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Archaeological Conservation Using Polymers PDF
Archaeological Conservation Using Polymers PDF
Texas A&M University Anthropology Series
D. Gentry Steele, General Editor
Archaeological
Conservation
Using Polymers
Practical Applications
for Organic Artifact
Stabilization
.
Foreword by J. M. Klosowski
•
Copyright ©
by C. Wayne Smith
Manufactured in the
United States of America
All rights reserved
First edition
Smith, C. Wayne.
Archaeological conservation using polymers : prac-
tical applicatons for organic artifact stabilization /
C. Wayne Smith.—st ed.
p. cm.—(Texas A&M University anthropology
series ; no. )
Includes index.
--- (alk. paper)—
--- (pbk. : alk. paper)
. Antiquities—Collecton and preservation.
. Archaeology—Methodology. . Archaeological
chemistry. . Polymers. I. Title. II. Series.
.
.'—dc
To Helen,
Foreword by J. M . Klosowski, ix
Acknowledgments, xm
Introduction, 3
CHAPTER
1 Laboratory Setup, 7
Major Instrumentation, 7
Small Necessities in the Laboratory, 8
Chemicals, 9
2 Baseline Mechanisms, 13
Dowel Experiment, 13
Mass Spectrographic Analysis of Out-Gases Created from the
Dehydration of Archaeological Wood Samples, 17
3 Archaeological Wood, 21
The Challenge of Conserving Waterlogged Wood, 21
Degradation and Shrinkage, 22
Waterlogged Wood from Saltwater Environments, 22
Case Study: Waterlogged Wooden Buttons with and without
Associated Thread, 26
Dry-Site Artifacts—Dry and Desiccated Wood, 28
Reprocessing and Stabilization of PEG-Treated Wood, 30
Tongue Depressor Experiment, 31
Case Study: Re-treatment of Two PEG-Treated Sabots, 40
Re-treatment of PEG-Treated Waterlogged Wood, 43
Case Study: Treatment of Waterlogged Wood Using Hydrolyzable,
Multifunctional Alkoxysilane Polymers, 45
4 Leather Preservation, 60
Archaeological Leather, 60
Cleaning, 62
Chemical Cleaning, 62
Treatment of Leather, 62
PEG/Air-Drying Treatments, 63
Freeze-Drying PEG-Treated Artifacts, 64
PEG and Other Polymers, 65
Passivation Polymer Processes, 66
Case Study: A Successful Treatment Strategy for a Waterlogged Shoe, 66
Passivation Polymer Treatment for Dessicated Leather, 69
An Effective Treatment for Dry Leather, 70
Suggestions for Treating Leather between Sheets of Glass, 72
Storage and Display of Leather Artifacts, 72
5 Composite Artifacts, 74
Case Study: Preservation of a Composite Artifact Containing Basketry
viii and Iron Shot, 74
6 Cordage and Textiles, 81
CONTENTS New Techniques for the Preservation of Waterlogged Rope, 81
Silicone Treatment Strategies, 82
Frankfurter Method of Rope Preservation, 82
Treating Waterlogged Rope in a Nonpolar Suspension Medium, 82
Incorporating the Use of Nonpolar Suspension Mediums and Elements
of the Frankfurter Method into “Traditional” Silicone Treatment Strategies, 83
Case Study: La Belle Rope, 83
Case Study: Preservation of Waterlogged Canvas from Port Royal, 90
7 Glass Conservation, 93
Devitrification, 96
Removal of Sulfide Stains from Lead Crystal, 96
Consolidating Waterlogged Glass Using Passivation Polymers, 96
An Effective Silicone Oil Treatment Strategy, 96
Reconstruction, 98
Case Study: Preservation of Seventeenth-Century Glass Using Polymers, 100
Case Study: Preserving Waterlogged Glass and Cork, 108
8 Ivory and Bone, 112
Basic Structural Differences, 112
Equipment Setup for Very Fragile Bone and Ivory, 113
Case Study: Consolidating Friable Bone, 114
Case Study: Ivory from Tantura-B Excavations in Israel, 115
Case Study: Waterlogged Tusks from Western Australia, 116
9 Expanding the Conservation Tool Kit, 119
Computerized Tomography and the Stereolithographic Process, 120
Case Study: Scanning an Encrusted Artifact—CT Scanning Used as a
Diagnostic Tool, 121
New Tools—New Directions in Research, 121
Notes, 125
Index, 127
Foreword
ix
Preservation with reactive chemicals can be mers and cross-linkers to penetrate cell walls
called by many names but the most promi- and then adding catalyst. Each technique has
nent is von Hagen’s term, plastination. Other its advantages.
terms are chemical bulking and reactive fill- Both techniques often require specimen
ing. They are all used to describe the process preparation, or preservation, which might
of coating and impregnating cells with ma- require rinsing them clean and setting the
terials that react with the walls to prevent tissues with formalin solution. Next is the
water from attaching and reacting. In many medium exchange, where water in cells and
cases, we are also talking about filling the cell cavities is exchanged for a more compatible
or opening to prevent collapse. and less reactive medium, usually acetone,
The goal is to place a substance on the but sometimes alcohols. The exchange is con-
cell that reacts to the carbonols (—COH) tinued until most of the water is eliminated.
present on much of the cell surface. Reac- The next step is penetration with reactive
tive silanes (cross-linkers) are particularly materials. The classic von Hagen procedure
adept at this and can be combined with poly- uses a mixture of a catalyst (typically dibutyl-
mers (carbonol or silanol [—SiOH] ended tindilaurate) and a silanol-ended polymer.
polymers) that also react with the silane This technique involves immersing the ac-
cross-linkers. Thus we have silane cross-link- etone-saturated specimen in a bath of this
ers that react to the cell wall, to each other, mixture under a very slight vacuum and boil-
and to the polymer. Almost always, this re- ing off the acetone with the vacuum to leave
quires one or more catalysts to hasten and little voids that are then filled with polymer/
complete the reactions. catalyst mixture. When the acetone is gone,
We can use very reactive cross-linkers like the cavities are drained of excess solution and
methyltriacetoxysilane MeSi(OCOCH3)3 or a cross- linker, typically tetraethoxysilane
less reactive cross-linkers like methyl- Si(OEt)4, is added. As this penetrates the cavi-
trimethoxysilane MeSi(OCH3)3. Typically, ties, the polymer, cross-linker, and catalyst
when deep penetration into cell walls or body converge and react. The reaction is permit-
cavities is desired, slower-to-react materials ted to continue until it is complete (typically
are used to postpone the reaction until pen- in some heated chamber since often the
etration is fairly complete. Alkoxy functional cross-linker is put into the system from a
(alcohol releasing) cross-linkers are pre- vapor).
