Poor storage condi­
tions are n ot sound a rguments to justify display. The traditional p ri nt-room
methods of access ing delicate graph ic artworks can be wel l applied to valued
photograph s . I t m ust be recognized t h at photographs, particu larly those of
vintage, m u st be considered as vul nerable and delicate as watercolors and
old-master drawings, and treated accordingly.
Perhaps those who are ignorant of the problem can be excused from
blame. B u t for those who read the h andwriting that Severson has placed upon
the wal l , no excuse is possi ble; let t h e m conduct si m ilar monitoring projects
if they m ust have their own evidence of the display effects on p hotographs.
P hotographic exh i b i t ions are u ndoubtedly a c h ronic and major conservati on
p roblem. T he only t h i ng t h at is hidden i s the severity of t h e problem. For

66 1
P a rt V I I I E X ll l B I T I O N l' B A C T I C L

those caretakers who va lue the i r photogra p hs a complete reeval uation of cur­
re nt p ractices is called for. To ignore the call is irresponsible. The cu rrent
exh ibition vogue amounts to a systematic program of accelera t i ng the degra­
dation of our most val u ed and important photographs. This practice can and
must be changed . N o doubt there will be many who will claim that such an
assessment is too ext reme and that the problem is being exagge ra ted. They
will say that we do not have enough information to cha nge our ways. I would
say we do not have enough information to maintain them.

662
 R e a d i n g 70

NANCY REINHOLD

The Exhibition of an E arly

Photogenic Drawing by
William Henry Fox Talbot ( 1 993 )

Nancy Reinhold was assistant conservator of photographs at the ]. Pau l Getty

Muse u ni when she wrote this article. She recounts how a Willic11n Henry Fox
Talbot early salt-stabilized 11hotogenic drawing (ca. 1 835) was irreversibly dam­
aged while on exh ibition for thirty-five days in 1989 under very caut iom display
conditions at the ]. Pa ul Getty Nl useuni. This regrettable inc-idenl caused art;
institu tions internationally to i: m: m.ediately ado11t more conservat ive policies
for the exh ibit ion of ea rly experi 1nental photogravhy. The Getty Mi1seum was
commended for openly sharing the experience in an effo rt to encourage a nd
promote fu rt her dialogue a nd awareness.

The focus of this paper will be a description of the exh ibition of a photogenic
d rawin g which was made by \Vi lliam Henry Fox Talbot around 1 835. Because
t hey are i mportant to the discussion of this image, Ta l bot's early experi ments
in photography will first be desc ri bed .
Although Talbot a nnou nced his i nvention of photography to the
Royal Soc iety in January 1 839, his experiments began i n 1 834. On a trip to
Lake Como i n 1 833, Talbot had been frustrated by his inabil ity to record
the scenery with a camera l ucida. He later wrote in 1 844 in the Pencil of
Nature that he found that "the fa ithless pe ncil had only left traces on the
paper melancholy to behold.'' 1 Earl ier attempts at d rawing with a camera
obscura had a lso been u nsatisfactory, and Talbot bega n to wish for a method

NANCY R E I N H OLD, "The Exhibition ol' a n Early Photogenic Drawing by Wil l i a m H e n ry Fox
Tal bot, " Topics in Pliotograpliic Preservat ion 5 (\,Vashi ngton, DC: American l nstilute For
Conservation, Photographic M aterials C roup, 1 993), 89-94. Reprinted by permission of
the author.
P art VIII E X H I B I T I O N P R A C T I C E

by which i mages wou l d " imprint themselves durably, and remain fixed upon
the paper!"2 'vVhen Tal bot returned from his conti nental tour to h is home at
Lacock Abbey i n 1 834, he began h i s ex'Peri ments.
I n i t ial ly, Tal bot coated drawing paper with a solution of sodi um ch lo­
ride, and brushed si lver n itrate on its dried su rface. H e then placed a specimen
on this sensitized paper and, once sec u red, exposed it to s u n l ight. \Nhen the
paper grew da rk, as the silver salts were reduced to metallic si lver by the action
of the sun, the specimen was removed, leaving its i mpression on the paper.
Talbot knew that i mages made by this met hod would da rken over
t i me and sought to prevent this by the application of stabilizing solutions,
notably potass i u m iodide and sod i u m ch loride, which converted the remain­
i ng unexposed silver salts to a less sensit ive form. H e was not yet using the
sod i u m t h i os u l fa te fixer, o r hypo, which later beca me standard. Properly
used, sod i u m th iosu l fate wil l remove u n exposed si lver salts from the paper
su pport, producing an i m age which is much less sens i t ive to l ight than those
i mages which have been stabi l ized with salt solutions.
( For the pu rposes of c la rity i n this discussion, only sodi u m thiosulfate
has been referred to as fixer, while salt solutions have been called stabil iz­
ers. H owever, it is i m portant to note that the d isti nction in nomenclature is
a modern one and should not be u nderstood as the terminology that Ta lbot
hi mself u sed, which is substa ntially different t han the one chosen by the
au thor for this paper.)
I n a 1 839 letter which was read before the Royal Society, Talbot dis­
cu ssed his early attempts to stabi l ize photographs. H e wrote, "After having
t ried ammonia, and several other agents, with i m perfect success, the first
t h i ng which gave me a successfu l result was the iod ide of potass i u m , much
d i l uted with water.3 I n the same letter, Talbot stated that i mages stab i lized
in this way were pri m rose, meaning yel low colored,4 and he cautioned that
the potassi u m iodide solution must be carefully prepared, or it would cause
i mage fadi ng. The actual d iscovery of the usefu l ness of potassium iodide was
apparen tly made near the encl of 1 834.'
Tal bot su bsequentl y discovered the sta bilizing property of sod i u m
ch loride early i n 1 83:;, w h i l e searc h i ng for a sensitizer.6 H e observed that
the most sensitive parts of the paper were the edges and recognized that
these areas would have absorbed less of the salt duri ng its application in the
sensitizat ion step. So he correctly surm ised that if less salt promoted greater
l ight sensitivity, more salt would lessen sensitivity. Talbot ex'Peri men ted with
other stabil izers, but u l t imately decided that a sat u ra ted solution of sod i u m
ch loride was a s reliable a n d s i mple a s a n y o f t h e others. H e also observed
that images stabil ized by sod i u m chl oride might eventual ly "colour them­
selves of a pale l i lac t i n t"7 in h igh l ight a reas.
 Reading 70 H E I N i-i O L D

I n spite of the i mpressive scope of Talbot's scientific knowledge, he

apparently was not aware that sod i u m thiosulfate was a solvent for certa i n
si lver salts u n t i l h e was i ntrod uced t o it b y S i r J o h n Herschel i n February
1 839.8 While Talbot i m mediately began to explore the usefu lness of sod i u m
th iosu lfate, he also continued h i s i nvestigations w i t h salt solutions a n d other
reagents meant to deter darken i ng.9 Therefore, w h i l e we may assume that
the photographs that Talbot made before 1 839 were stab i lized with salt or
other experimental means, it is i mportant to recognize that photographs
made after February 1839 were not i nevitably fixed with sod i u m th iosu lfate.
Beca use Tal bot conti nued to experi ment with photographic chemistry
well after his introduction to sod i u m thiosu lfate, it is d i ffic u l t to determine
the light sensitivity of i nd ividual i mages. I n addition to origin a l processi ng,
there are other factors, such as conditions [of] storage, previous use, and
subsequent restoration treatments, wh ich affect the stab i l i ty and the appear­
ance of Tal bot's early p hotographs.
Following i s a n account of the ] . Paul G etty M useum's experience
exhibiting a photogenic drawing entitled Linen Textile Fragment. Th is
image is bel ieved to have been made by Talbot i n 1 835. The a uthor was not
employed by the m u seu m when this object was displayed in 1 989; therefore,
this i n formation was recon structed from fi les at the Department of Photo­
graphs at the ] . Paul G etty M useum and with the i nput of departmental staff
members who were i n volved with the exhibition.
Linen Textile Fragment was made by Talbot's early process, described
above. That is, a piece of paper was first coated with a solution of sod i u m
c h loride, fol lowed by a solution o f si lver nitrate. After exposure, the photo­
genic drawing was pres u mably stabilized with a solution of sod i u m ch lori de,
which wou l d have converted unexposed s ilver salts to a form which was less
sensitive, but not stable, to l ight. While i n the past there has not been u nani­
mous agreement about what kind of salt was used for stabi lization, we are
certa in that the photogenic drawing was not fixed with sod i u m thiosul fa te,
which wou l d have removed unexposed si lver salts, producing a more light
stable i mage. The tentative identification of the sensitizing and stabil izing
solutions was provided by scholars, based on their experience with Talbot's
work and the color and tonality of the i mage. 1 0 To the a uthor's knowledge,
there are no specific tec h n ical references i n the l iteratu re of art history or
conservation which describe this i mage.
B efore exhibition, the highlights of this p hotogenic d rawing had a
brownish p i n k tona l i ty. D u ring exhi b i t ion, they began to prin t out, that is,
to darken. This printing-ou t occu rred because the salt solution which was
used to stab i l ize the i mage d i d not completely render the u nexposed silver
salts i nsensitive to light. S u bsequent exposure to light caused these residual
P a rt V I I I E X ll l B I T I O N P H A C T I C E

si lver salts to be red u ced to metal l i c si lver, resulting i n increased density

to the i mage.
The photogenic d rawing now appears da rker and redder in the h igh­
l ight areas. I t cannot be positively stated that it has also darkened i n the
border areas, which were a l ready quite dense. U neven mottl ing has occu rred
in the i mage areas, obscu r i ng the i mage in some places, especially around
its edges. Although the subject is s t i l l visible, the photogenic d rawing is con­
siderably da rker overa l l , and much of the deta i l has been lost. G iven the
c u rrent state of conservation research , these changes may be described as
irreversible at this time.
U nfort u nately, no densitometric read i ngs were made before this
i mage was d isplayed , so quant itative i nformat ion about the color cha nge is
not avai lable. In the absence of densitometric data, color cha nge must be
described i n s u bject ive terms; however, such change has defin i tely occur red,
and the empirical evidence i s compe l l ing. I t is not the author's i n tention to
m i n i mize the i m portance of quantitative data, but to state that, in t h is case,
data would also serve to rei n force what can easily be seen.
The i mage was observed to have printed out after about flve weeks of
exhi bition i n the photographs gal lery of the J. Paul Getty M u seu m , 1 1 but it
can not be stated defi n itively when darkening began or how qu ickly i t pro­
gressed. The ga l lery generally maintains a temperature of 70° F :±:: 2°F and a
relative humidity of 50% :±:: 5%.
The photogenic d rawin g was displayed, framed under U F4 Plexiglas,
at approximately 5 foot-candles, and the i l l u m i nation used was tu ngsten
i nca ndescen t with UV nitration. It is estimated that the fra med object was
exposed to 5 foot-candles of i l l u m i nation, 8 hours per day, for 35 days. 1 2 N o
viewer operated curtain was used.
Th is regrettable i ncident has caused the J. Pau l Getty l\l l useum to
adopt a more conservati ve exhibition pol icy for experimental photographs.
As a conservator, it is the author's opinion that t hese images should not be
put at unnecessary risk, and that facsimiles can serve for the pu rposes of
exh i bition. However, the pressure to show fragi le photographs may some­
t i m es be strong, as the c u ratorial responsibility to share the col lection occa­
sionally conA icts with the responsibility to preserve it. This is a topic which
conti nues to be the focu s of discussion, and at t i me dissension, between
conservators and cura tors. It is hoped that knowledge of the J . Paul Getty
M u seum's experience w i l l be usefu l to this ongoi ng dialogue.
The author wishes to acknowledge the i nput of Ernie Mack and Gordon
Baldwi n of the Department of Photographs at the J. Pa u l Getty M useu m .

666
 Reading 70 11 E I N I I 0 L D

Figure 1
v\lilliam Henry Fox Talbot (British, 1800-1877),
Li11e11 Te.\t.ile Frag111e11t. ca. 18151 photogenic drawing
negative ( 1 1 . 1 X 4.8 cm [4' X 1 7/8 i n . ] ) , before
exhibition. The J. Paul Getty M useum, Los Angeles.
Figure 2
Wi l l iam Henry Fox Ta lbot ( British, •800-1877),
Li11e11 Textile Fmg 111e11l, ca. 1 835. photogenic
drawing ncgaLive ( 1 1 . 1 X 4.8 c m [4� X 1 7fa i n . ] ) .
after approximately fi v e weeks of exhibition a t 5 foot­
candles. The J. Pau l Getty M useu m , Los Angeles.

N otes

\•Vi l l i a m H enry Fox Talbot, The Pencil of Nat u re ( London: Longma n , Brown,
Green , and Longmans, 1 844). Talbot made this comment in the u n paginated
preface, " Brief H istorical Sketch of the I nvention of the Art . "
2 Talbot, Pencil of Nat 1 1 re, preface.
3 Talbot, ''An Account of the Processes employed in Photogenic Drawing, in a
Letter to Samuel H . C h ristie, Esq. Sec. R. S . , from H . Ta lbot. Esq., F. R. S . "
( reprinted i n Gail B uck.lan d , Fox Talbot and the Invention of Photography,
Bosto n : David R. Godine, 1 980, p. 48). This was read before the Royal Society,
February 2 1 , 1 839 and s u bseq uently publ ished i n Pliilosophical Maga:ine 14,
no. 88 ( March 1 839).
4 Talbot, letter to C h ristie.
P art VIII E X ll l B I T I O N P l1 A C T I C E

5 Talbot, Pencil of Nat u re, preface.

6 Talbot, notebook on deposit at the Fox Talbot M useu m, Lacock (reprinted i n
Buckland, p. 29). This specific section is u n dated, b u t d i rectly Follows entries
for January 1 835. Talbot also d iscussed this in Pe11cil of Nature. preface.
7 Talbot, letter to Christie.
8 Sir John Herschel, notebook at the Science M useum Library, London
( reprinted i n Larry J. Schaaf, Out of the Shadows: 1 -/ e rschel, Talbot and
tlie ln.ven.l.ion of Pliotogra 11fiy, New Haven: Yale U n iversity Press, 1 992,
p. 50) . H e rschel, when Talbot visited him o n February 1, 1 839, fixed half' of'
a photogenic drawing with sod i u m t hiosulfate and preserved both of the
p i eces in his notebook.
9 Tal bot, notebook i n the Herschel Collection, Hoyal Society, London (reprinted
in Buckland, p. 40-59) . Talbot's notebooks and correspondence discuss h i s
con t i n u i n g experiments with sod i u m t hiosulfate a n d stab i l izers.
10 Date of manufacture and notes o n original proces s i ng ( i .e. sal t i ng and
stabi l izing solutions) are contained in the catalogu i ng records of the
Department of Photographs at the J. Paul Getty M useu m.
11 E rn i e Mack ( Depart m e n t of Photographs, J . Paul Getty M useu m), personal
com m u nication with t he author, J a n uary 1 993.
12 Ernie Mack ( Depart m e n t oF Photographs, J . Pau l Getty M useu m), personal
communication with t he au thor, J a n uary 1 993.

668
 R e a d n g 71

jOHN M C E LHONE

Determining Responsible Display

C onditions for Photographs ( 1 993)

John McElhone has been 11hotograp h conservator a t the National Callery of

Canada since 1 986. This reading, drawn from the a uthor's light-aging t rials
and real-thne exhibit;ion experience, is a logical continuation of the photo­
graphic monitoring 11rotocols and challenges described in prior readings in this
part. I-I ere, IVIcElhone cautions that, in addition to light exposu re, ot;her factors
may directly i nfluence pri n t degradation, including relative h u michty, fra m i ng
materials, a need for t rained handlers, a nd acclimatization of crates when trav­
eling t;o and from loan locations.

Introduction

In order to provide meani ngful i n formation regarding the conditions u nder

which original photographic prin ts should (or shou ld not) be disp layed ,
museum conservators must equip themselves with a broad knowledge of
how l ight interacts with organic and i norganic materials and with a spec i fic
knowledge of how l ight i n teracts with individual p hotographic prints i n the
collections t hey oversee. The advice we provide on the advisa b i l ity of display
and loan m u st a lso estimate the risks i n herent i n packi ng, transit and han­
dling d u ring i nstallatio n .

"Determ i n i ng Responsible Display Conditions fo r Photographs, " Topics

Jo1-1N M C E L H O N E ,
in Phof.ogrnphic Preserval.ion 5 (\-Vas hi ngton, DC: American Institute fo r Conservat ion,
Photograp h i c Materials C roup, 1 99 3 ) , 60-72. Originally published in The l mpe1fecl I mage:
Pho1.ogra71hs, Their Past, Present and Fu1.11re ( London: The Centre For Photographic Con­
servat ion, 1 992), 185-87. I S B N No. 0-9521 393-0-8. © The Centre for Photographic Conser­
vation. Text and i mages reprinted by permission.
P a rt V I I I E X H I B I T I O N P H A C T I C E

Th is approach to identi fying responsible display con ditions has noth­

ing to do with incantation of the "30 lux max i m u m " formula [and does not]
resort to a sanctioned set of i n tensity/d u ration conditions. The use of such
standard policies may be expedient i n overworked and understaffed institu­
tional settings but they should never be t hought by conservators to be a real­
istic eva luation of the opt i m u m display conditions for a particular print.
The coll ection of photographs a t the National Gallery of Canada
i nc l u des items which cannot be exposed to light, even at a low level of i l l u ­
m ination, for more than a brief period without suffering noticeable l ight­
i nduced damage. Fortu nately, there a re re latively few ite111s with this h igh
sensitivity in the collection . Also present are prints which can withstand,
without observable da111age, display i n a seven-ve nue touring exhibition
extending over 1 9 111onths during which they will be exposed to approxi 111ately
460 klux-hours 1 of UV-Filtered t ungsten i ncandescent i l l u 111 i nation. There is
a relatively large number of these stable objects i n the collection, as we l l as
a large nu m ber of photographs whose stabi l ity is somewhere i ntermediate
between the extremes.
The conservator's role, in this context, is to provide the best possible
determ ination of the relative degree of sensitivity which applies to a particu­
lar print and to provide housing and exhibition conditions that will opti mize
print stabi l i ty.
M i chalski's recent writ i ngs ( 1 987, 1 99oa, 1 99ob) on the effects of d is­
play on m useum objects point to the wide range of l ight-fastness observed i n
various materials a n d colorants. Th is factual information should b e used i n
arriving at

. . . t h e i n st i t u t i o n a l c o n s e n s u s ( w h i c h ) fo l l ows the s a m e m ix as t h e gov­

ern m e n t's b u dget : one t h i rd p o l i t i c s , one t h i rd i n t u i t i o n and one t h i rd
facts. This is not necessa r i l y a bad t h i ng, b u t I w o u l d l i ke at least lo keep
t h e p o l i t i c s exp l i c i t , t h e i n t u i t i o n m a t u re, a n d the facts cu rrent ( M i c h a l ­
s k i , 1 99oa, p . 39).

In the case of photographic pri nts, we have the opportun ity to supply c ur­
ren t and relevant facts by accurately observing and record i ng the density of
various i mage areas before and after display (\t\li lhelm, 1 98 1 ) .
Ro111er has warned ''. . . that we are squandering the largely u n re­
newable resources of o u r photograph ic heri tage in an ignorant fashion" by
subjecti n g u n ique \ri ntage prints to disp lay ( 1 986, p. 24 ) . This conclusion
was supported by a densito111etric 111011i toring study by Severson i n which
38 prints i n a touring exhibit ion were 111onitored before and i 111111ediately
after exh ibition and agai n after a dark storage period ( 1 986). Severson noted
density changes after transit and exh i bi t ion i n 21 of the prints mon itored.
The possible deteriorative agents noted were l ight exposure (esti mated as
 Reading 71 1\ I C E L l l O N E

a maxjmurn of i 56 l<lux/hours of u ltra-violet-fi ltered tu ngsten i ncandescent

i l l u mination) , poor air q u al ity ( u n known) and Fluctuating temperature and
humid ities (crates exposed to h igh h u m id i ty at least once in trans it) .
The observations presented below are drawn from the author's light
ageing trials and from exhibition experience. Compared to Romer and Sev­
erson's observations, they suggest less dire consequences for photographic
prints exhibited i n wel l con trolled museum cond i t ions. Before looking at
these resu lts we should brieAy review the two crit ical factors which m ust
i n fl uence our choice of d isplay conditions: What level of i l l u m i nation is nec­
essary to see photographs on disp lay? What are the possible ways in which
exhibition can cause deteri oration in p hotographs?

Visib i l i ty

D i scussions with curators on exhi bition l ight i ng levels i nevitably centre on

whether the light level i s sufficient for the i mage to be seen (and seen well ) .
The scientific investigation o f vision can give us l i ttle help here since there
appears to be no optim u m i l l u m i nation level at which visual acuity and
colour discri m i nation reach a plateau ( Boyce, 1 987, p. :;5). While 50 l ux may
al low a younger person to d iscrim inate colours in a low reAectance object, it
may not be s ufficient for a viewer over 55 years of age to do so. As i l l u m i nance
increases to 1 000 lux and beyond, visual acu ity and colour discri mi nation
clearly i mprove.
Viewers' opi n ion on the "quality" of i l l u m ination, as stud ied by Loe
( 1 987), does not give c lear direction either. M ichalski points out that t hese
viewers' " . . . j udgement of the ' quality' of lighti ng shows l i t tle i mprovement
between 50 l ux and 400 l ux" ( 1 99ob, p . 584 ) .
I n one i nstance, a curator of photographs h as i nsisted t h a t a room wi t h
a relatively high level o f north daylight is inappropriate for t h e exa m i nation
of p hotographs, this strong i l l u m i nation tending to wash out and flatten
tonal details of both colour and monochrome prints. 2 Th is is not surpri s i ng
since m ost p hotographers produce and edit their own work u nder moderate
levels of artificial light, often from tungsten i ncandescent sources.
M ichalski ( 1 99ob, p . 584) s u mmarizes the visib i l i ty data by saying:

- \!\le see most of what there is to see by 50 l ux. This has been
the standard argument of conservation.
- We see objects not only sl igh t ly better, b u t differently with
more light (such as the brightness of colours ) .

Conservation m u s t n o t deny that d i fference, or trivialize it. Our j o b i s t o

explicitly predict t h e cost i n deterioration . . .
P a rt V I I I E X H I B I T I O N P l1 A C T I C E

D eterioration of Photographic Prin ts on Exhibition

Visible light and u l tra-violet radiation ( UV) potentially affect every compo­
nent of the p hotograph i c print. These effects are briefly l isted below.

- I mage silver, no matter what i ts particle m orphology or toni n g

adj u ncts, is n o t d i rectly affected by light/UV ex'Posu re. However,
some products of p hoto-oxidation of organic components [ . . . ] may
oxidize metallic s ilver ( Eastman Kodak Co., 1 985, p. 1 08 ; Reilly, 1 986,
p. 1 03 ) ; residual s ilver halide, such as that present in u n fixed or par­
tially fixed prints,3 w i l l darken when exposed to light; many of the
silver-thiosu l p hate and other silver complexes which acc u m ulate i n
poorly washed si lver prints can b e photo-oxidized causing sta i n i ng or
further reactions; s ilver ions, produced by the action of moisture and
oxidizing agents, m ay be reduced by l ight exposure ( Eastman Kodak
Co., 1 985, p. 84). The l ight-i n duced deterioration of polyethylene i n
resi n -coated papers [ . . ] may affect i mage s ilver (Wi l helm, 1 992).
.

The factors affecti ng oxi dative-reductive deterioration of i mage sil­

ver has been reviewed by H endri ks ( 1 989, pp. 645-650) .

- Organic dyes comprising t h e p hotograph i c i mage or present a s filters

or sensitizers are subject to l ight-induced changes i n density ( Giles,
1 973; Wi lhelm , 1 979; Schwalberg, 1990) . Dyes used to tint the paper
su pport of some albume n pri n ts are extremely fugitive ( Burgi, 1 982;
R e i l ly, 1 986, p . 1 06 ) .

- T h e i ron compounds w h i c h comprise cyanotype i mages m a y b e

faded b y l ight exposu re. T h i s fading i s partially reversible by dark
storage ( Rei l ly, 1 986, p. 43).

- P rote i ns are subject to light/UV deterioration. Albumen i s subject

to bond-breaking and photo-oxidation by UV (Messier, 1 99 1 , p. 1 34 ) .
Gelat i n , less sensitive t h a n albumen, m a y b e yellowed and embrittled
by prolonged l ight exposure; this is u n l i kely to happen at museum
l ight exposure levels ( Reilly, 1 986, p. 103; Eastman Kodak Co., 1 985,
p . 84).

- Paper may be b leached and weakened by l ight (pri ncipally UV) expo­
sure. Ligni n contain i ng papers may be discoloured ( Re il ly, 1 986, p .
1 03; M ic halski , 1 987, p . 1 0 ) . Gelatin emu lsions wi ll absorb most of
the i n c ident U V energy and a baryta layer wil l b lock most i n cident
l ight from reach i ng the paper support.
 Reading 71 1\ I C E L l l O N E

- Polyethylene i n early resi n-coated papers is subject to light-induced

d i s i ntegration, catalyzed by t i ta n i u m d ioxide in the opac ifying/
reflect ing layer below the i mage ( Parsons, 1 979) . Wilhelm states that
this continues to be a problem with resin -coated prints ( 1 992) .

- Monochrome a n d colour prints have freq uently been heightened,

spotted or painted overal l with a variety of media. These may con­
stit ute the most fugitive co mponents of a print. Note that the black
colour of a paint o r ink is no guarantee of its permanence; it may be
com posed of several fugitive colorants.

- Photographers frequently coated their prints with waxes in the 1 93o's

and 1 94o's. M ost pre - 1 988 black-and-wh ite Polaroid prints are stabi­
l ized with a proprietary coati ng (Wilhel m , 1 992) . The light stab il ity
of t hese and other organic coatings u sed on prints are not wel l char­
acterized in the l i terature of photographic conservation.

Notwithstanding a ll the foregoing possibilities of light-induced da mage,

m ost photographs which are lent and displayed face the greatest risk through
agents other than light. An incomplete l ist of these factors incl udes:

- extremes of temperature producing extremes of re lative h u m idity

inside closed packages;
- cycling or extreme relative hum idity levels;
- poor handling and accidents;
- expos u re t o enviro nmental pollu tants;
- theft and va ndal ism.

Densitomet.-ic Studies of D isplayed P hotographs

Presen ted first are the cu rrent Q u ne 1 992) results of ongoing l ight expos u re
studies u nder conditions which resemble those of m useum d isplay. Some
additional data is d rawn from densitometric records of pri nts belonging
to the National Gal lery of Canada which have been exhibited over the past
several years.
Densitometry has been carried o u t according to Wilhel m 's met hods
except that Status A fil ters are used rather than \l\fratten filters ( 1 98 1 ) . A
M acbeth TH924 densito meter measuring a 4 m m d i a meter area was used to
make all read ings . Headings are accu rate to ::'::: 0.02 density u n its ( D U ) . Differ­
ences between read ings of 0.03 DU4 or less are not considered signi ficant.
Visual, reel, green and blue dens ities have been recorded for all prints
studied . Blue filter density only is reported for m onochrome p rints, this
Part VIII E X 11 I B I T I 0 N I' B ,\ C ' I I C E

being the m ost sensitive measure of changes in these prints. Reel, green and
blue filter densities are reported for colour pri nts.
I n the l ight exposu re study, the pri nts have been matted and framed
under Rohm & Haas Plexiglas G ( U F- 1 Fil tration rati ng) and hung in a room
where they experience a temperature oF 22 ± 1 °C and relative h u m idity of
46 ± 5% supplied by a m u seum air hand l i ng system equ i pped with pa rticu­
late filtration and water scrubbi ng. They are constantly exposed to tungsten
i ncandescent i l l u m i nation which varies From 1 05 lux to 1 30 lux. This repre­
sents some 800 k l ux-hours oF c umu lat ive exposure to elate. The prints studied
have been acq u i red by the aut hor or by the National Gal lery of Ca nada for
experimental p urposes. A selection of the results is shown in Figures 1-7.
Of the gelat i n-si lver prints monitored, the print by the Schaul Stu­
dio ( Figu re 2) showed some t ransitory yellowi ng i n one of the shadow a reas
monitored. The Ali nari Studio print ( Figure 1 ) and the Azo paper step scale
( Figure 3) show no cha nges.
Figures 4 and 5 each show the results of exposu re of a pair of albumen
pri nts printed from the same negative, one relatively faded compared to t he
other. One of the '' u n faded " prints shows some yel lowing in the shadow area
monitored. The modern step sca le albu men print (Figure 6) shows some yel­
lowing i n the higher density end of the scale. Exa m i nation of the graph may
suggest that proportional ye llowing is taking place at lower dens i ty steps but
that these have not yet reached the 0.03 DU sign i ficant di ffere nce leve l .
Th e E ktacolor print, printed from a negative i n 1987, contains various
colour patches and a grey scale. Prese nted in Figure 7 a re the reel density pro­
files of two cyan patches, green density from mage n ta patches and blue den­
sity from yel low patches. The print shows transitory yel lowin g of the yellow
patch shown here and of s i m i lar h igh density colour patches. After 800 kl ux­
hours of exposure over 10 months the cyan dye loss has become sign i ficant.
Figures 8-1 5 present densitometric data gathered duri ng actual exhi­
b ition and loan experience. These prints a re from the col lections of the
National Gal lery of Canada . In genera l , they have experienced less than
5 percent of the total exposure used i n the preceding exa mples. They are
matted , fra med and glazed as described above . Temperature and relat ive
h u m idity cond i t ions are si m i lar to those descri bed above except for the
Lisette M odel print ( F igu re 14) which is part of a touring exhibition.
The two p ri nts made in the 1 85o's ( Figures 8-9) were exh ibi ted For
a short period of t i m e with i l l u m i n ation below 1 00 l ux. They show no sig­
ni ficant cha nges although in both cases the nom i nal density readi ngs have
decreased slightly.
Figures 1 0- 1 2 show exa mples of Atget's principal printing media: albu­
men, m atte albu men and ge latin pri n t i ng-out paper. Aga i n , no sign i ficant
changes have been observed over the display period but the nominal density
 Reading 71 ,\ I C E L l l O N E

1.6 1 .4 ----,
.,-
1.4
1.2

1 .2
�
�
m
I No significant changes
I .�
UI
c
1 .0

1.0 m
Cl
0 0.0
ffi
m m
� Significant changes shown as
iii
0.8
< < 0.6 change from initial reading
� UI
�
1ij
0.6
1ii
Ui Ui 0.4
0.4

0.2 0.2

200 400 600 800 1 000 100 200 300 400 500 600 700 000 900 1 000
Tungsten Light Exposure (klux-hours) Tungsten Light Exposure (klux-hours)

Figure 1 Figure 2
Gelatin-silver print (Alinari Studio). Gelatin-si lver print ( Schaul Studio).

1 .8
1.0
1 .6
1.6
1 .4-
faded
�
1.4
UI -+­
�c c
1 .2
1.2 m
Cl
'unfaded'
m
Cl m 1 .0
m 1.0 �
iii
�
iii
< 00 1 I No significant changes <
"
0.8
Significant change shown as
UI �
�
1ij 0.6
1ii 0.6
change from original

Ui u;
I
0.4- 0 .4

0.2- 0 .2

0.0
100 200 300 400 500 600 700 800 900 1000
0.0
0 100 200 300 400 500 600 700 000 900 1 000 0
Tungsten Light Exposure (klux-hours) Tungsten Light Exposure (klux-hours)

Figure 3 Figure 4
Gelatin-siker print, untoncd (Azo paper, 1985). Two vintage albumen prints ( Ca msby Studio).

read ings have decreased in the shadow areas of the matte albu men-silver
print ( Figure 1 1 ) and the P . 0 . P . print ( F igure 1 2 ) .
The coated \i\Tal ker Evans pri nt ( Figure 1 3 ) showed n o s ignificant
changes d u ri ng 3 3 2 klux-ho u rs of t u ngsten light expos ure .
Figu re 1 4 is typical of t he 2 0 prints wh i ch have been monitored over the
course of the Lisette M odel exh i bit ion tour. These prints have been exposed
to over 4 50 kl ux-hours of t u ngsten i l l u mi nation as well as to extensive han­
d l i ng and transi t in relatively u ncontro l led environments; d u ri ng this time no
densitometric changes have been noted.
 P art VIII E X l- l l B I T I O N P H A C T I C E

1 .6
��
�
20

l
tJ
=-
l.
4
--
�-
--
----+
- -----+-
- -------<
• faded
1 .8 1--
- ---< :�
EJ
1.6-

�
1.2
:;-faded . -� 1 .4-1----+----l---t--<
"
� 1 .0 c

0 I � 1.2
[
ffi�
..
No significant changes
Significant changes shown as change from initial
ffi
�

0.8 1.0
<( <(
� 0.6
������*;;;;�;;����
" 0.8

6
w 0 .6
0.4
0.4
·----+---- -
-+- -----1
0.2
2 --
G. -
i ---+---- -
+-- -- -l

o.o
0 100 500 600 700 800 900 1000
0.0
0 200 400 sbo sbo 1 000
Tungsten Light Exposure (klux-hours)
200 300 400
Tungsten Light Exposure (klux-hours)

Figure 5 Figure 6
Two vintage albu men prints ( U n known studio). Modern albumen prinl. gold-toned (Ch icago Albumen \r\/orks, 1 983).

2.4
1 .4
2.2 I

Red
2.0 1.2
1 .8 �
I
I Green
- - +- - - - -
- - -..-- - - -
- - - - t 10
I �1�e
- - - -- - -

� 1.6 1- - - - - - -
-�
"c
"
c ..
" 1 .4 0 0.8
0
..
<( 1.2 :J
"
:J 1.0
iii
<( 0.6
I No significant changes
I
1ii "
w 0.8
:J

Significant changes shown as 1ii

w 0.4
0.6 change from initial reading

0.4
0.2
- -- - - - -- - - - - -
0.2 -
0.0
0 200 400 600 800 1 000 20 40 60 80 100
Tungsten Light Exposure {klux-hours) Tungsteo Light Exposure (klux-hours)

Figure 7 Figure 8
Dye-coupler prinl ( Ektacolor. 1967). Heel, green and blue densities oC S<1hed paper print ( B enjam i n Tu rner. NCC 20622).
respectively, cyan, magenta and yellow patches.

The dye-coupler print (Figure 1 5) shows significant cyan dye loss

i n a neutral tone i m age area after 10 weeks which i ncluded a 29 ld ux-hour
expos u re .

D iscussion

Viewed generally, the results prese nted above i ndicate that many p ho­
tographic prints are unaffected by disp lay of l i m ited duration at typical
 Reading 71 M C E L H O N E

1.4 1.8

1.6
1 .2

1 .4
�
�
1.0
0c 1.2
c
" "
0 0.8 0
"
j " 1.0
j
iii iii
<( 0.6 <( 0.8
3
1ii
0
j
1ii 0.6
I No significant changes
u; 0.4
I No significant changes
I i
u;
I 0.4

I
0.2
0.2

0.0
20 40 60 80 1 00 0 20 40 60 80 1 00
Tungsten Light Exposure (klux-hours) Tungsten Light Exposure (klux-llours)

Figure 9 Figure 10
Light albumen print ( Edouard Baldus, 1 85), NCC 30804). Albumen-si lver print (Eugene Atget, 1922\ NCC 21 1 1 8).