ferred, as their reaction to the cell wall or to Our technique uses formalin (if desired)
the polymer usually requires a catalyst. The and acetone to displace water. A mixture of
von Hagen procedure uses a polymer and a polymer and cross-linker is then added to
catalyst to impregnate and coat the cells fol- accomplish cell penetration. The polymer
lowed by the introduction of the cross- and cross-linker mixture is preferable be-
linker. Our technique involves using poly- cause it is more stable than the polymer and
catalyst mixture. Our mixture thus has a . Air exposure yields partial hydrolysis
longer shelf life, and material that is left over followed by condensation:
x or drained from the cavities can be stored and a. SiX + HOH SiOH + HX
reused. The lack of reactivity of the first two b. SiX + SiOH SiOSi + HX
ingredients allows most of the work to be
done at ambient temperature and not in the The work done by C. Wayne Smith, oth-
freezer, providing both an equipment and a ers, and me concerns the investigation of
time advantage. different combinations of cross-linkers, poly-
The next step is the addition of the third mers, and catalysts, along with variations in
ingredient, the catalyst. Dibutyltindiacetate the exposure techniques. For instance, in
is preferred to dilaureate because the dia- most of Dr. Smith’s work we use methyl-
cetate, being smaller, penetrates cells faster. trimethoxysilane MeSi(OMe)3 as the cross-
Typically, catalyst is painted on the surface linker instead of the tetramethoxysilane
and rinsed through open cavities, putting a Si(OEt) 4 favored by von Hagen. The
maximum catalyst dose at the surfaces to MeSi(OMe)3 is only trifunctional while the
enhance penetration. The specimen is then ethylorthosilicate is tetrafunctional: using
put out in the air to cure. The cure in the von MeSi(OMe)3 thus yields a lesser cross-link
Hagen procedure takes place when the cross- density and a more pliable specimen. The
linker penetrates the system. The von Hagen remainder of the procedure is like cooking:
procedure could also use the painting or dip- ingredients are mixed and matched to achieve
ping technique to expose the specimen to this a desired effect. To get a more pliable, leath-
third ingredient (the cross-linker), but that ery touch, use a trifunctional cross-linker and
might require a posttreatment procedure of a higher molecular weight polymer. To get a
exposing the specimen to air. Our procedure less leathery, stiffer touch, several procedures
exposes the specimen to air to bring it into can be performed: add more cross-linker to
contact with the water in the air to allow ex- the polymer/cross-linker mix to get some in-
cess cross-linker to react. Our method uses situ formed resin in the system; use a
an excess of cross-linker whereas von Hagen’s tetrafunctional cross-linker; use a lower mo-
does not; the water in the air completes the lecular weight polymer; or use some combi-
reaction. Our mostly room temperature pro- nation of these procedures.
cedure adds cross-linkers to polymers in the In addition to the variations in the func-
initial step and postpones the use of the tionality of the cross-linker and length of the
smaller catalyst to the final step. The proce- polymer chain, there are also variations in the
dure is relatively quick. The specimens can catalysts that can be used. The workhorse
usually be allowed to cure in the air after one catalyst for our purposes is dibutyl-
or two weeks. tindiacetate. However, this is a forever active
The following equations illustrate the cure catalyst, and the system is forever equilibrat-
reactions: ing; this also happens with the dibutyl-
tindilaurate generally used with the von
. The reaction to the cell wall is SiX + Hagen procedure. Divalent tin catalysts yield
HOC SiOC — + HX X = alkoxy a nonequilibrating system because they even-
. The reaction to the polymers is SiX + tually become noncatalytic tin oxide, but they
HOSi SiOSi — + HX are difficult to use because they hydrolyze and
. The reaction with an excess of cross- lose activity if excess water is present or if
linker and insufficient water is SiX + SiX ø no the catalyst is prematurely introduced. They
reaction are best reserved for special situations.
Titanate catalysts are another possibility, to give good penetration of cells and cavities
but again their high reactivity makes for diffi- and to sufficiently complete reactions to pre-
culty in use, so they are also best reserved for vent degradation. Science also provides some xi
special situations. The polymers, cross-link- order of additions that favor penetration and
ers, and catalysts used with silicone sealants the various combinations to give the tough-
are the types of materials that can be used in ness when needed. Art is needed to choose
preservation. However, in preservation, we acceptable combinations to give the desired
can and do sometimes use no polymer, just effects to all manner of things one might wish
catalysts and cross-linker. It is an especially to preserve, such as skin, hair, glass, wood,
effective way to preserve old glass retrieved paper, or leather.
from the sea. Only short polymers can be Preservation with reactive chemicals is like
used with glass systems since a leathery touch cooking. The science of cooking provides
is undesirable in this application. This is all nutritious combinations to sustain health,
part of the science of preservation with reac- but the art of cooking provides the combi-
tive chemicals. With glass, polymeric cross- nations that taste good. The science of pres-
linkers are also quite useful. With hair, and ervation yields many combinations that will
hide with hair, one often wants to rinse out penetrate and preserve, but artistry deter-
the preservation chemicals before the cure mines which combination gives the result
proceeds. This is again part of the art of pres- desired in a specific specimen. That art is
ervation with reactive chemicals. what is primarily depicted in this book.
There is an art and a science to preserva-
tion with reactive chemicals, both of which J. M. Klosowski
must be practiced to achieve a desired result. Independent Consultant
Keep this in mind as you read through this and Scientist Emeritus for the
book. Science provides proper combinations Dow Corning Corporation
xii
Acknowledgments
xiii
As a graduate student, I had the great privi- of artifacts, this is irresponsible archaeology.
lege of working with Donny Hamilton at the Delving into their comments more deeply,
Archaeological Preservation Research Labo- however, I was not surprised to learn that lack
ratory at Texas A&M University. In the field of funding was not the sole reason for the
and in the laboratory, I was given the oppor- backlog of artifacts waiting to be conserved.
tunity to excavate and conserve a wide range Lack of knowledge and lack of faith in exist-
of artifacts from nautical excavations at Port ing technologies were key reasons expressed
Royal, Jamaica. It did not take long to see that, for holding off on the preservation of some
to some degree, our conservation efforts were artifacts.
in vain. Since there were no facilities for long- All my mentors have taught me the same
term controlled curation, many artifacts con- valuable lesson: knowledge is not static. Ar-
tinued to deteriorate even after appropriate chaeological chemistry and the development
conservation strategies had been applied. of better conservation solutions have been a
The long-held tenet that all conservation serendipitous adventure, resulting in the
methods had to be reversible also proved trou- awarding of three patents—the first ever
bling to me. As a graduate student, I had ob- awarded in the Department of Anthropol-
served firsthand that, in many situations, at- ogy. While Donny Hamilton, head of the
tempts at first removing bulking agents from Nautical Archaeology Program at Texas A&M
fragile organic artifacts and retreatment us- University, and Jerome Klosowski, senior sci-
ing new conservation methods and materials entist at Dow Corning Corporation, are
resulted in additional damage to the artifacts coinventors of the Passivation Polymer tech-
that I could not justify. I soon found that con- nologies, their contributions have been more
servators from many countries held similar than scientific. I thank them both for their
doubts about the true reversibility of conven- encouragement, scientific visions, and deep-
tional treatment strategies. The most impor- seated belief in this research. I would also like
tant early lesson learned was that there were to thank Ole Crumlin-Pedersen, Senior Re-
very few conventions in the conservation of searcher at the Center for Maritime Archae-
organic artifacts; each artifact presented a ology in Roskilde, Denmark, for bringing the
unique challenge. It became apparent that if problems of long-term stability of PEG-
we were to truly address the conservation edict treated artifacts to my attention. His insights
of long-term well-being of the artifact, have had a tremendous impact on my re-
different treatment methods and materials had search and on the science of maritime archae-
to be devised to ensure long-term survival in ology. Many thanks, also, to Research Coor-
a noncurated environment. dinator Mark Gilberg of the National Center
Lack of funding was also an issue. Archae- for Preservation Technology and Training, for
ologists everywhere said they could not afford supporting initial research in deveoping Pas-
to conserve all the artifacts recovered from sivation Polymer technologies.