1 .6 2.2

2.0
1 .4
1.8

� �
1.2
1.6
0c 0
" 1.0 � 1 .4
0 0
"

I j
j
" 1 .2
iii 0.8
<(
0
No significant changes iii
<( 1 .0 I No significant changes
I
j 0.6
1ii
� 0.8
u; u; 0.6
0.4
0.4
0.2
0.2

0.0 0.0
0 20 40 60 80 1 00 0 20 40 60 80 1 00
Tungsten Light Exposure (klux-hours) Tungsten Light Exposure (klux-llours)

Figure 11 Figure 12
!\1latte albumen-silver print ( Eugene Algct, NCC 2 1 1 8 1 ) . Gelatin-si lver P . O . P . print (Eugene Atget, NCC 2 1 226) .

museum i l l um ination levels. This should not come as a surprise since most
photographic prin t components are remarkably light stable when compared
to materials comprising, say, 1 9th-century oil paintings or watercolours.
The yellowin g of the gelatin-silver prin t ( Figure 2) i s u n usual but not
aberrant. The sensitivity of this print points out the risks of making gen­
era l statements about the stability of particul ar processes; each photographic
print may exhibit u nique reactions determined by i ts u n i que h istory. Other
gelatin-s ilver prints (Figures 1 , 3 , 1 2-14) show no significant changes d u ri n g
display; t h e possible trend shown b y t h e P . 0 . P . print (Figure 1 2) would be
consistent, if confirmed, with the greater tendency of photolytic s ilver to be
 P art VIII E X ll l B I T I O N l' H A C T I C E

2.0 1 .8;�-------�

1 .8 1 .6 1-----· 1-----1---;

1 .6 1 .4

I
"' �c
No significant changes
.?; 1 .4
"
1 .2
c
m
0 1.2
�
!------<---�·--;
m 1.0
j No significant changes j

iii 1 .0

j
iii

"' "'
< < 0.8
o8 j
j
1i 1i 0.6
iii 0.6 iii 1-----<----1---<
0. 4
0.4
1
0.2+-----+----<---<
0.2

0.0
I
0 20 40 60 80 100 100 200 300 400 500
Tungsten Light Exposure (klux-hours) Tungsten Light Exposure (klux-hours)

Figure 13 Figure 14
Gelatin-silver print. wax-coated (\Valkcr Evans. 1 93 1 . NCC 1 9 qo).
: C c l a t i n-si lvl·r print � Lise t t e J\ lodcl. 193o's. N C C 3 5 1 0 1 ) .

1 .2·�-----
--- ----,

-+-

Red
-+­

Green
Significant change shown as --·­

change from initial reading Blue

20 40 60 80 1 00
Tungsten Light Exposure (klux-hours)

Figure 15
Dye-co u p l e r print ( H oger M a rt i n . 1990, N C C 35527).

affecled by oxidat ive-reductive delerioration due to the higher su rface/mass

ratio of its par t icles ( Lavedrine, 1 99 1 , p. 8 ) .
The 1 9th-ce ntury s a l t a n d a l bu men prints shown i n Figu res 5 a n d 8-1 1
show no sign i ficant changes d u ri ng d isplay. The l ight sensitivity of the added
matting agent in Atget's matte a l bumen print ( F igure 1 1 ) (Cartier-Bresson,
1 987) is not we ll characterized. The yellowing in two of the a l b u me n prints
( Figures 4 and 6) may be re laLed to Severson's observation that albumen
prints 1n excel lent i n itial condilion tend to lose density more read ily than
pri nts i n i n ferior condition ( 1 986, pp. 40-.p) . All t hose prints which show
 Reading 71 1\ I C E L l l 0 1'i E

trends-as yet below the sign i ficance level-should be monitored closely a t

the time of their next exh i bition i n order to confirm or discount t h e i ndica­
tions of h igh l ight sensitivity.
The evidence from the dye-cou p ler (chromogen ic) colour prints is vari­
able. The test print ( F igure 7) shows a remarkable degree of l ight stab i l­
i ty, cyan dye loss only beco m i ng evident after a rela tively long period, wh i le
the exhi b ition print ( F igu re 1 5) shows substantial cyan dye loss over a brief
period. Severson's data also shows wide variation between i nd ividual prints;
his sample 1126 shows no density cha nges while sample #27, by the same art­
ist and dated to the same year, shows a 1 0% loss in one of the dyes in a mid­
tone area ( 1 986, p. 4 1 ) .
T he photograph conservatio n l iterature is consistent i n indi cat i ng that
dye-coupler prints fade during d isplay but observations on the nature and
rate of these changes vary widely. Wilhelm shows a 0.05 DU loss i n a cyan
shadow area of a 1 97o's-vintage E ktacolor 37RC print exposed to some 5,000
klux-hours of m i n imally fil tered daylight over a year. The average dayt i me
i l l u m i nation i n this case i s 1 .3 l<l ux (vV i l helm , 1 979, p. 1 20) . J n a subseq uent
publ ication Wilhelm shows 20% l oss of magenta dye (from 0.60 DU) i n an
E ktacolor Plus print after a 23,300 kl ux-hou r exposure using a 2 1 . 5 klux fl uo­
rescent sou rce (Schwalberg, 1 990, p. 44). Anderson and Larson cite acceler­
ated l ight fadi ng studies of E ktacolor 74RC pri nts using a 5-4 l<l ux fl uorescent
i l l u m i nant in which an exposure of 2,600 klux-hours produces a 3% magenta
dye loss from a neu tral patch with an i n itial density of 1 .0 DU ( 1 987, p. 53).
In a study fo l lowing E ktacolor 74RC pri nts displayed u nder an average i l l u ­
m ination of 2 1 4 l u x from m ixed so urces, they i nd i cate t h a t t h e 5% cyan dye
loss observed after 4 years is due to dark fad ing rather than the result of l ight
exposure. This p henomenon is also noted i n the older Ektacolor 78RC paper
(Anderson, 1 987, pp. 50, 54) .
\!\fhat of changes n o t observable using densitometry? These i nc l ude
cha nges below the threshold sensitivity of the densitometer and changes such
as embrittlement and c racking which are not measured by a densitometer.
I nstru ment i nsensitivity is a real problem, particu la rly for observ i ng
cha nges i n low density areas. The best a conservator can do is to be aware
of potential fading trends and treat these suspect objects cautiously. 1-1 igher
sensitivity for print moni toring could be achieved with colorimetry using a
UVNisible spectrophotometer or with digita lly based electronic imaging.
These technologies may eventually replace densitometry but this will prove a
difficult cha ngeover for those of us who have i nvested heavi ly in densitomet­
ric monitoring programs.
As for changes which are not quantifiable using available instrumen­
tation, the acute visual memory of a conservator or curator is the ul t imate
record.
Part VIII E X H I B I T I O N P ll tl C T I C E

Conclusions and G u i d e l i nes

The sign i ficant c hanges observed by Severson a fter some 1 50 klux- hours expo­
su re duri ng a one-venue tour must make i nstitut ional conservators cautious
i n specifying d isplay conditions for photographic prints i n their collections.
H owever, neither Severson's data nor those presen ted here suggest that ALL
photographs are damaged by display. On the contrary, some photographic
pri nts appear to have superior l ight-fast ness to a ll other tvvo-d i mensional
pictorial media.
Reliance on institutional or depa rtmental standard policies allows po l i ­
tics t o p lay too predominant a role in t h i s regard, ignoring the particular
characteristics of a print. Even general izations about photographic processes
can be m isleading or m istaken in particular cases. I l l u m i nating all photo­
graphs at 50 lux wil l critically degrade t he visibility of some i mages for a l l
viewers and w i l l degrade t h e vis ibility of all i mages for some viewers, particu­
larly those over 50 years of age. Standard time l imi ts on the length of loan or
the nu mber of venues al lowable for loan ignore the variabi l i ty i n the qual ity
of i l l u m ination and other environmental factors to which a travel l ing exh i bi t
will be e>..1JOSed. These are t he factors wh i c h conservators must u n derstand
and eva l u ate in order to make meani ngfu l recom mendations. M ichalski says
that " . . . conservators could drop the role of 'l ighting police' and i nstead
become e>..1Jert counsel, if they are expert" ( 1 99ob, p. 586) .
For p hotograph conservators, becom ing expert and m a i ntain ing that
status i ncludes the i mplementation of a reliable, wel l calibrated monitoring
program, u si ng a densitometer or another colour measuring device. This wi l l
a llow t h e creation of an object- level record of display, storage and colour
c hange h istory. This data is req u i red i f i n formed and confident recom men­
dations are to be made. S u ppleme n t i ng this is any i n formation known (or
guessed) about the p rocessing treatments used to produce a particular print.
Prior to the collection of colour change data it may be advisable to
i n i tially recommend only l i m i ted exposure, say 30 klux-hours, for "suspect"
material such as dye-coupler pri nts, early salted-paper prints, cyanotypes,
painted prints or pristine albumen prints. Loan agreements for this type of
uncharacterised pri nt might be designed to provide for extension of the loan
conditional on monitoring of the print at its home i nstitution after one or
more ven ues i n a trave l l i ng exh ibition.
All prints should be monitored i mmediately on return from display and
agai n before su bseq uent display i n order to determine colour changes that
are i ndependent of l ight exposure. This is particularly i mportant for colour
photographs.
M aterial that has been recorded as having undergone su bstantial
colour change during display should be regarded as l ight sensitive and

680
 Reading 71 1\ I C E L l l O N E

recommendations for su bsequent display (or restriction) should expl icitly

state the losses predi cted for a given ei.. 'Posure. This is a much more e ffect ive
strategy for protection of:' sensi tive i mages than blanket prohibitions. Expo­
sure levels for sensitive objects can be drastically reduced by i nstallation of
sim ple viewer-operated c u rtai ns or automatic l ight controls.
M aterial that has shown itself to be l ight stable should be favoured
with higher i l l u m i nation (to a l i m i t of, say, 300 l ux) and with longer d isplay
periods, where requested.

In all cases:
- i l l u m ination should be exc l u sively tu ngsten i ncandescent;
- glazing shou ld be UV-fi ltering acrylic sheet;
- prints should be reliably attached to mats made of h igh al pha cel-
l ulose content cardboard ;
- rigid p lastic backi ngs should be i nstalled behind mats;
- glazing/mat/backing packages should be sealed aroun d the perimeter
with a rel iable adhesive tape before fram i ng;
- frames should be strong eno ugh to ful ly support the weight of the
packages which they conta i n ;
- rooms receiving photographs, includ i ng storage vaults a n d ga l leries,
should have stable temperature ( ± 2°C) and re lative h um id ity ( ::':: 6%);
air fi ltration and clean i ng equipment should be operati ng, especially
in c ities where ai r pol l utant levels are h igh;
- i nstallation crews should be professional and trai ned i n handling
works of art; i n trod uction of works of art i nto ga l leries should begin
only when all refurbishment work is termi na ted; a l kyd-based pai n ts
should not be u sed in exh i bition gal leries;
- security surveil lance should be presen t i nside the ga l leries d uri ng
opening hours; small fra med works should be attached to the wa lls
with security c l i ps;
- for travelling exh i bitions, c rates should al low vertical placement of
fra mes in padded slots, should seal well when closed and should
conta i n a maxi m u m amount of hygroscopic material;
- transit time i n u ncontrolled environments should be kept to a mini­
mum; crates should be Fu l ly temperature accli mat ized at their desti­
nation before being opened.

If conservators base their recommendations for d isplay and loan on acc u ra te

observation and carefu l forethought, the museum's collections, as wel l as
the m u seum's public, wi l l be best served.
P a rt VIII E X ll l H I T I O N P H A C T I C E

Acknowl edgements

The aut hor wou ld l ike to thank Boris Pretzel (Victoria & Al bert M u seu m ) ,
Doug Severson (Art I n stitute of Chicago) a n d H enry \l\filhelm ( Preservation
Publishi ng, Ltd . ) For the comments and corrections they offered d uring the
preparation of t h i s paper.

List of References

Anderson, Stanton, and Larson, George. 1 987. "A st udy ol' cnviro n 111ental cond itions asso­
ciated with cu sto111cr keeping of' photographic pri nts. " Journal o.f f maging Tec/111. o l­
ogy . 13. No. 2 : 49-5+
Boyce. P . R . 1 987. "V isual acu i ty, colour d i scri 111 i nation a n d l ight level . " I n Ligh t i 1 1g Pre­
Pri 11 t : A Co11fere11ce 011 Ligl1ti11g i1 1 J\l/ 11se11111s, Galleries and Historic l-/011ses.
pp. 50-57. London: The i\ I uscu 111s Assoc iation.
B u rgi, Sergio. 1 982. " Fading of dyes used f'or t i n t i ng u n sensit ized a l b u 111en paper. " Paper
presented al t he S PS E I nternational Sy111posiu 111 on the Stabil ity and Preservation
or Photographic I 111ages, Ottawa. C i ted i n Heilly, 1 986. p. 1 1 2 .
Carl ier- B resson , A n n e . 1 987. "Tec h n iques d'ana lyse appliq uces aux photographies
d'E ugcne Atgcl dans les collections de la v i l l e de Paris. " Prepri nts: ! CO M Co111111it­
tce ror Conservation 8th Triennial M eeti ng, Sydney, Austra l i a , Vol . 1 1 . pp. 653-658.
Los Angeles: Getty Conservation I n stitu te.
East man Kodak Company. 1 985. Conservatio11 o.f photograp/1s. Rochester: East man Kodak
Company.
G i les, C . H . , Forrester. S.D . . H as l a 111, H . . a n d Horn, I�. 1 973. " Light fastness of colour
photographs. " )011rnal o.f Pl10tograp/1ic Scie11ce . 2 1 : 1 9-23.
H e n d riks, Klaus 13. 1 989. "The stabil ity and preservat ion or recorded i 111ages.'' In / 11ingi11g
Pmcesses a11d Materials: /\Jeblelle's Eig/1 t /1 Edition . E d ited by Joh n S t u rge, Vivan
Walworth and Alan Shepp. pp. 637-68+ New York: Van Nostrand Reinhold.
Lavcdrinc, Bert ra n d . 1 99 1 . "The study o r the m i c rostructure or the silver grains i n geb t i n
pri n l i n g out paper during accelerated age i ng. " Topics i 1 1 Photographic Prese111atio1 1.
-1 : 1 - 1 8 .
Loe, David . 1 987. " P rererred l ighting f'or the d i splay or pa i n t i ngs w i t h conservation i n
m i n d . '� I n Li�hting Pre-Pri-n l : A Conference on Li�h l i ng i n JV]use·un1s, Galleries a11d
1- / istoric /-/u11ses. pp. 36-49. Londo n . The M u seu ms Assoc i a t i o n .
Messier, Pau l . 1 99 1 . " Protein c h e 11 1 i stry or a l b u men photographs. " Topics i n P/10tograp'1 ic
Preserl'atinn. -+: 1 24-135.
M ichalski, Stefa n . 1 987. " Damage to museum objects by visible radiation ( l ight) and u l tra­
violet rad iation ( U V). " I n Lighti11g Pre-Pri11ts: A Co11fere11ce 011 Ligh t i ng i11 M11se-
11111s. Galleries w1d 1-/istoric Ho11ses. pp. 3- 1 6 . London: The M u scu 111s Assoc iation.
i\ l ichalski, Stefa n . 1 99oa. "Time's e ffects on pa i n t i ngs. " In Sliared Responsibility: Proceecl­
i11gs of n Se111i1wrfor Curators and Conser11alors. pp. 39-53. Otlawa: National G a l ­
lery of Canada.
M ichalski. Stefa n . 1 99ob. "Towards spec ific l ighting gu i d e l i n es. " In Preprints: ! CO M
Commi ttee ror Conservation 9 t h Trien n i a l M eeti ng, Dresden, G D R , Vo l . I I .
pp. 583-588. Los Angeles: Getty Con servation I n s l il ute.
 Reading 71 1\ I C E I. 1 1 0 8 E

Parsons, T. F., G ray, G . G . , a n d Crawford. J . H . 1 979. "To RC or nol lo HC." )011mal of

Applied P/10tograp/1ic Engi11eering 5, No. 2: 1 1 0- 1 1 7.
Reil ly, James J\11 . 1 986. Care and Identification. of 1 9 t li-Ce11t111)' Photographic Pri1its. Roch­
cslcr: Eastman Kodak Company.
Romer, G ra n t B. 1 986. "Can we a fford to exh i b i t our va l u ed photographs)" Topics i11 Pho­
tographic Preservation 1 : 23-30; and Pict11rescnpe 32, no. 4 (\!\linte r 1 987): 1 36-137.
Schwal bcrg, Bob, Wilhelm, H e n ry, a n d B rower, Caro l . 1 990. "Goi ng! go i ng!! gon e ! ! ! "
Pop11/ar Phot.ograph.y (J une 1 990): 37-49, 60.
Severson, Douglas G. 1 986. '" T 'hc effects of exh ibition on p hotographs." Topics i11 Plwto­
graphic Preservat.io11 1 : 38-42; and Picl11rescope 32, no. -+ ( \1\/i ntcr 1 987): 1 33- 1 35 .
W i l h e l m . H e n ry. 1 979. ''Color print stabi l i ty. " Modern Pl10tograp/1y 43, No. 2 : 9 2 ct seq .
.
\•Vi l h c l m , H e nry. 1 98 1 . " M on i tori ng the Fad i ng a nd st a i n i n g ol' color photogra phic prints . .

}011r11al of t he A111erica11 Inst ill/le for Conservat ion 2 1 : 49-64.

\>Vi l h c l m , H e n ry. 1 992. Personal com m u n icati o n .

N otes

Calcul ation ol' tota l l ight exposure in lux-hou r u n its can be made by u s i n g
the !'actor of 3000 hou rs/yea r l ight exposure i n a typical museum ( M ichalski,
1 99oa, p. 43). In this paper the total l ight exposure l'or a trave l l i ng exh i b i t i o n i s
calcu lated by m u l t i plying t h i s factor by the a c t u a l d i splay l i m e (converted t o
years) and by the max i m u m i l l u m i n ation i n tensity.
2 J . \�/. Borco m a n , C u rator of Photographs al the l\l ational G a l l e 1·y of' Ca nada,
prefers a space l ighted with 1 50-300 l ux tu ngsten i n ca ndesce nt to one with
dayl ight i l l u m i nation which varies between 300 and 2000 l ux. In this i n stance
both colour temperature and i ntensity arc i nvolved in the prcl'c rence.
3 I n c l uded in this category are some early sal ted paper prints, some commerc i a l
prool' prints and "stab i l i zation-processed " p r i n t s . S o m e calotype negatives
arc i ncom p letely f-ixed and will Fade i i' exposed to u n i n t errupted exh i b i t i o n
i l l u m i nation.
4 .y ( 0.02' + 0.02')
 R e a d i n g 72

S A R A H S . WAG N E R , C O N STA N C E
M cCABE, AND BARBARA LEM M E N

Guidelines for Exhibition Light

Levels for Photographs (2009)

Coau thored by Sarah Wagner, Const;ance McCabe (see also Reading 1 1 ), and
Barbara Lem -men, t h is reading began as a contribut ion to the A merican I nsti­
t u te for Conservation 's Photographic Materials G roup ( PM G ) catalogue for
a c hapter foc used on exhibition gu ideli nes for photographi,c materials, Sarah
\!Vagner is a 11hotogrc111h conservator in 11rivate pract i,ce in 'v\lashington, D , C ,
Const;ance McCabe -i s senior p hotograph conservator at t he National Gallery of
A rt;, \i\lashingt;on, O,C., and Barbara Lemrnen is senior phot;ograph conservat;or
at t he Conservation Center of A rt and l+istoric A rt ifacts in Philadelphia. Prior
to the publica t ion of the catalogue cha11ter, the 1n-esent reading was published
fri the PMG pu bUcation Topics in Photograph ic Preservation. TI,,, is easy-to­
read doci,1 ment is i,1sefu l as a quicl� reference to basic exh ibition gu idelines for
a -wide range of 71hotographic materials.

These gu idel ines are based on the expe rie nce and opinions of the aut hors
and have not been scientifically establ ished for each type of media.
The l ight stabi l ity of i nd ividual items is often u npredictable beca use
the background of hi storical materials, including past l ight exposure, storage

SAHA l l s . vV1\GNEH , CONSTANCE M c C A B E , and BAH IJAHA LE�IMEN, "Guidel i nes For Exhi­
bition Light Leve l s For Photographs " ( u pdated J a n u ary 2009 for this vol u me ) , Original
version compiled i n 1 990 as i n-house guideli nes for G.S. Li b rary of Congress by Sarah S .
Wagner and p u b l i shed as " G u id e l i nes for Ex h i b i tion Light Levels For Photographic Mate­
rials," Topics in Pho/,ographic Preserva/,ion 9 (Wash i n �to n , DC: American I n stitute for
Con servation, Photographic M a terials Croup, 200 1 ) , 1 27-28. Reproduced by permission of"
t he aut hors.

684
 Reading 72 W A G N E 11 , �I CC A ll E , !I N D L E M �I E N

conditions, and i nitial p rocessi ng, may be u n known. These factors h ave a n
i mpact on l ight stab i l i ty. Therefore:

• A conservative approac h has been used to assign l ight level catego­

ries. For example, if a particu lar process is i n one l ight l evel category
but does not meet all of the qualifications, it should be moved to the
next, more-sensitive category, unless otherwise i ndicated.
• M ic ro-fade testing, an accelerated test method originally described
by Paul Whitmore, can be used to determine the l ight fastness of a
given photograph . 1

Cases, mounts, hand colori ng, coati ngs, ton i ng, inscriptions, and other
manipulations and attach ments may i n c rease the l ight sensitivity of a p hoto­
graph as a whole.
The categories below give the maxim u m l ight exposure a n object i n
that category should receive during one display cycle. A total o f 9 months
total wa ll time or less, for one or m ore ven u es within each display cycle is
suggested ( i .e. , 3 venues with 3 months disp lay each per year). Many i nsti­
tutions wil l not loan for more than one year. Disp lay that exceeds the sug­
gested l i m its in any category should only be clone if the items have been
shown to be light stable by m icro-fade test i ng or are i nstrumentally moni­
tored for color or density changes i n the i m age; if the item cha nges, disp lay
should be halted and substitutes or facsi miles rotated i n .
Although not addressed here, total l i fetime exposure is just as i mpor­
tant as si ngle d isplay levels/duration and rest periods. Total l ifetime exposure
is especially crucial with the more l ight-sensitive categories and with items
that a re frequently requested for display. Light exposure and the damage
it produces are cumulative over the l i fe of the object; the rest period is not
regenerative. Faded prints may have the least margi n of error for any addi­
tional im age loss.
O ne footcanclle ( ft-c) equals approxim ately 1 1 lux.
Any combination of l igh t l evel and intensity, which gives the maxim u m
e)qJos ure o r less, may be used.
For example:
3 ft-c X 10 hr/clay X 10 mos (300 days) = 9,000 ft-c h rs
5 ft-c X 10 hr/clay X 6 mos ( 1 80 d ays) = 9 ,000 ft-c h rs
1 0 ft-c X 1 0 hr/clay X 3 mos (90 days) = 9,000 ft-c h rs
These standards assume that a l l other environmental conditions meet
conservation standards: all UV and I R radiation have been filtered out; R H
at o r below 45-50%; air conta m in an ts filtered out; exh ibition materials pass
the P hotographic Activity Test, etc. For i tems to be loaned, sealed frame
packages are recommended to m i n im i ze e)qiosure to high or A uctuating R H
and gaseous pollutants i n transit a nd/or o n disp lay.

68 5
Part VIII EX I I I B I T I 0 1'> P ll 1\ C T I C E

M an y fluorescent lamps, including energy-efficient bulbs, emit highly

en ergetic UV radiation, which has the potential to be especially damagi ng to
photograph s; u se of effective fi ltration is essential either on the b u l b or i n
the glazi ng.

Extraordinarily Light-Sensitive

Only facsfrniles should be dis11layed.

Autochromes and Other Early Dye Processes

Experimental Processes
E.g., early u n fixed salted paper.
Stabi l ized G e l atin S i lve r Prints
Sensitized s ilver h al ide may prin t out.

Very Light-Sensitive

Total exposure per year ( u nless otherwise notecl )-5,000 ft-c hours ()o,ooo
l ux hours); e.g. 3 ft-c for 5 months at 10 hours per day or 5 ft-c for 3 months
at 1 0 hours per clay. Rest for 3 years m i n i mum between d isplay cycles.

Any Poorly Processed or Deteriorated Prints

Arch i tectural Plans or Photoreproductions
E .g. blueprint (cyanotype), d iazotypes, brownl i nes, van dykes, photo­
stats, pellet prints.
3 months at 3 ft-c maxim u m ; consider using a facs i m i le.

Carbon Prints
With non-earth, colored pigments ( not carbon black or earth pigmen ts)
or on poor-quality papers.
Color Photographic Processes
E .g. pre- 1 990 transparencies, pre-1 990 pri nts, and i nstant prints ( Pola­
roid types). Dye transfers, C iba/Ilfo-chromes, and post-1 990 pri nts a re
more stable to l ight. H igher light levels may be necessary to see color
wel l ; consider h igher l ight level category for shorter duration.
Computer-generated Pri n ts (digital i n kjet p ri nts, e tc ) .
The dye set, printer, a nd support all inA uence the fadi ng rate. Assu me
poor l ight stabi li ty u n less light stability ratings are p ublished for the
exact combination for the year that the pri nt was generated (see manu­
facturer websites and www.wilhelm-research.com ) . More i mportant i s
i n kjet sensitivity t o ozone and h u midity which c a n cause drastic i mage
changes. Sealed packages reduce exposure to ozone and h u m idity d u r­
ing display. Dry pri n ts thoroughly before sealing-usually a m i n i m u m
2-week period is suggested. Protect from UV light.

686
 R e a d i n g 72 \\I A (.; i\! E H , 1\ I C C r\ B E , A 1\/ D L E 1\ I 1\ l E N

Cyanotypes ( Blueprints)
3 months at 3 ft-c maxi m u m ; consider u si ng a facs i m i le.
Gum B i c h romate Prints
\l\fith non-earth, colored pigments (not carbon black or earth pigments)
or on poor-quality papers.
Res i n -coated (RC) Supports
Pre- 1 980 RC papers ( both color and black-and-wh ite) may be prone
to c racking; black-and-white si lver HC papers may be prone to image
oxidation i n l ight, espec ially UV. These should not be d isplayed u n less
toned for preservation (e.g. si lver converted to stable compound).
Optical brighteners (dyes visible under UV) may be fugit ive and a re
da maged by U V exposu re. Optically brightened papers will not appear
as white under i ncandescent l ight, or when the brightener is faded or
exhausted. Use of facsim iles is recommended .
Woodburytypes
VVi th non-earth, colored pigments (not carbon black or earth pigments)
or on poor-qu al i ty paper.
Photographs with Ti n ted Base or B i nder
Tinted baryta layers or binders (pi nk, green , blue, etc. ) contain Fugit ive
dyes; these a re often fou n d in h istoric[ a l ] p hotographs.
3 months at 3 ft-c maxim u m ; consider u si ng a facs i m i l e .
Hand-col ored Photographs of A l l Types
C ased Obj ects where the Case is Exposed
Colorants i n case components may be fugitive-e.g. velvet or other
cloth in the case i nterior and dyed leather/leatherette cove ri ng.
Col ored Paper and M ounts
E .g. colored constru ction or dyed papers.
Modern I n ks
E.g. dye-based fou n tain pen, ballpoint, fel t tip, p u rple man uscript inks.

Moderately Light-Sensi tive

Total expos u re per year- 1 0,000 ft-c hours ( 1 00,000 l ux hours); e .g. 3 ft-c for
10 months or 5 ft-c for 6 months at 10 hours per day. Rest for 2 years mini­
m u m between display cycles.

Albumen Prints
I f concerned abou t the i m pact of an u n known processi ng, toni ng, or
coating h istory, move to the very l ight-sensitive category.
Cased Photographs ( Daguerreotype, Ambrol:)1Je, Tinl:)1Je)
No hand coloring; no non-metal case components exposed .
Collodion Printing-out- Paper Pri nts ( PO P)
Part VIII E X H I B I T I O N P R A C T I C E

Color Photographic Processes

Dye transfers, C i ba/I l fo-ch romes and post- 1 990 prints.
Gelatin Printing-out-Paper Prints ( POP)
Platinum (Pt) or Pal ladium ( Pd) Prints
And combinations of Pt, Pd, and/or silver. No pinkish or yellow staining.
Paper support i n good condition. However, if signs of i mage or paper
deterioration are present, place in the "very light-sensitive" category.
S a l ted Paper Prints
If concerned about the i mpact of an unknown p rocessing, ton ing, or
coating h istory, move to the very light-sensitive category.
AJI M anuscript I nks
Except black I ndia i n k.

Less Ligh t-Sensitive

Total exposure per year-30,000+ ft-c hours (300,000 lux hour s ) ; e.g. 10 ft-c
for 9 months at 1 0 hours per day. Rest for 1 year m i n i m u m between display
cycles.

B l ac k-and-whi te F iber-based Gelatin S i lver Deve loped-out Paper Prints

( G S DOP)
Known to be wel l-processed and without hand colori ng, color ton­
ing, or optical brightener; otherwise, place in the "very l ight-sensitive"
category.
Post-1980 resin coated ( RC) papers that have been toned for preserva­
tion (e.g. si lver converted to a stable compound) may also be i ncl uded
in this category. Optical brighteners (dyes visible under UV) may be
fugitive and are damaged by UV exposure. Optically brightened papers
wi l l not appear as white under i ncandescent light, or when the bright­
ener is faded or exhausted.
Carbon Prints
Support paper i n good condition and l ight stable. Colorant known
to be carbon or other earth pigment. Otherwise, p l ace in "very light­
sensitive" category.
Gum Bichromate Pri n ts
Support paper in good condition and light stable. Colorant known
to be carbon or other earth pigment. Otherwise, place in "very l i gh t­
sensitive" category.
Photomechan ic a l Prints
E.g. p hotogravures, halftones, and col lotypes. Coated paper stock and
carbon or earth pigment. Paper support of good quality and in good
condition. Otherwise, p lace in "very l ight-sensitive" category.

688
 R e ad i n g 72 \·V A G N E H , 1\ I C C A B E , A N D L E 1\ I !\ I E N

Woodburytypes
S u pport paper i n good condition and l ight stable. Colorant known to
be carbon or earth p igment. Otherwise, p lace i n "very l ight-sensitive"
category.

N ote

1 Andrew Lerwill, Joyce H. Townsend, H a i d a L iang Jacob Thomas, and

,

S teph e n H ackney. A Portable Micro-Fading Spectrometer for Versatile

Lightfastness Testing . e- PreservationScience (e-PS) 2008, Vol. 5: 1 7-28.
 Appendices

Proper identification of photographic materials is vital to determ i n i ng how

to treat i ndivid u al objects and care for col lections. Throughout the h istory of
photograph conservation, several guides have been developed to help profes­
sionals meet t h i s challenge; this book wou ld be incomplete without ci ting
such tools. The following three appendices provide critical exa mples of such
gu ides.

Appendix A
RoREHT A. \"1E I NSTE I N a n d LAnnY BooT 1 1 , " Early Photogra p h i c Process I d e n t i fication
G u ide," i n Collec1 io11, Use, and Care of 1- / istorical Pl1otogmp/1s, eds. Hobert A. '"'e i nstein
a n d Larry Booth ( Nashvi l l e : American Assoc iation f'or State and Local H i story, 1 978) ,
208-9. Hepri nted w i t h perm ission of' American Assoc iation for State a n d Local H istory,
Nashville, TN, www.aash l.org , and George Eastman H o u se, I n ternat ional M useum oF
Photography and F i l m . Original compilation by Dr. Wa lter C l a rk. This appendix is not
c u rrent. Heproduced l'or historical p u rposes o n ly.

Appendix B
]AMES i\11 . H EI LLY , " M ajor 1 9th-Ce n t u ry Photographic and Photomechanical Processes:
Flowchart,'' in Care c111cl ldent.ificalio11 of 1 9t /1-Cenl 11ry P/10togra·phic Prin.ts ( Hochester:
Eastman Kodak Company, 1 986), i n sert. Adapted 2009 by James M. Rei l ly and Hespen­
heidc Design.

Appendix C
From M O N I Q U E C. F 1 sc1 1 E H a n d A N D HEW H o 1 m , " I dent i fication oF F i l m - Base Photographic
Materials: I n structions a n d Chart,'' i n Topics in Photographic Prese111at.ion. 5 (\,Yashi ngto n ,
DC: American I n stitute for Conservation, Photographic Materials G roup, 1 993), 1 1 7-22
( 1 1 9-2 1 cxccrptcd here). Reprinted by perm ission o F the a u t hors.

Hill & Adamson (Scottish, ac1ive 1843-1848). Coli111011 \\/ood (deta il ) , 1843-47. Salt (from calotypc
negative), 1 9 . 1 X 1 ;.2 cm ( Y2 X 6 i n . ) . Los Angeles. J . Paul Ceuy i\ l u sc um, 8+n1.966.9
 H E /\ D I N G S I N C O N S E H \1 1\ T I O N

Appendix A
Early Photographic Process l de n t i ficalion Guide ( 1 977)
Hobert A. \rV einstein and Larry Bood1

G E O R G E EASTMAN H O U S E , R O C l·I ESTE R , N EW YO R K

Material Technique Period R e m ar k s

I . D i rect Positives

Metal-

Copper, s i lver-plated Dague rreotype 1 839-c . 1 855 S i lver tone, before 1 842, b rown
tone, after 1 84 1 .

I ro n , japan ned b lack Ti ntype ( Ferrotype, 1 854-c. 1 900 Chocolate colored, after 1 870.
M c l a i notype)

Glass Earl i est have black velvet backi ng.

Later colored glass.

Leather a11d Oilcloth Extremely rare.

1 1 . Ne gatives

Paper-

U ncoated, often waxed Calotype Extremely rare in America.

or o i l ed

With gel a t i n su rface Eastman paper Rare, u s u a l l y of poor q u a l ity.

negative

Glass-

Thick, edges often grou nd, Col lodion 185 1-c. 1 880 Not used to any extent in America
coati ng grayish, u neven u n t i l c . 1 855. By c. 1 860 u n iversa l .

Thin, edges sharply c u t , Gelatin dry plate c . 1 880-c. 1 920 Occasionally used today.
coa l i n g b lack, very smoolh
and even

Ge/at.in-

Looks l i ke " f i l m , " but Eastman American 1 884-c . 1 890 Used i n Kodak N o . 1 ( 1 888):
comp letely ge l a t i n ; brittle; Film circular i mage 2- i/2", Kodak N o . 1
edges u n even ( 1 889), circ u l a r i m age 3 - 1 h".
 Appendix A

Clear plastic (nitro-ceUulose)

Extrc111cly t h i n , curls u p n o l l f-il 111 CAUTI O N : I N F LA M M A B L E

and wrin kles eas ily

N . C . ( non-curl). So111ewhat nail f i l m Test b y c u t t i n g s m a l l piece From

thicker, coated on both corner, p u t in ash tray, touch with
sides with gelatin to l ighted match. IF i t Rares, base is
p reve n t curling n i trale.

Mach i ne c u t sheets, Sheet fll 111 or 1 9 1 3- 1 939

exactly rectangular, edges Cut f i l m
stamped with name of
manu fact u rer

Clear plast.ic (cellulose acetate)

Marked SAF ETY on edge nail f- i l m 1 939 to present

Sheet f i l m

I I I . Pri n ts

Paper

U ncoated, brown to yel l ow- Silver pri n t Also called salted paper.
brown tone

Coated paper, extremely Albumen p ri n t " P r i n t i ng u pon a l b u men ised

t h i n , brown i mage, h igh paper seems to be dyi ng a slow
gloss, usually o n m o u n t but natural death. " Amateur
Pliotograplier, August 3, 1 894.