their excavations. Apart from the tragic loss The contributions of the extended research
team at Dow Corning Corporation have been forms the unique alchemy of art and chem-
innumerable. I thank Leon Crossman and istry that is the basis of my research.
xiv Arthur Rathjen for championing the cause It is impossible to personally acknowledge
of advancing archaeological chemistry and all the conservators who have contributed to
joint research with Texas A&M University. my research. Your questions, concerns, and
Their generosity and commitment to provid- requests for assistance in the preservation of
ing educational resources for schools and artifacts have been the driving force behind
universities are inspirational. this research. I hope this book answers some
Without the financial support and encour- of your questions. My greater hope, of course,
agement of Woodrow Jones and Ben Crouch, is that this work serves to generate new ques-
both of the College of Liberal Arts, develop- tions and directions in conservation research.
ment of Passivation Polymer technologies Where new insights abound, there is no stasis.
would not have been possible. Their vision
for advancing archaeological chemistry re- C. Wayne Smith
search within the College of Liberal Arts Texas A&M University
Archaeological Conservation Using Polymers
2
Introduction
3
T
he archaeological conservation of highly with which many of these techniques can be
perishable organic matter has always used makes them viable for various conser-
been problematic. In , for example, vation challenges and for laboratories work-
the Texas Historical Commission began ex- ing with limited budgets.
cavating René-Robert Cavelier, Sieur de La In addition to discussing the advantages
Salle’s vessel, La Belle, which sank off the offered using Passivation Polymer technolo-
Texas coast in . The recovery of this ves- gies and materials, I consider a concept sel-
sel has presented a host of unique challenges dom addressed in conservation: artistry.
in conserving wood, basketry, leather, and an Variance in equipment, relative humidity,
assortment of supplies necessary to start a laboratory layout, intended end results, and
colony in the New World. Entombed in the level of expertise are a few variables that play
mud that sealed it from decay for more than an important role in the development of
three centuries, the waterlogged hull and preservation strategies and protocols that
hundreds of thousands of fragile artifacts, work for each technician. The key to consis-
including brain matter in the skull of one tent and aesthetically correct samples using
unfortunate sailor, would have been a futile Passivation Polymers, and indeed all conser-
conservation effort without new preservation vation materials, is a willingness to explore
technologies. treatment parameters and combinations of
The aim of this book is to help conserva- polymers.
tors develop successful treatment strategies In chapter the Archaeological Preser-
for organic materials using Passivation Poly- vation Research Laboratory at Texas A&M
mers. These polymers are part of a series of University is used as a model to illustrate
chemistries and techniques developed at an effective layout for day-to-day conserva-
Texas A&M University to provide efficient tion of small organic artifacts using poly-
and cost-effective conservation strategies for mers. Too often, the entire working budget
the purpose of archaeological preservation. of a conservation facility is spent in the ac-
Museums and historical societies have ex- quisition of elaborate equipment. This is a
pressed the need for durable artifacts used shame since well-trained conservators
in traveling exhibits and interactive displays. should be the first consideration of any labo-
In many cases, traditionally treated artifacts ratory. Accordingly, a short list of essential
cannot withstand the rigors of extended trav- instrumentation is discussed in chapter .
eling and handling. Passivation Polymer– The distinction is made between equipment
treated artifacts are more stable than their needed for conservation of artifacts and
counterparts preserved using older technolo- equipment and necessities for the purpose
gies and can withstand sensible handling ex- of research and development; small neces-
tremely well. These preservation processes are sities and chemicals are also discussed.
not a panacea for all artifacts, but the ease While conducting postdoctoral research at
Dow Corning Corporation, I learned from ing polyethylene glycol (PEG) methods. Con-
professionals how to work effectively and eco- served during a time when PEG technology
4 nomically in the laboratory. Since it seems was new, these artifacts have not fared as well
that all archaeological projects are as artifacts preserved using the well- defined
underfunded and understaffed, these cost- PEG treatment strategies developed in the
saving suggestions can remove some of the latter half of the twentieth century by Per
economic stresses involved in outfitting a Hoffmann, David Grattan, and others. Re-
conservation facility. treatment strategies developed to stabilize
Chapter examines some of the mechani- these difficult artifacts are discussed in a sec-
cal processes used for Passivation Polymer tion entitled “Reprocessing and Stabilization
processing of organic materials from marine of PEG-Treated Wood” and in the case study,
and land sites. Two experiments are provided “The Re-treatment of Two PEG-Treated
to demonstrate water/solvent and solvent/ Sabots.”
polymer exchange processes that are funda- New wood treatment strategies using self-
mental to many of the experiments and case condensing alkoxysilane polymers are cov-
studies throughout the book. In “Dowel Ex- ered in another case study, “Treatment of
periment,” penetration depth of polymers Waterlogged Wood Using Hydrolyzable,
and the presence of water in organic materi- Multifunctional Alkoxysilane Polymers.”
als are discussed. The experiment illustrates These treatment strategies enable the conser-
the relationship between solvent dehydration vator to successfully preserve waterlogged
and time in the treatment of wood. A second wood by introducing an alkoxysilane that, in
experiment, “Mass Spectrographic Analysis the presence of atmospheric moisture, self-
of Out-Gases Created from the Dehydration condenses to form polymers that accurately
of Archaeological Wood Samples,” illustrates maintain the diagnostic attributes of water-
the differences in exchange potential of or- logged wood.
ganic artifacts that have been dehydrated us- Numerous approaches and suggestions for
ing a single solvent dehydration process as the preservation of waterlogged and desic-
compared to combined solvent processing. cated leather are outlined in chapter . Case
Chapter discusses the preservation of studies are offered to demonstrate the adapt-
wooden artifacts using Passivation Polymers ability of the baseline treatment process to
and is divided into two sections: waterlogged accommodate even badly fragmented and
wood and dry-site artifacts. Bacteria, fungi, desiccated artifacts. Important consider-
and the loss of structural integrity can be ations for the storage and display of leather
caused by waterlogging or desiccation from artifacts are also covered.
extreme dryness. Regardless of the object’s One area of great concern for all conser-
archaeological provenance, stabilizing ar- vators is the treatment of composite arti-
chaeological wood is a great challenge for the facts. Often, it is necessary to disassemble
conservator. Mechanical destruction caused an artifact into its component parts prior to
by freeze-thaw cycles in lakes, swamps, and treatment. However, this can damage frag-
bogs may act to accelerate the degradation ile portions of the artifact. Additionally,
of wood. Regardless of what type of degra- structural changes in one or more compo-
dation has occurred in a wooden artifact, nents of the artifact often make the reassem-
Passivation Polymer technologies have proved bly stages of conservation difficult. In chapter
effective in preserving diagnostic attributes. the case study “Preservation of a Composite
Conservators face another challenge: mu- Artifact Containing Basketry and Iron Shot”
seums around the world are filled with arti- details how wicker basketry was stabilized
facts, big and small, that were preserved us- prior to removing heavy layers of concretion
encasing the basket of shot. After the basket preserve sections of ivory tusk from a ship-
was processed in stages, the iron shot that had wreck off the coast of Australia.
been removed from the basket were preserved In chapter I explore some of the new 5
using electrolytic reduction. The ease with tools and technologies that can help conser-
which calcareous material was removed from vators devise more effective conservation
the surfaces of the iron shot and the result- strategies. Until recently, the conservation
ant treatment of the iron suggest that expo- process has been hindered by the inability of
sure to Passivation Polymers may have acted traditional radiographs to supply sufficient
to preserve the iron, arresting surface exfo- data to give the conservator a complete view
liation and pitting up to, and during, treat- of an artifact concealed in a concretion.
ment. Through computerized tomography (CT)
Preservation of cordage and textiles from and computer-aided design (CAD), however,
marine and land sites is discussed in chapter three-dimensional models of artifacts can be
. Numerous conventional treatment strate- created using laser-driven polymerization of
gies adapted for use with polymers are illus- each “slice” of CT data. Stereolithography is
trated in a series of case studies. another technology that is discussed.
It has been argued that glass is not an or- Many conservation materials, considered
ganic substance. While this is true, fluxes used part of the conservation tool kit, are poly-
in the making of ancient glass are organic mers. Research has shown that these materi-
materials, which accounts, in part, for the als, once thought to be reversible, have a ten-
unique chemical structure of ancient glass. dency to cross-link with the organic substrate
Treatment methods, accelerated weathering of the artifacts they were intended to stabi-
testing, and scanning electron microscopic lize. While most of us tend to visualize chem-
analysis of polymer-treated glass are pre- ists in white lab coats when we think of cross-
sented in chapter . Several case studies illus- linked polymers, the process of cross-linking
trate the abilities of alkoxysilane materials to is a natural process. As archaeological chem-
stabilize badly deteriorated glass. Treatment istry plays an ever-increasing role in our dis-
techniques used for preserving extremely thin cipline, research scientists and conservators
sections of onion bottle glass are discussed alike will see the expanding role of polymers
to illustrate the degree of creativity that can in archaeological conservation. The polymer
be employed in the treatment of friable ob- chemists who helped define the initial
jects. Like polyvinyl acetate and other tradi- mechanisms at work in Passivation Polymer
tional treatment strategies, reversibility of processes found the task of adapting their
these treatment methods remains an issue. thinking to fit archaeological perspectives
Data from accelerated weathering and challenging. Though new terms will inevita-
nuclear magnetic resonance imaging experi- bly find their way into the conservation lexi-
ments indicate that such glass remains re- con, I have tried to keep the use of new ter-
markably stable much longer than glass minology to a minimum in this book.
treated using conventional methods. Experience at the Archaeological Preser-
A discussion of ongoing research in the vation Research Laboratory (APRL) at Texas
preservation of badly deteriorated ivory and A&M University has taught us that while
bone from marine and terrestrial sites is the complete reversibility of conservation treat-
focus of chapter . In one case study treat- ments is desirable, it is a state that is some-
ment strategies applied to the preservation times easier philosophized than realized. Re-
of finely carved ivory from the Tantura La- treatability may be a more realistic end goal
goon excavations in Israel are discussed. An- when determining suitable conservation
other case study illustrates methods used to methods for any given artifact.
The experiments and case studies offered Invariably, success in using any conserva-
in this book have proved successful for the tion strategy requires patience and a marriage
6 preservation of a wide range of artifacts. I of technical and artistic know-how. There-
hope these materials give the reader a broad fore, time should be spent experimenting
understanding of how Passivation Polymers, with baseline processes before attempting
and other silicone oils, may be used for the conservation of artifacts. There is no substi-
preservation of organic artifacts. Because no tute for hands-on experience, which allows
two pieces of wood are exactly alike, selected the conservator to better understand how to
treatment strategies must be adapted to treat use polymers in the preservation of organic
artifacts on a case-by-case basis. Polymer- material culture and how these treatments
based materials offer the conservator infinite can be adapted to suit each artifact. This type
combinations of material, so that the preser- of experimentation will also help the conser-
vation needs of individual artifacts can be vator understand and better utilize the equip-
addressed. ment used for silicone oil preservation.
Anyone experienced in the complexities of The goal of this research has been to fuel
field conservation would agree that artifact new dialogues in conservation and to en-
triage and stabilization play a major role in courage research along new avenues. Most
the eventual state of an artifact. Passivation important, this research encourages the
Polymers allow the conservator to stabilize reader to gain a new understanding of the
friable materials in the field so they can be material culture we strive so hard to pre-
more easily transported to the laboratory, serve. The development of polymer chem-
where continued preservation can be under- istry for use in archaeological conservation
taken. Polymers can help stabilize artifacts, is in its infancy. To date, development of Pas-
even if more traditional conservation meth- sivation Polymers has helped bring new per-
ods are used once the artifact is secured in spectives to bear on the treatment of organic
the laboratory. artifacts.
CHAPTER 1
7
Laboratory
Setup
E
xperimentation conducted on the de proof freezer system is essential for develop-
velopment of Passivation Polymers re mental research. For routine conservation Fig. .. A functional
quired the use of sophisticated labora- work, such equipment is not necessary. research–working
tory equipment. This book, however, offers laboratory: (A) double-
some basic processes that can be imple- sided workbench; (B) sink;
(C) eye wash system;
mented without the need for elaborate tech- Major Instrumentation
(D) under-cabinet
nology. While there is no one ideal setup for
flammable liquid storage;
a functional lab, layout and location of equip- The investment in elaborate equipment to
(E) vented fume hood;
ment and materials should always adhere to outfit a laboratory for polymer research and (F) vented warming oven;
guidelines established by reputable agencies artifact conservation is minimal. When (G) explosion-proof
such as the Occupational Safety and Health outfitting a laboratory, safety should be the freezer; (H) air-drying
Administration (OSHA). Worldwide, a num- primary concern. High-flow ventilation and shelves; (I) computer with
ber of agencies act in the interest of promot- an eye-washing system are two of the most digital imaging camera;
ing laboratory safety. Many of these have important considerations. (J) electronic scales.
Web-based resources available, free of charge.
Although safety was a major consideration
in choosing material for the development of
Passivation Polymer technologies, many of
the materials suggested for use in the labora-
tory require proper handling and storage. All
technicians working in a chemistry lab need
to be familiar with proper procedures for han-
dling and disposing of chemicals. A complete
inventory of chemicals should always be kept
in case of an emergency, and material safety
data sheets (MSDS) for chemicals used in the
facility must be available for immediate con-
sultation. The MSDS catalog contains vital
contact information as well as important in-
structions if medical assistance is needed.
Figure . shows the floor plan of the Ar-
chaeological Preservation Research Labora-
tory at Texas A&M University. Much of our
developmental research was conducted in
this facility. Equipment such as the explosion-
Because solvents are used in conjunction beaker with a vacuum plate acting as its
with many preservation processes, selecting lid. All major suppliers sell these beakers
8 equipment that will not break down when and most sell vacuum plates and gaskets
exposed to vapors is essential. Often, stain- that fit perfectly. Many restaurant supply
less steel beakers and small supplies can be houses carry the same name brand
found at a restaurant supply store for a frac- beakers at much lower cost.
tion of the price of identical equipment sold Fume Hood. For many laboratories,
through a chemical supply company. Gener- acquisition of a fume hood is a major
ally, however, it is best to select equipment expenditure. While building codes vary,
certified for laboratory use. OSHA and other agencies have estab-
lished standards that should be followed.
Vacuum Pump. Older piston-type pumps These agencies have Web sites and
work best in the laboratory. Modern personnel willing to assist with design
pumps are more efficient, but they are questions.
lightweight in construction, and many Electronic Scales. Electronic scales, capable
companies use plastic internal parts. of measuring in milligrams, are also an
These tend to break down rapidly in the essential tool. Many of these instru-
presence of acetone or acetone vapors. ments can be zeroed after each chemical
Vacuum Gauge. A simple manometer is addition, making the measurement
essential, preferably one with an all- process easy and more accurate. Be sure
metal construction. In more inexpensive to account for the full range and volume
manometers, gradation marks are of materials that will be used in the
generally painted onto the back plate. laboratory when choosing a scale.