Sizes of Mounts

Carte-dc-visite, 4 - 1 /4 x 2-1h I ntroduced to U . S . c . 1 8 59

Cabi net, 4-1h x 6-1h I ntroduced to U . S . 1 866

Victoria, 3- 1/4 x 5 I ntroduced 1 870

Promenade, 4 x 7 I ntroduced 1 875

Boudoir, 5- 1/4 x 8- 1h Date i n t roduced u n known

Date i n t roduced u nknown

Panel 8 - 1 /4 x 4 Date i n troduced u n known

Stereo, approx. 3 x 7 I ntroduced to U . S . 1 859 ( nou nded corners . )

"Art iste," "Cabinet," " Del uxe" Stereo, I n troduced t o U . S . 1 873

approx. 4- 1h x 7 or 5 x 7
Ap pendix B
1\l l ajor 19Lh-Ccntury Photographic and Photomechanical Processes: Flowchart ( 1 986). James i\ I . Hcilly

HOW TO US E T H E FLOWCHART: Choose between Photomechanical and True Photograph.

For True Photographs, choose one-, two-, or three-layer structure, then choose individual characteristics.

P H OTO M E C H A N I C A L Patterned Image Grain' No Image Fading 1

Layer Structure and Individual Process Approximate

Surface Character Characteristics Dates of Use

1 885-
Poor reproduction of detail1
LETTERPRESS HALFTONE
Sharp-edged, large dot pattern3

Good reproduction of detail1

1 880-
May have multiple layers
Aquatint grain or grid screen PHOTOGRAVURE
May be matte or glossy
pattern2

Fine reticulation pattern2 COLLOTYPE 1870-

T R U E P H OTO G R A P H . continuousTone lmage2

Red-brown, purple, or yellow­

brown image hue1 SALTED PAPER PRINT
One layer
Signs offading1

Blue image hue1 CYANOTYPE

No binder laye r2
No baryta layer2
Paper fibers clearly visible2
Neutral image hue1
Matte surface3 PLATINOTYPE
No image fading 1

Signs of fading 1
Highlights yellow'
Red-brown, purple, or yellow-
Two layers brown image hue1 ALBUMEN PRINT

If binder is cracked, tiny cracks

overa ll1
Paper fibers visible through
binder in all areas3 CARBON PRINT
Binder layer present2 No image relief3 True Photograph
No baryta layer2
Paper fibers visible
through binder in
No image fading 1
highlights' WOODBURYTYPE
Image relief3
Some surface gloss3 Photomechanical
If binder is cracked, large cracks in
dark areas only3

GELATIN PRINTING-OUT
PAPER
Three layers
Warm or purple image hue1
Paper fibers invisible2

COLLODION PRINTING­
OUT PAPER

Binder and baryta layers

present2
Paper fibers partially or MATTE COLLODION
completely obscured in No image fading'
PRINTING-OUT PAPER

L·· 1
highlights2 Paper fibers partially visible2
WITH GOLD AND PLATINUM
No mirroring3
TONING 1 894-1920

.-{] 1 Examine visually �-;.. I

Near-neutral image hue1

�·__ I
2Examine
microscopically
at 30X
Paper fibers invisible2
1 885-
GELATIN DEVELOPING-OUT

•� 30bserve surface
Often mirrored in dark areas and
at edges3
PAPER

character
 Appendix B

Example Prints

PHOTOGRAVURE LETTERPRESS HALFTONE

COLLOTYPE

SALTED PAPER PRINT CYANOTYPE

PLATINOTYPE

ALBUMEN PRINT

CARBON PRINT

COLLODION P R I NTING-OUT
PAPER

GELATIN PRINTING-OUT PAPER

MATTE COLLODION
PRINTING-OUT PAPER
WITH GOLD AND PLATINUM
G ELATIN DEVELOPING-OUT PAPER TONING
 H E ,\ D I N C S I N C 0 N S I: ll 1· ti I I 0 N

Appendix C
Identification ol' F i lm- BasL" Photographic fV lu t cria ls : I nstructions and Chart ( 1 99 3)
1\ l oniquc c . F isc her and /\ndrC\\' nobb

ld
__ e_
n_ i c_
if_
t_ a_ i o_
t_ f _
n_o_ il m
F_ _ B_
-_ a_e_
s_ P
_ h_o
_ t_
o"""
g_ra--"p
_ h
_ c M
i_ _a_t_
e_i a_
r_ l s_ li
:__ t i_
s_
e_ n_
g_____ . . � 1,.

Po l a r i z a t i o n D i pheny l a m i n e Tes t
When viewed between cross-polarized filters, polyester and Handle this solwion with caution.
other highly birefringent materials exhibit red and green inter­ It colllains 90% sulfuric acid!
ference colors like those seen on soap bubbles. Cellulose
A solution of diphcnylamine and sulfuric acid can be used 10

�
nitrates and the cellulose acetates do not show these interfer­
idcntify cellulose nitrate. In this solution cellulose nitrate turns
ence colors. The Polarization Test can be performed with lhe
a deep blue color. Cellulose acetate and polyester do not
simple viewer illustrated below.
produce this color. However, cellulose nitrate is used in very
To use the viewer unfold the viewer small amounts in the manufacture of cellulose acetate and
and place a comer or the material in polyester products. This "subbing layer" does not appear to
question over one polarizing filter. ·
� effect either the longevity or the safety of these materials, but
Close the viewer and hold the viewer may cause a very faint blue tinge to be seen in the support of
up to a light source. Tilt viewer back- . .... . . . .. .... . . .. . ... . . . the cellulose acetates and polyester.
and-forth and side-to-side, red and
Place sample on a microscope slide and apply a drop of the
green interference colors will be most apparent in clear areas.
prepared solution. After one minute, a cellulose nitrate sample
If a material is badly deteriorated, examine it on a light table
will tum completely blue while the cellulose acetates and
with one polarizing filter underneath it and one on top of iL
polyester will nol. In some cases, a large cellulose nitrate
lnstruclions for Makinga Viewer sample may exhaust the solution and no blue color will form.
l. Tape together two pieces of split board. Be sure to place the Therefore, to confirm a negative test.. apply Lwo more drops
mat board along their long filters so that they are almost at and wait another minute to confirm that the sample is not
edge. cross polars lO one another. This
will be at t.he point at which
cellulose nitrate.
2. Al the lefl corner of each mat
they block the most light The solution is somewhat sensitive to light. Before testing
board split an area slightly
larger than the polarizing fil­ passing through them.
unknowns, test the efficacy of the solution with a known
ter 5. Apply double-sided tape to re­
sample of cellulose nitrate such as DUCO Cement or UHU
3. Cut a hole in each split area auach Lhe split boards and 10
All-Purpose Clear Adhesive.
hold the filters in place.
smaller than the polarizing
filter. (Polarizing filters are available Instructions for the preparation of this solution can re found in:
4. Slip polarizing filters into each aL toy s1ores in many children's Canadian Conservation Jmtitute. (1989). 'The diphenylamine spot
science kits.) test for cellulose nitrate in museum objects." CC/ Noles (1 7/2).

F l o a t Tes t B u r n Test

Trichloroe1hylene is toxic and a carcinogen! Conduct this Do nOI perform in your collection! Cellulose nitrate is
test in a we/l-ven1ila1ed area, wear rubber gloves, and use extremely difficult to exlinguish.

The bum test uses the nammable nature of cellulose ni trate for
with ex1reme caution.

The noat test may be used to identify film base types due to identification since bmh the cellulose acetates and polyester
their differing densities. Cellulose nitrate being the most dense are much less nammable. Cellulose nitrate bums quickly and
will sink, while cellulose acetate will rise to the top. Polyester has a characteristic yellow name. Having known materials for
should remain in the center of the solution. comparison is particularly important for this test.

Results from this test may be difficult to interpret because Hold sample vertically with metal tongs. Be sure to ignite the
deteriorated acetate film may sink to the bottom like nitrate strip from the top, only cellulose nitrate will bum downwards.
rilm. Another complicating factor is that the specific gravities For safely , have a large container of water nearby.
for cellulose nitrate and the cellulose acetates fall within a
fai rly broad range which may cause materials to behave
differently. As with the other tests, having a known sample for
comparison can be extremely helpful.

Place sample in a test tubeof trichloroethylene. Shake test tube

so sample is completely immersed. Observe location of sample
in the liquid.

Identification of F i l m-Base P h otographic Materials: In struction s
Edg e Printing
Edge Printing may include the name or type o f lhc film-base
material in question, cspeciaJly in the case of the cellulose
acetates and polyester. Cellulose nitrate materials rareIy contain
any edge printing. However, many cellulose acetate and
polyester materials do not have edge printing; many never
contained edge printing or it may have been Lrimmcd off. Also
keep in mind that a copy negative may contain edge printing
of the original negative in addition to its own.
Olhcr edge printing information may include: the name of the
manufacturer, manufacturing code data, and notch codes. This
information may be very useful in identifying materials which
have had parLicular deterioration problems. The Acetate
Negative Survey Fiool Report by Horvath is an invaluable
resource for identifying cellulose accuues using Lhis infonna·
Lion.
Notch codes can also be used to quickly identify tl1e binder
side of Lhe material: when the nOLch code is in the upper right
comer, the binder is facing you.
Start identification by looking for Edge Use of this Chart
Printing and Date Information. Check or
mark the result of each identification step in each section, then
summarize your findings in the section's Conclusion box.
These two steps arc the fastest and may be sufficient for
identification. I f still in doubt, or if the material is deteriorated,
fill out the Deterioration Chamcteristics section. This section
Deterioration characteristics of cellulose nitrate and Lhe cellulose
acetates, as well as those common to both materials, arc l s
i ted
according to a six level scale used by Horvath. Level I indicates
no deterioration, Level 6 severe deterioration. If more than one
level has been checkedoff, consider the material to be in the more
deteriorated level. These levels can be used to establish Rehous·
ing, Duplication, & Trcaunent priorities.
The nitric acid produced by the degradation of cellulose nitra1e
may cause deterioration characteristics of cellulose nil.rate (such
as image fading and stickiness) to be seen in cellulose acetates
and polyester. This can make identification by deteriora1ion
characteristics difficult.
While no material is completely stable, polyester is considerably
more stable than the cellulose esters and is not included in this
chart.
Only inherent deterioration characteristics are included on the
chart: it does not include external factors such as poor processing
or poor handling.
Deterioration Characteri stics
Appendix C
Dating I nformation
This chan gives the earliest and latest dates of manufacture of
sheet and roll formats of film-base materials in the United
States. Manufacturing dates of a specific company may fall
within a narrower range than the one shown. For example,
Kodak stopped producing cellulose diacetate materials in Ille
early 1940's, while Agfa continued to make them until Ille
mid-1950's.
Like other idemifying procedures, assigning a date to a mate·
rial may be quite subjective. In some cases only a guess from
the subject matter of an image is possible; however, in others
a date may be found on a housing or in the photograph itself.
Even very general information can be quite helpful in identi·
fication. For example, cellulose nitrate was the only film
material produced before Ille 1920's, and polyester was not
made before Ille mid-1950's.
is not only important as an identification
procedure but also as a way of evaluating
the condition of your collection. Testing, especially destruc·
tive testing, should be pcrfonned last Since all of these tests
are subjective to some degree, it is advisable to have a
reference set of known film-base materials to aid in identifi·
cation and ensure consistency in evaluation.
Tests provide a more exact, but n o tcompletely definitive, way of
identification. The Polarization test is particularly useful because
it is not destructive. The other three tests are destructive; they
require that a sample be taken from the film-base material in
question. Any destructive tests should be performed only after all
other identification procedures have been conducted and iden·
tification remains uncertain.
Carefully consider your reasons for conducting a destructive test,
it should nOL be necessary to perform all three destructive tests.
For example, the use of the polarization test in combination with
the diphenylamine test should make additional destructive tests
unnecessary. Many examiners only use destructive tests when
auempting to identify a representative sample from a large group.
Do not conduct the destructive tests unless you have been given
proper instruction-not only can you cause harm to your callee·
tion, more importantly you can harm yourself.
Tes ting Information
 11 E 1\ D I .'I G S I :-/ C 0 :-/ S L l l \' 1\ I I 0 :-/

Id e ntification of F i l m-Ba se Photographic Materials: Chart

Edg e Printing Dating I nformation

Film-Base Material Coding Information 1890 . .

.

D n ltrato 1900
.

itrate Film Code

D safety
. .
Acetates
D Estar 1910
sheet roll
Polyester film film
0 Cronar Polyester
1920
Notch Code
O other

:
( only aftef 1925)

•<Aillulose Diacebte

1 930 • • •Cellulose Ace1.i111 Propionate

Manufacturer •
•

1 940
C.llulose Acetate Butyfate
. .

ii rate Acetates Polyester • • Cellulose Triacetate

D AgfalAnsco 1 950 . .

0 Defender
D DuPont 1 960
0 Hammer
. .
1 970 .
D Kodak
.

D other
1 980 . .
. .
Other Textual Information 1990
Cellulose Cellu se
!irate Acetates
Polyesler

Edge Printing Conclusion Dating information Conclusion

Id e ntification
Conclu s ion

Deterioration Characteristics Testing Information Conclusion

Polarization Test Dlphenylamlne Test

Nitrate Acetates
Common Level No Sample Needed 111 Sample Size

D intanse bluo lirnis

C haracteristics Non-destructive

0 no colors ii rate
N o Deterioration color in sample
and solution
0 no colors
O y o ll ow D curl D faint blue or no
Acetates
0 red or green
Acetates
D mirroring D red
Polyester
color
0 faint blue or no
interference
D blue colors Polyester
color

D nitric acid D acetic acid D shrinkage

3
0 sticky D brittle
Float Test Burn Test

D amber D warpage ITIJ

4 Sample Size
0 image fade 0 orange dots
O bottom Niiraie D burns down Nliraiis
D bubbles very quickly
5
O solt D top Acetates
D crystals D middle
yellow flame
Polyester
0 difficuh to ignite Acetates

0 stuck D channelling burns only briefly

6
D brown D difficuh to ignite Polyester
burns only briefly

Deterioration Characteri stic s Te sting I nformation

 Further Readin g

M ore than fifty international photographic preservation professionals were

i nterviewed d u ring the i n itial stages of t h is project to identify the most
i mportant readi ngs pertai n i ng to and i nfl uen c i ng the history of p hotograph
conservation. The foll owi ng list i n c l u des s uggested readings that are not
reprinted in this vol u m e . Wh ile not comprehensive, this l i s t represen ts the
wide array of publ ications that have i n fl u enced, i nformed, and i nspired the
photogra ph ic preservation profess ionals i nterviewed. As such, i t serves as an
excellent resource for fu rther reading.

P a r t I: H i st o r y of P h ot o graph C o n s e rvat i o n

Al bright, Gary. "Storage Enc losures For Photographic
M a terials. " Preservatio11 of Library crnd Archival Materials:
A Manual, edited by Sherclyn Ogde n . 3nl ed . , revised and
expanded. Andover, MA: No1·theast Doc u m e n t Conserva­
tion Cen ter, 1 999, 309-3 1 4 .
--- . ''Photographs. " I n Conservat.ion in. the Library: A
/-/andbooh of Use and Care of Tradit. iunal and Nont.raditional
Mat;erials, edited by Susan Swartzburg, 79- 1 02 . \•Vestport,
CT: G reenwood Press, 1 983.
Coe, Bria n , and Mark H aworth-Booth. A Guide to Early
Photographic Processes. London: 1-1 u rtwoocl Press in associa­
tion with the Victoria and Al bert M useu m , 1983.
Collins, Charles W. The 1-/andbooh of Photography, 11/ust.rat.­
ing the Process of Producing Pict11res by t.he Chelllical f njlu­
ence of Light on Silver, G lass, Paper cmd Ot.ha S 'lllfaces, to
which Is Added an Appendix Con.t.ain.ing Fu/. l Inst.ructions for
the Prepamt. ion of, and Mode of Using, tlie Cl1emicals and
Other S·ubstances Employed. Lo ndon: C . W. Col l i n s , 1 8 53.

Baldwin, Gordon. Loohing at Photographs: A G uide to Tech­
nical Tenninology. Malibu, CA: J . Pa u l Getty M u s e u m i n
association with B r i t i s h M u seu m Press, 1 99 1 .
Cartier- B rcsso n , Anne, L e 11ocab11laire technique de la plio­
tograpliie. Paris: M a rve l , 2007.
Colson� Rene. i\!lci111oires origiuaux cles crdaieurs de la ph.o­
tograpliie. Paris: George Carre ct C. l\l a u d , 1 898.
Coppens, Jan, Laurent Hooscns, and Karel Van Dcurc n .
. . door de enhele 1verhing van /,wt Licht . . . ': l r a roductie en
integratie van de fotografie in Belgiii en Nederland,
 l l E 1l l J I N t : S
1 839-1 869 ("By t '1e sole act ion of light ": / 111 rocl11ct io11 and
lntegrat io11 o( P/1otogmphy in Belgi11 111 and The Nether­
lands). An lwerp: Gemeen tekred iet, 1 989.
Crawford, W i l l i a m . Tlie t<eepers of Lig/1 1 : A 1- fistory a11d
\Morhillg G u ide to Early Photogmpliic Processes. Dobbs
Ferry, NY: Morgan and Morgan, I nc . 1 979. . ---. "The Stab i l i l y and Preservat ion o f Recorded
Dava n n c , Alp honse. La Pliotographie: Trnite l i1eoriq11e et
praticf11e. Paris: G a u t h i e r-Vi l la rs et Fils, 1 888.
Les clocu 111e11ts p,raphiques et pliotographiques cuu:tlyse et
conservatiol'l: T'rava11x cl11 centre de recherc'1es s11r la co11ser-
11at.io11 des doc11 111e11.ts graphiq11es 1 986-87. Paris: Arch ives
Nationales , 1 987.
Do n n i thornc, Alan. "The Conservation ol' H i storical Pho­
tographs at t he British i\ l useu m . " The Paper Conservator:
)011mal of I fie lnst i/11/e of Paper Co11Servatio11 17 ( 1 988).
Downey, Laura, and Therese M u l l iga n . "A Voice for the
Print. " In Tlie Plwtography of Alfred St ieg/it.=: Georgia
O 't<eeffe � E11d11 ri11g Legacy. Roch ester, NY: George East­
miln House, 2000.
Eaton, George T. Co11ser11ation ()( Plwtograplis. Rochester,
NY: East man Kodak Company, 1 985.
Eder, Josef' i\ l aria. Tlie /-listory of Plwtogrnphy. Translated
by Edward Epstea n . New York: C o l u mbia U n iversity Press.
1 945 ·
Enyeart, James L .. Adelaide B. Anderson, Steven J . Perron,
D . K. R o l l i ns, and Q u i n tus Fernando. " N on-Dcsl ruct ivc
Elemental Ana lys is oF Photogra p h i c Paper and E m u lsions
by X-ray F l uorescence Spectroscopy. " 1-list.ory of Phot.ogra­
phy 7, no. 2 (April-J u n e 1 983): 99- 1 1 3 .
Frizol, M i c h e l . No11velle 1-/istoire de l a photograpliie. Paris:
Bo rdas/Adam B i ro. 1 99+
Gernsheim, H e l m u t . Co11cise /-listory of Pliotogrnphy. New
York: Dover P u b l i cations, 1986.
--- . The Origins of Pl1otograpl1)" New York: Thames &
H u dso n , 1 982.
C real Brilain Patent Office. Patent.sfor l 11ve11tions: Al1ridg-
111ents of Specifications Relating to Pl10tography. Lo ndo n :
Prinled by George E . Eyre and W i l l i a m Spottiswoode, 1 86 1 .
700
I N C O N S E H V ,\ T I O N
Haas, Pa mela. "The Conservation of' Photogra phic Col lec­
tions. " C11rntor 26, no. 2 ( 1 983): 89- 1 06 .
H en d riks, I la us B . "The Conservation o f ' Photographic
M ateria l s . " Pict11resco{Je 30, no. 1 ( Spring 1 982): 4-1 1 .
I mages. " In I 11/(/gi11g Processes a11d Materials, ecli led by
J o h n Stu rge, Vivian Wa lworl h , and A l l a n S hepp, 637-8+
Neblelles 8 l h ed. New York: Van Nostrand Re i n hold, 1 989.
H e ndriks, Klaus 13., Debra H ess Norris, and James M.
R e i l l y. " Photograph Conservation: The State ol' the Arl. "
I n Tl1e A 111erican l11Stit11tefor Conservatio1t of 1-/ist.oric and
Artistic \'Vorhs, prepri11ts of papers presented at t.he fo11rleenth
a1t11 11al 111eeli11g, C/1 icago, Illinois, 21-25 May, 1 986. Wash­
i ngton , D C : American l ns l i t u le !'or Conservation of' H i sloric
and Artislic \!\forks, 1 986.
H e ndriks, Klaus 1 3 . , and Lincoln Ross. "The Restoration
of' D iscolored B lack-and-W h i t e P h otogra p h s i n C he m i ca l
Sol u t ions." I n Tlie A 111ericc111 l11st.it111efor Conservat.ion of
1-/istoric an.cl Art,istic Worhs, preprints of papers presented al
t:lie sixt,eenlh an1111al nieet.ing, /\Jew Orleans, Lo11isiana, 1-5
J une, 1 988. \i\lashi nglo n , D C : American l n s l i l u t e for Con­
servation ol' H i storic and Arlislic \Norks, 1 988.
Hockin, John B rc n l . P/101ograpl1y 011 Class and Paper. Lon ­
don: Hock i n , 1 85+
Jenkins, Reese. /11/(/ges am/ E11terprise: Tech11ology r111d the
A111erica11 Pliotographic l11d11slry: 1 839 to 1 925. Baltimore:
Johns Hopkins U n ivcrsily Press, 1 975.
Jones, Bernard Edward. E11cyclopedia of Photography. New
York: Arno Press, 1 974.
Jcirge ns, M a rt i n C. "Towa rd a Melhodology for lhe I dentifi­
cation of D igilal Prinl Formals. " In Postprints: Preservalirm
and Conservr1tio11 lsrnes Related to Digilal Printing, 60-65.
London : l n s l i l u t e ol' Physics, 200 1 .
Ken nedy. Norn, and Pclcr i\ l u stardo. "Contemporary Pho­
togra phy From a Conscrvalion Perspective. " In T/1e l111pe1fecl
ln1age: Pliolograp/1s, Their Pas/, Presen t and F11t u re, 367-75.
Conference Proceedings, V\/indcmere, 6th-1olh April, 1 992.
London: Centre !'or Pholographic Conservation, 1 992.
--- . "Cu rre nt I ssues in the Preservation of Photographs."
A.B. /300/w1an's Weehly 83, no. 1 7 (April 24, 1 989): 1 773-83.

Kingsley, H ope, and Cori n n e 1-1 i l l m a n . " N i netecnth­
C e n t u ry Photographic Research-A Legacy of' Conservat ion
Prob lems or a n I ns p i ration to Con temporary Conserva-
tion \Nork. " I n Th.e Tmpe1fecl. I 111age: Phot.ographs, Their
Past , Present and Fut. u re, 367-75. C o n ference Proceedi ngs,
vVindemere, 6th-10th Apri l , 1 992. Londo n : Centre for Pho­
tographic Conservati o n , 1 992.
Klijn. E., and Y. de Lusenet. In the Pict11re: Preser11alio11
and Digil. isal.ion of European Pl1olographic Col/.ections.
Amsterd a m : E u ropean Commission on Preserva t i o n and
Access, 2000.
Koch, M ogens S . "Education i n Photographic Conserva­
t i o n . " Getty Conservation / 11st.it111e Newsleller 1 7, no. 1
(2002): 6-8.
Leggat, Robert. A History of Photography j.-0111 its Begin­
n ings Till Lhe 1 920s. Robert Leggat, 1995. http ://www.rlegga t .
com/photoh i story/.
Long, C h a rles A. Practical Photography 011 Glass C111d PC1per.
A MC111ual Cont.aining Simple Direct ions for I.he Prod11cLion
of Port.rails, Views Etc. by the Agency of Light l ncli1ding Col­
lodion, Albu'l1'1en, Calotype, V\/axe Paper . . London: Bland
a n d Long, 1 854.
M alone, Thomas A . " P h otography on Paper and on C lass. "
PhoLograph.ic Art. Jonrnal 1 , no. 1 ( 1 85 1 ): 44-46.
Maynes, Pa u , and Grant 13. Romer. " Documenting Conser­
vat ion Through Oral H i story: A Case Study. " I n Pre-Prints
of 1 /1e 13th Triennial Meeting Hio de]aneirn, /COM Co111-
1nillee for Conservation, 1 72-75. Londo n : J a 1ncs and Ja111cs,
2002.
Messier, Pau l , Valerie Baas, Diane Tarilowski, and LaL1 1·en
Varga. "Optical B righte n i ng Agents in Photographic Paper."
]ournC1l of Lhe American I 11sl ii ule for Co11Serva1 io11 44, no. 1
( Spring 2005): 1 - 1 2 .
Moor, I a n L. "The Ambrotype-Rescarc h into i t s Restora­
tion and Conservation-Part I . " The PC1per Conser11C1lor:
JomnC1l of the Instit u te of Paper Comervat.ion, 1 ( 1 976),
22-25.
Moor, I a n L . , and Angela 1-1 . "\,Vork Study: A Method of'
M o u n t i ng a Photograp h i c and M ixed Media Col lection."
I n Tl·1e / 111. p er/ecl. I m.age: P/10tograpl·is, Their Past, Present
and F11 t u re, 1 52-59. C o n ference Proceedi ngs, VVindcmere,
Further Reading
6th- 1 0t h April, 1 992. Londo n : Centre for Photogra p h i c
Conservation, 1 992.
Nadea u , Luis. EncyclopediC1 of Pri11t.i11g, P/101ograpliic, and
Phot. 0111echan.i.cal Processes. Vol s . 1 and 2, A-Z. New Bru ns­
wick, Canada: Ate l i e r Luis Nadea u , 1 989.
N ewhall, Beaumont. T/1e 1- / islory of Pl1utograpl1y: Fro111 183 9
lo the Prese11I.. N e w York: M u se u m of' M odern Art, 1 982.
Norris, Debra Hess. " P hotogra phs. " Wi111ert.l111r G11ide to
Caring for Yo11r Collecl irm. \Ni n terth u r, D E . : H e n ry Francis
d u Pont vVin tert h u r M u seum I H a n over, N H : U n iversity
Press of New England, 2000.
Norris, Debra H ess, and Nora vV. Ken n edy. "Recent
Adva nces and F u t u re D i rections i n the Education and
Tra i n i ng of Photogra p h Con servators. " In Pre-Prints of the
131/1 Trie11nial Meeli11g Hio de ja11eiro, /COM Co111111il.lee for
Co11servatio11, 65 1-57. London: Ja mes and James, 2002.
Orraca, Jose. "The Conserva t i o n o f Photographic i\ l ateri­
a l s . " /3 ulle1.i11 of I. he A 111ericc111 I nsLil u le for Conser11a tio11 of
1- /ist.oric and Artistic Wurhs 1 3, no. 2 ( 1 973): 32-38.
Ost roff, Eugene. " E<irly Fox Tal bot Photographs a n d Res­
toration by Neutron l rrad iat ion . " Jo11 mC1/ of P/1ologrnphic
Science 13 ( 1 965) : 2 1 3-27.
---. "Conservi ng and Hest oring Photographic Col lec­
tions. " f\11 1 1self111 News 52, no. 8 ( M ay 1 974): 42-45.
--- . "Conservi ng and Hestori ng Photographic Collec­
tions, Part 2 : The E ffects of Residual C hemicals. " M11se11111
News 53, no. 1 (September 1 974 ) : 40-42; 48.
--- . "Conservi ng and Restori ng Photographic Col lec­
t ions, Part 3 : Restorat ion .'' !Vl11senrn f\leu1s 53, no. 3 ( Novem­
ber 1 974): 42-45.
--- . "Conserving and Restori ng Photographic C o llec­
t ions, Part 4 : Storage. " M useu m. News 53, no. 4 ( December
1974 ) : 34-36 .
Photography: Processes, Presen·a t ion, Coi1ser11a tio11. New
York: The Metropol it<in M u seum of' Art, 200 1 (ex h i b ition
hroc h u re ) .
Poitev i n , Al phonse. 'J'rail.e des /111pressio11s Phot.ographi.ques
Sam Sels d 'A rge11. I. Marse i l le , France: Laffitte. 1 983.
70 1
 H E ,\ D I N C S
Pon t i ng, Thomas C. P/10tograp/1ic Oif(icu lties a11cl I- low to
S 1 1 rn 1011 11t Then1; l11str lll t a 1 1eo11s Pic t 1 1 res: f-10111 to Obtai11
Tl1en1. Bristol: Bland and Co., 1 862.
Poto n n iee, Georges. The f- listory of t he Oiscot>ery of P/10-
tography. Trans lated by Edward Epstea n . New York: Arno
Press. 1 936.
Re i l ly, Ja mes M. Care a11cl lcle11ti.ficatio11 of 1 9th Ce11 t 1 1 ry
Photographic Pri 11ts. Rochester, NY: East man Kodak Com­
pany, 1 986.
Rempel, Siegfried. Tf1e Care of Photogrnphs. New York:
N i ck Lyons Books, 1 987.
Romer, Grant B . "An Overview ol' t he C u rrent Development
of' t he Field ol' Conservation of' Photographs. " Co11serva:io11e
clei J\l l a teriali Lil1rari Arichit>istici e C rafici 2 ( 1 999): 243-46.
--- . "Some Notes on the Past, Present and F u t u re ol'
Photographic Preserva t i o n . " l11wge 27, no. 4 ( 1 984 ) : 1 6-23.
Saretzky, G a ry D . " Recent Phot ographic Conservation a n d
Preservation Li terat u re. " Pict11 rescope vo l . 32 no. 4 (\>\lin ter
1 987): 1 1 7-32.
Schaal', Larry J . 011t of Shadotl's: f -lerschel, Talbot, a11cl tl1e l11Fe11-
tio11 of Photography. New Haven: Yale U n iversity Press, 1992.
S heppard. Samuel Edward. Cela t i 1 1 i11 Photogmp/1y, Vol .
New York: D . Va n Nostra n d C o m pany, 1 923.
S t u rge, J o h n , Vivian Walwort h , and Allan Shepp, eds.
/ 111age Processes a 1n l Ma terials: Neblet t e 's 8th Edi t ion. New
York: Van Nostrand Re i n hold, 1 989.
Swa n , Alice. "Conservation ol' Photographic Print Collec­
tions. " Library Tre11ds 30, no. 4 ( Fa l l 1 98 1 ) : 267-96 .
Taft, Robert . Pl1otogmpl1y a11cl the A n 1erica11 Sce11e: A Social
f- listory, 1 839-1 889. New York: Dover Publ ications, I nc . , 1964.
Thomas, Ke l l y Devine. " H ine Case Set t l ed, Prints That May
Be Questionable \l\l i l l 13c Tested. '' A1·t News ( J une 200 1 ) .
Tissa n d icr, G . A f- l istory and /-laHclfJooh of P/10tograp/1y.
E d i ted by J. Thompson. London: Sam pson Low, M a rston,
Searle Hivington, 1 878.
I N C 0 N S E H \' A T I 0 N
Towler, J o h n . Tl1e S ilver S 1 1 1 1 bea111. New York: Joseph H .
Laclcl, 1 864.
Van Monc khovcn. Des i re . A Pop ular Treat ise 011 P/10togra­
phy. London: Virtue Brothers & Co., 1 863.
\•Vagncr. Sarah. " B lack a n d White Resin Coated Paper.''
Topics i11 P/10tograp/1ic Presert'at io11 8 ( 1 999). Was h i ngton.
D C : American I nstit ute for Conservation, Photographic
i\ l aterials G ro u p . 1 999.
\ �la rc, M i ke. Cyanotype: T/1e f- l istory, Scie11ce and Art of
Photographic P1·i 1 1 t i 11g i1 1 Pr11ssia11 /3/11e. Londo n : National
M u seum of' Science, 1 999.
\�lc n t zcl, Fritz. J\lle111oirs of a Phot;ochen1ist. P h i lade l p h i a :
American M u seum o l ' Photography, 1960.
\�lilson, Edward L. Wilson's Photograpliics: A Series of Les­
sons. P h i l adelphia: Edward L. \l\li l son, 1 88 1 .
�lit k i n . Lee, a n d Ba rbara London. The P/10tograp/1 Collec­
tor's C11 icle. New York: Ba l l a n t i n e Books, 1 979.
�loodbury, \�fal ter E . Tlie E11cyclopaeclic Oictio1rnry of Pho­
tography. New York: Scov i l l & Adams, 1 898. Repri n t , New
York: Arno Press, 1 979.
Woodward. R i c hard B. "Too i\ l u c h of' a Good Th i ng: Pho­
1. tographv. Forgery, and the Lewis H i ne Sca n d a l . " A t lr lll t ic
Mo11t lily 29 1 , no. 5 ( J u n e 2003 ) : 67-76.
Part II: Silver Image Structure and Sta b i l ity
Anon . "The l n n uence of' Va rious i\l l o u n ta n ts on the Perma­
nence of Photographs. " Brit ish )011mal of P/1otograpl1y 23
no. 833 ( 1 876): 1 83-84.
B lanchard, Va l e n t i n e . "On t h e Best Means ol' Hcnderi ng
S i lver Prints Pe rma n e n t . " Pf10tograp/1ic )011mal 1 2 , no. 1 8 1
( 1 867): 38-42.
Brandt. E. S . " M echanistic S t u d ies of S i lver I mage Stab i l ­
i ty. 1 : Redox C he m i st ry o f Oxygen a n d Hydrogen Peroxide
at C l ean and at Adsorbate-Covered Si lver Electrodes.'' P'1.o­
tograpl1ic Science ancl Engineeriiig 28, no. 1 ( 1 984): 1- 1 2.