During water/acetone exchange pro- Explosion-Proof Freezer. Not all the
cesses, any solvent fumes passing experiments in this book require the use
through the unit will cause the painted of an explosion-proof freezer. The use of
surfaces to crack and fade. a freezer may be beneficial, however,
Dewar Flask and Gas Traps. The best way when a treatment strategy calls for
to trap harmful out-gases that contami- mixing even a small amount of catalyst
nate the vacuum gauge and vacuum into a Passivation Polymer solution. The
pump oil is to use a Dewar flask (fig. catalyzation process is slowed apprecia-
.). These flasks are available through bly when artifact processing is con-
any major chemical supply company. A ducted in a freezer. A freezer unit is also
Dewar flask should be well insulated helpful when a conservation strategy
and large enough in volume to hold requires a slow, controlled acetone/
two cold traps hooked in parallel, along Passivation Polymer exchange.
with a generous quantity of dry ice.
With the Dewar flask and cold trap
assembly placed in-line between the Small Necessities in the Laboratory
vacuum chamber and the vacuum
pump, the cold environment should Disposable Cups. Disposable containers are
condense solvent fumes and prevent practical when working with Passivation
their escape into the manometer and Polymer solutions. Before purchasing a
vacuum pump oil. large supply of any particular brand,
Beaker and Vacuum Plate. A small, however, test the container to be sure it
countertop vacuum unit can be con- does not react with solvents. While it is
structed from a one-liter stainless steel possible to clean glassware, paper cups
and plastic containers that can be
discarded after use are time savers.
Stir Rods. Plastic or glass stir rods work 9
best with Passivation Polymers. Never
use wooden stir sticks or tongue depres-
sors to mix polymer/cross-linker
solutions. The wood will absorb the
chemicals differentially and interfere
with the stoichiometry of the solution.
Tongs and Tweezers. Because artifacts come
in all shapes and sizes, it is a good idea
to have a variety of big and small tongs
and tweezers in the lab. Restaurant
supply companies are an excellent
Fig. .. Dewar flask with
source for large stainless steel utensils.
cold traps and vacuum
For specialty tweezers and implements
lines.
for handling fragile materials, hobby
shops and chemical supply companies
generally have a better selection. precautions are taken. After treatment,
Acetone. Many processes outlined involve artifacts are generally allowed to drain of
an acetone/Passivation Polymer ex- excess free-flowing oils while sitting on
change process. Acetone and other screen material. Since these materials are
solvents are necessary for expedient, often reusable, it is advisable to save
thorough exchange of water with runoff Passivation Polymers. After
polymer preservatives. Proper handling, draining, however, the surfaces of the
storage, and waste management proce- artifact need to be wiped of excess
dures are mandatory. Stainless steel or Passivation Polymer solution. Layers of
high-density polyethylene safety cans lint-free paper and, in some cases,
outfitted with spring-loaded safety caps newspaper can facilitate cleanup.
are the safest and easiest way to handle
solvents in the laboratory. These are
available in a variety of sizes from Chemicals
chemical and safety supply houses.
Metal Screens and Vegetable Bags. For Conservators working with Passivation Poly-
smaller artifacts, aluminum window mers to preserve organic artifacts need ac-
screen can be friction-fitted on top of cess to a variety of chemicals, but they must
the artifact in solution to prevent them keep in mind important considerations in
from floating during acetone/polymer selecting and safely storing chemicals for use
exchange processes. Mesh bags, such as in a laboratory. Hundreds of silicone oils,
those used for bagging perishable foods cross-linkers, and catalysts are available for
in a grocery store, can help keep small use in an archaeological chemistry labora-
objects together during treatment. tory. The most important consideration in
Because of their open mesh design, these selecting polymers is the safety of laboratory
bags do not impede treatment. staff and students. Passivation Polymers were
Absorbent Materials. Working with selected for developmental research at Texas
Passivation Polymer–treated artifacts A&M University because they are relatively
can be messy unless some simple safe to use and because research has proven
Table . Cross-Linkers
that they do not have detrimental effects able for all materials being used in the labo-
when applied to organic artifacts. ratory. These sheets contain the necessary in-
Regardless of the relative safety of the formation for lab personnel to work safely
chemicals chosen, the conservator should al- with chemicals. In the event of a spill, these
ways work in a well-ventilated environment. sheets also contain guidelines for safe and
Accordingly, a fume hood large enough to controlled cleanup. Medical treatment infor-
conduct day-to-day work is essential. While mation and emergency contact numbers
a fume hood may be the biggest investment should also be listed on the sheets. MSDS in-
when outfitting a laboratory, it is essential formation is available on the Web. If the labo-
equipment. If used properly, the airflow cre- ratory has a computer, it is advisable to have
ated by a fume hood will ensure that contami- a “hot key” or posted instructions so that per-
nants and harmful vapors are not a problem. sonnel can easily access safety information
Material safety data sheets must be avail- and emergency assistance.
Baseline
Mechanisms
S
ilicone oils do not mix with water. This, Removing water from any waterlogged
then, is the first challenge a conserva- artifact can be harmful, especially if water-
tor faces after deciding to preserve logging has caused severe cellular damage. In
waterlogged materials using polymers. Passi- many cases, water in the cells is all that is
vation Polymer artifact treatment involves maintaining the diagnostic attributes of the
three main steps: water/acetone displacement artifact. The conservator must therefore un-
(WAD) or dehydration, acetone/polymer (AP) derstand the importance of proper dehydra-
displacement or Passivation Polymerization, tion as a precursor to treatment with any
and catalyzation of the polymer-impregnated bulking agent, including Passivation Poly-
artifact. mers. Pretreatment dehydration is generally
Two experiments in this chapter demon- not required for dry and desiccated organic
strate the relationship between dehydration materials. If wood or basketry feels damp due
of water from organic materials and the abil- to absorption of atmospheric moisture, ei-
ity of silicone oils to penetrate into organic ther dehydration of the samples or storage
substrates. In “Dowel Experiment,” the im- in a low humidity environment for a few days
portance of WAE displacement is illustrated. may be necessary to ensure the rapid uptake
Dehydration processes and length of time in of polymers during treatment.
dehydration influence penetration depth and
rate of AP exchange in wooden dowels. The
second experiment, “Mass Spectrographic Dowel Experiment
Analysis of Out-Gases Created from the De-
hydration of Archaeological Wood Samples,” The purpose of this experiment was to de-
discusses single- and multiple-solvent dehy- termine rates of acetone and silicone dis-
dration techniques for organic materials and placement into the matrix of groups of
how multiple-solvent dehydration may en- structurally solid wooden dowels that had
hance penetration depth. undergone water/acetone displacement for
Experimentation is ongoing to develop one, two, three, or four days before treat-
processes for determining nondestructive ment. Because of the tight, undamaged cel-
percentage dehydration of organic materi- lular structure of the dowels, this experiment
als. Many processes are available for deter- represents a difficult conservation scenario
mining absolute dehydration in organic for wood. The cellular structure of most wa-
substrates. Unfortunately, most require test- terlogged and desiccated timbers facilitates
ing methods that either damage the sample the AP process and shortens the time re-
or are potentially stressful to the artifact in quired to impregnate the wood. This ex-
general. periment showed that () the penetration
depth of acetone is dependent on time and into the core, than did day- dowels. (Day-
vacuum processing, and () Passivation Poly- dowels received hours dehydration; day-
14 mers will only penetrate the dowels to the , hours; day-, hours; day-, hours.)
depth of acetone within the samples. Each day, the dowels were immersed in
Forty-eight dowels, each four inches long PR- and then treated to continuous ac-
and one inch wide, were prepared so that their etone/Passivation Polymer displacement for
cut ends could be sealed by dipping them in hours at a reduced pressure of . Pa
a tray of five-minute epoxy. Sealing the end ( Torr). During this -hour period, two
surfaces ensured that all penetration of ac- samples were removed from the Passivation
etone and Passivation Polymers into the core Polymer solution after ., , , , , and
of the dowels was through the sides of wood hours. Hence, the time of dehydration and
cells and not the tangential, porous ends of the time of treatment were the only variables
the dowels. After the epoxy had dried to in the experiment. At the designated times,
form hard end caps, the dowels were placed dowels were removed from the beaker and
into a five-gallon pail and immersed in fresh quickly surface-wiped with a paper towel.
industrial-grade acetone. A section of alu- Each dowel was labeled and then promptly
minum screen and a five-pound weight were cut in half on a band saw. The wet line of
placed over the dowels to ensure that they Passivation Polymer penetration could be
remained submerged throughout treatment. seen and marked with a ballpoint pen on
The pail was then placed into a large vacuum the crosscut surfaces of each half of the
chamber. dowel. It was important to mark this pen-
All the samples were dehydrated for etration depth (PD) as quickly as possible
hours at room temperature and a reduced because, in many cases, this line of penetra-
pressure of . Pa ( Torr). Twelve tion diffused quickly after the samples were
Fig. .. Cross-sectional
samples were removed from the pail daily and cut. Figure . shows a typical cross-sectional
view of dowel and
penetration depth
placed into a beaker of PR- silicone oil so- view of Passivation Polymer penetration of
measurement: (A) dry lution. While the first samples were being a dowel.
core; (B) Passivation analyzed, the remainder of the dowels con- In this experiment, it was reasoned that
Polymer wet zone; tinued in dehydration so that day- dowels as long as all samples were processed in the
(C) measured mean had four times as much dehydration and, same manner and within the same time
penetration depth. presumably, deeper penetration of acetone frame, the data should accurately represent
the PD for each sample and the differences
in PD between samples. The mean PD was
then calculated for each collection time. Af-
ter four days, four series of dowels had un-
dergone the same processes of acetone/Pas-
sivation Polymer displacement and the same
assessments for PD. Data for PD among all
the dowels for all four days could then be
compared (see tables .–.). Dehydration
time was expected to correlate with PD of
acetone into the matrix of the samples. These
same samples should also have a greater PD
of Passivation Polymers into their matrix as
compared to samples treated with a shorter
period of acetone dehydration.
Table . One-Day Dehydration Data
gassing from the sample was comparable to gases from samples C and D is interesting
samples B, C, and D. A lack of media to sup- because the higher levels of methyl and ac-
port the degraded cell structure resulted in etone gases suggest that alcohol-acetone
greater damage to this section of waterlogged process dehydration may have been more
wood. Not surprisingly, the levels of out- effective in raising the overall levels of vola-
gassing methyl and ethyl were the highest in tile vapor exchange. Thus this process may
this sample, and molecular acetone levels have a higher potential for exchanging sili-
were % (. intensity) higher than those cone oils, or other bulking agents, into water-
recorded for sample D. logged materials.
With the exception of sample A, which reg-
Trends istered water levels of ., samples registered
water levels of ., which may suggest that,
Sample E, which acted as a control for this from the standpoint of the removal of free
experiment, served to indicate the maximum water from waterlogged wood, all processes
out-gassing potential that might be expected were relatively equal. Differences in bulking
for this group of wood samples. Because heat potentials, then, lie in the heightened levels
was used to accentuate the effects of out- of volatile gases that result in cold process,
gassing, methyl, ethyl, and acetone levels for vacuum assisted alcohol-acetone dehydra-
the sample were the highest recorded. While tion. Table . includes the out-gassing data
less than the levels recorded for sample E, the for all five samples. The data suggest that the
levels for sample D were appreciably higher rise in molecular acetone and methyl levels
than out-gassing levels recorded for samples resulting from multiple-solvent dehydration
processed at room temperature. makes two-stage cold dehydration potentially
A comparison of the relative levels of more appropriate for silicone bulking.
CHAPTER 3
21
Archaeological
Wood
O
ne of the biggest problems conserva of wood from the denser interior. Passiva-
tors may encounter when developing tion Polymers seem to effectively prevent this
a conservation strategy for waterlogged problem.
wood is determining the degree of deteriora- The use of silicone preservation technolo-
tion that has occurred within the matrix of gies also allows the conservator to better con-
the artifact. Whether from a bog, a river, or a trol the strength, flexibility, exterior finish,
swamp, a piece of wood will suffer structural and color when treating waterlogged or se-
deterioration as a result of bacterial decay and verely desiccated wood. As with polyethylene
fungal and microbial attack. Effects of water glycol, Passivation Polymers can be blended
flow and natural abrasion from sands and silt to accentuate structural and aesthetic quali-
also compromise the physical integrity of ties that the conservator may wish to apply
wood if deposition has occurred in shallow to archaeological wood.
water. Because silicone oils do not mix with wa-
ter, all free-flowing water must be removed
to allow impregnation of the wood. This can
The Challenge of Conserving be easily accomplished with solvent baths. To
Waterlogged Wood prevent stress, a series of baths should be
used, starting with alcohol dehydration and
While it is safe to assume that it is easier to working through to two or more acetone
penetrate the matrix of heavily waterlogged baths. For small artifacts, reduced pressure
wood with a bulking agent, to use the same applied to the wood in solution will facili-
bulking material for all artifacts would be tate water removal. Care must be taken in
too simplistic. Indeed, in the case of the large applying a vacuum to acetone as vapors will
oak timbers in the hull of La Belle, the pen- contaminate the vacuum pump oil, and this
etration rate of a bulking agent into the can hinder performance of the equipment.
outer, heavily waterlogged timbers, will be Acetone will also damage a pump with plas-
fast. The inner core of wood, however, is ex- tic components. Older vacuum pumps are
tremely solid, exhibiting nearly the same invaluable in a conservation laboratory be-
strength and density as freshly sawn timbers. cause their all-steel construction is impervi-
Penetration of a bulking agent into these ous to contamination. A Dewar flask with dry
timbers is much more difficult. As formi- ice should always be used to house two in-
dable as the task may be, however, the intro- line gas traps between the pump and the
duction of a stabilizing and consolidating vacuum chamber. This is the safest way to
agent is necessary to prevent exfoliation that prevent acetone vapors from entering the
occurs with the separation of the outer zone pump.