--- . " M echan istic Stud ies oF Si lver I mage Stabil ity. 2:
I odide Adsorption on S i lver in t he Presence oF Thios u l fate
and the I n fl u ence oF Adsorbed I odide on the Catalytic
Properties of S i lver toward Hydrogen Peroxide. " Photo­
graphic Science and Engineering 28 no. 1 ( 1 984): 1 3- 1 9 .
---. " M echanistic Stud ies o F S i lver l 111age Stab i l i ty. 3 :
Oxidation of S i lver fro111 the Va n tage Poi n t oF Corrosion
Theory. " Journal of llllagi11g Scie11ce 3 1 no. 5 ( 1 987): 1 99-207.
B ri l l , Thomas B. "Chapter XI I-Light-Se n s i tive M a teria l s :
T h e Photographic Process. " I n Light: Its /11teractio11 wit.Ii
A rt. and Antiquities. New York: Plenum Press. 1 980, 247-73.
B u rge, Daniel i\1 1 . , James i\1 1 . Reil ly, a n d Douglas W.
N i s h i m u ra . " E ffects of Enclosure Papers and Paperboards
Contai n i n g Lign i n s on Photographic I m age Stability.··
)011rnnl of the A 111erican Inst itute for Co11servatio11 4 1 , no. 3
( Fa l l-Wi n te r 2002): 279-90.
Dodd, J. N I . "On the Fading oF Positives. To the Editor for
the Photographic Journal. ·· Journal of the P/10tographic
Society 48 ( November 2 1 , 1 8 56): 1 68-69.
Eaton, George T. Photographic Che111ist.ry in. /3lach-a11d­
\!\fl1ite and Colo1· Photography. H asti ngs-o n - H udson, NY:
M o rgan & M orga n , 1 957.
Foard, J. T. "Re111arks Oil the I n f l u ence or Da111p Air U po n
.
P hotogra p h i c Pri n ts . . Liverpool Phot.ographic Jo'llmal 3 ,
no. 30 ( J u n e 1 4 , 1 8 56) : 88-89.
C l afkides, Pierre. Plwt.ograpliic Chemistry. Vols. 1 and 2 .
Tra nslated b y K . H ornsby. Lo ndon: Fou n t a i n Press, 1 958.
C ray, M ichael. " Problems of Photographic Permanence: A n
Overview and Exa111 i nation of Conte111porary Knowledge
and Data, T icd bot to Hardwich 1 835 to 1 855. " I n The I mper­
fect. /wage: Photographs, T/1eir Past., Present and F11.t11re, 34-
42. Conference Proceedi ngs, V\l i n de111ere, 6th- 1 0 t h Apri l ,
1 992. London : Centre F o r Photographic Conservation, 1 992.
H e n d ri ks , l<laus B . " I mage Pcrmancncc . n E n t ries in Focal
Encyclopedia of Phot. ography, Third Edit.io11. Boston, Lon­
don: Focal Press, 1 993, 377-85.
H e n n , R . V\I., and Bernadette D . Macie " M icroscopic Spots
in Processed M icrof il m : I n spec t i o n of Collections to Eva l u -
Further Reading
ate the E ffect oF I odide. " Photographic Science an.cl Engi­
neering 13, no. 5 (September-October 1 969): 276-77.
H e n n , R. W. , and D. C. V\liest. " M icroscopic Spots i n
Processed M i crofi l m : The i r Nat u re a nd Prevention." Phot. o­
grnpliic Science and Engineering 7, no. 5 ( September-Octo­
ber 1 963): 253-59.
H u n t , Robert. '" O n the Fad i ng o F Photographic Pictures."
/-/ 11111 ph i-ey's Jo11 rnal of t 11e Daguerreotype and Photographic
Arts, 7, no. 13 ( 1 855): 25 1-55.
Koppcrl, D . F., and T. J. H u ttema n n . '"Effect of R es i d u a l
Thios u l fate I o n on the I mage Stab i l i ty of M icro f i l m s . " Jou.r-
11al of l111aging Tech11ology 1 2 (August 1 986): 1 73-80.
Lee, \•\ !. E . , B . Wood , and F. J. Drago. 'Toner Treatments
For Photographic l 111ages to E n h ance I mage Stabi l i ty. " Jour­
nal of Applied Plwtograpkic Engineering 10, no. 3 ( 1 984):
1 1 9-26.
Lee, \!\!. E . , F. J. Drago, and A. T. Ram. " N ew Procedures
for Processing and Storage of KODAK Spectroscopic
Plates, Type 1 1 l a -J. . . Jo'llrnal of Applied Photographic En.gi­
neerin� 10, no. 3 ( 1 984): 22-28.
Lytc, F. M axwe l l . "On the Causes of the Fading or ProoFs. "
Phot.ographic .Jo11rnal 5, no. So ( 1 859) 2 1 5- 1 7 .
S p i l ler, J o h n . "Observations U pon Fadi ng." Tl1e Plwto­
grapliic News, 28, no. 1 3 1 5, New Series ( J u ne 1884): 373-74.
Wa re, i\11 i kc . Mechanisll'IS of f. 1nage Deterioration in. Early
Plwtographs: t /1e Sensitivity to Light of WHF Talbot 's Halicle­
jixecl l lllages 1 834-1844. London: National M u seum o f Sci­
ence, 1 994.
--- . "On the Stabil ity or Robert Adamson's Salted Paper
Prints. " History of Phot.ography 27, no. 1 (Spring 2003).
Wendero t h , F. A. "On t he fad i ng oF si lver photographs."
Philaclelpliia Pliot.ographer 1 6 ( 1 879): 1 30-33.
'v\/ilson, George. "On Dryness, Darkness, a n d Coldness as
Means oF Preserving Photographs from Fading."' Jo11rnal of
the Plwtographic Society 8 5 ( M ay 23. 1 859) : 290-93.
 H E 1\ D I N G S
Part III: S i lver, M e r c u ry, a n d G o l d :
P h i l o s o p h i cal a n d Practi c a l Ap proaches
i n t h e P reservat i o n o f D a g u e rre otypes
Barger, M. Susan, A. P. C i ri , W i l l i a m B . White , and
Thomas M. Edmondso n . "Clea n i ng Daguerreotypes . "
St. 11dies i n Conservat io11 3 1 , n o . 1 ( 1 986): 1 5-28.
--- . "Corrigenda." St 11dies in Conservation 32, no·. 3
( 1 987): 14 1-43.
Barger, M . Susan, Deane K. S m i t h , a nd W i l l i a m B. \Vhitc.
'
" C h aracterization of Corrosion Prod ucts on O l d Protective
G lass, Espec i a l ly Daguerreotype Cover C lasses. " )011mal of
Material. Science 24, no. -J (Apri l 1 989): 1 343-56.
Barger, M . Susan, R. Messier, and W. 1 3 . White , ''A Physi­
..
cal Model for the Daguerreotype . Pl1otograpl1ic Science
and Engineering 26, no. 6 ( 1 982): 285-9 1 .
Daffner, Lee A n n . Dan Kushe l , and John i\t l . Messi nger.
" I nvestigation of a Su rface Tar n i s h Found on 1 9t h -Century
Daguerreot�1Jes.'' Journal of t he A 111ericrm I 11st.it u l e for Co11-
servation 35, no. 1 ( 1 996): 9-2 1 .
E n yeart, Ja mes L . " Reviving a Daguerreotype. " Pl10tograpliic
Journal vol . 1 1 0 (September 1 970): 338-4+
H ardw i c h , T. Frederick. A Manual of Photographic Che111-
i.st.ry, l ncl.t1ding t he Practice of t.f.1e Collodion Process. New
York: H. H. S n e l l i ng, 1 8 58.
M c El hone, John P. ''Restoration and Conservation of' the
Lambert C i ft Col lection of Daguerreotypes. " Topics i n Plio­
t.ograpliic Preser11al.io11 3 ( 1 989): 22-27. \�la s h i ngt o n , D C :
American I nstitute for Conservation, Photographic M ateri­
als G roup, 1 989.
Swa n , Al ice, C . E . Fiori, and K. F. J. H e i n ri c h . " Daguerreo­
types: A Study of the Plates and The Process. " Scanning
Elec t ron Microscopy 1 ( 1 9 79): 4 1 1-2+
Wood, R. Derck, and M rs . E. D . S horl a n d . ''The Daguerrco­
t)1Je Portrait of Dorothy Draper. " Pl1otographic Journal
vol . 1 1 0 ( Dece mber 1 970): 478-8 1 .
I N C O N S E H \ ' i\ T I O N
Part IV: A l b u m e n Print M aterials: M a n ufactu re ,
Structure, a n d Treatment
Baas, Va lerie, C h ristopher Foster, and Karen Trentclma n .
"The Effect of' i\ l u l t i p l e \Vet Treatments o n Cracking i n
A l b u me n Pri nts." Topics / 1 1 Pl10tograpliic Conserval io11 7
( 1 997): 38-42.
Coale, George 1 3 . Ma1111al of Pl10tography, Adapted to A 11rn­
te11r Praciices. \!\fl1 ipple's Alb1111ien Process. P h i ladelphia:
Lippi ncoll, 1 858.
C rouc her, J. H . , and G u stave Le C ray. Plain Directions for
Obtain ing Pliotograpliic Pic t u res by t l1e Calotype a11d E11er­
giatype, A lso 1 1 po11 Allm111e11 i:ed Paper and Class by Collo­
dio11 a11d Alb11111e11 Etc., Etc. P h i ladelphia: A. H art, 1 853.
Dava n ne. Lou i s Al phonse. "On the Advantages of f\m mo­
n iacal Albumen in Positive Pri n t i ng." Pl10tographic Notes 3,
no. -13 ( 1 858): 25.
Divine . Silas R . A Pract ical Trenl ise on Alb1111ie11 Plwtog­
rapliy, Co11tai11ing tlie Collodio11 Negative Process r111d tire
Met hods of Prepari11g, P1-i 11t.i11g, and Toning Alb11111e11i:ed
Paper, also tlie Most ApproPed Modes of Mahi11g Carles-de­
Visite. New York: J. 1-1 . Ladd, 1 862.
Eder, Josef ' M. Die Phot.ographiscl1en Copirl'e1Jahre11 111iet
Silbei-sril:e11 ( Posit iv- Process) a11f Sal:-, Starhe-, 11 nd Alb11111in­
Papir etc. H a l le, Germany: Knapp, Wilhelm Verlag, 1857.
H a rt, L. W. Photography Si111plijiecl. A Pract ical Treatise on
t he Collodio11 and Allm111e11 Process. Southampton: i\ l a r­
sha l l , 1 857.
Hearn, C ha rles \,\I, The Pracl ical Print.er: A Complete
Mr11nwl of Photographic Pri 1 1 t i ng, Con.t.ai1 1i11g Full Details
Co11cemi11g all t he S tyl.es and Processes of Plain a11cl Albu-
11·1e11 Paper Pri 1 1 t i 1 1.g. Philadelphia: Edward L. W i lson,
1 8 7+
H eath, /\. 1-1 . , and A. S. Heath. Pliotograpliy: A New Trea­
t ise, Tl1eoret.ical and Practical, of the Processes and Mc111ip11-
latio11s on Paper, Dried and v\le t , C lass, Collodion c111cl
Alu11111e11. New York: Heath and Brother, 1 85 5 .
Heisch, C harles. Plain Directio11sfor Obtai11ing Photogmpliic
Pic t u res 11po11 I \lrc�ed a11d AllJ11111e11.i:ed Paper n11d C lass by
Collodio11 a11d Allm 111e11. London: H ichard \,\Ii i lats, 1 8 53.

Lea, M . Ca rey. " Heactions of H ypos u l fltes and Su/phocy­
a n ids u pon A l b u 111cn Prints. " Ph iladelphia Ph.ot.ograph.er 5,
no. 57 ( 1 868): 3 1 5- 1 6 .
L e G ray, G u stave. Plwt. ographie: Tra it.e No11vea11, Theoriq11e
et Pratiq11e, des Procedes et Man ip11lat ions: S11r Papier, Sec,
H11111ide: S u r Verre, a11 Col/odio11, a l 'A lb11111i11e. Pari s : Lere­
bours et Secretan, 1 854.
i\ l m·er, I a n . · · so111e Hesearch i nto Met hods of Mounti ng, Li n­
i ng, or Hepa i ring Albu 111en Prints.'' In Tirn l111pe1fect I mage:
Photographs, T/1eir Past, Present and F11 t u re. Conference Pro­
ceedings, \"lindemere, 6th- 1 otl1 Apri l , 1 992. London: Centre
For Photographic Conservation, 1 992.
M essier, Pa u l . " P rote i n C hemistry in A l b u me n Photo­
graphs. " Topics i n Phot.ographic Preservation 4 ( 1 99 1 ) : 1 24-
35. \Vas h i ngton, DC: American I nstitute for Conservation,
Photogra p h i c M ateria l s G roup, 1 99 1 .
--- . "Work i n Progress: A n Analysis o F the Effect o F
\•Vatcr o n t h e Cracking o f A l b u me n Photographs.'" Topics i n
Plwtographic Preservat io11 4 ( 1 99 1 ) : 1 24 . Was h i ngton, DC:
A111erican I nstitute For Conservation, Photogra p h ic M ateri­
als Grou p , 1 99 1 .
M essier, Pa u l , and Tim Vitale. "Albumen Photographs:
E ffects o f Aq ueous Treatment and F u ndamental Proper­
t ies." I n The l111pe1fect l 111age: Pl1otogmp/1s, Their Past,
Present and F11 t 1 1 re, 34-42. Con ference Proceed i ngs, Win­
demere. 6th- 1 0 t h Apri l . 1 992. London: Centre For Photo­
graph i c Conservation, 1992.
--- . "Cracking i n A l b u me n Photographs: An E S E M
I nvest igation. " Microscopy Hesearc/·1 and Teclrn.iqHe 25,
no. 5-6 ( 1 993): 373-84.
Price, George. "O n the Atomic vVeight o f Albu men a n d the
Compounds Formed by Sensitisin� a C h l orided and Non­
C h lorided Albumen ised Paper u pon a Solution of N i t rate
S i l ver." Jo11mal of British Photography 16 ( 1 869) : 209- 1 0 , 354-
H e i l ly, James M. "The M a n u facture and Use of Albumen
Paper. " Jo11mal of Photographic Scie11ce 26 ( 1 978). 1 56-6 1 .
--- . Th.e Albull' l.en and Salted Paper Booh: The Hist.ory
and Practice of Phot.ogmphic Pri n t i11g 1 840-1 895. Hochester,
NY: Light I m pressions, 1 980.
Further Reading
--- . 'The H i story, Tec h n iq u e and Structure of Albumen
Prints." A I C Preprints ( M ay 1 980) : 93-98.
---. " Hole of t he M a i l lard, or ' Prote i n - S ugar' Heact ion
in H ig h l ight Ye l lowing o f Albume n Photogra p h i c P r i n ts."
A J C Prepri nts ( M ay 1 982): 1 6o-68.
H e i lly, James J\11 . , Douglas G . Severson and Constance
McCabe. " I mage Deterioration in A l b u me n Photograp h i c
Prints.•· Science & Technology in t h.e Service of Conserva t ion.
Was h i ngton , DC: / I C Congress, Septe111ber 1982, 6 1-64.
Vitale, Timothy, and Pa u l Messier. " Physical and M echani­
cal Properties of A l b u 111e n Photogra phs." Jo·u rncil of t.he
American. Institute of Conservation 33 ( 1 994) : 279-99.
Von \.Va ldthausen, C l ara. Non-Destrnct.ive Met.hodsfo1·
the fden. t ijicat.ion of Original Coa t i ngs Used as Fi 11isl1in.g
Techniq ues on 1 9 t '1-Ce11l11ry Salted Pa11er and Alb11111en
Photographs. A111sterdam: E i ndverhandel i ng i . s . 111. l ns t i t u u t
Col lectie Nederland, 2000.
Part V: P h o t o g ra p h i c N e gat ives:
P r o b l e m s a n d Issues
Adelstei n , P. Z. "Wedge Britt leness Test f'or Photogra p h i c
F i l m . " P/1otograp/1.ic Science a n d E11gi11eeri11g 1 ( 1 957):
63-68.
--- . "Stabil ity of Processed Diazo a n d Ves i c u l a r F i l ms . "
Micro-News 8 111/et iu 1 ( 1 972): 9.
Adelste i n , P. Z., J. L. Bigo u rdan, and J . M . Hei l ly. " M oisture
Helationsh ips oF Photogra p h i c F i / 111. " journal of the A meri­
can l n.stit.u.te fo1· Conse1·vat.ion 36, no. 3 ( 1 997): 1 93-206.
Adelste i n , P. Z., and J . M . C a l h o u n . " I n terpretation of
D i 111e nsional Cha nges in Cel l u lose Ester Base Motion­
Picture F i / 111s . " SM PTE )ournal 69 ( 1 960): 1 57-63.
Adelstein, P. Z. . and J . L. M c C rea. " Per111anence o f Pro­
cessed Ester Polyester Base Photogra p h i c F i l ms . " Plwt. o­
grapliic Science and Engineering 9 , no. 5 ( 1 965): 305- 1 3 .
--- . "Stabil ity oF Processed Polyester Base Photographic
F i l ms . " journal of Applied Photographic Engineering 7, no.
6 ( 1 98 1 ) : 1 60-67.
 H E A D l N C S 1 1\/
Adelste i n , P. Z., J . M . R e i l ly, a n d F. G . E 111 mi ngs. "Stabi l i ty
of Photographic F i l 111: Part V I-Long Te r111 Agi ng S t u d ies.''
SM PTE )o111·1ial. vol . 1 1 1 , no. 4 (2002 ) : 1 36-43.
Ade l s te i n , P. Z., J. M. R e i l l y, and D . W. N i s h i 111ura. " Recent
Cha nges in Reco111 mended S torage of Photographic F i l m . "
Actes des Deuxie 1 11es }olln11ies l ntenwt.ionales D 'E t lldes de
l' A RSAG, Paris, M ay 1 6-20, 1 994, 1 09- 1 3 .
B a l l , S tephen, S u s i e C l a rk, Peter \Vinsor. Tl1e Care o f Pi1o­
t.ograph.ic Materials and Related Media: G l l idelines 011 t l·1e
Care, Handling, Stol'Clge, and Display of P/10togl'Clpl1y, Fi/111,
Magnetic and Digit.al Media. N ew York: M u s e u m s and G a l ­
l e ries Commission, 1 998.
Bigelow, Sue. "Cold Storage of Photographs a t t h e C i ty o f
..
Vancouver Arc h i ves . C a n a d i a n Cou n c i l or Archives Preser­
vat i o n Committee, 2004.
B igou rd a n , Jean-Lo u i s , Peter Ade l s t e i n , and J a 111cs R e i l ly.
"Acetic Acid and Paper A l ka l i n e Reserve: Assess111ent or
a Practical Situation in F i l 111 Preserva t i o n . " In 1 1 1 /1 Trien­
nial Meet i ng, Edi n b l l rgli, Scorlc111d, 1-6 Septe111ber, 1996,
preprints edited byJanet 13ridgland. London: J a 111es & J a 111es
( Sc i e nce P u b l ishers) Ltd . , 1986, 573-79.
--- . " U se of i\l l icroenvi ron111e n ts For the Preservation of
C e l l u lose Triacetate Photogra p h i c F i l m " jo ll rn a/ of / 11rng­
. 1 99+
i11g Science and Tec l1 1 1ology 42, no. 2 ( i\ l a rch-April 1 998):
1 55-62.
Booth, Larry, and J a n e Booth. " Du p l ication of C e l l u lose
N i t rate Negatives. " Pic l 1 1 rescope, vo l . 30, no. 1 ( Spring 1 982):
1 2- 1 8 .
C a l h o u n , J . i\11 . " A i r Condition i ng i n Storage a n d H a n d l i ng
M otion Pict u re F i l m . " /-feating and \!e11tilati11g 46 ( 1 949):
66-70.
Cal hou n , J. i\1 1 . , P. Z. Adelste i n , and J. T. Parker. " Physical
Properties or Estar Polvester Base Aerial Fil 111s for Topo­
graphic f\11appi ng. " Pho1,ogrc11u111etric Engi11eeriug 1 27 ( 1 96 1 ) :
4 6 1 -70.
C a l h o u n , J . .\ � . , and D . A. Leister. " E ffect of Gelat i n Layers
on the D i 111ensional Sta b i l i ty of Photogra phic F i l m . " Photo-
graphic Science C111CI EHgi neering 3 , no. 1 ( 1 9 5 9) , 8 - 1 7.
C 0 :'\1 S E H V A T I O N
Carro l l , J . F., and John i\ I . Calhoun. " E ffect or N i t rogen
Oxide Gases on Processed Acetate F i l m . " SM PTE .fo1mwl
64 ( Septe111bcr 1 955): 501-7.
C lark, Susie, ed. Care of P/10togl'Clpl1 ic, Moving / 111age &
Soll11d Collections, 2ot h-2.+ t l1 .J11ly 1 998, Yo.-lz, England (co11-
ference papers ) . Le igh: The I n stitute or Paper Consen«1 t i o n ,
1 999·
D ro u i n , F. Lo Pelliclllarisat io11 Des Clicl1es au Celati110-
l3 m11111re. Paris: i\l l e ndel, 1 898.
Edge, J\ I . " Factors I n fl u e n c i ng t h e Breakdown of' Photo­
gra p h i c F i l m : l 111pl ications f'or Archival Storage . . . " I n
Associotion pour la recherche scie n t i.{lcf ' W s 1 1 r les arts
grapliicl '1es. Enuiro11111eut et co11sen1at io11 de l 'ecrit, de
l 'illwge et d" su1 1 : Actes des De11xi&rnes .Jo11 n16es / 11ternnl io­
nales cl'Et ucles de f 'A R SAC, M ay 1 6-20, 1 99+
Fischer, i\ l o n i q u c . A S/101-1 G 1 1 ide to Fi/111-based P/1010-
graphic t\l late1·irils lde n t i}icatio 1 1 . News ( N ortheast Docu­
ment Conservation Center) 1 2, no. 1 (\�linter 2003 ) : 4-5.
Fischer, M o n i q u e C. and James 1\l l . Reilly. " U se or Passive
i\ l o n itors in F i l m Collections. " Topics i11 Photographic Pres­
ervatio11 6 ( 1 994): 1 1 -40. \�la s h i nglon, DC: American I nsti­
t u te for Conservat i o n , Photographic i\ l aterials Group,
Kopper!, D . F., a nd C. C. Bard . " Freezefrhaw Cyc l i n g of'
Motion- Pict u re F i l ms . " S M PTE }ollrnal 94, no. 8 ( 1 985):
526-27.
McCabe. Constance. "G lass Plate Negatives: The I mpor­
tance or Relative H u midity in Storage. " I n Preprin ts/
Proceedings from the ARSAG Con rcrence: Sauvegardc
ct Conservation de Photographies, Dessi ns, l m pri mcs ct
i\ l an u scri t s . " Actes des }ollmees / 11temat ionales d 'Et ll{/es de
L 'A R SAC, Sept. 30-0ct. 3, 1 99 1 .
--- . " P reservat i o n o f 1 9th-Ce n t u ry Negatives i n t h e
N a t ional Arc h ives." .fo11 mal of t l1e A 111e.-icc111 / 11sl it lite for
Conservation 30 no. 1 ( 1 99 1 ) : 4 1 -73.
--- . " Preservation of the Stan tor. Negatives. " In Robert
1-1 . We bb, G 1'C1 1 1 d Callyon, A Cen l l l r)' of Clw11ge: Hepl1otog­
rapliy of t l1e 1 8 89-1 8 90 S t r llllo11 Expedition, 34-35. Tucson,
AZ: U n iversity or Arizona Press, 1996.

M cCormi ck-Goodhart, M ark 1-1 . '' C lass Corrosion and its
Relation to I mage Dcterior-ation in Col lodion \Net-Plate
Negatives. " I n The l mpe1fec t I mage: Pholograp/1s, Their
Past, Prese11I and F111.·11re, 256-65. Conference Proceed i ngs,
\,Vinde mere, 6th-1 0t h Apri l , 1 992. London: Centre !'or Pho­
tographic Conservation, 1 992.
M essier, Pau l . "Preserving Yo u r Col lection of F i l m - Based
Photogra p h i c N egatives. " Rocky M o u n t a i n Conservation
Cen ter, 1 993.
N ishi mura, Douglas W. " F i l m S u pports: Negatives, Tra ns­
parencies, M ic roforms, and M otion P i c t u re F i l m ." I n S1or­
age of Nat 1ffal 1 -/istory Collections, eds., Camly11 L. Hose,
Cal. liarine A. /-law/is, 1-/ugli I-/. Cenoways and A mparo H.
de Torres. \Nashi ngton, DC: Society f'or the Preservation o f
NatLmil H i story Collections, 1 995, 365-93.
Orraca, Jose. "The Preservation and Restoration or C lass
P late Negatives. " Image 1 6 , no. 2 (J u n e 1973): 8-9.
Puglia, Steven T. "Dupl ication Options ror Deteriora t i n g
Photo Col lections." I n Phologmpli Presen1at.ion and 1 /ie
Hesearcli L ibrary, 29-35 . J\l l ou n ta i n View, CA: Research
L i b raries C roup, 1 99 1 .
--- . " N ega t i ve D u p li c a tion : Eva l u a t i ng the Repro­
duction a n d Preservation Needs or Col lect i o n s . " Topics
i11 Pliol.ogmphic Preservalion 3 ( 1 989). Was h i ngton, D C :
A merican I ns t i t u te for Conservat ion, P h otogrnphic M ate­
rials C ro u p , 1 989.
R e i lly, J ames M. I Pl Storage C11ide for Acetale Film:
lnst r11ction for Using the Wheel, Graphs, and Table: Basic
..
SI ralegy for Fil111 Preserval ion Rochester, NY: I mage Per­
m a nence I nstitu te, 1 993.
--- . "Accelerated Agi n g Tests.'' In Hesearch Tec'1 11iq11es
in Photographic Co11servalio11: Prepri n t , 67-78. Ed. M ogens
S . Koc h . Copen hagen: Royal D a n ish Academy of F i n e Arts,
School of Conservat ion, 1 995.
R e i l ly, J ames M . , P. Z. Adelstei n , D . \�/. N is h i m ura, and
K . M. C u p r i ks . " Protection of iV l icroform I m ages Aga i nst
Oxidat ion . " Journal of I maging Science and Technology 38,
no. 4 ( J uly-August 1994): 326-32.
Further Reading
Valverde, M aria Fernanda. Photographic Negal ives: Nal. 11.re
and Evo/.ill ion of Processes. New York: I mage Perma nence
I nst it ute, 2003.
Vian, Paolo, Sylvia Berse l l i , Anne Carti er- Bresso n , Kar i n
E i n a u d i , M ichael I-lager, a nd G ra n t B . Romer. " La f'ragi­
l ita 111 inacciata: f\spetti e problemi della conscrvazione dei
negativi fotogra l -ici .'' Union.e l ntenza:ionale degli lslilttli di
A rcheologia, Ro111c, 1 99 1 .
You ng, Christine . " N itrite F i l m s i n t h e P u b l i c I nstituti on . "
/-lislory News 44, no. 4 ( J u ly-August 1 989). Heprin ted as
Technical Leajlel 169. N ashville: American Association for
State and Local H i sto ry, 1989.
Part VI: The P rese rvat i o n o f C o l o r P h ot o graphy
Bugner, Douglas, et al. "Su rvey of Environ mental Condi­
tions Relat ive to the Storage and Display of Photographs i n
Consu mer H omes, Phase 1 . '' ]011r11al of l 111agirig Science and
Technology 50, no. 4 (2006 ) : 309- 1 9 .
Coote, J a c k 1-1 . /ll11SI rated 1-1 isto1·y of Colour Photography.
S u rbito n , U K: Fou n t a i n Press, 1 993.
Cost, F. Pochet C11icle lo Digilal P1·i11ling. Albany, NY: Del­
m a r P u b l i s hers, 1 997.
Dela m o i r, Jean nette, and Grant Romer. "The F i rst Color
Photos . " Scient ific A11wrican 260, no. 12 ( 1 989): 88-96.
Gschwind, Rudolf, Franziska Frey, and L u kas Rosenthaler.
''Electronic I magi ng: a tool for the 1·econstruction of faded
color photographs a n d color movies. " 1 n Proceedings of
SPI E-l111age a!ld Video Processing I l l . Eds., L. Steve nson
Robert and Sarah f\. Rajala. San Jose, Cf\, U SA : Society of
Photo-Optical I nstru 111entation Engi neers, 1 995, Vo l . 242 1 :
57-63.
H ai s t . Grant. Modem P/101ographic Processes. Vols. 1-2.
New York: John \Viley and Sons, 1 979.
H anson, \V. T. " Forty Years of Color Photography." Pho­
togrnphic Science and Engineering 2 1 , no. 6. ( N ovember/
December 1 977) , 293-96.
 H E A D I N G S I N
H e idke, Ronald L. , Larry H . Feld m a n , and C harleton C .
Bard. " Evo l u t ion of' Kodak Photogra p h i c Color Negat ive
Pri n t Papers." Journal of I maging Technology 1 1 , no. 3 ( J u ne
1 985) : 93-97.
J ti rgen s , M. C. ' ' l de n t i fizier u ng van D igitaldrucke n . " Papier­
resta11rier11ug 2, no. 4 (200 1 ) : 2-7.
Labarca, Joseph E . , and Scott F. O ' De l l . "The i m portance
of the bala nce of l ight and thermal i mage sta b i l i ty effects
i n the design of' p hotographic color paper. " I n IS&T\ 12th.
l n.lernal.ional Symposiu m on Photofinishing Tech nology, Feb­
niary 20 & 2 1 , 2002, Fort La11derdale, Florida. Eds. , S111nrt
Gordon., Daniel English and Steven M. /-/owe. Spri ngfield,
VA: IS & T: The Society For I magi ng Science and Tec hnol­
ogy, 2002, 38-47.
Lavedrine, Bertran d , Jean-Pa u l Gandolfo , and Jean-M ichel
S us b i e l les. " Ana lyse des Colora n t s Dans les Autoc h romes. "
Sauvegarde el Conservnlion des Plwtograp/1ies, Dessi11s,
Imprimes et Ma1111scrits, A cles des jo11rnees 1 nlernnl io11ales
d 'Et 11des de l 'A HSAG ( September/October 2004 ) , 9 1 - 1 03.
McCormick-Goodhart, M. H., and M. F. Meckl e n b u rg.
"Cold Storage E nvironments for P hotographic M a teria l s . "
I n I S&T's 461.h Annual Conference, May 9-1-1, 1 993, The
Bostoll Marriott Cambridge 1-lotel, Cambridge, Massac/1 11-
sel.ls. Bost.on S p r i ngfield, VA: IS & T: The Soc iety f'or I m ag­
..
i ng Science and Tec h n o logy, 1 993, 277-80.
Reil ly, J ames i\1 1 . Storage G11ide for Color P/101ograpliic
Materials: Caring for slides, negal.ives, and movie fil111s.
A l bany, NY: U n iversity of the State of New York, 1 998.
Sc hwalberg, Bob. "Color Preservation U pdate." Popular
Phot. ograpliy 89, no. 1 (January 1982): 8 1 -85, 1 3 1 .
Siege l , Rob i n . " P hotographic Materials Group C o m m ittee:
Meeting and M ission." In The lrn.peifecl I mage: Photo­
graphs, Their Past, Present and F11111re, 301-3 . Con f'erence
Proceedings, W i ndemere, 6th-10th April, 1 992. London:
Centre for Photogra p h i c Conserva t i o n , 1 992.
U pton, Joh n . Color as Fon11: A 1- l ist.ory of Color Photography.
Rochester, NY: I nternational M u seu m of' Photography at
George East man H ouse, 1982.
C O N S E H V f\ T I O N
Vern a l l i s , Kayley. "The Loss o f ' M ea n i ng i n Faded Color
Photographs." Jo11mal of I lie A111erican Inst itut.e .for Conser­
valio11 38, no. 3 (A u t u m n-Wi n t er, 1999): 459-76.
v\/a l l , Alfred 1-1 . " P ractical I nstructions Oil Colori ng Photo­
graphs." Britis/1 jo11mnl of P/101ograpl1y 7-8 ( 1 8 59-6 1 ) , 1 1 2.
Wal l , E. J . 1- /isto•)' of Three-Color Pl1olograpl1y. London and
New York: Focal P., 1 970.
\Ni l he l m , H e n ry and Carol Brower. Tlie Per111c111e11ce a11cl
Care o.f Color P/10togra11/1s: Trad it io11al ancl Digital Color
Prints, Color Negat.i11es, Slides, a11cl Motion Pict 11res. Grin­
n e l l , IA: Preservation P u b l i s h i ng Company, 1 993.
Part VII: Deve l o p i n g C riteria i n the
C o nse rvat i o n o f P h o t o g ra p h s :
C o l le cti o n M an a g e m e nt and Treat m e n t
A l b right. G a ry. "\<\l h i c h Envelope) Selec t i n g S torage E nc l o­
s u res For P h otogra p h s." Pict u resco11e 31 ( 1 985): 1 1 1-13.
Brown , Barbara N . " I nterim Report on the H H H HC Photo­
graph Album S u rvey: 3 . Photogra p h s i n A l b u ms: Observa­
t ions, Treatment Comments, and Some S u rvey Hesu l t s . " I n
Conservation o.f Scrn11boohs ancl Albums: Postpri11ts o.f tl1e
Booh a1nl Paper Gro11p/Pl1otograpliic Materials Gro1111 Joi111
Session. at t he 27t/1 A1w11al Meeting o.f t.he A merican ln.stil11te
for Conser11at.io11 o.f 1- /istoric r111d A rtistic Worl1S, j1111e 1 1 ,
1 999, St. Louis, Missouri, eclitecl hy Slrn1t11011. Zr1clwry . \Nash­
i ngto n , DC: Book and Paper Group [ a n d ] P hotographic
Materials G roup, American I ns t i t u te for Conservation oF
H istoric and Art i stic Works, 2000, 69-79.
--- . "The Treatment of 1-1 . P. Hobin son's ' B ringi ng
Home the M ay,' a 1 9th-Ce n t u ry E nglish A l b u m e n Print."
Topics in Photographic Preservat.ion 3 ( 1 989) : 37-45. Was h ­
i ngton, DC: American I ns t i t ute For Conservat ion, P hoto­
gra p h i c Materials G roup, 1 989.
Cartier-Bresson, Anne. "Synt hese des t ravaux rec u e i l l i s clans
la l i terature sur la resta u ration des photographies e n noir
et blanc." Les Doc u ments G ra p h i q ues ct Photographiques:
Analyse ct Conserva t i o n-Trava ux du Centre de Recherches
sur la Conserva t ion des Doc u ments Graph i q u es ( 1 98 1 ) .