Degradation and Shrinkage Table . Classifications of
Waterlogged Wood
22 After long periods in wet soil, peat bogs, or
marine sites, the cell wall components in all Classification Water
wood will be degraded by bacterial action. 1 More than 400%
In general, water-soluble substances such as 2 185–400%
starch and sugar are the first to be leached 3 Less than 185%
from waterlogged wood, along with mineral
salts, coloring agents, tanning matters, and even % water. Waterlogged wood is of-
other bonding materials. In time, through ten classed according to the amount of water
hydrolysis, cellulose in the cell walls disinte- it contains. The most commonly used clas-
grates, leaving only a lignin network to sup- sifications are shown in table ..
port the wood. Even the lignin will break All waterlogged timbers must remain com-
down over a long period of time. pletely wet up to, and throughout, the preser-
As a result of the disintegration of cellu- vation process. Wood recovered from saltwa-
lose and lignin, spaces between the cells and ter environments requires extensive rinsing in
molecules increase, and the wood becomes freshwater to eliminate as many soluble salts
more porous and permeable to water. All the as possible. Failure to eliminate salts in the
deteriorated elements of the wood, includ- matrix of the wood will cause problems once
ing cell cavities and intermolecular spaces, are the artifact is removed from treatment.
filled with water. The remaining lignin struc- Trapped salts will slowly crystallize, resulting
ture of wood cells and the absorbed water in possible distortion and exfoliation of large
act to preserve the shape of the wood. The layers of the artifact. Titration tests should be
loss of the finer cellulose tissue does not cause used to determine the point at which the bulk
much alteration in the gross volume of wood, of soluble salts have been rinsed from the
but the porosity is increased and the wood wood. As the results from the “Dowel Experi-
absorbs water like a sponge. ment” in chapter suggest, Passivation Poly-
A waterlogged wooden object will retain mers penetrate easily into an acetone-rich
its shape as long as it is kept wet. If the wood environment. Accordingly, prior to treat-
is exposed to air, the excess water evaporates ment, cleaned wooden artifacts should be
and the resulting surface tension forces of stored in an alcohol/acetone (:) environ-
the evaporating water cause the weakened ment. In many cases, artifacts can be stored
cell walls to collapse, creating considerable in % acetone—the longer the better.
shrinkage and distortion. The amount of
shrinkage is dependent upon the degree of
disintegration and the amount of water Waterlogged Wood from Saltwater
present. The amount of water in waterlogged Environments
wood can be determined by the following
equation: This procedure deals with any wood with an
internal structure that has been degraded by
the waterlogging process.
%H2O = weight of wet wood – weight of oven dried wood
X 100
weight of oven- dried wood
Pretreatment
Wood containing more than % water is All waterlogged timbers must remain wet
considered degraded; it is not uncommon to prior to treatment. Regardless of whether
find wood that contains more than % or they were recovered from saline or freshwater
environments, the water in the cell structures Calcareous deposits can often be removed
of these artifacts is preventing collapse and using dental picks or soft wooden dowels.
distortion. Any amount of air-drying or de- Small pneumatic chisels are useful for 23
hydration will cause potentially irrevers- removing slightly larger calcareous deposits.
ible cellular collapse. Care should be taken, however, to ensure that
There are additional challenges in the vibrations from the chisel do not shake the
treatment of waterlogged timbers from salt- wood to the point of causing additional
water environments. With evaporation, salts stresses. To minimize damage caused by
remaining in the wood will crystallize. Ex- vibrations, the artifact should be held in one
pansion and crystallization as the artifact hand or placed on soft vermiculite-filled
dries may result in extensive cracking and, cloth bags while removing concreted
possibly, exfoliation of large sections of wood. materials.
Even trace amounts of salts can damage . To enable deep penetration of polymers
structurally deteriorated wood. Because they throughout the wood, water must first be
remain soluble, salts within the cell structure eliminated. For small artifacts, this can be
of the artifact act to absorb atmospheric accomplished using a series of dehydration
moisture and are not completely stabilized. baths, starting with ethanol and working
Soluble salts and minerals must, therefore, through to several baths of fresh acetone.
be flushed from waterlogged wood prior Water/acetone exchange will take several
to treatment. The best means of removing days, depending upon the artifact’s size and
soluble salts is through freshwater rinses and, density. This phase of treatment cannot be
when possible, running water rinses. Over hurried. Incomplete dehydration or dehydra-
time, salts will dissolve into and be diluted in tion carried out too quickly may damage the
the volume of water in which the wood is artifact.
stored. Accordingly, large volumes of water Vacuum-assisted dehydration for the final
are best for long-term storage. Water should acetone baths is often an effective way to
be changed frequently. Titration readings and ensure complete dehydration. During
simple silver nitrate tests can be used to de- dehydration, the vat containing the artifact in
termine parts per million (ppm) salt content fresh acetone is placed into a vacuum
prior to changing rinse water. chamber. Two gas traps, immersed in dry ice
Vats containing waterlogged wood should or liquid nitrogen, should be placed in-line
be kept covered. Exposure to sunlight will between the vacuum chamber and the
encourage the growth of algae, which may vacuum pump. Escaping acetone fumes and
be detrimental to the wood. Covering the vats moisture in the wood will be condensed and
will also help eliminate deposition of air- trapped in the gas traps, preventing contami-
borne contaminants, as well as mosquito and nation and possible deterioration of the
other insect larvae. How biocides affect the internal components of the pump. Generally,
bulking agents used to stabilize waterlogged reduced pressure using a slight vacuum of
wood or the cell wall structures of the wood . Pa ( Torr) is sufficient to ensure
itself is not known. Accordingly, biocides thorough dehydration. Once dehydration is
should be used sparingly. complete, the artifact must be transferred to
the polymer solution while thoroughly wet
Methodology with acetone.
. A suitable volume of Passivation
. The surfaces of the wood should be Polymers (silicone oil mixed with a cross-
thoroughly cleaned using soft brushes, lint- linker) should be prepared in advance to
free cloths, and other appropriate tools. ensure quick transfer after dehydration. A
Passivation Polymer can be selected from immersed in the polymer solution during
table .. Because waterlogged wood is fragile, treatment. Throughout acetone/polymer
24 care must be taken to ensure that the chosen solution displacement, the artifact may have a
polymer/cross-linker solution is not so tendency to float as acetone vapors escape
viscous as to prevent rapid acetone/polymer from the wood. It may be necessary to place
exchange. The use of viscous polymer aluminum screen and sufficient weight on
solutions will have the same effect as using top of the screen to keep the wood sub-
too high an initial percentage mixture of merged (fig. .).
polyethylene glycol in water. If the chosen . To ensure the role displacement of
bulking agent cannot readily displace acetone acetone with a silicone oil solution, artifacts
in the cell structure of the wood, cellular the size of a sewing thimble may require
collapse and distortion of the artifact may treatment for one week at ambient pressure.
occur. A certain degree of experience is needed to
For wood that has a soft exterior zone determine the best treatment strategy for
surrounding a harder and possibly structur- small artifacts. If the artifact is in but not
ally sound core, it may be necessary to use a severly damaged by the waterlogging process,
blend of Passivation Polymers. Lower vacuum pressure may be used to assist the
viscosity Passivation Polymers will penetrate acetone/silicone oil solution displacement
the tight, solid matrix of less structurally process. If however, the artifact is more
damaged core wood, while more viscous severely damaged, it may be necessary to
Passivation Polymers will easily penetrate the conduct the acetone/silicone oil solution
softer exterior. Because higher viscosity displacement process at ambient pressure. At
polymers, such as PR- and PR-, are longer ambient pressure, acetone will vaporize more
polymer chains, they are excellent consolida- slowly from the cells of the wood, allowing
tors, binding the outer soft areas of water- the more viscous polymer solution slowly
logged wood to the more solid core. If the into the cells.