--- . '' Les divers n iveaux d i i nterve n t ion en restauration
des photograp h ies." Actes d u Col loquc i n ternational orga­
n i se par Anne Cartier-Bresso n . Conserval:ion et rest:aurat-ion
cl·11 patrimoine ph.otograpli ique, a l a D i rection des Affa i rcs
C u l t u rc l les de la Ville de Paris, Paris-Aucliovi suel. Paris,
Novc111ber 1 984.
--- . Les Papiers Sales, Alt. eratio11 et Restc111ratio11 des Pre­
mieres Photogrnphies s ur Papier. D i rection des a ffa i res cu l ­
t ur c l l es de l a v i l l e de Paris, Paris-Aucl iovisuel . Paris, 1 984.
--- . '' La protection des pho tograp h ies clans l e cadre
d'unc expos ition ou d ' u n archivage de longu c d u n:�e. "
Paysages Photographies. L a Mission. Pliotograph.- ique d e la
DATA R . Travc111x en Cou rs. H azan ( 1 985): 492-99.
--- . " Resta u rcr les Ph otograph ies: Les Enjcux
Thcoriques ct I 'evo l u tion cl 'u n e p ratiq u e." Sau.vegarde et
Conse rvat. io11 des Photographies, Dessins l m pri·1n.es et J\llam1-
scrits. Paris ( 1 99 1 ) .
--- . " Resta u rc r l a Reproduction, Reprocl u i re !'orig i n a l . "
Les Ca/1iers du JV111See National d 'ai·t J\lloderne 35 ( 1 99 1 ) :
59-68.
--- . ' ' lksearch i n Photographic Conservation." Getty
Conservat.ion lnstitu.te Newslett.er 1 7 , no. 1 (2002).
Clarke, Bryan. "So111e Observations on t he Develop111e n t
o l ' A l b u 111s Conta i n i n g P hotogra p hs and Aspects of their
Deterioration . " In The l rnpe1fec t Image: Photographs, Their
Past. , Presen t. and FH t u re, 3 0 1-3. Con fe rence Proceedi ngs,
\Ni n cle111ere, 6 t h- 1 0t h A p ri l , 1 992. London: Centre for Pho­
tographic Conservat ion, 1 992.
Davis, Nancy. "Tin types : Pre l i 111 i n a ry Research and Test­
i ng." Art CoJtServation Trai.n.ing Programs Conference Publi­
cation ( 1 984): 1 3-28.
Eaton, George T. " Preservation, Deterioration , Restoration
of P hotogra p h ic I mages." The Library Quarterly 40, no. 1
(January 1 970): 85-98.
G hent, Megan, a n d Jacqueline Ress. "A Conservation Treat-
111cnt to Remove Residual I ron fro111 Plat i n u m Prints." 17w
joumal. of the Institute of Paper Conservation. 1 8 ( 1 994):
90-95.
Further Reading
G u i c h e n , Gael de. Cliuu1t.e i.n M useums: Measu.renient.
l C C R O i\11 . Ro111e, 1 988.
H arriman, Lewis G . , eel . The Deli u.m idi.fi cation 1-/andbooi<.
211cl eel. A111esbu ry, MA: M u nters Cargocai re, 1 990.
Heisch, Charles. " M ou n t i ng P hotograph i c Prints." journal
of the Photographic Society 2, no. 30 ( 1 8 55) : 1 73-74.
H e ndri ks, Klaus 13., et a l . Funda1nentals of Photograph Con­
servation.: A St. 11dy G u ide. Toronto, CA: Lugus P u blications,
1 991 .
H i l l , G regory. 'The Conservation of a Photograp h Album al
t h e National Arch ives of Canada." journal of the American
Instit u te for Conservation of 1-/istori.c and Artist-ic Worh.s 30,
no. 1 ( 1 99 1 ) : 75-88.
H o rton, R i c hard W. " H i storical Photo A l bu m s a n d The i r
Structure s . " Conservation. of Scrapbooh.s and Albums. Post­
prin ts of t he Book and Paper G ro u p/Photograph i c M a t e ri ­
a l s G ro u p joint sess i o n at t he 27th AJC A n n u a l M e et i ng,
J u ne 1 1 , 1 999, S t . Lo u i s , M isso u r i . \Nashi ngton : A I C , 1 999.
Tiie lmpe1fect. Im age: Photographs Thei.r Past, Presen t and
F u t u re. Conference Proceedings, Windemere, 6th-10th April,
1 992, 34-42. London.: Cen.t:re for Photograph-ic Con.servat.ion,
1 992.
Joh nsen , Jesper S . "S u r veyi n g Large Col l ections of Photo­
graphs for Archival S u rviva l . " Prevent:ati.ve Conservation:
Practice, Theory and Hesearch ( 1 994) : 202-6.
--- . " S u rvey i n g for Archival S u rvival of Photographic
Col l ection s . " Goteburg StHd-ies in Conservat: ion 5 (2003 ) :
5i-71 .
Johnson, J . 1-1. '' M ou n t i ng Prints." Photographic joumal 8 ,
no. 1 24 ( 1 862): 1 03-4.
K n i pe , Pen l ey. "The Eval uation of Fou r Aqueous a n d Non­
Aqueous S u rface-C lean i ng Tec h n iq u es o n S ilver Gelat i n
P hotographs." Topics i n Pliotograpliic Preservation 7 ( 1 997) :
1 9-27. V,lash i ngton, DC: American I nstitute for Conserva­
tion, Photogra phic M aterials Group, 1 997.
 H E A D I N G S
Lavedrine, Bertra n d . A G11ide t.o the Prevelltive Co11serva-
i-ion. of Photograph Coflect.ior1s. Los Angeles: The Getty
Conservation I n s t i t utc, 2003.
M a rt i n , James. "On the Adhes ive M ateri a l s E m p loyed for
M o u n t i n g P hotogra phs. " British Jo11rnal of Phot.ography 9
( 1 862): 305, 306, a n d 350-5 1 .
M ar t i n , John H ., ed. The Corn.in.g Flood: M11sernn Under­
wat.er. Corning, NY: The Corning M u seum of C l ass, 1 977.
McCabe, Constance. " P hotographic Preservat ion: Address­
ing Complex I n stitutional Needs . " Rest.aural.or 1 2, no. 4
( 1 99 1 ): 1 8 5-200.
McCormick-Goodhart , 1\l l a rk H. ''The M u l ti layer Structure
of Tintypes. " I C O M 9th Trie n n ia l Meeti ng. Dresden, Ger­
man Democratic Republic, 26-3 1 August 1990, 262-67.
--- . " M oistu re Content l s o l i nes and the C lass Transi­
t ion of Photographic Gelatin: Their Significance to Cold
Storage a n d Accelerated Aging. " Research Tecli. 11iq11es in
Photographic Conservatio11: Proceedings of the Conference in
Copenl1C1gen , 14-19 May 1995. Royal Danish Academy of Fine
Arts, School of Conservation, Copen hagen ( 1 996), 65-70.
--- . '' Methods for Creating Cold Storage E nv i ron­
ments. " In Care of Photographic Movillg / 111age and So1111cl
Col/.ection.s: Conferellce Papers, l'orh, Eng/an.cl, July 20-24 ,
1 998, ed ited by S u s i e Clark, 1 9-24. Le igh, Worceste rs hire :
I ns t i t u te of Paper Conservat ion, 1 999.
Moor, I a n L., and Angela H. M oor. "The effect of aqueous
treatn1ents on photogra phs. " In Sauvegarcle et conservation,
cles p hotographies, dessins, i·1n.prinufs el. 1nanuscripl.s: J\ctes
cles jou rnees in.ternationales cl'et. 11Cles cle l 'A HSAG, Paris,
Sept.ember 30 to October -f, 199 1 . Pa ris: Association pour la
recherche scie n t i fi q u e s u r les arts gra p h i q ues, 1 99 1 , 62-66.
N i s h i m u ra , Dougl as \•\/. " Report on the C he m ical Treat­
ment of Photographic M ateri a l s . Pri nt M ateria l s Workshop:
A C h e m i st's Perspective. " Topics in P/101.ographic Preserva­
tion 9 (200 1 ) : 1-43. \,\fashi ngton, DC: American I ns t i t u te fo r
Conservation, Photographic M ateri a l s G roup, 200 1 .
Norris, Debra Hess. "Conservation Treatment o f Dete­
riorated Photogra phic Print Materials. " I n Tl1e l mpe1fect
/ .,,rnge: Photographs, Their Past., Present a11d F11t11re. Confer-
710
I N C O N S E H l' A T I O N
ence Proceedi n gs , \,Y i n clemerc, 61h- 1 0t h Apri l , 1 992. Lon-
don: Centre for Photographic Conservation, 1992.
---. "Current Research Needs i n the Conservation Treat­
ment of Deteriorated Photographic Print Material s . " Hesearch
Teclm.iq11es in Photographic Co11servation, Proceeclillgs of the
Confere11.ce in Copenhagen, May 1 4-19, 1 995, 1 0 1-5.
--- . Disaster Hecovery: Salvaging P/10tograp/1 Collec­
tions. P h i ladelphia: Conservation Center for Art and H is­
toric Artifacts, 1 998.
Primanis, O l ivia. " I n te r i m Report on the H H H RC Photo­
graph A l b u m S u rvey: 1 . N i neteent h-Ce n t u ry Photograph
Alb u m s : S t ru c t u re , Con d i t i o n , and Treatme n t s . " I n Conser­
vation. of Scmpboohs c111cl Alb11 111s: Poslpri11ts of t l1e Booh ancl
Paper Gro11p/Plwtograp/1ic Materials Gro11p Joi11t Session at.
the 2 7 1.h Ann 11al Meet. ing of I.he A111ericc111 lmtit11te for Con­
servation of 1- /istoric and Artistic Worhs, J11 11e 1 1 , 1 999, St.
Lo11is, Misso11ri, edited by Sl1a1111011 Zachary. \•\las h i ngton ,
D C : Book a n d Paper G ro u p l a n d ! Photographic M aterials
G ro u p , f\merican I nstitute for Conservation of H i storic and
Artistic \,Yorks, 2000, 47-6+
H e i l ly, James, Douglas N i s h i m u ra, L u i s Pavao, and Peter
Adelstei n . " Photograph E nclosures: Research and Specifi­
cations. " Hestaurat.or 10 ( 1 989): 1 02- 1 1 .
Rempel, S iegfried. "Enclos u res for H o u s i n g Photographic
Negatives. " Conservatio11. Notes 3 (January 1 983), 1-4.
R i tze ntha ler, Mary Lyn n , and Diane L. Vogt-O'Con nor,
with H e lena Zinkham, Brett Carne l l , Kit A . Peterson. Pho­
togmphs: Archival Care an.cl Managemen t . C h icago: Soc iety
of America n Arc h ivists, 2006.
Schenck, K i m berly, and Constance McCabe. " Pre l i m i nary
Tes t i n g ol' Adhesives Used in Photograph Conservation. "
Topics in Pl10tographic Preser11atio11. 3 ( 1 989): 52-6 1 . Wash­
i ngton, DC: American I n stit ute For Conservat ion, Photo­
gra p h i c M aterials C roup, 1 989.
Shadbolt, George. "1\ l o u n t i ng Photographs. " /-/11111p'1rey's
Jo11ma/ 1 5, no. 1 0 ( 1 863): 1 52-53.
S i m pson, C. V\lharton. "On M ou n t i ng Photographs." Phot.o­
grapliic News 5, no. 1 68 ( 1 86 1 ) : 55 1 .

S i n c l a i r, Col i n . " Experirnents on t h e Va rious Adhesive
S u bstances Used in M o u n t i ng Photographs, as Affect i ng
t h e Permanence of Prints. " Phot.ograph.ic journal 4 ( 1 857):
1 5- 1 6.
--- . ""An Account of t h e C o n t i n uation oF Forrncr Experi­
rncnts o n the Various Adhesive S u bsta nces Used in Mou nt­
ing Photographs as Affecting the Pe rmanence of the P r i nt.""
jo11mnl of the Pliotograpliic Society 68, New Series ( J u ne 2 1 ,
1 858): 23 1 .
Standards i n I.he Museu·m. Care of Photographic Co/.lect. ions.
London: M u se u rn s & G a l leries Com mission, 1 996.
S u t t o n , Tho1rn1s. ;;On M o u n t i ng Pos it ives." Plioiograph.ic
Notes 2 , no. 33 ( 1 8 57) : 304.
Further Reading
,
\�la lsh, Betty. ; Photographic E n closu res." Association of
Cc111adian Arch.ivisls B ullet.i.n 1 1 , no. 2 ( N ovc rnber 1 986); a n d
1 1 , no. 3 ( .Ja nuary 1 987) .
\.Vatkins, Stephan ie . "Origins and Development of Dry
M o u n t i ng. " A/C Booh and Paper G.-011p A1m11al 12 ( 1 993):
66- 1 3 -
Part VIII: E x h i b iti o n Pract i c e
Photographic Society of London. " Report of t h e C o rn m is­
sion Appoi nted to Consider the S u bject of Lighting P i c t u re
G a l l e ries by Gas." journal of the Photographic Society 88
(August 1 6, 1 8 59 ) : 1 6- 1 7 .
 About the E ditors

DE BHA H E SS N onn1s is the vice provost for graduate and professional educa­
tion, chair of the Art Conservation Department, and professor of photograph
conservation at the U n iversi ty of Delaware. She gradu ated with an i nterd is­
c i p l inary BA degree in chemistry, art h istory, and studio art ( 1 977) and a M S
i n conservation ( 1 980) from the U n iversity o f Delaware.
Si nce 1 985 Norris has authored more than 25 articles and book chapters
on the care and treatment of photographic materials, emerge ncy response,
ethics, and conservation education ; she has taught more than 95 workshops
and sem i n ars for conservators and a l l ied professionals. Norris has lectured
and consu lted on the preservation of photographic collections worldwide,
i ncluding in Russia, I nd ia, Lebanon, Denmark, France, Finland, the Nether­
lands, I s rael , M exico, Australia,. and New Zealand.
Norris was the chair of Heritage Preservation (2003-2008) and presi­
dent of the American I n stitute for the Conservation of !-I istoric and Artistic
Works ( 1 993-97). From 1 990 to 1 993 she chaired the A ! C Ethics and Stan­
dards Committee that developed a revised Code of Et hi.cs a nd Guicleli.nes for
Practi.ce. I n 2002 she was i n d u cted into t he U n iversity of Delaware's Al u m n i
Wa l l o f Fame. S h e has served a s president of t h e Conservat ion Center
for Art and H i storic Artifacts Board and as a member of the Preservation
Advisory Council to the National Archives and the Delaware H u man ities
Council. S he is c urrently a U . S . commissioner to U N ESCO and project
d i rector of The Andrew W. Mellon Collaborative Workshops in Photograph
Conservation.
In January 2004, Norris was appointed as the H enry Francis du Pont
Chair i n Fine Arts and i n J une 2004 she received the American l nstitute for
Conservation Sheldon an d Caroli n e Keck Award for excel lence in education
and trai n i n g of conservation professionals. In April 2008, Norris received the

712
 About the Editors

American I nstitute for Conservation U n i versity Products Award for Distin­

guished Achievement i n Conservation. I n November 2009, Norris co-chai red
a session at the S a lzb urg G lobal Seminar (organized in partnership with the
I nstitute of M useum and Library Services) addressing the preservation of
the world's c u l tural heritage.

J E N NIFER ]AE GUTI ER REZ earned her MS from the Win terthur/University of
Delaware Program in Art Conservation in 2004, spec i a l izing i n photograph
conservation. After completing her master's level studies, she began teach i n g
i n t h e Art Conservation Department at t h e U n i versi ty of Delaware. G u tierrez
teaches u ndergraduate courses i n p hotograph conservation and the p h iloso­
phy and ethics of conservation . She also teaches the first-year graduate c u r­
ric u l u m i n photograph conservation and conducts conservation treatment
seminars for second-year Fel lows. She i s an active member of the U n iver­
sity of Delaware's E mergency Respon se Working Group and is i n volved wit h
t h e Center for M aterial Culture Studies. G u tierrez is especia l ly comm i t­
ted to public outreach ; during the 2004-2005 academi c year, she i n itiated a
program about American art appreciation and preservation for elementary
students in 'v\/il m ington , Delaware. In 2007-2008 she chaired the American
I nstitute for Conservation's Public Outreach Tas k Force.

713
Advisory Committee

MARC VI/. H AR N LY is the senior conservator of photographs at the J. Pau l

Getty M useum i n Los Angeles, where he has been t h e head o f t h e Depart­
m e n t of Paper Conservation si nce 1 996. Marc received his MA and Certifi­
cate of Advanced Study from the Art Conservation Program at B u ffalo State
College, S tate U n iversi ty of New York.

N O R A K E N N E DY
is the Sherman Fai rc h i l d Conservator of Photographs at the
Metropolitan Mu seum of Art i n New York. She graduated from the Wi nter­
t h u r/University of Delaware Art Conservation Program with her M S in Pho­
tograph Conservation i n 1 986. She joi ned The M etropolitan M useum of Art
conservation staff in 1 990. She also serves on the adj u nct fac u l ty of the New
York U n iversity I nstitute of F i n e Arts Co nservation Center.

B E RTRAND LAVED R I N E is c u rre ntly d i rector of the Centre de recherche sur

la conservation des collections i n Paris and scientific coord inator for con­
servation stud ies at the I nstitut National d u Patri moine. Prior to that, he
was head of the Sorbonne conservation program . He has published va rious
papers and books and has received, among other awards, the E u ropean prize
for i n novat ion, the Kraszna-Krauz Photography Book Awards, and the title of
Chevalier des a rts et des lettres.

PAUL M E S I E H is an i n dependent conservator of photographs working in Bos­

ton. The susta i n i ng focus of his practice is the conservation treatment of
fine art photographic prints; authent ication research and conservation sur­
veys for c l ients worldwide are major additional pursu its. He holds an AB
c u m laude in art hi story from Vassar Col lege and an MA and Certificate of
 Advisory Committee

Advanced Study from the Art Conservation Program at B u ffalo Sta te Col­
lege, S tate U n iversity of New Yo rk.

KLAUS PoLLMEIER, p hotographic e ngineer, was head of the Photograph i c

Services Department of M useum Fol kwang, Essen, and taught photography
at Anhalt U n iversity of Appl ied Sciences, Dessau, Germany. He has been
involved in photograph conservation si nce the m i d - 1 98os and was one of
the first Fel lows in the M el lon Advanced Residency Program i n Photograph
Conservation at the George Eastman House, Rochester. Si nce 2005 he has
been coordinator of Conservation of New Media and D igital I n formation, a
new graduate program for the training of p reservation managers at the Stutt­
gart Academy of Art and Design, Germany.

]AMES M . REI LLY, di rector of the I mage Permanence I nstitute and professor
at the Rochester I nstitute of Technology Col lege of I magi ng Arts and Sci­
ences, graduated with a BA from Franklin & M arshall College i n Lancaster,
Pen nsylvania, in 1 968 and an MA from the State U niversity of New York
at Bu ffalo in 1 972. He continued h i s education in science at the Roc hester
I nstitute of Technology. He is well known for his research on the deteriora­
tion of n i neteen th-century photographic prints; the effect iveness of storage
enclosures for imaging materia ls; the major causes of i mage deterioration;
and optimizing conditions in storage vaults. Reilly is a u thor of nu merous
pub lications, i nc l uding Ca re and lden.tification of 1 9th-Century Photographic
Prints, IP/ Storage Guide for Acetat:e Film, and Storage Guide for Color Pho­
tographic Materials. He is a consu ltant to many m useu ms and government
agencies and is sought after worldwide as a teacher and sem inar speaker.

GRA 'T B . ROMER holds a B FA from Pratt I n stitute a n d an M FA from Roch­

ester I nstitute of Technology. In 1 976 he joined the staff of the George East­
man H ouse, becoming i ts conservator of p hotography i n 1 989 and d i rector
of its Adva nced Residency Program i n Photograph Conservation from 1 999
to 20 1 0 . Romer has had a d istinguished career as a teacher i n this field a n d
h a s served ma ny of t h e world's most i mportant institutions as a consultant,
i nc l u d i ng the State Hermitage M useum i n St. Petersburg, Russia; the M et­
ropo litan M useu m of Art in New York; Harvard and Yal e U n iversities, the
J. Pau l Get ty M useum ; the Vatican M useums; the ational Pa lace M useum ,
Ta iwan; the I srael M u se u m ; t h e British M useum ; a n d nu merous national
archives and l i braries. Cu rrent ly, he is scholar in residence at George East­
man House.

715

Not.e: page n u m bers i n i ta l ics refer to
figures; page n u m bers followed
by " t" refer to tables, while those
fol lowed by "n" refer to notes, with
note number.
A Advanced Residency Program in
Aardenburg I maging & Archives, 3 5 1
accelerated aging studies: accuracy
of, 409-4 10; A N S I standards on,
1 90- 1 9 1 , 191, 491, 561 ; on bleached
and redeveloped gelatin prints, 561-
562; by I P l , 408, 409; method for,
408-409; on photographic papers,
4 13 ; on resi n coated ( RC ) papers,
1 80-1 85. See also stabi lity testing for
color i m ages
accelerated keeping tests, for color
i mages: accuracy of, 49 1 , 494-495,
637; Arrhe n i u s equations and,
491-492; autochrome i mages, 506-
508, 5 1 1 , 5 1 9-520; h istory of, 408;
i nc u bation process, 494; i nstant
prints and, 487; l i m i tations of, 492;
procedu res for, 472-475, 492-493
acetate See cellu lose acetate f i l m ,
cel l ulose acetate fil m deterioration
acid detectors, 4 1 0
Ackerman, Rudolph, 2 1 3
Adams, Ansel, 554 n 1 9
Adelste i n , Peter Z . , 1 55-170, 383-395,
4o8, 409, 435-454, 49°
adhesives: assessment of, 582; effects
on a l b u men prints, 299; effects
Index
on silver prints, 4, 6, 1 2, 1 14,
2 3 1 , 232-233; as oxi d izing agenl,
232-233; and stabi l i ty of prints, 46;
i n storage envelopes, 13, 14; s u l fu r
i n , 544-545; wheat starch-methyl
cel l ulose paste, 303, 305n6; wheat
starch paste, 303, 305n7
Photograph Conservation, 34
aesthetics of i mage: a nd deterioration,
subjective nature of, 62; growing
i nterest in, 61-62
Agfa. See Agfa-Gevaert
Agfa-Gevaert, 1 0 1 -102, 1 48, 1 5 1 , 1 54,
i 59, 2o2, 393
AgGuard, 206, 2 1 0
Al PAD . See Association o f
I n ternational Photography Art
Dealers
Albert, Prince, 2, 1 1 2, 2 1 4
Albert Kahn M useum , 5 1 3
Albright, Gary E . , 297-304
albumen: i n dry collodion process, 343;
for glass plate negatives, 340-34 1 ;
formula for, 305n8
a l b u men paper: c haracteristics of,
307-308, 30 8 ; coati n g thickness,
and resi stance to cracking, 330,
3 3 1 ; popu larity of, 2 16; production
process, 298, 307-308, 327, 332-333;
a l b u men print(s): c haracteristics
of, 694-695; effect of sensitizi ng
solution on grain-size d istribution,
310, 3 10-3 1 1 , 3 1 1 ; efforts to i m p rove
process, 2 14; exh i b it ion, effects
or, 656-657, 674-680; gloss, loss
of, 320-326; gold toni n g of, 214,
2 1 6, 296, 3 13-3 14, 3 1 4 , 333; hand­
colored, treatment of, 299; h i story
of, 2 1 3-2 1 4 ; i dentificati on of, 693t;
l a m i nar structure of, 9 1 ; moistu re
and, 3, 6, 3 1 5, 3 1 7, 3 1 7-31 8 , 3 1 8 ,
3 1 9; oxidation of, 23 1 , 3 14-3 16, 3 1 5,
3 1 6 , 3 1 9; preservation problems
and procedu res, 9-1 0 ; sta b i l i ty of,
42, 43, 47, 50, 672; storage of, 3 1 9;
water soaking and, 57. See also
aqueous treatment of a l b u men
prints; deterioration of a l b u men
prints; silver i mage structure in
a lb u men pri nts
a lbumen print conservation: b leac h i n g
a n d redevelopment of, 558;
clean i ng of, 216, 300, 6 1 4-6 1 5;
considerations before treatment,
299-300, 323-324; exhibition
l ighting recommendations, 687;
remo u n t i ng of, 303-304, monitoring
of Fadi ng in, 638, 651 n5; treatment
tec h n i q ues, 300-304; water-soaked,
treatment of, 55. See also aqueous
treatment of a l bu men prints
albums: and artistic and h istorical
i ntegrity, 29-30; rehousing of,
582-583
alka l i ne hydrolysis of varni s h , 356-360,
3 59
a lpha cel l u lose content, of paper
products, 1 4
Altman, J . 1-1 . , 559

alum, and damp air, 4, 6
a l u m i n u m sulfate, i n kraf't papers. 13
an1alcur photography, growth of,
2 1 8-2 1 9
ambrotypes, 384, 583-584, 687, 692t
American I ns t i t u te for Conservation
( A I C ) : Code oF E t h ics, 93, 590,
627, 628-629, 630; Photographic
M aterials G roup, 26, 285, 684
American Nat ional Standards I nstitute
(ANSI): color image stabi lity stan­
dard, 422, 423; on microfi lm fixa­
Lion, 2 10; on paint in storage area,
198; recommended h u m idity levels,
573; residual hypo tests, 220; Speci­
fications for Photograph.ic Fi lms,
146; staff of', 1 55, 383; standard for
accclen1tcd aging tests, 1 90- 1 9 1 ,
1 9 1 , 49 1 , 56 1 ; standard for archival
photographic f i l m , 436; standard
For m icrofilm storage, 543; standard
For polyester film, 437; standard
for safety film, 437; Standard
IT9.2-1 988, 1 57-1 58, 1 68-169, 404,
580--58 1 : Standard P H 1 .28-198 1 . 56 1 ;
Standard P l- 1 1 .4 1 - 1 98 1 , 56 1 ; Stan­
dard PH 1 . 42-1969, 422, 490, 4 9 1 ;
Standard P H 1 .48-1974, 1 8 5- 1 86,
190. 192, 1 98, 203; Standard P H4.8-
1978, 220; Standard P H 4.32, 190--
1 9 1 , 1 9 1 , 56 1 ; Standard P l- 1 5-4-1970,
543; standards on storage of photo­
graphic materials, 1 56, 1 85-186. 1 92,
203, 436-437, 452, 543, 580-58 1 , 625;
tests for determi n i ng stability oF
si lver images, 190- 19 1 , 1 9 1
a m m o n i a : atmospheric, storage
e nvironment and, 1 3 ; and oxidation
of silver i mages, 543
ammonia solutions, for cleani ng, 247,
273, 274, 540
ammoni u m sulfocyan ide, as fixing
agent, 2 1 6
Anderson , Stanton. 679
Andrade, E. N. da C., 1 36
Andrew 'v\I. Mellon Fou ndation, 34
ANS I . See American National
Standards I nstit ute
Anthony, Scov i l l and Co., 366
aperture cards, and redox blemishes.
145
aqueous treatment oF a l bu men prints,
300-303; cracking and gloss reduc­
tion From, 320--324, 325-326; dry-
ing tec h n iq u e and, 328, 331-332;
n1i ni n1 izing of cracking and gloss
reduction, 326-331 ; recon11nenda­
t ions on, 33 1-332; types of, 326;
water:et hanol m ixture for, 330,
331-332
Archer, Frederick Scott, 2 1 3, 34 1 , 384
architectural plans, exh i b i t ion l ight i ng
recommendations, 686
Arget, E . , 339
Armed Forces I n s t it u te of Pat hology,
1 40
A rrange111e11.t of Specimens ( Bayard) ,
632
Arrhen i us, Svante, 408
Arrhen i u s equation, 1 80, 473, 49 1-492;
accu racy of, 491-492, 494-495;
application methods, 492-493;
appl ications of, 223, 435, 445, 520;
factors not accounted for i n , 492;
history of, 408
art-historical a nalysis of photographs,
dating oF p hotographic paper and,
1 05
Art I nstitute of C h i cago, 2 1 , 653 n 1 7,
654-657
art objects: conservators' respect
for photograph as, 28-30, 588;
photography's status in h ierarchy
of, 48-49, 50--5 1 , 63-64; recogn ition
oF photographs as, 61-62, 89-90
Association of I nternational
Photography Art Dealers (Al PAD),
106, 565-566
L'Atelier de Hestauration et de
Conservation des Photographies de
la Ville de Paris (AHC P), 58
a t t i t udes toward photographs:
aest het ics of in1age, growing
i nterest in, 6 1 -62; conservation and,
50-5 1 , 58-59; slowness of change
i n , 60; trivialization of, 60. See also
art objects
autochrome: d u p lication of, 508-5 1 1 ;
dyes used i n , 5 1 7-5 1 8, 5 1 8 ; exhibi­
t ion l ighting recommendations,
686; h i story of, 497-498, 513, 5 1 5;
manufacturing process, 5 1 6-519;
and oxidation, suscep t i b i l i ty
to, 502; process, 497, 5 1 5-5 1 6 ;
stabil ity o f images, 505-508, 5 1 1 ,
5 1 9-520; storage of, 508, 5 1 1 . See
also National Geographic Society
autochrome p lates
717
Index
automobile exhaust fumes, damage to
silver images, 1 48, 1 50-1 52, 230
Avedon, Hichard, 8
B
Baas, Valerie, 325-335
back p r i n t i ng, and dating of
p h otographic papers, 1 0 1- 1 02
bacteria c u l t u res, on glass plate
negatives, 347
Baekeland, Leo, 307
Bard, C harleton C., 490-495
Barger, M . Susan, 271-283, 284-290
bari um sulfate, and baryta coating, 44
baryta layer, 44-45, 535, 536; and hypo
retention, 220, 22 1 , 547, 549; l ight
exposure and, 672; si lver s ulfide
transfer i mages in, 230, 234, 557,
560; t i n ted, 687; X H F analysis of,
103-104; a n d yellow d iscoloration,
209, 2 1 0
baryta papers, i n troduction of, 2 1 8
base materia l . See supports
Bayard, H ippolyte, 343, 632
Beausoleil, Jeanne, 5 1 3
Becquerel, Edmond, 5 1 3
Bennett, C . H . , 343
benzoatc of gold toni ng, 296
Bermane, D . , 499
The Better I mage, 88
B i gourdan, Jean-Louis, 407-41 7
bi nders: assessment of, 582; calci u m
carbonate buffering a nd, 1 56;
common materials for, 50, 577;
and i mage stabi li ty, 42-44, 47, 50,
430, 491 ; swe l l i n g tendency, testi n g
of, 539; t inted, 687; water-soaked
photographs and, 55
B i s hop M useum ( Hawa i i ), 3 1 , 32
Black, Donald, 2 3 1 , 306-3 19
Blair, T. 1-1 . , 386, 387
Blanquart-Evrard, Lou i s Desire, 2 1 3
bleach i ng a n d redevelopment: defi n i -
t i o n of, 557; l a c k o f rel iable data o n ,
558; potent i a l p itfalls i n , 559-56 1 ;
procedures, 558, 559; stabil ity of
si lver images after, 561-562
Booth, Jane, 37
Booth, Larry, 37-39, 692-693
Booth H istorical Photograph Archives,
37
Boris Color Lab, 463
Brady, Matthew. See Meserve

Coll ection wet-pl a te negatives
B re n n e r, Howard, 284
B riJ ish Jou.ma/. of Photography, 206, 343
B r i t ish Library, 48
British Petro leum Research and
Ana lytical Centre, 48
B ritish Q11a1·terty Review, 297-298
brittleness: of motion-picture fi l m , 4 5 1 ,
4 5 1 -452; plastic deformation a n d ,
594
bromide prints, fad i ng of, 229
bronze powders, effect on silver
i n1ages, 583
B rooklyn M useu m , 32
brown/black spots o n daguerreotypes.
See daguerreotype n1easles
Bry, Doris, 22, 23, 24-25
b u b b l es, in cellu lose acetate/n itrate
f i l n1 s , 3 1 -32, 309, 373, 399
burn test, 696, 698
c cel l u lose acetate f i l m deterioration,
CAL. See Conservation Analytical
Laboratory
calcium carbonate bu ffering, a n d
b i nder layers, 1 56
c a lc i u m hypoch lorite, as b leac h i n g
age n t , 558
C a l h o u n , John M . , 23 1 , 368-374, 3 9 1 ,
393, 436
calibration standards, color
p hotograph, 638, 645-646
calotype, 9, 2 1 3 , 337, 692t
Cainera Notes, 74
Catneron, J u l ia !V l a rgaret, 524
Canadian Conservation I nstitu te, 53,
247, 6 1 5
Capa, Robert, 8
carbon, as image-forming s u bstance, 59
carbon prints, 294, 295, 686, 688,
694-695
Carbutt, John, 385
Carro l l , J. F., 23 1
Cartier- B resso n , Anne, 58-64
cased p hotographs: exhibition l i gh t i n g
recommendations, 687; i m age sta­
b i l ity oF, 46. See also daguerreotype
cases
casei ne, and d a m p a i r, effect of, 3, 5, 6
C e l l u loid Company, 385
cel l u lose acetate: enclos u res made
From , 58 1 ; as waterproof paper
coating, 1 73
H E 1\ D I N C S I N C O N S E H \1 1\ T I O N
cel l u l ose acetate b u tyrate, 389, 390, 394
cel l u lose acetate f i l m : Acetate N egative
S u rvey ( Horvath), 397-400, 405;
assessment of, 575, 579; collections,
survey of, 4 1 0-4 1 1 ; d i mensional
sta b i l i ty, 438; d u p l ication of, 575,
576; f l uctuating tempera t u re and
h u m i d i ty, effects of, 4 1 2-4 1 7 ;
history of, 1 0, 3 2 , 2 1 9, 370-37 1 ,
389-390, 394, 402; ide n t i fication
of, 693t, 696-698; i mage pellicle,
attaching to new base, 378-379,
3 8 1 -382; i mage pellicle, removal
oF, 376-377, 38 1 ; i mprovements
needed in, 395; I Pl p u b l ications o n ,
408; 111oisture content, as fu nction
oF tem perature and h u mi d ity, 595;
mon itori ng, i m portance of, 405;
plati n u m and, 583; sta b i l i ty oF, 46,
401-402, 404, 437, 580; storage of',
4 1 0-4 1 1 , 4 I 1-4 1 2 , 452, 573, 575, 576,
579; uses of, 394-395
574-575, 697, 698; accelerated
aging stud ies on, 408-4 1 0 ; acidity
level and, 409-4 1 2 ; a n d clamp a i r,
effect oF, 6; a u tocatalytic poi n t ,
402, 4 1 0; nat u ra l agi ng st udy of,
4 1 1-4 1 2 ; stab i l izat i o n , 4 1 2; stages of,
309, 404; and destruction of silve r
i mages, 1 50; a n d paper storage
prod ucts, 13; v i n egar syndron1e i n
c e l l u lose acetate fi l m , 409-4 1 2
cel l u lose acetate propionate, 389, 394
cel l u lose cliacetate. See c e l l u lose
acetate
cel l u l ose n i trate: as adhesive between
f i l m layers, 32, 38 1 ; m a n u facture of,
387; i n va rnish, 5 1 9, 520
cel l u lose n i t rate fi l m : a mate u r
negatives, characteristics of, 37 1 ;
an1ateur negatives, storage of, 369;
attachment to new base, 378-379;
desirable characteristics of', 387-
388; destruction of, 580; d u p l ication
oF, 33, 36, 376, 379, 388, 437, 575,
576; as f i re hazard, 10, 3 1 , 46, 368,
370, 37 1-372, 388, 389, 402 . 574;
ge latin backing, benefits of, 37 1 ,
372; history of, 2 1 9, 369-3 7 1 , 370,
37ot, 385-388, 394 ; ident ification
of, 693t, 696-698; i mage pellicle,
attaching to ne\.V base, 377-378;
i mage pel l i cle, removal of, 376-378;
i n spection oF, 579; m a n u facturing
process for, 385-387, 386, 387;
moisture conten t , as Fu nction oF
temperature and h u m id i ty, 595;
ongoing use in E u rope and Asia,
371 ; plati n u m and, 583; storage of,
368, 372, 389, 437, 573, 575, 576,
579; t h ickness oF, and safety, 371
cellu lose nitrate f i l m deterioration,
574-575, 697, 698; accelerated
aging stud ies on, 408-4 1 0 ; as auto­
catalyti c , 372, 448; fu ndamental
insta b i l i ty, 44, 45-46, 346, 368, 369,
372, 388, 389, 401-402, 404, 436,
437, 580; gases released in, 9- 10, 45,
372-373, 389; poor process i ng and,
373-374; preservation problems
and procedures, 1 0- 1 1 ; stages of', 3 1 ,
372-373; u n resolved issues i n , 374
cellu lose triacetate. See cel l u lose
acetate fi 1 m
cellu losic fi bers, chemistry of, 1 72, 1 72
Center for Creat ive Photography
Collection ( U n iversity o F Arizo n a ) ,
68
Center for Polymer S t a b i l ity, 575
Centre de Recherches sur La
Con servation des Doc u ments
G ra p h iques (CRCDG), now
cal led Centre de Recherche sur
l a Conservation des Collect ions
( C R C C ) , 338, 5 1 2
Centre for Photogra p h i c Conservation,
48
cert i fication, of' conservators, 97
Charriou, Andre , 2 2 1
chemica l treatment: as b r a n c h o f
conservation discipline, 5 5 6 ; con­
temporary abandonment oF, 555;
lack oF experi mental data on, 558;
tec h n iques, overview oF, 557
chemistry of photographic processes,
conservator's u nderstan d i n g oF, as
necessity, 9 1
C h icago A J b u m e n v\lorks (CAW), 326,
332, 335, 380, 38 1
chlora m i ne-T, as b l eac h i ng agent, 558
ch loride: effect on s i lver f i l a ments,
1 1 7, 1 26- 1 32, 132, 1 33t, 1 42, 543; and
reclox blem ishes, 1 42-1 4 3
ch loride o F gol d . See gold ch loride
ch loride toni ng, 296
chlorinated hydroca rbons, 6 1 2 , 6 1 7,
62o n4, 62on6, 622 n 1 8, 622n 1 9

c h lorine dioxide, as bleac h i n g agent,
558
c h romogenic (dye-cou pler) prints:
c1'1rk sta b i l i ty of, 470, 650112;
development process for, 65on2;
exh i b ition, i mpact of, 676, 6 76,
678, 679, 680; preservation of, 470;
wa te r-soa keel , 55
C i bachrome, 462-.+63, 47ot, 509-5 10.
S e e also si lver dye bleach
C i ba-Geigy Photochemic, Ltd . , 202,
496, 499
citrate of gold toni ng, 296
citric acid sensi tization of a l b u men
prints, 3 1 0, 3 1 1 , 3 1 6
C lark, D . E . , 363
C lark, \i\la l ter, 34-36
C larke, 1 -1 . T., 389
cleani ng. See dagu erreotype c lea n i ng;
clectroc lean ing; s u rface cleaning
C leveland C l i n ic f i l m fire, 10, 370
coatings: and dan1p a i r, 4, 6-7; effects
of, 1 2 ; and l ight sta b i l ity, 672, 675,
678; wax, 4, 6-7, 672, 675, 678 . See
also varn i s h
Coke, Van Deren, 2 1-25
cold storage: for cellu lose acetate f i l ms,
4 1 0-4 1 1 , 4 1 1-4 1 2, 579; for ce l l u lose
n itrate f i l m s , 368, 369, 579; for
c h romoge n i c pri nts, 470; for color
materials, 4 2 1 , 435, 460, 474, 490,
573-574, 637, 647-648, 653n 1 9 ;
for color motion-pic t u re f i l m ,
444, 445-446, 448-449, 453; for
color photograph c a l i b ration stan­
dards, 638, 645, 646; condensation
and, 446; determi n i ng needs for,
606-607; faci l ities for, 470, 653 n 1 7,
654; for f i l m-base materials, 409;
h a n d l i n g i tems i n , 597-598, 606;
history of, 435; and loss of p l astic­
ity, 597-598; for photographic mate­
rials, 597, 605
cold storage, time spent outside
of: al lowed temperature and
h u mid ity ranges for, 596-600, 598;
determ i n i ng appropriate amount
of, 605, 606-607; a n d ge latin glass
transi tion temperature, 595-596,
606; i m pact on image sta b i l i ty,
603-605, 604t; m i c roclimate effect
i n sealed packages and, 600-603,
602, 606; need for safe practice
guideli nes, 592-593; and plastic
deformation damage, 593-594, 599;
warm-up procedure for, 444, 446,
584, 597, 600-603, 602, 606
Colin.I. on. Wood. ( H i l l and Adamson),
690
collecting of h i storical photographs,
h i story of, 38
Collec/.ion, Use and Care of 1-/is/orical
Pl'IOtographs (Wei nste i n a n d
Boot h ) , 37
col lodion prints: exh i b i t i o n gu idel i nes,
687; h istory of, 2 1 8 , 3 4 1 ;
identification of, 692t, 694-695;
preservation problems a n d
procedures, 9- 1 0; stabil ity of, 42,
43-44, 50, 346; s u rface cleaning
tec h n iques, 6 1 5-616; water-soaked,
treat ment of, 55, 57. See also
dry col loci ion process; wet-plate
negatives
colloidal silver: c hloride exposure and,
1 42- 1 43 ; destructive gases and, 1 54 ;
development of, 1 62- 1 64 , 1 63 ; and
oxidation, sensitivity to, 230-23 1 ;
oxidation of, o n R C papers,
1 93- 1 95, 194; as prod uct of s i lver
degradation, 1 34, 140, 1 42- 143, 209 ,
209l, 229-230, 232, 234, 543; redox
blemi shes and, 1 42-1 4 3 ; spots of,
removing, 153, 1 54, 202, 203; as
Lest Lo identi fy gases destructive of
si lver i mages, 1 50-154, 230-23 1 . See
also fade detector for PAT
col lot ypes, 60, 688, 694-695
color balance, changes i n , 459, 584,
636, 647
color dyes. See entries under dye
color materials: A N S I standards on
archival q u a lity, 436-437; I P l
publ ications o n , 408; processing
of, 223; rapid i n n ovations i n . 439;
separat io n n1asters For, 4 2 1 ; storage
of, 42 1 , 435, 460, 474, 490, 573-574,
584, 637, 647-648 , 653 n 1 9
color motion-pi c t u re fi l m : d i mens ional
stabil ity of, 437-438, 43 8 ; and
h u m i d ity, effects of, 449-450, 450;
moi s t u re conditio n i n g of, 452-454;
projectio n , effects of, 446-447
color motion-picture f i l m conservation :
need for, 436; recom mendations
for, 448-449; separation masters
for, 438-442, 448; storage
conditions, 443-452, 444, 450, 451
719
Index
color photography, history of, 5 1 3-5 1 6
color print(s): acceptab i l ity of, factors
i n , 424; common characteristics of,
460-469; exhi b i t i o n , effects of, 657;
exhibition, l ight levels for, 459, 574,
637, 686, 688; i nstab i l i ty of, 42 1 ;
process identi fication, i m portance
of, 460; recommendations on
materials, 469-470, 47ot; su rface
cleaning tech n i q ues, 6 1 7-6 1 8 ;
water-soaked, treatment of, 5 5 , 57.
See also dark fad i n g of color pri nts;
deterioration of color prints; l ight
fad i ng of color prints; sta b i l i ty of
color i mages; stab i l ity testi n g for
color i mages
color s l ides, color i mage stabi l ity
testing for, 425-426
Com m i ttee Appoin ted to Take i n to
Cons ideration the Question of the
Fad i n g of Positive Photographic
Pictures u po n Paper ( Fading
Committee), 2-7, 1 1 2-1 1 5, 228-2291
298, 53 1 , 532112
competence, conservation practice
within l i m i ts oF, 93
compu ter-generated prints, exh i b i tion
l ighting recom mendations, 686
connoisse u rship, in conservators:
necessity of, 589; t ra i n i ng i n , 96
conservation: a n d attitudes toward
photographs, 50-5 1 , 58-59;
complexity of, 63, 92; vs. cosmetic
efforts, 3 1 , 60-6 1 ; vs. d u p l ication,
6 1 ; George Eastn1an H ouse program
objectives, 35-36; h istory o f i n terest
i n , 50-- 5 1 , 6 1 -62, 207, 530-53 1 ; mass1
589 ; new concept oF, 62-63; present
state of knowledge regardi ng,
38, 39; researc h , need for, 304,
533-534, 539, 552-553, 587-588; vs.
restoration, 28; u n ique c h a l lenges
of, vs. paper media conservati o n ,
556; u rgency of, 5 1-52. See also
a l b u me n p r i n t conservation ; color
mot ion-picture fi l m con servation ;
conservation treatn1e n t ( s ) ; gela t i n
silver prin t conservation; research
l i b rary collection conservation;
restorat ion
conservation, as disc i p li ne : areas of
activity, 556; d igital photography
and, 1 07-w9; as form of art conser­
va t i on, 587; fu ndamental princ iples

of, 26-3 1 ; goals of, 63; h istory of,
38-39, 62-63, 1 07, 586-587; nascent
state o f dcvelop111ent, 660; need for,
90-92; need for separation fro111
photographic i nd ustry, 587; prog­
ress of, 63-64; treatment as core or,
589 . See also ethics
conservation, c1npirical, d amage done
by, 60-6 1 , 63, 2 1 3
Conservation Analyt ical Laboratory,
S 111 ithsonian I nstituti o n (CAL),
320, 625
Conservation Cen ter of Art and
H i storic Art i facts, 684
The Conservation of Pliot.ographs
( Eato n ) , 2 1 2
conservation treat111 c n t ( s ) : appropriate­
ness of, eva l u al i ng, 550-55 1 , 589,
590; c a l l s for caution i n , 285, 53 1 ,
533, 545, 553; comn1on practices
oF 1 970s and 'Sos, i nvasiveness of,
533; as core of' conservators' profes­
sion, 589; cri lcria for evaluation of,
624 ; docu 111e ntation of, 6 1 0, 630; of'
f i l 111-base 111ate1·i als, considerat ions
in, 404-405; of' gelat i n s ilver prints,
considerat ions in, 545-552; h i story
and spi rit o f i mage, i m portance oF
u nderstanding, 624: history oF, 525:
i mproved sto rage conditions as best
approach lo, 55 1 , 553; i nnovation
in, 623, 625-626, 626-627, 629-630;
need for research on, 533-534, 552-
553, 629-630; preve n tive measures,
conten1 porary cn1phasis on, 63,
94; retouchi ng, 303, 379, 627-628;
standards for, d i ffic u lty of develop­
i ng, 590; types of', 624-625. See also
chemical treatment; daguerreotype
clean i ng; clcctroc leani ng; restora­
tion; s u rface cleaning
conservators: certi fication of, 97; con­
noisseurs h i p in, 96, 589; discussions
with c l ients, 589-590; i ncreas i n g
demand for, 9 0 ; i n formation­
sharing bclwecn, 93, 95; profes­
sional, need for, 92-93, 96; q u a l i t ies
required by, 588; research by, 95.
See also eth ics
con servators, l ra i n i ng of: exi s t i ng
progran1s, ave nues for in1proving,
95-96; expe rience as co111ponent
in, 587, 6 1 0; h i story of, 89-90; ideal
standards and practices, 93-95;
720
H E A D I N G S I N G 0 N S E H \ I ,\ T I 0
speci a l ization areas, 92
''Conserving a n d Restoring Photo-
graphic Collections" (Ostroff), 8
core set properties of su pports. 395
Cosindas, M arie, 468
cosmetic efforts, vs. conservalion, 3 1 ,
60-61
Les co11leHrs e n phot.ograpliie, solution
du probliww ( D u cos d u l- l a u ro n ) ,
514
Courtellemont, Gervais, 502-505
Crabtree, J o h n I . , 2 2 1 , 525, 557, 558, 559
Crabtree-Ross merc u ri c c h loride test,
220
cracking: in a l b u m e n prints, 299, 30 1 ,
302, 330, 3 3 1 ; o f gelatin en1ulsion,
538; in RC papers, 1 76- 1 78 , 1 77, 1 78 ,
1 83 , 1 83-1 84, 1 84 . See also aqueous
treatm e n t oF a l b u me n prints
Crawford, I rwin 1-1., 1 7 1 - 1 86, 192
Crawford, W i l l i a m , 70, 74
CHCC (Cen tre de Recherche s u r la
Conservation des Collections), 338,
512
C RC D G (Centre de Recherches s u r
L a Con servation des Col lect i o n s ) ,
338, 5 1 2
Cromer, Gabriel, 60
Cros, C harles, 5 1 4 , 5 1 5
Crystal Palace ga l l e ry, 2 1 4
C u 1n m i ngs, J . \A./., 3 1 , 373
C u n n i n ghan1, l 111ogen, 8
cu pric bro m i de, as bleac h i n g agent, 559
curli ng: of' gelat i n s i lver prints, 537-
538, 6 1 6 ; of motion-picture f i l m ,
4 5 1 , 4 5 1 -452
cyan dye: dark fad i n g of, 483-484,
485t, 49 1 , 493, 495; i m age sta b i l ity
techno logy, 483-485, 485t; stabil ity
of, 430, 444, 44 5 , 473, 474 , 487 t , 488
cya n ide: i n c lea n i ng of daguerreotypes,
1 7115; merc u ric, as b leach i ng age n t ,
5 5 9 ; potass i u m ferricyan ide, a s
b leac h i n g age n t , 559 . See also
potass i u m cya n i de
cyanotypes, 672, 680, 687, 694-695
D thiou rea/acid cleaning solutions
Daguerre, Louis Jacques i\ � andC, 2 1 3,
513
dagu erreotype(s): care of, need for
conservator t ra i n i n g i n , 269; col­
lectors' i n terest in, 266-267, 269;
components oF, 267, 268; exh i b ition
N
l ighting recommendations, 687; h i s­
tory of, 249-250, 266; identi fication
of, 692t ; l a bel i ng of, 269; preserva­
tion problems a n d proced u res, 9;
stabi l i ty of, 207-208 ; storage of, 252,
258, 268-269; structure of i n1age,
250-2 5 1 , 266-267; v u l n era b i l i ty to
damage, 267; wel l-preserved, m i cro­
scopic anal ysis of, 250-252. See
also deterioration of daguerreotype
s u rfaces
daguerreotype ( s ) , hand-colored:
clea n i ng of, 248, 2 5 1 -252, 283;
coloring process, 2 5 1 , 252; storage
of, 252, 258
daguerreolype cases, 267, 268; glass
deterioration in, 258, 362; a n d
i mage dclcrioration, 238-239; as
i n tegral part of daguerreotype,
267; record i ng of changes to, 269;
rehousi ng, 583-584; rep l ications,
i nadequacy of, 268; sea l o n , i m por­
tance of, 245, 252, 253, 259, 267
daguerreotype clea n i ng: acidic
a m m o n i u m th iosu l fate for, 247;
c i rc u mstances c a l l i n g For, 253, 269;
and daguerreotype measles, 246-
247, 254; e lectrolytic cleani ng, 2 7 1 -
272, 3 7 3 : eva l uation prior lo, 289;
with hyd rogen p lasma, 260-265,
2 6 1 , 262; P M G moratori u m on, 285;
potas s i u m cyanide for, 238-239,
240, 24 1 , 243, 246, 27 9 , 279-280;
potential for dan1age i n , 248, 2 5 1 ,
267-268, 289-290; proced u re
for, 1 6n 5 ; research o n , 247; s i lver
dip cleaners, dan1age fron1, 279,
279-280; spu tter cleani ng, 2 7 1 ,
280, 2 8 3 ; u l t rason ic, dan1age from,
282, 282-283; as u nsolved prob l e m ,
2 5 3 . See also electroclea n i ng;
thiourea cleaning solutions for
dague rreotypes
The Dcig11erreotype in A ·1nerica
( N ewha l l ), 250
daguerreotype measles, 254; sca n n i n g
electron m icroscopy of, 247, 24 8;
a n d , 246-247. 254
dark Fad i n g o F color pri n ts , 458,
636-637, 649n 1; accelerated
kee p i ng tests of, 473-474, 4 74 ,
474 t ; atmospheric constituents
causi ng, 49 1 ; charactc rislics of,

642; c hemical reactions i n , 49 1 ;
hu m i d i ty and, 492; lack o f data
on, 637; l ight Fading and, 459, 638;
temperature and, 458, 473-474,
474, 474t, 4 9 1 , 492-494, 65on 1
dark stabi l i ty, of masking dyes, 486
dark sta b i lity of color pri n ts:
autochrome i mages, 505-508,
520; c h romogenic development
process, 4 70; collectors' preference
for, 459; of common color pri nt
materials, 460-469, 470; cyan dyes,
483-484, 485t, 49', 493, 495; and
dye couplers, residual, 478; Factors
affecting, 49 1 ; i mportance of,
472; i nstant prints, 488; of Kodak
color photograp h i c materials, 479;
magenta dyes, 479; pred iction
of, 49 1 -495; relationship to l i ght
stabi l i ty, 459; yellow dyes, 48 1-483,
483t. See also accelerated keeping
tests, for color i m ages
dark storage: for c hromogen i c prints,
470; for color materials, 223, 460,
584; for color motion-picture f i l m ,
446-447; for film-base materials,
403-404; hu m i dity and, 492; for
resin coated ( R C ) paper, 1 86
dating i n formation, i n identification of
fil m-base materials, 697, 698
Davanne, Louis-Alphonse, 59, 526-529
Dead Leaf ( Ray), 1 10
Deck, N. C . , 229
Delamotte, P h i l i p H., 1 1 2-1 1 5
Deming G l i nsman, Lisha, 68-85
densitometer: calibration of, 638, 644-
646, 655; characteristics of, 638;
mai n tenance of, 639; sensitivity or,
679; sources for, 639, 6 5 1 11 7 ; use
of, i n monitoring of print fadi ng,
424-425, 637, 639-64 1 , 641 , 655,
673-674
Department of Commerce, U .S . , 1 39
deterioration of albumen prints:
cracking, 299, 301 , 302, 330,
33 1 ; Fad i n g, 298, 302, 325-326;
microstructural changes i n ,
3 1 4-3 1 6 , 3 1 5 , 3 1 6, 3 1 7 , 3 1 7-3 1 8, 3 1 8 ;
s t a i n s , 302-303; types of, 298-299;
yellowing, 43, 62, 2 1 7-2 1 8, 294-296,
298, 302, 3 1 7, 468. See also aqueous
treatment of a l b u me n prints
deterioration of color prints: acceptable
levels of, 472; detection of, Factors
i n , 459, 475-476; difficulty or
predicting, 637; irrevers i b i l ity
of, 556-557; monitori ng or, 459;
recommended l i mits of, 646-648:
selective vs. neutral Fadi ng, .-175-
476; stages of, 459; stains, 459, 467,
636; types of, 458-459; yel lowi ng,
459, 466, 478-479, 636. See also
dark fad i ng of color pri n t s : l ight
fadi ng of color prints; monitoring
of pri n t fading; stabil ity or color
i n1agcs
deterioration of daguerreotype
su rfaces: case seal and, 245, 252,
253, 259, 267; c lear, golden crystal
spots, 255; daguerreotype measles,
246-247, 248, 254; embedded
polish particles, 256, 257; glass
deterioration and, 258; green and
blue salt accrertions, 254-255; loss
of image surface, 256-257, 257;
mold growths, 258-259; orange and
i ridescent f i l ms, 255-256; smooth
tarnish fil m s showing i n terference
colors, 252-254; types of, 252-259
deterioration of glass plate negatives,
types of, 345-347
deterioration of silver i mages: causes
of, 1 1 2- 1 1 4 , 228-229, 298, 532112;
d iscoloration, types of, 208-209,
209t; u nder exhi b ition conditions,
672; Factors in, 49-50; h igh rate or,
50; h istory of research on, 2 1 4 , 2 1 7;
subjective nature of, 62. See also
filamentary s ilver; gas(es) dest ruc­
t ive of si lver i n1ages; s i lver degrada­
t i o n ; yel lowi ng of si lver pri nts
Detroit I nstitute of Arts, 325
developed-out prints: bleaching
and redevelopment of, 558;
characteristics of, 694-695; si lver
i n1age structure of, 3 1 1-3 1 3, 3 12,
3 1 3t, 54 1-542
developing-out paper ( DOP), 540-54 1
development: of albumen process
glass plate negatives, 34 1 ; or si lver
i mages, 228, 344-345; of' wet
collodion glass plate negatives, 342.
See also processing
Diamond, H ugh W., 1 1 2-1 1 5
D ickson, J . T., 392
dicyand iamidi ns u l Fate residue, 286-287
digital i mages: and cataloging of'
research l ibrary collections, 57 1 ;
721
Index
conservation issues For, 571-572;
and definition of photograph,
1 07-109; and market value of silver­
based i mages, 90
d i mensional stabi lity: of cel l u lose
acetate fil m , 438; of color motion­
picture fil m , 437-438, -f38; of paper
supports, h umidity and, 44; of
polyester fil m , 438; vi nyl su pports
and, 390. See also cracking; plastic
deformation
d iphenylami ne test , 696, 698
d i rect development, 541-542
d i rect-duplicating film, 580
d i rect method of color photography,
5 1 3-51 4
D i rect Reproductions Corp . , 465-466
d i saster preparedness, 579
d i saster recovery, water-soaked photo-
graphs, treat ment of, 53-57, 56t
DOP. See developing-out paper
Draper, Dorothy Catherine, 246, 248
d ry collodion process, 2 1 5, 343, 346
d rying: or albumen prints, fol lowi ng
aqueous treatment, 328, 33 1 -332;
of gela t i n silver prints, 539-540; of
water-soaked photographs, 53-57,
56t
dry moun t i ng, problems associated
with, 537-538
dry-mount tissue, 1 2
Ducos du Hauron, Louis, 5 q , 5 1 5
d u p l ication: o f acetate f i l ms, 575,
576; of autochrome prints,
508-51 1 ; as branch of conservation
science, 556; vs. conservation, 6 1 ;
duplicate negatives, a s identical
to origi nal, 626; education in, 95;
for exhi bitions, 66 1 ; of fil m-base
materials, 404-405, 579-580;
and fu ndamental princi ples of
conservation, 27; harmfu l effects
of, 27; i nnovations in, 627; issues
in, 580; of n itrate f i l ms, 33, 36,
376, 379, 388, 437, 575, 576; For
ordi nary \�ewi ng, 63, 269, 508, 569,
66 1 ; of scrapbooks and albums,
582; Stiegli tz collect ion conditions
regarding, 25
dye(s), i n autochromc, 5 1 7-5 1 8, 5 1 8
dye coupler(s): fu nction of, 476-477,
65on2; magenta, and yellowing,
478-479; residual, effect of, 477-
478, 479, 483-484; temperature

and, 430; yellow, and dark keeping,
482-483
dye-cou pler prints. See chromogenic
prints
dye-diffusion prints, clea n i ng of, 6 1 8
dye stabil ity: emu lsion p H and, 430:
u nder exh i bi t ion conditions, 672;
h u m i d i ty and, 443-446, +H; vs.
i mage stabi l ity, in stab i l ity test-
i ng, 424; in low- vs. high-density
regions, 642; rate oF fadi ng, predic­
tion or, 435; ten1perature and, 4 2 1 ,
422-423, 430; unequal sta b i lity
or t h ree dyes, 424, 446-447 , 459,
475-476, 584 . See also dark stabil­
ity of color prints; light stabi l i ty,
oF color prints; sta b i l i ty tes t i n g for
color i mages
dye transfer prints, 46 1 -462, 47ot, 4 86 ,
-186, 64 7, 649
E also sca n n i ng electron microscopy
E. & H . T. Anthony Co., 352
E. I. du Pont de Nemours, 143, 392
Eastman, George, 2 1 8, 384
Eastman American r i l m , 385
Eaton, George T. , 2 1 2-223
E cole Nat ionale S u perieure Louis
Lum iCrc. 5 1 2
edge pri n t ing, i n identi fication o f frlm­
base materials, 697, 698
Edison, Thomas, 385
E d monson, Thomas M . , 284-290, 2 8 5 ,
2 87
Eggleston, Wi l l iam, -120
Ektachrome: advantages and
disadvantages of, 509; image
stabil ity in, 477, 478, 483t, 485,
485t, 495; HC Paper Type 1 933, 461
Ektacolor paper, 646, 649; 37 HC,
495, 679; 74 H C , 460-46 1 , 470,
637, 647, 648, 679; dark fadi n g i n ,
637; exhibition, effects of, 674,
676; stab i l i ty oF, 480, 4 8 1 , -181 , -185,
4 8 5-48 6 , -186 , 488, 647, 679
EktaFlex prints, 648
elcctroclca n i ng: c he m i s t ry of, 27 1-273,
273; conservator's abil ity to use
effectively, 280-282; electrode
composition, 275-277, 276;
electropolishing i n , 278-279;
experi mental results, 274-277,
276, 278-280, 278-281 ; guidelines
722
H E A D I N G S I N C O N S E B V t\ T I O N
!'or use of, 283; h istory of, 285;
process, 272-274, 2 74, 275, 277-278;
to remove th iourea breakdown
prod ucts, 287; sol u t ion For, 273
electrolyt ic cleaning. See
electrocleaning
electronic i magi ng. See d igital in1agcs
electron m icrobe x-ray a na lysis:
or deteriorated daguerreotype
su rfaces, 2 52- 2 59 , 257; of wel l ­
prcscrvcd daguerreotypes, 250-252
electron micrographs: oF albumen
print deterioration, 3 1 5, 3 1 5-3 1 6,
3 1 7 , 3 1 7-3 1 8 ; of albumen print
structure, 308, 308-31 1 , 3 10, 3 1 1 ;
o r gold toning i n albumen prints,
3 1 3-3 q , 3 q : of h u m i d i ty's effect
on si lver fl laments, 1 22-1 23, 123; of
potassium thiocyanate 's effect on
si lver f ilaments. 1 26- 1 27, 127, 1 2 9 ,
1 3ot: of redox b lemishes, q2- 1 43 : or
si lver in1agc structure, 1 1 2, 1 1 7 . See
(S E M ) ; t ra n s m i ssion electron
microscopy
electron prube analysis, 143
electropolishi ng, i n electroclcani ng,
278-279
Emerson, Hon. 648
e m u l sions. See b inders
energy-dispersive X-ray analysis, of
electrocleaning results, 275
England, W i l l iam, 2 1 5
envelopes, storage, 1 2 , 1 + See also
storage n1aterials
Enyeart, James, 68, 246
Erwitt, E l l iott, 8
e t h ics: American I nstitute for
Conservation Code of Ethics, 93,
590, 627, 628-629, 630; competence,
practicing w i t h i n l im i ts or. 93;
exh i b i t ion or u n stable pri nts and,
634-635, 658-662, 680-68 1 ; and
t rcat n1cnt, eva l uation of, 590
et hyl cel l u lose, 389
Evans, Chris, 555-562
Evrard, B lanquart, 297
exh ibition: effect on photographs,
654-657, 663-666, 667, 670-67 1 ,
672-679, 675-678; i ncentives for
con t i n u i ng, 659; print-specific toler­
ances, necessity of determ i n i ng,
670; responsible d i splay cond i t ions
for, 680-68 1 ; sou rces of damage
Lo, 672: temperature and h u m i d i ty,
characteristic, 655, 666; \Vicic vari­
ety of cond it i o n s i n , 637. See also
cold storage, time spent outside of;
monitori ng of pri nt fad i ng
exh i bition, trave l i ng: i mpact on
prints i n , 675; responsible d isplay
conditions For, 68 1 ; sou rces of
damage Lo, 656
exh i b i t ion l ight levels: characteristic
levels, 637; For color prints, 459,
574, 637, 686, 688; gu i d e l i nes for,
684-689; and l ight fad i ng, 636-637;
measuring of, as inadequate
monitori ng of prin t deteriorat ion,
638; recommendations on, 68 1 ;
standard policy, i nadequacy of, 670;
and visibil i ty, 67 1 , 680
exhibition of u nstable prints:
alternat ives to, 66 1 ; ethics of. 634-
635. 658-662. 680-68 1
F
rade detector for PAT: development of,
1 62- 1 64, 163 ; optimal i n c u bation
condit ions, determination or, 1 59-
1 62, 1 6ot, 1 6 1 t, 162t; pass/Fa i l limits,
selling or, 1 64; practical application
of, 1 67-1 69, 1 68t, 1 69; selection of
colloidal s i l ver as, 1 58-1 59, 1 58L
radi ng. See ent ries 1mcler deterioration
Fad ing Committee. See Committee
Appointed to Take i n to Consider­
ation the Question of t he Fad ing
of Positive Photographic Pict u res
upon Paper
fad ing mon itors, 637; l i m i tations or,
639, 642-643, 646; preparation or,
643-644; specific print materials
i n rormation, 648-649; use of, 639,
642-643, 644
Farnday, M ic hael, 2 1 3
Feldman, Larry 1- 1 . , 1 88-204, 230, 3 1 8,
501
Felix Schoeller Co., 1 00
Fenton, Hoger, 2 1 5
Fergg, 1 3 . , 309
Ferguson B u i l d i ng F i l m Excha nge l i re,
10, 370
l'errotype prints: cleaning of, 6 1 0-6 1 1 ,
6 1 6 ; defrned, 62or12; and emulsion
embrittlement, 538; ident ification
of, 692t

f'errotypes. See tintypes
i·errotypi ng, causes of, 58 1
fiber base black-and-white papers:
availability of, 185; and oil-based
paints, effect of, 1 98-1 99; oxidation
and, 1 88, 20 1 , 201 , 202-203; process
sta b i l i ty of', 1 9 1 , 1 92: yel lowing of',
195, 1 96
Field, Ruth K . , 240, 242-244, 284
fila111entary silver, 42; i n developed-
out prints, 541-542; effect or
thiocyanate and chloride solution
on, 1 1 7, 1 26-1 32, 127, 1 29, 132, 1 33t,
134-137, 543; h u m i dity, effects or,
1 1 7, 1 1 8- 1 24, 1 23t, 1 24t, 125. 1 34, 1 90;
instability of, 1 1 6-1 1 7, 1 42, 1 89-190;
oxidation process i n . 1 40. 1 93-195:
I'S. p hotolyti c . 228; redox ble111 ishcs
and, qo, 1 42: stabi lization with
iod ide, 1 1 7, 1 24-1 26, 125, 1 32, 135-
1 36, 1 37, 233-234, 542, 543; stabiliza­
tion with l -phenyl-5 111ercaptotclra­
zole, 1 1 7; stabi lization with sod iu 111
thiosulfate, 1 17, 1 18-1 24, 1 23t, 124t,
132, 1 35-1 36, 1 37, 190; stab i l ization
with sul f-lde, 542; trans111 ission elec­
tron microscopy of, 189
f i l m-base materials: adsorption of'
oxi d izing gases, 1 50; deteriorated,
health hazards of, 403: d i sposi ng of',
405; d u p lication of, 579-580: han­
d l i ng procedures, 402-403; iden­
t ification of, 696-698; i n spection
of. 579; 111onitoring, i 111portancc
of', 405; resi d u a l che111icals i n , 6,
1 1 ; Stability of, 45-46; storage or,
403-404, 409-410. See also cellu lose
acetate fil111; cellulose n itrate fil111 ;
polyester fd111
f i l 111 reels, and redox ble111ishes, 1 4 1
Fi ngerpri nts: damage from , 233, 6 1 1 ;
re111oval of, 6 1 8 , 622n 1 8
Fiori, C . E . , 250
Fischer, Monique C . , 40 1-405, 696-698
Fisher, Frankli n L . , 502
Fisk U niversity, 2 1
rLxation: of a l b u 111en glass p late nega­
t ives, 34 1 ; of a l b u 111en prints, 302: of'
cellu lose n itrate fi l 111, 373-374; early
research on, 664-665; Fixing agents,
and print stabi l i ty, I L6; fixing baths,
co111position of, 220-2 2 1 ; of' gelat i n
silver prints, 548-549; length of',
221 ; of n1icroftlm, 2 1 0 ; of mot ion-
picture separation masters, 440;
and oxidation, resistance to, 502;
and redox blemishes, 142; and sta­
b i lization oF silver i mages, 1 90; and
water-soaked photographs, 54
Flieder, Fran.;:oise, 338-347
noat test, 696, 698
F l uctuating temperature and h u m idity:
and cracking of HC paper e111 u ls ion
layer, 1 76-178, 1 77, 178; effects on
cellulose acetate fi l 111, 4 1 2-4 1 7 ; and
gelatin glass transition te111pcrature,
595-596, 606; a nd 111 i croc l i mate
effect in sealed packages, 600-603,
602, 606; opti111al range for, 599,
602; a n d p l astic defor111ation, 592,
593-594; safe range for, 596-600,
598, 625-626: trave l i n g exhi b i t ions
and, 656; and yield point, 593-59+
See also cold storage, time spent
outside of
nuorescent l i gh t i ng, 426-427, 433-434,
686
forgery: and attitudes toward
photographs, 5 1 ; identification of,
68, L OO-L O I , L02, 105; USC of old
paper stocks, 102, L05
formaldehyde: and dest ruction oF
si lver i 111ages, 1 50; as hardener, 539;
released from paper boxes, 142. See
also p henolformaldehyde
formalin stabi lization of color Iii ms, 430
for111i c acid, released fro111 paper boxes,
142
Foster, C hristopher, 325-335
Fourier transform i n frared spectros­
copy ( FT IH ) : of eleclroclean ing
resu l ts, 275; of t h iourea-cleaned
daguerreot)1Jes, 286-287, 288; of
var n i s h on Meserve Collection col­
lodion wet-plate negatives, 355-358,
3 56, 357
freeze-drying, of water-soaked
photographs, 54-55
Fresnel's law, 1 75, 1 75t
Fresson Quadrichromie prints, 463-
464, 47ot, 642-643
FTI H. See Fourier transfor111 i n frared
spectroscopy
Fuji dyecolor p ri n ts, 462, 47ol
Fuji Photo F i l m Co. Ltd . , 206, 232
rungus: on gelatin prints, 574; on glass
p late negatives, 347; h u m idity and,
450
Index
c
Gale, H. 0., 436, 440, 443
Gandolfo, Jean- Pa u l , 5 1 2-52L
Garnier, Chantal, 338-347
gas(es) destructive of silver i n1agcs.
148: effects oF, 1 49-1 50: i ncreasing
a t 111ospheric amou nts of. 209, 210:
in oi l-based paint fu111es, 1 88, 197,
L 97-20 1 , 1 98t, 1 99, 230, 573; lest to
identify, 1 50-1 54, 230-231
gasl ight paper, 2 1 8
gelatin adhesive, and stability of prints,
1 14
gelatinate silver, as product oF si lver
grain degn1dation, 140, 1 50, 543
gelatin-bromide developi ng-out paper,
218
gelatin-chloride prints, 2 1 8
gelatin developed-out prints, 69.J-695
gelati n dry-plates: deterioration i n ,
346; history of, 2 1 8; identification
of, 692t; process for, 343-345;
rehousing of, 582; separation and
tearing of e111 u lsion layer, 346;
surface cleaning techniques,
6 1 8-6 1 9
gelatin layer: baryta coat ing and, 136;
bleachi ng and redevelopment
process and, 560-56 1 ; glass
transition temperature, factors
affecting, 595-596, 606: h i story
of, 42, 9 1 , 2 1 8, 59 1 -592; Licscgang
rings in, 143 ; moisture content,
as fu nction of le111perature and
h u 111i d i ty, 594-595; redox blemishes
and, 143- L 4 5 (See also redox
ble111i s hes); and stab i l ity oF pri nts,
42, 43, 46, 1 36; types of, 592; \·Vater­
soaked photographs and, 55, 57
gelatin pcllicle. See image pel liclc
gelatin pri nted-out pri nts, 688, 694-695
gela t i n s i lver print(s): co111plexily of,
534; curl i ng of, 537-538, 6 1 6; dat i ng
of, 98-106; drying of, 539-540;
e111 u lsion tearing a nd cracki ng i n ,
5 3 8 : exh ibition. effects of, 674-675,
675, 677, 677-678, 678; exh i bition
l ighting recommendations, 686,
688; fixer pH and. 220; hardening
of, 561-562; h istory of', 2 1 8-219;
identification or, 72, 92, 534;
l a m i nate print structure and, 535-
536; 111ounted, problems associated
with, 537-538; oi l-based paints and,

1 8 8-204; resi dual c hemicals i n ,
546; silver in1agc structure i n , 536,
540-542 ; stabil ity oF, 10, 1 1 6- 1 37 ,
1 46; stab i l i ty u nder exhibition
conditions, 6 7 2 ; storage of, 5 4 3 , 574
gelatin si lver print conservation, 1 46,
206-2 1 0 ; clea n i ng tec h n iques, 540,
6 1 6-6 1 7; Fad i ng, monitoring or, 638;
harmful su bstances, identif-ication
of, 1 48- 1 54 , 1 55- 1 70; problems
related to, 537-540; water-soaked,
treatment of, 54-55, 57; water­
soaking, effects of, 44, 54-55,
57, 1 1 7. See also bleaching and
redevelopment; reprocessing of
gelatin s ilver prints
Genda, H . , 1 1 7
General Electric Co., 246
George Eastman H ouse ( I nternational
M useu m of Photography):
Center for the Conservation of
Photographic Materials, objectives
of, 34-36; and cold storage of color
f-ilms, 460; and conservation of
color materials, 457; daguerreotype
research, 247; fade monitoring by,
6 5 1 n5; history of, 60; " Pioneers
of Photographic Science and
Tec h nology" conference ( 1 986) , 2 1 2;
role i n conservation education, 38;
staff of, 26, 1 07, 249, 530, 588, 648;
Stiegl itz collection, 2 1 -25 See also
Advanced Residency Program i n
Photograph Conservation
Gernshei m , Alison, 249-250
Gernshei m , H e l m u t , 249-250
Getty Conservation I nsti t u te, 68, 1 03
G ibbs Gal lery ( North Carolina), 32
G i l let, rvl artine, 338-347
G i rard, Aime, 526-529
Glafkides, P., 535
glass deterioration: alkali oxides and,
360-36 1 ; in daguerreotype cases,
258, 362; and i mage deterioration in
wet-col lodion negatives, 358-363,
359, 3 6 1 ; in plate negatives, types
of, 345-347; sodi u m content and.
363-364; stages of, 36 1-362
glassi n c paper, 13, 24
glass plate negatives: deterioration,
types of, 345-347; h istory oF,
339 ; manufacturing processes,
339-345: preservation problems
and procedu res, 9- 1 0 ; rehousing of,
H E A D I N G S I N C O N S E H V A T l O N
582; storage of, 573 glass supports:
composi t ion or, in collodion wet­
plate negative, 360-36 1 , 3 6 1 , 363,
365t; and stabi l i ty, 45
glass transition temperature: defm i t ion
of, 595; oF gelatin, Factors affecti ng,
595-596, 6o6
gloss, loss of: in albu men pri nts,
320-324, 325-326; in gelatin si lver
prints, 562
Gold, Jens, 1 02
gold chloride bath : and damp air, effect
of, 4 , 5 ; and i mage stab i l ity, 22 1 ;
and redox b l e m ishes, 1 40; to restore
yellowed silver images, 529
gold toning: advantages of, 529; of
a l b u men pri nts, 2 1 4 , 2 1 6, 296,
3 1 3-3 1 4 , 3 14 , 333; and art i st ic
and h istorical i ntegrity, 28.
30-3 1 ; of daguerreotypes, 250; and
damp air, effects of, 3-4, 5; of
developi ng-out papers, 54 1 ; effects
of, 71, 1 1 4 ; Fadi n g Commi ttee
recon1mendations on, 1 1 5, 298;
and oxi dation, protection against,
20 1-202, 2 1 0, 573; of printing-out
papers, 54 1 ; procedu res for use of,
1 1 ; S t i eg l i tz's use of, 73
Goodrich, Alan, 435
Goodwin, Hannibal, 385
Graham , C . Loren, 435-454, 490
G ray, G len G., 1 7 1 - 1 86, 192
G reen, A., 561
green and blue salt accretions on
daguerreotypes, 254-255
green spots and l ines, on autochrome
plates, 500-50 1
G rosvenor, G ilbert H . , 497-498
G rum, Franc, 428
G u i l l u mette, Pau l G., 498
gum, effects of, 1 1 4
gum bichromate prints, 687, 688
G urney, Jeremiah, 236
H 560
Hacken, Joanne, 62 1 n 1 4
halftones, 688, 694-695
Hammond, Howe l l , 490-495
hand-colored photographs, 680, 687.
See also daguerreotypc(s), hand­
colored
hand l i ng mats, 23, 24, 538
hand l i ng of photographic materials :
i n c o l d storage, 597-598, 606;
d u p l ication, for ordi nary viewing,
63, 269, 508, 569; enclosure
types and, 58 1 ; establ i s h ment of
procedures for, 269, 578-579;
procedures for film-base materials,
402-403; research l ibrary pol icies
on, 569; St ieglitz collection
condi t ions for, 24
Hanfstaengl tricolor carbro pri nts, 465
harden i n g, 539, 561-562
Hardwich, Thomas Frederick, 1-7,
1 1 2- 1 1 5, 2 1 5, 2 1 7
heating systems, a n d gases destructive
of s ilver i mages, 1 5 1
Hebborn, E ric, 1 05
Heinrich, K. F. J . , 250
hcliochromes, 5 1 4
Hench, L. L. , 363
Henderson, C . , 1 36
Hendriks, Klaus B . , 53-57, 227-234,
555-562, 588, 623-630
Henn, R. W. , 1 39, 1 40, 1 4 1 , 148, 229,
5o 1 , 543, 557
Herschel, John Frederick W i l l iam,
2 1 6 , 665
1-leugh-Edmonson Conservation
Services, 284
1-leymer, Gerd, 558-559
H i c kman, K. C. D., 2 1 9-220
H i l l , Le,�, 5 1 3
H i l l a n d Adamson, 690
H i ne, Lewis, 30. 100- 1 0 1 , 1 0 2
historical i ntegrity, conservation a n d ,
28-30, 62-63, 66n27
Historical Portraits ( Meserve), 366
h istoric process recreation, in
conservator education, 95, 109
Hofenk de Graaff, J., 4 1 3
Horvath, David, 397-400, 404, 405
H u bbell, David C . , 422-434, 436
h u m i d i ty. See relative h u m i d i ty
H u nt, R . , 2 3 1
hydramine, 3 4 5
hydrochloric acid, as b leac h i ng agent,
hydrogen peroxide: as bleaching agenl,
558; effect on si lver f ilaments, 1 37,
573; as hypo e l i m i nator, 222; and
yel l ow d i scoloration, 2 1 0
hydrogen plasma treatment o F
daguerreotypes, 260-265, 261 , 262
hydrogen s u l p h ide, 1 1 , 1 4 , 228-229,
543

hydroq u i none, 344-345
hydrm.yproline test, 534
hypo (hyposulph ite). See Sod i u m
t h i osul fate
hypo e li n1 i nators, 2 1 6, 2 2 1 , 222, 546,
549-550
I C O iVI ( l n ternational Council of
M useu ms), 338
l lford, I nc., 496
i mage-formi n g s ubstance, and stabil ity,
4 1-42, 47
i mage pellicle: attaching to new base,
378, 381-382; removal of from
film-base materials, 375-377;
unsu pported, fragil i ty of, 380, 3 8 1
I mage Permanence I nstitute ( I P l ) :
accelerated aging studies by, 408,
409; and Advanced Residency
Program in Photograph Conserva­
tion, 34; cellu lose films research,
368-369, 4 1 1 , 4 1 3, 575, 580; m i ssion
of, 1 55; poll utants research , 574;
preservation research , 407-408:
publications, 397, 408, 409; and
redesign of PAT. 1 55, 1 57; redox
blemishes researc h , 1 40; staff of,
40, 1 55, 245, 407; storage conditions
research, 573, 591
i mage quality: definitions of, 49;
and deterioration , acceptable
levels of, 62, 472; and market for
photographs, 48-49
i mbibition processes, and water-soaked
photographs, 55
i ndirect (solution physical)
development, 542
i n d i rect method of color p hotography,
514
i n ferential color process, h istory of,
51 5
i n ks, manuscript, exh i bi t ion l ighting
recommendations, 688
i n sect i n festations, treatment or, 405
instant prints: fad i ng of, 470;
processes, c haracteristics of, 466-
469; sta b i l i ty of, 467-468, 486-488,
487t ; as unique objects, 467
I nstitute of Fine Arts ( New York
U niversi ty), 88
l nstitut National du patri moi ne, 58
I ntegrated Paper Services, 1 00
i n tensification, 7 1 , 557, 558-559,
565-566
I nternational Center of Photography,
457
I n ternational Council of M useums
( J COiVI ), 338
I nternat ional M useum of Photography.
See George Eastman House
I n ternational Orga n i zation for
Standard ization ( I SO): accelerated
aging study standards, 409;
on m icrofil m fixation, 2 10;
recom mended h u m i d i ty levels,
573; and redesign of PAT, 1 57;
staff of, 1 55, 383; Standard 1 8 9 1 6 ,
1 56; standards on storage o f
photographic materials, 625
iodide: and redox b lemishes, resistance
to, 14 1-142; stabi l iz i ng of si lver
i mages by, 1 1 7, 1 24-1 26, 125, 1 32,
1 35-1 36, 1 37, 233-234, 542, 543
iodine, and restoration of colloidal
silver spots, 1 54, 202
I PL See I mage Permanence I ns t i t u te
/ P l Meclia S t.orage Quiel< Reference
( J PJ ) , 408
I Pl Storage C u icle for Acetate Fi/111.
( ! P l ) , 397, 408, 409
iridium Lan i ng, Stieglitz's use of, 73
i ron, as i mage-creating su bstance,
672
i rreversi b i l i ty, Jaw of, 27, 30-3 I , 62,
589, 629
I saacs, C harles T., 565-566
l wano, H aruhi ko, 206-2 10, 232
J stability research , 422-434, 435;
J. Pau l Getty M useu m, 663-666, 667
Jacobson, L. , 246-247
Jaenicke, \1\1. , 1 1 7, 1 34-1 35, 1 36
James, A., 65n 1 9
James, Thomas 1-1 . , 1 1 6-1 37, 1 42, 190,
202, 233, 502, 542-543
J a n i s , E. Parry, 65n 1 9
Javitz, Hon1ana, 38
John F. Kennedy Library, 435, 470,
584, 64 1 ' 653n 1 7
Johnsen, J . , 625
Joly, John, 5 1 5
Journ.al of t.he A merican ln.st.·it1J.l.e .for
Canserval-io n , 105
joHmal of I.he Society of Mot.ion. Pict.11 re
an.cl Television Engin-eers, 31
Index
K
Ka h n , Albert, 502, 5 1 3
The Keepers of Light (Crawford ) , 70,
74
Keit h , H. D., 1 1 7
Kennedy, Nora, 88-96, 23 1 , 306-3 1 9
Kisner, \Iv. I . , 440
Klein, E., 1 1 6-1 1 7, 1 34
Knott, Frank l i n Price, 498
Koch , Mogens S . , 260-265
Kodachrome f i l m , 477, 478, 498, 509-
5 1 0 . See also a u tochrome
Kodacolor f i l m , 477, 486
Kodak: back p ri n t i ng on photographic
papers of, 1 01 - 1 02; cel lu lose n itrate
film manufacture, 370, 37ot; color
materials, dark stability of, 479;
densitometers, 639; dye transfer
prints, characteristics of, 46 1-462,
47ot; and f i l m-base materials, 385,
386, 389, 390; films by, 392; and
Aexible f i l m su pports, deve lopment
of, 384; i n stant prints, stabil i ty
of, 486-488, 487t ; mou n t i ng
methods, 28; notch references,
309; photographic papers by, 1 85,
204, 2 1 9; processing manual, 440;
P u bl ication F-30, 202; H C paper
stabi lization methods, 1 79, 1 95, 1 9 5 ;
on restoration of silver i1nages, 202;
shrinkage in motion-picture f-ilms
of, 438, 438
Kodak I nstant Print F i l m P H 1 0, 467,
468-469, 648
Kodak Research Laboratories: albu­
men print research , 306; cellu lose
films research, 575; color i mage
h istory of, 65n 1 1 ; image perma­
nence researc h , 587; redox blem­
i shes research, 1 39, 140; staff of,
1 16, 1 7 1 , 1 88, 2 1 2, 368, 375, 4 7 1 , 490;
water-soaked prints, research on
drying methods for, 57
Koh lschlitter, V., 1 34
Kol f, C . , 200, 202, 203
Kolody, Dave, 651 n5
Krause, Peter, 496-5 1 1 , 622n 1 8
Kunhardt, Dorothy M eserve, 366
Kurt h , D i rk, 286
Kwik-Prinl prints, 465-466

L i nstant prints, 488: magenta dyes
L . ]. M. Daguerre (Gcrnsheim and
Gernshcim), 249-250
Lacan, Ernest, 60
lacquers , 1 2 , 202
Lady Mary /- la11 1 ilto11 (Cai11 11bell)
R Hl./111en ( H i l l and Adamson ) , xviii
Lamb, J a mes, 2 1 8
Larson, George \/\/. , 490-495, 679
latex paints, effect on si lver i mages,
1 97 , 1 98t, 200
Laved rine, Bertra n d , 5 1 2-52 1
law of irrevers i b i l ity, 27, 30-3 1 , 62, 589,
629
Lea, i\!lat hcw Carey, 2 1 5, 2 1 7, 2 1 8 ,
294-296
Le G ray, G . , 59, 339, 34 1
Leh mbeck, Donald, 1 40
Leica camera, i n t roduction of, 498
Lemmen, Barbara, 684-689
Lesser, Bria n , 53-57
l etterpress h a l ftone, 694-695
Levenson, G. I . P., 561
Leyshon, W . E . , 246-247
Library of Congress, 2 1 , 26, 38, 40 1 ,
470, 588
Liesegang rings, 143
l i gh t exposure, of dagu erreotypes,
m i n in1ization of, 252
l ight exposure, of s i lver i mages: A N S I
recommendations o n , 1 86, 1 92 ;
A N S I t e s t for effect of. 190- 1 9 1 ,
1 9 1 ; effects of, 4 , 7 , 1 50, 1 80- 185;
and oxidation of polyet hyle ne, 1 76;
Stieglitz collection conditions for,
24; a n d toners, 203
l ight fad i n g of color 1Hi n ts, 458;
accelerated keeping tests,
425-429, 432-433, 473, 474-475,
637; characteristics of, 49 1 , 642;
c h romoge n i c prints, 470; dark
fad i ng and, 459, 638; exh i b i t i o n
l ight levels a n d , 636-637; factors
a ffecting, 4 1 , 574; i n stant prints,
470; a n d motion-picture f i l m
storage, 446-447. See also
mon i toring of print fad i ng
Light I mprcssions Corp . , 465-466
l ight stabi l i ty, of color prints:
acceptable, determi nation of', 472:
autochrome i mages, 505-508, 5 1 9-
520; coati ngs and, 672, 675, 678; o F
c o m m o n c o l o r print materia ls, 460-
469; exhibition l ighting a n d , 459;
H E 1\ D I N G S I N C O N S E H V A T I O N
a n d , 479-480, 480; progress i n , 485 ,
485-486; ra nking of prod ucts by,
475; relationship to dark stab i l i ty,
459; u n p redictability of, 684-685
l ight sta b i l ity, of maskin g dyes. 486
l i g n i n , in kraft papers, 1 3
l i me toni ng, 296
Linen Text.ile frag went (Ta l bot),
665-666, 667
L i p p m a n n , G abriel, 5 1 3-5 1 4
Loe, Dan i e l , 671
Lu ckey, G. W., 202
L u m i Crc, Auguste, 5 1 4-5 1 5
L u m iCre, Louis, 5 1 31 5 1 4-5 1 5, 5 1 6-517,
5 1 8-5 1 9
Lu micrc Com pany, 497, 505, 5 1 2, 5 1 6
L u m icrc process. See a u tochromc
M G a l lery), 3 5 1 , 352, 365-366
mac h i ne processing, a n d res idual
c he m icals, 220
M addox, H i c hard Leach, 2 1 8 , 343
magenta dye: h u 111an sensitivity to
fad i ng i n , 476; i mage sta b i l i ty
technology, 478-4 8 1 , 480; sta b i l ity
of. 427, 430, -f7+ 48 7t, 488
M a l m , C . T., 389
iV l alone, Thomas A . , 1 1 2-1 1 5, 2 1 5, 2 1 7
M a n nsdorfer, 1-1 . H . , 499
Ma1111al of Photographic Cl1e1nistry
( H a rdwick), 1
A Man ual of Pl7.otogra 11hy ( Lea), 294
"The M a n u facture a n d U se of
A l b u m e n Paper" ( He i l ly ) , 306
ma rket For photographs: and conscrva­
t ion. 5 1 , 6 1 , 90, 660; daguerreotypes,
266-267, 269; dating of prints
and, 98; i mage q u a l ity and, 48-49;
insta b i lity of color materials a n d ,
4 5 8 ; and management o F research
l i brary col lect ions, 570; and neglect
of' non markcta b l e images, 49; a n d
security problems, 269; s i lver-based
syste111s, val u ation of, 90
M a rt i n , S . , 429
masking dyes, stabi l i ty of, 486
M aterials Hescarch Laboratory
( Pe n n sylvania State U n ivers ity), 2 7 1
M at h iot, George, 2 1 7
M cCabe, Constance, 68-85, 3 5 1 ,
684-689
M cCa my, Calvin S . , 1 39-146, 148, 50 1 ,
543-544
McCorklc, Ja mes, 74
McCorm ick-Goodhart, M ark H . , 351-
366, 591-607, 626
Mc El hone, J o h n , 669-68 1
M c Ki n ney, Hobert G . , 422-434
measles. See daguerreotype measles;
redox blem i shes
M ecklenburg, M. F. , 626
mclai notype, 692t
M e l n ick, Jack, 555-562
n1cn1ory, photographs as archive of,
59-60, 64n2, 64n3
Me1n11his ( Eggleston ) , 420
n1ercuric ch loride, as b l eac h i ng age n t ,
559
mercuric cya n ide, as bleaching agent,
559
Meserve, Frederick H i l l , 365-366
Meserve Col lection ( National Portrait
Mese rve Collection wet-plate nega­
t i ves: conditi on of, 352-353, 3 53 ,
3 54 , 364; glass corrosion i n , 358-
363, 3 5 9 , 3 6 1 , 365t; va rnish deterio­
ration in, 352, 355-360, 3 56 , 3 5 7
Messier, Pa u l , 68, 98-106, 293, 320-
324, 326, 328, 6 1 4
metal cans, for f i l m storage, 1 4 1 , 445-
446, 447, 453
Metropo l i ta n M useum of' Art, 21, 88,
92, 1 06
Metz, H . J . , 1 34
M ichalski, Stefa n , 670, 6 7 1 , 680
m i croc l i matc e ffect in sca led packages,
600-603, 602, 606
micro-Fade testi ng, 685
micro f i l m : bases For, 394;
discolorat ions on, 1 92; gold toning
of, 54 1 ; residual c hemicals, effect
of, 2 1 0. See also redox b l e mishes
" M i croscopic Spots in Processed
M icro f i l m : Their N a t u re a n d
Prevention" ( H e n n and V\/iest ) , 139
i\ll irrori ng. See silver niirroring
M issouri H i storica l Society, 240, 242,
246, 284, 285, 29on2
M i tchel l , J. W., 1 1 7
moi s t u re : adsorpt ion of by photo­
graph i c papers, 1 -7, 1 72; and a l b u ­
men print deterioration, 3 1 5, 3 1 7,
3 1 7-3 1 8 , 3 1 8 , 3 1 9; a n d c e l l u lose
acetate f i l m , 389; cold sto rage
condensation, 446; e ffect on s i lver

hal ide prints, 2-7, 1 13-1 14; l i l m ­
basc malerials and, 392, 393; glass
t ransition tcn1peraturc of gelatin
and, 595-596, 606; and hydrogen
sulfide action, 228-229; sealed stor­
age contai ners and, 445-446. 447,
453; sheet plastic storage itc111s and,
1 3 ; vinyl su pports and, 39 1 . S e e also
relative h u m id ity
moistu re cond i t ioning methods, for
motion-picture fil m , 453-454
moisture cond i t ioning rates, for
motion-pict ure f i l m , -1-52, 452-453
mold growth, 6, 258-259, 405, 574, 582,
616
Monckhovcn, Desire Charles Emanuel
van , 2 1 5
monitoring o f print Fad i ng, d i rect: case
study, 654-657, 659, 674-675, 676,
677, 678; densitometer calibration,
638, 644-646; l ight exposu re 111ca­
suremenl, as i nadequate, 638; need
for, 637-638, 658, 680; procedure
for, 639-642, 641 , 654-655; recom­
mended l i m its or deterioration,
646-648, 657; research on, 673-674,
675, 676
monitori ng of print Fadi ng, i n d i rect.
See fading monitors
Moor, Angela, 48-52
Moor, I a n L., 48-52
motion-picture can1era, development
of, 385
motion-picture f- i l m : bases for, 394-
395; britt leness and curling i n , -1- 5 1 ,
4 5 1 -452. See also cellu lose acetate
fil m ; cel lu lose n i t rate f i l m ; color
motion-picture film
motion-picture f i l m , cellu lose nitrate:
characteristics of, 37 1 ; degradat ion
losses i n , 388; as fire hazard, 1 0 ,
368, 370, 372, 388; l a s t dates o f
manufocturc, 37o t ; regu lations on
handling and storage of, 370. See
also ce l l u lose n i t rate f-il 111
mounts: for Al fred Stiegl itz collection,
23; and artistic a nd h istorical i nlcg­
rity, 28-29; colored, 687; precau­
t ions regardi ng, 12. 13; preservation
techniques, 29; recommended, 14;
s izes, h istory of, 693t; and stability,
46. See also adhesives
M ueh ler, L. E . , 558, 559
M u nich arch ives, destruction of siker
ime1ges in, 148, 149, 1 53- 1 54
i\� u nson, Douglas, 332-333, 375,
380-382
iV l u rray, John, 336
M usee Camavalet, 58
!V I Hse11111 News, 8
M useum of Modern Art , 2 1 , 1 04, 460
N 555-562
Nadar, F., 339
Nagina Mosq11e, Agra Forl, India
( M u rray), 336
NASA, 57 1 , 584, 653n 1 7
N at ional Archives ( U .S . ) , 1 39, 3 5 1 , 460
National Archives oF Canada. 53, 1 55.
579
National B u reau of Standards, 1 39, 1. 10,
1 4 1 . 220, 250, 59 1
Nat ional Endowment for the Arts, 34
Nat ional Endowment for the
1-1 umanil ies, 1 57
National Gallery, London , 627, 65 1 n6
Nat ional Callery oF Arl ( U .S . ) , 2 1 , 69,
68+ See also S t i eglitz collection
( National Cal lery)
National Callery oF Canada, 669, 670,
613- 674
National Geographic Society, adoption
of autochrome process, 497-498
N a tional Geographic Society
autoc h rome plates: condition or,
499-505, 503, 50-1-; �onservation
research on, 499-505, 5 1 1 ; d iscovery
of, 496; d u p lication oF, 508-5 1 1 ;
storage oF, 498-499
National H istoric Publ ications and
Records Commission, 1 57
National M i c rofi l m Association, 1 40
National M useu 111 Act. 1 57
Nat ional M useum of Denmark, 625
Nat ional Photography Collection, 56
N a tional Portrai t Callery. See Meserve
Collection
Ncblette, C . B., 560
ncgative(s): d u p licate, as identical to
origi nal, 626; l ight stability of mask­
i ng dyes i n , 486; su pport materials,
variety of, 337; wrinkled (chan­
neled) , restoration of, 375-382. See
also cellu lose acetate f i l m ; cell u lose
n itrale f-il m ; glass plale negatives;
polyester Film; wet-plate negatives
Ncgre, Charles, 60, 339
Index
Nettles, Bea, 466
Newh a l l , Beaumont, 2 1 , 250
New York Public Library, 38
New York Un iversity ( Institute or Fine
Arts ) , 88
N iepce, N icephore, 340, 384, 5 1 3
N i e pce d e Saint \liclor, C laude Felix
Able, 340, 384
..
N is h i mura , Douglas W 1 55-1 70,
nitrate plastics (cel l u loid), 369-370
n i t rates, storage environn1ent and, 1 4
n itric oxides, from automobile exhaust,
151
n itroce l l u l ose. See cellulose n i l rate
n i troge n , and yellow discoloration, 208
n itrogen oxides: effect on color
materia ls, 4 9 1 ; effect on si lver
prints, 23 1 , 346
Norris, Debra Hess, 567, 577-585,
6 1 0-6 19
Northeast Document Conservation
Center, 297, 401
notch references, 309
0
O h m u ra , Kunioki, 206-2 10, 232
O'Keeffe, Georgia: conditions for the
Stieglitz collections, 2 1 -25; grant
to Orraca (Jose), 26; and St iegl itz
National Callery collection, 69;
Stieglitz portraits of, 82. 83
optical brighten i ng agents, 99-100
Oral H istory of Photograph
Conservation project, 1 07
Orraca, Jose, 26-33, 35, 586-590
Osaka Expo time capsule, 207
osmium toni ng, 73
Ostroff, Eugene, 8-1 5, 198, 247
oxidation: in albumen prints, 23 1 , 3 1 4-
3 1 6, 3 1 5 , 3 16 , 3 1 9; causes of. 5-7;
gelatin glass transition te111pcrc1t u re
and, 596; of glass p late negatives,
346-347; oxidizing agents, 230-23 1 ;
o F polyethylene, 1 76, 1 77; i n pri nted­
out vs. developed-out in1agcs,
3 1 2-3 1 3 , 3 1 3t; protective treatments
aga inst, 201-202; of RC papers, 1 88,
1 93-1 95, 1 9 4 , 202-203, 208; of si lver
i mages, process of, 1 40, 1 93-195,
208, 209, 229-230, 232, 234. 543.
557, 572; and s ilver m irrori ng, 144;
of' t hiou rea. 288. S e e also gas(es)

destru c tive ol' si lver i mages; redox
blemishes; si lver degradation
ozone: effect on color materials, 49 1 ;
and oxidation o f si lver i mages, 543;
as oxidizing agcnl, 230; storage
environment and. 1 1
p Perri n, Fred H . , 559
Packard, C larence, 490-495
Padfield, T., 625
paint, oil-based: activity of, vs. d rying
t i me, 1 98-199. 1 99 : peroxides from ,
188, 200-20 1 , 2001, 230, 573; storage
environment and. 1 4- 1 5
pallad i u m prints: characteristics of, 7 1 :
d i fficulty o f iden t i fyi ng, 69, 72, 84;
exh i b ition, effects of', 657; exh i b i ­
t i o n l ighting recommendations,
688: identification of, with XH F
analysis, 77-80, 78, 7 9 , 84-85; i ntro­
duction of, 59; printing process,
70-72, 86n6; Stieglitz and, 69
pan notype, identification of. 692t
Pantano, J r .. C. G . , 363
paper prin ts: fadi ng, causes of,
1 1 2- 1 1 5; moist u re adsorption by,
1-7, 1 72; preservat ion problems
a nd procedu res, 9: stabil ity u nder
exhi b ition condi t ions, 672; water­
soaked, treatment of, 54
paper products, f'or photograph
storage: alpha cel l u lose content,
1 4 ; paper enclosures, 404, 581-582;
precautions, 1 3- 1 4
paper supports: residual chemicals i n ,
6, 1 1 ; a n d stabi li ty, 44-46
Parsons, Timothy, 1 71 - 1 86, 192
paste, n1o u n t i ng, 4, 6, 1 1 4
PAT. See Photographic Activity Test
Peabody M useum ( H a rvard
U niversity), 65311 1 7
Peary, Hobert E . , 498, 499
Pennsylva n i a Stale U niversity,
M aterials Hesearch Laboratory, 271
pepper spots, on autochrome plates,
501
Percy, John, 1 1 2-1 1 5
The Pennanence and Care of Color
Photographs (\"1ilhelm), 457
peroxides: From automobile exhaust,
1 5 1 ; and fil a mentary s ilver, 1 93-1 95,
543; from oil-based paints, 1 88,
200--20 1 , 2001, 230, 573; as oxidizing
ll E A D I N G S I N C 0 N S E ll \' 1 1 T I 0 01
agent, 230, 232, 543; papcr­
generated, and redox blemishes,
1 40- 1 4 1 , 144- 1 45, 229-230 :
protective treatments against. 201-
202; storage environment and, 1 1 ,
1 4 ; titanium d ioxide coa t i n gs and,
1 7 1 ; and yellow d i scoloration, 208.
See also hydrogen peroxide
p henolformaldehyde, 1 48 , 1 53-1 54, 230
Philadelphia M useum of Art. 2 1
Photo Conservation Treatment
Catalog, 627-628
Photographic Activity Test ( PAT) ,
1 48 ; detector selection, 1 57- 1 59;
h istory of', 1 55. 1 56, 1 57; i ncubation
condi t ions. optimal, 1 59-1 62, 1 6ot,
1 6 1 1 , 1 62t: pass/fai l l i m i ts, set t i ng
of', 1 64 ; practical appl ication of',
1 67-1 69, 168t, 1 6 9 ; revised standard,
1 57; sandwich pressure, 165, 166t :
and specimen cond i t i o ning, 1 64-
1 65, 1 65t; and specimen thickness,
1 65, 1 66t; for storage materials, 404,
580-58 1 ; test procedure, 167: as
worldwide standard , 1 56
Photograph ic Cliell'l ist ry in 13lach­
and-White and Color Plwtogmpliy
( Eaton), 2 1 2
photographic collections: assessment
of, 578, 582; d iversity of', and
complexity of' conservation, 577;
h a n d l i n g procedures, 578-579;
i nspection of f i lm-based negatives,
579; size of', and complexity oF
conscrvalion, 577; s ize or, and
d i fficu l ty of assessment, 578;
storage environment assess ment
and control, 578 . S e e also research
l ibrary collection(s)
photographic i ndustry: cooperation
with, 26, 587; development of', 60;
research laboratories, contribution
oF, 61, 65n 1 1 ; research on image
permanence, 586-587
The Photogmphic Journal, 298
photographic papers: accelerated aging
studies of', 4 1 3; additives, problems
caused by, 2 1 5-2 16; adsorpt ion
of' hypo, 221, 222; adsorption or
nioisture, 1-7, 1 72; adsorption of
oxidizing gases, 1 50; adsorption of
residual chemicals, 1 1 , 220; back
pri n t i ng on, 1 0 1 - 1 02; history of,
2 1 5-2 161 2 1 9; oxidation of, 1 93-1 95,
1 9-1 ; paper fiber a na lysis, 1 00-J0 1 ,
10+ See also baryta layer; f i ber base
black-and-white papers
photographic papers, dating oF: emerg­
i ng melhods, 102-104; exis t i ng
met hods. 99- 1 02; i n formation­
cxchange foru m , need for, 105-1 06;
l i m i tations oF cu rrent met hods, 102;
reference collections for, 100, 102-
1 03: value and uses of', 98, 104-1 0 5
photographic processes: identification
of'. 72-73, 692t-693t: 19th century,
characteristics of', 69-1-695
Photographic Society of' London. See
Hoyal Photographic Society
photogravure, 60, 688, 69-1-695
photolytic reduction process, 309-3 1 0
photolyt ic si lver, 227, 677-678
photomechanical prints, 468-469, 688
photoreproduclions, exh ibition l ight i ng
recommendations, 686
physically developed silver, 42
pigments, optical properties oF, 1 75,
1 75t
pink-toe l'ade, 430
"Pioneers ol' Photographic Science and
Tec h nology" conf'e rence ( 1 986) , 2 1 2
plasma cleaning See sp11ller cleaning
plast ic(s), gases released by, 1 50
plast ic deformation: i n cyc l i ng between
storage and user enviro n n1ents,
592, 593-594; l i m ited range of, in
cold storage, 597-598; photographic
materials' tolerance for, 599,
625-626; physical rest rai nts, i mpact
of', 593-594. See also d i mensional
stabi l i t�y
plast ic enclosures, 581
plastic su pports, accelerated agi ng
studies on, 408
plat i notype, 694-695 See plathumi
prints
plat i nu m , n1etal lic, as image-forming
su bsta nce, 4 1 , 47, 59, 577
plat inum prints: and cellu lose deterio­
rat i o n , 583; characteristics of, 7 1 ;
d i ffic u l ty of' iden t i fying, 69, 72, 84;
exhibition of, 657, 688; identifica­
tion of', with X H F analysis, 77-80,
78, So, 84-85; pri n t i ng process,
70-72, 86n6; Stieglitz and, 69; s u r­
face cleaning tec h n i q ues, 6 1 3-6 1 4
plat i n u m toni ng, 54 1 , 583

Pobboravsky, I rvi ng, 245-248
Poitras, Pierre, 555-562
polarization test, 696, 698
Polaroid Corporation, 466, 468-469
Polaroid Polacolor prints, 467, 468,
4 70L, 648, 649
Polaroid SX-70 i nstant prints, 466,
470L, 642, 646, 647, 649
polishing materials, embedded i n
daguerreotype su rface, 256, 257
Pollakowski, Goetz, 560
Pollock, Henry, 1 1 2- 1 1 5, 2 1 5
polycarbonate film base, 393, 39-f
polyester f i l m : accelerated aging
stud ies on, 408, 409; A N S I standard
for, 437; dimensional stability of,
438; d i sadvantages of, 402; h istory
or, 392-393, 394, 574; identi fication
of, 696-698; i m provements needed
i n , 395; splicing of, 395; stability of,
-i. 6, 394, 402, 437; storage oF, 452;
uses or, 394-395, 437
polyethylene: l ight stabil ity or, 672;
oxidation of, 1 76 , 1 76; stabil ization
or, 1 78-1 80, 1 79 , 1 79t; structure and
characterist ics of, 1 75- 1 76, 1 76
polyethylene-coated paper. See rcsin­
coatecl ( RC) paper
polyethylene terephthalate. See
polyester
polystyrene base, 391-392, 39-f
polysulfide treatment, and oxidation,
protection aga inst, 573
polyvinyl ch loride base, 39 1
POP. See printing-out paper
Pope, C hester I . , 1 39- 1 46, 1 48 , 50 1 ,
54 3-544, 5 47 , 560
Porter, Mary Kay, 1 59
Portrait of cm American Youth.
(Gurney), 236
potass i u m bromide, protective effect
on s i l ver i mages, 233
potass i u m cyanide: as bleac h i ng agent,
559; for daguerreotype cleani ng,
238-239, 240, 24 1 , 243, 246, 279 ,
279-280; as fixi ng agent, 2 1 5
potass i u m clichromate, a s bleac h i ng
agent, 559, 560
potass i u m fcrricyan icle, as bleach i ng
agent, 559
potassium iodide, protective effect on
si lver i mages, 233
potassium permanganate, as bleaching
agent, 559, 560
potas s i u n1 t hiocyanate, as a ntioxidation
treatment, 202
Pourbaix d iagram, 272, 273
T/1e Print (Adams), 55411 1 9
printed-ou t prints: printing-out paper
( POP), 42, 228, 309, 3 1 7, 540, 54 1
printi ng-out process, 227-228, 3 1 1 -3 1 3,
312, 3 1 3t; colloclion, 687, 69-f-695
processi ng: of albu men prints, 333; of
cellu lose n itrate f i l m , a nd decom­
position rate, 373-374; of color
materials, 223, 430, 458, 460, 479,
493; of color motion-picture fil ms,
443; recreation of, i n conservator
education, 95, 109; of separation
masters, 440; and stabil ity of s ilver
i mages, 1 90- 1 92, 23 1 ; standard
method, in 1 9 th century, 527. See
also development; fi,x ation; water
washing
P u b l i c Archives of Canada, 460, 59 1
p u bl ication programs, as alternat ive to
exh ibits, 6 6 1
pyrocatech i n , 3 4 5
pyroxylin, 369
R 537-538; daguerreotype storage
radi a n t energy testing of color
materials, 425-429
radioactive imaging, for d u p l ication,
626-627
HA I R . See reFlection-absorption
i nfrared ( RA I R ) spectra
Hanclal l , R. F. Y., 1 36
Rantanen, V\/a l ter, 1 00, 1 02-1 03 , 1 04
Ravenswaay, Charles van, 240-24 1 ,
284
Hay, i\1an, 1 00, 102, 1 10
RC. See resin-coated (HC) paper
redevelopment. See bleach i n g and
redevelopment; reprocessing of
gelatin si lver prints
redox blemishes: on autoc h rome
plates, 501-505, 503, 504; causes
of', 222, 543-544; c i rcular ring
pattern in, 143; Factors affecti ng,
1 42 ; history of research on, 1 39- 1 40;
i mage dependence of, 1 43- 1 44 ;
iodide and, 1 4 1 - 1 42; naming of,
145; paper-generated peroxides
and, 1 40- 1 4 1 , 1 44-145, 229-230;
Photographic Activity Test and, 1 57;
precautions aga i n st, 146. See also
Index
daguerreotype measles
reel spots. See reclox blemishes
Reed, Vilia L., 375-379
reFlect ion-absorption i n frared ( HA I H )
spectra, 286-287, 288
Regnault. V., 342
rehousi ng: of a l b u m s and scrapbooks,
582-583; of' daguerreotypes,
a mbrotypes, and t i ntypes, 583-584;
of' f i l m-base materials, 404; of
glass-plate negatives, 582; of
photographic prints, 580-582
Heichenbach, 1-1 . , 385
Heil ly, James iVI . , 40-47, 1 55- 1 70, 2 3 1 ,
306-3 1 9 , 567-576, 577, 588 , 6 5 1 n5,
694-695
Heinholcl, Nancy, 663-666
relat ive h u m i d i ty: vs. absol u te hu mid­
ity, 449; A N S I recommendations
on, 1 86, 1 92 ; in cold storage,
i m pact on i mage stabil ity, 604-605,
604L; and color i mage stabi li ty,
.j 2 1 , 429-430, 460, 573 , 584; and
color motion-picture f i l m storage,
443-446, 444, 448-449, 450-452,
4 5 1 ; and contaminant action, 1 2 ;
and c urli ng of gelatin si lver prints,
and, 258; a nd dark fad ing of color
prints, 458, 4 9 1 , 492; effect on
color motion-picture f i l m , 449-450,
-f)O; effect on resin coated ( HC )
papers, 1 80- 1 8 5 ; effect on silver
fi laments, 1 1 7, 1 1 8- 1 24, 1 23t, 1 24l,
125, 1 34 , 1 90, 543-544; and f i lm-base
materials decomposition, 372-373,
373-374, 403, 4 1 2-4 1 7, 575, 576,
579; and fungus growth , 450; and
gelatin moisture content, 594-595;
and glass plate negatives, 346-347 ,
362; m icrocl i mate effect i n scaled
packages, 600-603, 602, 606; and
oxidation in autochrome plates,
502-503; and paper s u p port con­
traction, 44; and plastic enclosures,
58 1 ; recommendations For, 1 5, 223,
578; and reclox blemishes, 1 4 1 , 1 4 5 ,
1 46 ; and silver degradation, 230,
232, 543, 573; and stain forn1ation
i n color prints, 467; and yel lowi ng
or silver i mages, 229. See also Fluc­
tuating temperature and h u m i d i ty;
moisture
Hempel, Siegfled, 247

reprocessing of ge latin s i lver prints,
545, 546, 550-5 5 1 , 5 5 1 -552, 629
Hesearch Libraries G ro u p (Stanf'ord
U n iversity), 567, 576
research l ibrary collection
conservation: assessment and
cataloging of collect ion, 568, 57 1 ;
fu t u re strategics fo r, 576; i mage vs.
object preservation, 570; selectivity
and, 57c-57 1 ; storage environment
and materials, 568-569, 572-576
res i d u a l chcn1 icals: clean i ng niateri als,
285, 286-287, 288-289, 6 1 1 ; dye
coupl ers, 477-478, 479, 483-484;
effects oF, 6, 2 1 0, 23 1 ; in F il m-base
materials, 6, 1 1 ; on glass plate
negatives, 346; m ac h i ne processing
a n d , 220; i n m i c rofi l m , 2 1 0; opt i m a l
levels of, deter m i n i ng, 2 1 0; paper
adsorption oF, 6, 1 1 , 220; and redox
b l e m ishes, 145: and stabil ity of'
color motion-picture i mages, 443;
and stabil ity o F si lver i mages, 6,
1 1 2- 1 1 4 , 1 89, 546. See also s i lver,
residual; sod i u m t h iosulfote,
res idual
resin-coated ( H C ) paper: accelerated
aging studies on, 1 80- 1 8 5 ; advan­
tages of. 1 74 , 1 74- 1 75, 203-204, 208;
cracking of e m u l sion !aver, 1 76-178,
1 77 , 1 78; cracking o r HC layer, 1 78 .
1 83 , 1 83- 1 84 , 1 84 ; deterioration of,
458; d i splay l i fe, 183, 1 83- 1 85, 1 8-f ,
1 8 5 : exh i b ition l ighti ng, 687; h istory
of, 1 73 ; hypo measurement i n , 223;
i ncorporation oF stabil izer w i t h i n ,
1 95, 1 9 s , 222-223; loss of· p l i a b i l ity
in HC layer, 1 76, 1 78 , 1 83 ; and oil­
based paints, effect or, 1 98- 1 99;
oxidation or, 1 88 , 1 93- 195, 194, 202-
203, 208; polyethyle ne structure and
characteristics, 1 75-1 76, 1 76 ; stabil­
ity of, 191, 1 92 , 536; sta b i l i zation ol·,
1 78- 1 80, 1 79 , 1 79t, 1 84, 1 8-j. ; storage
recom mendations, 1 85-186; and
s u l fi de d i scoloration, 209; t i ta n i u m
d ioxide layer of, 1 75; toning or, 20 1 ,
20 1 , 2 1 0; ye l lowing of, 19 5, 1 9 6 , 2 1 0 .
See also polyethylene
Restaurator ( period ical), 338
restoration : chem ical baths, pol icy
on, 629-630; vs. conservation,
28; debate on va l u e or, 627-630;
in photographs vs. painti ngs and
H E A D I N G S I N C O N S E H V A T I O N
drawings, 50; p u rpose of. 628. See
also conservation; conservation
treat ment(s)
reto uchi ng, 303, 379. 627-628
Heynolds, E. J . , 2 1 6
Hobb, Andrew, 40 1-405, 696-698
Hochester I nsti t u te of Tec h nology. See
I mage Permanence I nstitute
Hock, Joseph, 499
ro l l f i l m syste ms: base core set
properties and, 395; i n trod uction of,
2 1 8 , 384-385
Homer, G ra n t 13. , 1 07- 1 09, 266-270,
648, 6 5 1 n5, 658-662, 670-671
Hoyal Danish Academy o f F i n e Arts,
260
Hoyal Photogra phic Society
( Photographic Society of Londo n ) ,
5 9 , 1 1 2, 2 1 4, 2 1 7 , 2 2 8 , 2 9 8 , 4 5 7 , 53 1 )
634-635, 663
H u ssel l, H . D., 557
s sen si t i z i n g sol u t ion, effect on albumen
safety f ' il m . See ce l l u lose acetate Vil m
St. Denis, H u t h . 498
Sakagu c h i , T., 1 1 7
Salesi n , E. D . , 1 37
sal iva, in s u rface clea n i ng of pri nts,
6 1 7, 62 1 11 1 0
salted paper prints, 42; and ad hesives,
clfcct of1 232-233; bleaching a n d
redevelopment of, 5 5 8 ; characteris­
tics of, 694-695; exhibition, effect
or, 6 7 6, 678, 680; ex h i b ition light i n g
recom mendations, 686, 6 8 8 ; s u rface
c leaning tec h n iques, 6 1 3-6 1 4 ; water
soaking and, 57
salt sta b i l ized prints, l ight sensitivity
oF, 663-666, 667
San Diego H i storical Society, 37
San Diego Save Our Organization , 37
Sandys, Les l i e G., 560
sca n n i ng, d u p l ication of i m ages by, 627
sca n n i ng electron m i c roscopy
( S E iVI ) : cross-section of wet-
plate negative, 353-354, 3 5 5 ; of
dagu erreotype measles, 247, 248;
of electroclean i n g res u l ts, 275, 278,
279; of hydrogen plasma-treated
daguerreotypes, 262, 263 , 264 ; of
M eserve Col lection collodion wet­
pl ate negatives, 356-357. See also
electron m i c rographs
Schafer, H . K . , 4-12
Schellen berg, i\11 . , 499
Sc h i l l i ng, 1 3 . , 1 34- 135, 136
' The Science, Tec h n ology and
Treatment of Albumen
Photographs·; (Web site), 293
scrapbooks, re housing or, 582-583
sealed packages: for cold storage,
584: for color motion-pic t u re f i l m ,
445-446, 447, 448-449, 453 · 454;
daguerreotype case sea l , and i m age
sta b i l ity, 245, 252, 253, 259, 267;
for F i l m - base materials, 409, 4 1 1 ,
4 1 4-4 1 6 ; m icroc l i mate effect i n ,
600-603, 602, 606; a n d moisture ,
445-446, 4 4 7 , 453
secondary s u pports, and i mage
stab i l i ty, 46
sel d'or ton ing, and d a m p a i r, clTcct or,
3, 4, 5
selen i u m ton i ng, 2 1 0, 54 1
S E iVI . See sca n n i ng electron
m i croscopy
print grain-size distribulion, 3 1 0 ,
3 1 0-3 1 1 , 3 1 1
sensitometric tablets, 424, 432
separation masters: for color motion­
pict u re Vilm preservation, 438-
442, 448; for color photograph
preservation. 42 1 ; l i m itations of,
460; movie fi l m aging s h r i n kage
a n d , 437-438, -JJ S ; printing and
processing oF, 439-440, -J.4 1 , 44 1 -
++2; printing fro n1 , 437-.4J 8, 439;
storage or, 440, 448, 450
Sergeant, C h ristopher, 555-562
S E H S . See S u rface Enha nced Haman
Spectroscopy
Seton, Tho mas, 2 1 5
Severso n , Douglas G . , 65 1 11 5 , 654-657,
658, 659, 660-66 1 , 670-67 1 , 680
Seyewetz, A., 345, 5 1 7-5 1 8, 5 1 8
Shadbolt, G e o . , 1 1 2-1 1 5, 2 1 7
Shaha n i , C., 4 1 3
Shawn, Ted , 498
sheet f i l m s , 394, 575
sheet plastics, preca utio ns Fo r, 1 3
S h u l l , H e n ry A., 499
Siege l , Hobin, 499
si lver, meta l l i c , as i mage-Forming
su bstance, 42, 577
si lver, reactivity with t h i o u rea, 287-288
si lver, res i d u a l : common levels oF,

551-552; effects or, I I 3- 1 1 .j , 1 90 , 1 9 1 ,
1 92, +10, 546: preserva tion problems
and procedures, 9: re111oval of'. 546:
test ror, 1 5n 2 , 5-16-548, 549; u neven
d i s t ri b u t ion of, 547
s i lver bron1 idc, as i mage-form i ng sub­
stance, 1 1 6- 1 1 7, 1 22- 1 27, 1 32, 1 3-1,
2 1 8, 227. 229, 342-344. 5 1 9, 536, 548
s i lver c h loride: as i111age-f'o r111 ing
su bstance, r 1 6- 1 17, 1 34 , 1 90 ,
2 1 8 , 298, 309-3 1 0 . 3 4 4 , 54 1 ; and
photolytic red uction process i n
a l b u 111cn p r i n t s , 309; as prod uct or
s i lver grain degradat ion, l.. f2, 233,
543; in toning baths, 527
s i lver degradat i o n : in a l b u m e n prints,
3 1 4-3 1 8 , 3 1 5 , 3 1 6, 3 1 7, 3 1 8; i n ge latin
s i lver prints, types of, 542-545;
h istory oF research o n , 59, 228-23 1 ;
p rocess of, q.o, 1 93- 1 95, 208, 209,
229-230, 232. 234, 527, 542-543,
557. 572; s u l ru r and, 544-545. See
a lso deterioration of silve r i mages;
llla111entary s i lver; sta b i l i ty or s i lver
i mages
silver dye b l each prints, cleaning or,
6 1 7-6 1 8
s i lver dye bleach process, 462-463
s i lver ri la111ents. See f i l amentary si lver
s i lver gela t i n . See e11t ries u nder gelatin
s i lver
s i lver halidc(s), as i mage-forming
s u bstance, p, 227-228. See also
..
si lver brornide: s i lver c h l oride; s i lver
iodide
s i lver h a l ide photography: early
research o n , 663-664; efforts to
replace, 59; history of, 2 1 3-223;
obsolescence or, 90, 1 08, 1 09;
photogra phers' enthusiastic
response to, 2 1 3 : stability of, 20]:
tradeoff between pe rmane nce and
ease or use, 207-208
silve r image structure: in chemiGd
development process, 228; i n
developed-nut prints, 54 1 -542;
early research on, 527-528; i n
ge lat i n s i lver prints, 536, 540-5 p ; ..
i n tensi fication and, 5 5 9 ; i n pri nted­
out prints, 228; and res istance to
s u l ricl i n g and oxidat ion, 1 58- 1 59,
307. See also f i l a rncntary si lver;
s i lver degradat i o n ; stabili ty of silver
images
s i lver i mage structure in a l b u men
prints, 308, 308-3 1 0 ; deterioration
of, 3 1 4-3 1 8, 3 1 5 , 3 1 6, 3 1 7, 3 1 8 ; vs.
developed-o u t prints, 3 1 1-3 1 3, 3 1 2 ,
3 1 3t: effect of s e n s i t i z i n g solution
compos i t io n , 3 1 0 , 3 1 0-3 1 1 , 3 1 1 ; gold
t o n i ng, effects of, 3 1 3-3 1 4 , 3 14 ;
predict i ng cha nges i n , 3 1 6-3 1 8
si lver iodide: a s i n1agc-form i n g
su bstance, 1 1 6, 1 35, 250-252;
protect i ve effect on s ilver i n1ages,
233-234
s i lver mirroring, 1 93- 1 95, 1 94 , 232, 543.
545, 572, 596, 6 1 6, 6 1 7, 629
s i lver n i t rate sensit ization of a l b u 111en
prints, and grain-size distribution,
3 1 0, 3 1 0
si lver n i trate test, 220
s i lver salts, sol uble, detection or,
1 49-1 50
s i lver s u l fide: in daguerreotype
tarn ishes, 253, 254; as prod uct
ol' s i lver gra i n degradation, 543,
544-545; transfer images i n baryta
layer, 230, 234
S i n c l a i r, C o l i n , 2 1 5
Sjogren , A n ker, 260-265
s l i de projectors, color irnage stability
testi ng w i t h , 425-426
S rn i t hsonian I nstitution, 8, 247,
320, 35 1 , 59 1 , 653n 1 7. See also
Conservation A n a lytical Laboraton·
Socicte Fran�aise de c h i 111i e , 526
Socicte Fra n�aisc de photographie, 59,
2 1 4 , 238, 526-529
Society of I 111agi n g Science a n d
Tec hnol ogy, 1 4 8
Society o F Photographic Scient ists a n d
E ngi neers, 2 1 2
sod i u m ch loride: as component i n
sweat, 233: protective effect of, 233:
as st<i b i l izer, 664
sod i u m s u l l'ate, as wash, 22 1
sod i u m thios u l fote ( hypos u l p h i te ;
hypo) : a nd a l b u me n print ton ing,
296; and damp air, effects oF, 3 ,
4-5; i n f- i x i n g of daguerreotypes,
250; h i story of, 2 1 4, 2 1 5, 665; i m por­
tance oF rapid removal, 220; paper
adsorpt i o n of, 22 1 , 222; preservat i o n
problems a n d procedures, 9 ; a n d
redox ble111 i s hes, 1 42, 1 46; sta b i l i ­
z a t i o n or si lver fi la111ents by, 1 1 7,
1 1 8- 1 24, 1 23t, 1 24t, 1 32 , 1 3 5- 1 36, 1 37,
Index
1 90 ; tests for, 1 5 11 1 , 2 1 6-2 17, 223; as
toning bath, and 1·esidual s u l fu r,
527-529
sod i u m thios u l fate, res i d u a l :
appropriate levels o r , 548; baryta
layer rete n t i o n or, 220, 2 2 1 . 547, 549;
common extent or, 552; effects or,
45. 1 9 1 , 1 92. 208. 2 1 0 , 222. 228-229.
254, 346, 440, 532n2, 546; a n<l
l'a d i ng of si lver prints, 1 1 2-1 1 4 ; in
gel a t i n s i lver print layers, 220, 22 1 .
547, 549; h u m i dity and, 550; opt i rn a l
level or, 2 1 0 ; removal or, 546;
testing ror. 220, 546-548; u n even
distribution of, 547
Spcck111 a n , J. A . , 140
spectrophotometry, i n color i mage
sta b i l i ty testi ng, 425
Spencer, D. A . . 2 1 9-220
S p i l ler, J o h n , 62, 2 1 5, 2 1 7-2 1 8
spokiness, of 111otion-pic t u re f i l m , 4 5 1
" S pon ta neous I gn i t ion or Deco111posing
Cel l u lose N i t rate F i l m"
( C u rn m i ngs) , 3 1
S . P. S . E. 1-/andbooh of Photographic
Science and Engi11eeriJJg (Thomas),
54
spu t te r clea n i n g, 271 . 280. 283
stabil ity or color i 111agcs: A N S I stan­
dard for, 422; balancing oF, w i t h
o t h e r factors, 47 1-472; i mage stab i l ­
ity technology, 476-488: i n stabil ity
at room tempera t u re. 42 1 : i n stant
prints, 467-468, 486-488, -t87t; and
market for color works, 458; pro­
cessi ng a n d , 430, 443. See also dark
rad i ng or color prints; dark stabil­
ity oF color prints; deterioration of
color prints; l ight fad i ng of color
prints; light sta b i l i ty, of color prints;
stab i l i ty test ing for color i mages
sta b i l i ty of daguerreotypes. case sea l
a nd , 245, 252, 253, 259, 267
stabil ity ol' s i lver i mages: al'tcr
bleac h i ng and redevelop111ent, 56 1 -
562; A N S l -ddi ned levels of, 1 90 ;
and early history of photograp hy,
526-527; fingerp rints and, 233;
h istory oF research o n , 59-60,
2 1 4-2 1 5 , 2 1 6-2 1 7, 2 1 9-22 1 , 22 1-222;
pri nted-out vs. developed i mages,
228; processing and, 1 90- 1 92 , 23 1 :
protect ive treatments, 201-202,
222; res idual c he111 icals, eFFects oF,

6, 1 1 2-1 1 4, 1 89, 546 ; su periority oF,
207; tradeoff between ease oF use
and, 207-208. See also deterioration
oF s i lver i mages; light exposure, of
s i lver i 1nages
sta b i l ity testing for color i mages:
con1 b i ncd rad i a n l e n ergy, heal a n d
h u m i dity testi ng, 4 2 9 ; correlating
with real-world conditions, 423,
428- pg. 43 1 ; history of, 457; i n1age
...
s ta b i l i ty vs. dye sta b i l i ty, 424; by
Kodak, 422-434; objectives of, 423;
procedures. 424-433; reporti n g of
data, 430-43 1 . See also accelerated
kee p i n g tests, for color i mages
sta b i l ization process, identificat i o n of
prints processed by, 548
sta i n detector for PAT ( Photographic
Activity Test): optimal i ncubation
conditions, determ i nation oF. 1 60-
1 62, 1 62t; pass/Fa i l l i m its, set t i ng
of', 1 64 ; pract ical appli cation of',
1 67-1 69, 1 68t: selection of', 1 59
Stanford U n iversity. Hesearch Libraries
Group, 567, 576
starc h , mounti ng, 4, 6, 46
Stenger, Erich, 558
step registration printi ng, 439
Stiegl i tz, Alfred: o n a u tochrome, 497;
O'Kee lfe's conditions For col lections
oF, 2 1 -25; processes a n d materials
used by, 69, 7 1 -72, 73
S t iegl i tz collection ( National Gallery),
XHF a n alysis of': reference
standards for, 73-74, 7 7-80, 78, 79,
So; resu l t s of, 80-83. 81, 82, 83 , 84
storage: A i\ S I standards on, 1 56,
1 85- 1 86. 1 92, 203, 436-437, 452,
543, 580-58 1 , 625; of' autochrome
i m ages, 508, 5 1 1 ; basic recom men­
dations for, 605-606; of ce l l u lose
acetate F d n1 , 4 1 0-4 1 1 , 4 1 1-4 1 2 ,
452, 573, 575, 576, 579; o f ce l l u l ose
n i t rate fi l m , 368, 372, 389, 437, 573,
575, 576, 579; of' color materials,
42 1 , 435, 460, 474, 490, 573-574,
584, 637, 647-648, 653 n 1 9 ; of' color
motion-picture f l l m , 443-452, 444,
450, 4 5 1 ; of' daguerreotypes, 252,
258, 268-269; of' f i l m-base materi­
a ls, 403-404. 409-4 1 0 ; of' ge la t i n
s i lver prints, 543, 574; o f glass plate
negatives, 573; i m proving, as best
conservation trcatn1ent, 55 1 , 553; of
732
H E 1\ D I N G S I N C O N S E B V A T I O i\1
Nati onal Geographic Society a u to­
c h rome p lates, 498-499; oxid izing
agents and, 235; for p holographic
collections, assess ment and con­
trol of', 578: of' polyester f i l m , 452;
recommendations for, 223; records
on, i mportance of, 1 4 6 ; for research
l i b rary collections, 572-576; of' sep­
aration masters, 440, 448, 450
sto rage at mosphere: f'or albumen
prints, 3 1 9; f'or color motion-
picture f i l m , 447-448, 448-449,
450-452, 4 5 1 ; and dark Fad i ng of'
color materia ls, 49 1 ; dust and d i rt
and, 448, 578; f'actors other than
i mage sta b i l i l y i n , 600; ge lal i n
moisture conte n t , as !'u nction of'
tem perature and h u m id ity, 594-595:
glass t ra nsilion lemperature of'
ge lat i n , factors affecti ng, 595-596,
606; hannful su bsla nces i n , 1 1 , 1 3,
14-15, 578; i nert gas slorage, For
color movie I l l ms, 448; oxidants,
re111oval of, 258; s u l fu r gases,
removal of', 258. See also cold
storage; cold storage, time spent
outside of; F l uctuating tempera t u re
and h u m i dity; gas( es) destructive
of' s i lver images; relative h u m i d ity;
tc111pcraturc
.
Storage G u ide fol' Colo, Pl10tograpl1ic
Malel'ials ( I P I ) , 408, 409
storage 111aterials: archive-qual ity, i nad­
equacy of, 50, 1 68-1 70 ; assess ment
of', 1 46, 1 48, 1 67- 1 70, 1 68t, 404, 545'
580-58 1 ; for color motion-pict u re
f i l ms, 447; conta m i n a n t s i n , 1 1- 1 4 ;
and deteriora t i o n , 580; effect o n
ce l l u lose acetate r i l m , 4 1 2; metal
cans, for film storage, 1 4 1 , 445-446,
447, 453; paper products, gases
released by, 140- 1 4 1 , 1 42, 1 44- 1 4 5 ,
1 53- 1 54, 229-230; paper prod ucts,
types and stan dards for, 1 3- 1 4 ;
l'or research l i brary collections,
568-569; sheet plastics, 1 3 ; su lfur
in, 544-545. See also adhesives; f i l m
ree l s ; P hotogra phic Activity Test;
re housi ng; scaled packages
Stoughton, Cec i l , 641
S t u l i k, Dusan, 103
s u l fide: discolora t i o n of silver i mages
f'rom , 208-209, 209t, 307, 544 ;
stabil izat ion of' filamentary s i lver
with, 542; toning by, and oxidati o n ,
210
s u l fu r: i n adhesives, 46; a n d
dagu erreotype storage, 9; extrin s i c
sou res of', 544-545; i n herent
a m o u n t i n egg w h ites, 298; and
s i l ve r degradation, 543, 544-545 ;
i n storage materi a l s , 544-545; a n d
tarnishing o f ' daguerreotypes, 245;
and yel lowi ng o f s i lver i m ages, 229
s u !Furation: as antioxidation treatn1ent,
1 42, 202; causes of', 208; effects of,
3-4, 5 , 7, 1 42, 544-545
s u l fu r oxides: e ffect on color materi a l s ,
4 9 1 ; a n d oxidation o f ' s i lver i m ages,
543; storage environ111cnt and, 1 1 ,
1 3 , 1 4 ; and yellow d i scoloration, 208
s u l f'ur ton i ng, 296, 541
s u n l ight. color image stab i l i ty tes t i ng
u n der, 428-429
supports: for color f i l m , density
cha nges with t i me , 423-424; For
color pri nts, deterioration oF, 458;
common 111aterials for, 577, 592;
core set properties of, 395; cu rrent
techno logy, 393-395; desirable
characteristics of, 387, 388;
Flexi ble, i n t roduction of, 384-385;
for m i c rofi l m , 394; necessity of,
383-384; non -paper, most pop u l a r,
9 1 ; non- plastic, history of', 384-385;
polyester, h i story of, 392-393, 394;
secondary, surface cleaning of,
6 1 2, 62on7; and stability, 44-46, 47,
50; u n iversa l , i m possi b i l ity of', 395;
vinyl, h istory of, 390-392. See also
specific rn pporls
su rface c leani ng: eva l u ation and
lcsting prior to, 6 1 0-6 1 1 , 6 1 2; goals
of', 6 1 1 ; need for research o n ,
6 1 9 ; residual c l e a n i n g materi a l s ,
effects of, 28s, 286-287, 288-289,
6 1 1 ; risks a nd benefits of', 6 1 1 , 6 1 2 .
See also daguerreotype cleani ng;
c l cctrocleaning
su rface clea n i ng tec h niques: albumen
pri nts, 6 1 4-6 1 5 ; cho ice of', factors
i n , 6 1 1 , 62o n4; collodion ch loride
prints, 6 1 5-6 1 6; color print materi­
als, contem porary, 6 1 7-6 1 8; gel a t i n
dry-plate negatives, 6 1 8-619; gela­
tin s i lver prints, 6 1 6-6 1 7; general
procedures, 6 1 2; p l a t i n u m pri nts,
6 1 3-6 1 4 ; salted paper, 6 1 3-6 1 4

S u rface E nhanced Ra111an
Spectroscopy ( S E R S ) , 287-288
S utton , Tho111as, 2 1 7
Swan, Alice, 247, 249-259, 3 2 1 , 328,
53 o-53 1 ' 533-553
T 288-289; uses of, 253-256
Tal bot, 'v\/ill ia111 H e n ry Fox, 59, 2 1 3-
223, 337, 339, 663-666, 667
talbotypes, preservat ion problems and
procedures, 9
T a u penot process, 343
tear(s), in a l b u 111en prints, repair of,
3°3
temperature: A N S I reco111111endations
on, 1 86, 192; and cellu lose acetate
f i l m deterioration, 4 1 1-4 1 2, 4 1 2-4 13,
4 1 5-4 1 7 , 575, 576; and cel l u lose
n i t rate film deterioration, 372-373,
575, 576; and color i111age stab i l ity,
..p9-430, 435, 573-574, 584: and
color 111otion-picture fi l 111 stability,
444, 445-++6; and conta111 i n a n t
action, 1 2 ; for daguerreolype
storage, 258; and dark Fading of
color prints, 458, 473-474, 474,
474t, 4 9 1 , 492-494; and effect of
thiocyanate and c hloride solution
on si lver f ila111ents, 1 3 1 , 132; effect
on resin coated ( RC) papers,
1 80-1 85; effect on si lver fila111ents
deterioration, 1 21 - 1 22, 1 22, 1 90;
for fil 111-base 111aterial storage,
403; and gelatin moisture content,
594-595; and 111oisture content of
color motion-picture fi l m , 449-450,
-150; and rate of c he111ical reactions
(Arrhenius equations), 180, 435,
4 9 1 -492; and rate of moisture
conditioning in 111otion-picture
f i l m , 453, --153; recommendations
for, 1 5, 223; and rcdox blemishes,
1 45, 146; and si lver i 111age stabil ity,
573; Stieglitz collection conditions
for, 2+ See also accelerated aging
studies; Fl uctuating te111perature
and h u 111idit)'
th iocyanate, 1 1 7, 1 26-132, 127, 1 29, 1 33t,
1 34-137, 1 90, 543
t h i o u rca: in a n i m a l glue, 233; as
oxidizing agent, 233, 288; reactivity
with si lver, 287-288; as stabilizer,
202, 288
thiourea c leani n g solutions for
daguerreot)1>es, 240-24 1 , 242-244;
da111age caused by, 246-247, 285,
289-290; form ula for, 24 1 , 253,
290112; h istory of, 284; research on,
2 8 5; residual thiourea breakdown
products on surface, 285, 286-287,
Thompson's Seedless Grapes (Watkins),
292
Thomson, Garry, 6 5 1 n 6
t i111e-weighted preservation i ndex
(TWPI ) , 4 1 3, 4 1 6, 4 1 7
t i n t)1>es, 56, 384, 583-584, 687, 692t;
hydrogen plasma lreat111ent of, 264
t i t a n i u m dioxide (Ti02), 1 75, 1 76, 1 77
Tom, Ben L,, 555-562
t o n ing: oF a l b u me n prints, 2 1 4, 2 16,
296; and damp air, effects of, 3-4,
5; oF developi ng-out papers, 54 1 ;
hypo adsorption by paper and,
222; with hyposu l fite and acetic
acid or s ilver c hloride, 527-529;
and oxidation, protect ion agai n st,
-
20 1 , 2 0 1 202, 203, 629; of printing­
out papers, 54 1 . See also specific
11rocesses
Topics in Phot.ographic Preservation, 1 07
Torigoe, J\llasaaki , 206-2 10, 232
Toropoff, T , 134
Torrington (Connecticut) H i storical
Society, 285
Townshend, Frederic, 2 1 6
t ransmission electron m icroscopy: i n
analysis o F i mage stru c t u re, 85; oF
oxidized emulsion area, 1 95, 196;
of s ilver degradation, 232; of si lver
f ilaments, 189. See also electron
micrographs
Trentel111an, Karen, 325-335
Tri p henol Phosphate, 32
trithionate toning, of albumen prints,
296
Tu i te, Robert ]. , 47 1-488
Tumosa, C, S , , 626
tungsten lighting: color i mage stabil ity
test i ng u nder, 425-426, 427-428; oF
exhibitions, 637, 655, 666, 675, 68 1
t u rpenti ne, oxidizing properties of, 6-7
T'v\/P I . See t i111e-weighted preservation
i n dex
733
Index
u
u ltrasonic cleaning of' daguerreotypes,
damage fron1, 282, 282-283
U n iversal Exposition, 60, 5 1 5
U niversity o f Ch icago, 3 1
U niversity o f Delaware. See
'v\/interthur/Un iversity oF Delaware
Program in Art Conservation
U n i versity of Lou isville Photographic
Archives, 397
U pton, John, 648
urani u m toni ng, 7 1 , 73, So, 541
u l tra violet bleach i ng, oF albumen
prints, 302
u ltra violet exa111ination of
photographs. See optical
brightening agents
v
Vai llat, Eugene, 238-239
Van Dam, 'J'heodore, 2 3 1 , 306-3 1 9
Vanselo1vv, \A/., 2 02, 233
varnish: on autochromc prints, 5 1 9 ,
520; a n d damp a i r, effects of, 4, 7 ;
deterioration of, 346; effects of, 1 2 ,
1 1 4: of glass p late negatives, 342,
345, 346
varn i s h , on collodion wet-plate nega­
tives, 353, 355-356; deterioration
process i n , 352, 356-358; FTIH
analysis oF, 355-358, 3 56 , 357; glass
substrate as source of deterioration
i n , 358-360, 3 59; S E NI analysis of,
356-357
Vericolor f i l m , image stab i l i ty i n , 483,
485, 485t, 495
Vil le de Paris, 58
vinegar syndrome, in cellu lose acetate
film, 409-4 1 2 See also cel l u lose
acetate fil111 decay
vinyl su pports, history of', 390-392
Vitale, Ti mothy. 293, 320-324, 326,
328, 6 1 4
w
Wagner, Sarah S., 684-689
.
Wal l , E .J . , 558
Ware, M i ke, 630
'v\/arwick, A. N , , 2 1 9
wash i ng aids, 549
VVatern1an, S. E . , 386, 387
water-resistant papers, history of,
1 72- 1 7 3

water-soaked photographs, trea tment
of. 53-57 56 t . 405
·
water wash i ng: of a l b u me n prints,
302; oF cellu lose nitrate film, and
sta b i l i ty. 373-374; of color f i l ms,
and stabil ity. 430; i n dague rreotype
cleani ng. 282, 282-283: of d u p l icate
f i l m s , 33; h i story of' research on,
2 1 9-220; methods. history of, 2 1 6 ;
o f si lver i mages. a n d stab i l i ty, 3-4,
5, 6 . 9, 1 6 11 3 , 1 1 3 , 1 1 5, 1 90; standard s
for, 22 1 ; L i m e req u i red For, efforts lo
red uce, 221
\"la t k i n s, Carleton, 292
wave le ngth d i spersive electron
m icroprobc a nalysis, of glass
s u pports. 360, 360-36 1 , 365 t
wax coat i n gs, 4, 6-7, 672. 675, 678
..
We i nstein, Roben f\ 37-39, 692-693
Wen tzel, Vol kmar I \ . . 496, 498-499
West. Ll ovd E . 422-434 . 435-454 , 443,
.
490
\Ncslon, N . E., 1 43
wet-plate negatives, 34 1 -342: a l b u me n
papers a n d , 293; H rady"s u s e of,
352; cross-section oF. 353-354,
355: deterioration . causes or.
346: history of, 2 1 3, 2 1 4 , 2 1 5, 384;
rehou s i n g of, 582: storage of, 56 :
varnish o n , 353, 355-356: and water
soaking, 55-56, 57. See a l.�o M eserve
Col lect ion wet-plate negatives
Weydc, E d i t h : i n n u cnce of, 1 55 , 1 58 :
on oxid izing gases. 1 4 8- 1 54, 1 89 ,
5 4 3 : on restoration o F colloidal
si lver spots, 1 54 , 202; on s i lver
deterioration, 1 1 6- 1 1 7, 1 34, 230, 3 1 5-
3 1 6 , 50 1 , 557: on si lver m i rroring.
629; on was h i ng, 221
734
B 1:: 1\ D I ;� C S I N C 0 N � E H \' r\ T I 0 N
Tl1e Whisper of the Muse (Camero n ) ,
524
White. D. R . , 1 4 3
Wh ite, V\l i l l i a m B . , 27 1-283
\•V hi tmorc. Pau l , 685
\•\ liede m a n n , H. E., 240
Wiest, D. G . , 1 39, 1 40, 1 4 1 , 1 48 , 229,
5oi , 543
Wi ley, F . E., 39 1
Wiley, R . E., 1 4 0
W i l h e l m , H e n ry, 33. 457-470, 636-649,
654-655, 657, 673, 679
W i l l iams, f\. L., 436, -143
W i l l is , W. , 73
Winfield, J. H . , 392
\Nintert h u r/Un iversity ol" Delaware
Program in Art Conservation, 26,
89, 40 1 , 586-587, 6 1 0, 6 1 5, 62 1 n 1 4
Witkin G a l lery ( New York). 466
\�lo l bers. Richard , 6221120
woodbu rytypes, 687, 689, 694-695
x on, 2 1 7-2 1 8 ; h u n1 icl i ty and, 229;
xenon-arc l i ghti ng, color image stabil ity
test ing u n der, 428-429
x-ray R i m , r o , 370, 37ot , 393
x- ray Fl uorescence spectrometry ( X R F ) :
i n d a t i n g of photographic pape1·s.
1 03-10-J; i nterpretation o f data, 75-
76, 76; l i mitations or, 85, 87n23; as
nondestruct ive tec h n i que, 68, 72-
73; proced u re for, 76-77: process,
overview of, 74-75, 75; refere nce
standards for, 73-74, 1 03 : resu lts or
refere nce sta ndard am1lysis, 77-80,
78, 79. So; secondary target, varying
of, 79-80: usefu l n ess or, 72-73.
83-85. See also St iegl ilJ. collect i o n
( N ational G a l lery), X H F a nalysis ol"
X R F . See x-ray f l uorescence
spectrometry
y
Yaga m i , S h u nzo, 206-2 10, 232
yellow dye: h u ma n sensit ivity to fad i ng
i n , 476; h u m idity a n d , 492; hydroly­
zation of", 49 1 ; i m age stabil ity tech­
n o logy, 4 8 1 , 4 8 1 -483, 483 L ; sta b i l ity
of, 430, 474, 483 L , 487t
ye l lowi ng of a l b u me n prints, 43, 62,
2 1 7-2 1 8 , 294-296, 298, 302. 3 1 7, 468
yel l owing of cel l u lose n i trate f i l m , 1 0
yel l owi ng o r color prints, 459, 466,
478-479, 636
ye l lowing or glass plate negatives,
346-347
yel l owing oF si lver prints: causes oF,
1 1 , 1 34, 1 42, 208-2 1 0, 209, 209t,
228-229, 543-544, 572; fi ber base
papers, 1 95, 196; h i story of" research
hypos u l fite fixing and, 528-529;
process ing, i n adequate, and, 549;
removal of, 529 ; res i n -coated ( RC )
papers, 1 95, 1 96, 2 1 0 ; s u lfu r a n d ,
544-545
yield poi n t , temperature and h u mid ity
nucluations and, 593-594
"Young America: The Daguerreotypes
ol" Sout hworth & Hawes"
(exhib i tion, 2005hoo6) , 266
z
Z u i dema, J. W .. 442
 K O D A K Rapid KODAK KODAK
Untreated Sele n i u m T o n e r PO L Y - T O N E R Sep i a Toner

Reference
Print