PEG is too viscous, cell walls will be collapsed For larger artifacts such as musket stocks
as the solution tries to enter the cells. and tool handles the conservator may choose
Similarly, an overly viscous solution of to use vacuum-assisted acetone/polymer
silicone oil will cause cell collapse. Acetone/ displacement. Low viscosity polymers must
silicone oils solution displacement will have be used for low-pressure treatment of wood.
the same damaging effects as PEG if the Accordingly, PR- is generally the best
solution tries to displace acetone, which is in choice. To a given volume of PR- polymer,
this case dispersed rapidly as water. use a % (by weight) addition of CR- and
Once a suitable volume of polymers or mix thoroughly. The artifact should then be
blended polymers, sufficient for total carefully transferred and totally immersed in
immersion of the artifact, has been selected, a the vat of polymer solution. Aluminum mesh
cross-linker must be added. CR- is the best or some other mechanism is required to
choice of cross-linking agents to use with prevent the artifact from floating during
PR-, PR-, and PR- for preserving acetone/polymer displacement. Once the
waterlogged wood. A % (by weight) addition artifact is secure in the solution, place the vat
of CR- should be mixed in with the into a vacuum chamber. A slight reduction in
polymers. pressure is sufficient to cause small bubbles to
. After thoroughly mixing the polymer/ flow from the artifact. When slight bubbling
cross-linker solution, quickly and carefully occurs, lock off the vacuum chamber and
transfer the acetone-laden wood to the turn off the pump. Never allow extensive
polymer solution. The artifact must remain bubbling to occur as this means acetone is
probably being driven from the wood faster drain until its surfaces are nearly dry to the
than the polymer solution can displace it. touch. This may take one or two days. To
Vacuum-assisted treatments work best when remove surface-pooled polymers from the 25
pressure is reduced slowly over several days. wood, use lint-free cloths and soft brushes. A
Generally, a reduced pressure of . Pa Q-tip dipped in CR- is often an ideal tool.
( Torr) is sufficient for the treatment of any To remove excess amounts of bulking agent
small wooden artifacts if the conservator has from cracks and crevices, it may be necessary
elected to use a reduced pressure environ- to immerse the artifact in a small vat of
ment to speed up the acetone/polymer CR- and then wipe it with soft cloths and
displacement process. brushes.
Experience and good observations dictate . A list of catalysts is supplied in table .,
the amount of vacuum pressure that can be which also lists the attributes of each catalyst
applied to an artifact. If it is obvious that the and its intended end result. The best general-
diagnostic attributes of the artifact are being purpose catalyst is CT-, which has a working
maintained, it can be held at pressure in time of hours in a closed environment.
solution from to hours. With badly Catalysts can be applied either topically or as
degraded wood, acetone/polymer solution vapors to the surfaces of artifacts. In either
exchange is usually fast since the wood’s case, an applied catalyst will continue working
deteriorated structure allows rapid and safe to polymerize the polymer-impregnated
exchange of acetone for the more viscous artifact.
polymer solution. For less degraded wood, Topical applications are effective ways to
exchange of acetone for polymers must be initiate polymerization and attain total
conducted at a slower rate to prevent distor- stabilization of the artifact. Use a soft brush
tion and cellular collapse. or cloth to apply a thin, even layer of catalyst
. After bubbling has ceased, the artifact to the artifact’s surfaces. After allowing the
should remain in a reduced pressure environ- catalyst to coat the surfaces of the wood for
ment for several hours, if not days. Care two or three minutes, use soft cloths to wipe
should be taken to ensure that the reduced off the solution. Place the artifact into a
pressure in the vacuum chamber is returned Ziploc bag and seal it shut. After hours,
to ambient pressure slowly. After the artifact remove the artifact and inspect it to ensure
has been allowed to sit in solution at ambient that it is dry to the touch. If it is not dry, it
pressure for at least hours, it can be may be necessary to return it to the Ziploc
removed from the Passivation Polymer bag, along with a small piece of cloth
solution. The artifact should then be carefully containing several drops of fresh catalyst.
placed on a screen suspended over a clean Seal the bag again and allow fresh catalyst
container to allow the polymer solution fumes to complete the catalyzation process.
flowing from its surfaces to collect. Recovered A more aggressive form of vapor catalyst
solution can be reused almost indefinitely, as deposition can be accomplished by placing
long as it is periodically placed for hour in the artifact into a Ziploc bag or plastic
a warming oven set at ˚C. This will ensure container, along with a dish containing
that remaining acetone and water are several grams of CT- catalyst (fig. .).
evaporated from the polymer solution. With Seal the container and place it in a vented
each reuse, a new % addition of CR- is warming oven set at ˚C. Warming the
required. catalyst will accelerate its reactivity with the
The conservator need not be concerned polymer solution in the artifact. Generally,
about the safety of the wood while it is the artifact will be completely stable after
draining. It is best, in fact, to let the wood hours. When in doubt, you can store wood in
second day. To complete the desalination
process, the buttons were rinsed in five baths
Fig. .. Artifact in bulking
26 of deionized (DI) water, which were also
agent with friction-fit
changed every second day. Titration testing
screen in place: (A) open
of the rinse water was conducted periodi-
container; (B) sufficient
bulking agent to submerge cally throughout the desalination process.
artifact; (C) friction-fit Generally, a level of ppm or lower is con-
screen to ensure immer- sidered adequate for starting the next phase
sion during treatment; of treatment.
(D) artifact. Dehydration of the buttons was con-
ducted using a series of organic solvent baths.
a Ziploc bag for several days, as long as fresh Starting with a solution of % ethanol in
catalyst is added daily. After catalyzation, DI water, each successive bath included a %
allow the artifact to sit in a fume hood for increase in ethanol until the buttons were
one or two days. The smell of the catalyst will dehydrated in % ethanol. Each phase of
dissipate quickly. alcohol dehydration lasted days. The sol-
vent baths continued, with each successive
bath receiving a % increment of acetone.
Case Study: Waterlogged Wooden Each bath lasted days. The final stages of
Buttons with and without Associated dehydration included three successive baths
Thread of % acetone, each lasting days.
A solution of PR- with % CR- added
After their recovery from the shipwreck La by weight, sufficient to immerse the buttons,
Belle, wooden buttons with and without as- was prepared. To ensure that the buttons and
sociated thread were stored in freshwater. attached threads did not float during treat-
Initially tap water, with a chloride level of ment, small sections of aluminum window
approximately ppm, was used to desali- screen were friction-fit over them in the con-
nate the buttons. Over the course of one tainer (fig. .). During acetone/polymer dis-
Fig. .. The artifact in a month, the bath water was changed every placement, the solvent vaporizes and escapes
Ziploc bag with a dish two days. For the next two weeks, the but- from the wood, creating voids; continuous
containing several grams tons were rinsed in baths of rainwater, which immersion of the buttons is therefore needed
of CT- catalyst. like the tap water baths were changed every to ensure that these voids are rapidly filled
with polymer solution. The buttons re-
mained immersed in the polymer solution
for days.
After days, the buttons were removed
from the solution and placed onto a screen
so that runoff polymers could be collected
for reuse (fig. .). Each button was then in-
dividually wiped, first with paper towels, to
remove the bulk of polymers, then with soft
cloths to remove any remaining solution. As
each button was dried, it was immediately
dropped into a bath of % CR- for a
period of no longer than two minutes so that
additional polymers could be washed from
its surfaces. Each button was then removed
from the CR- and carefully surface-dried, need for additional cleaning. After hours
taking care not to dislodge any associated of vapor deposition catalyzation, the buttons
thread. felt both dry and nonwaxy. They were then 27
The buttons were then placed on an el- removed from the Ziploc bag and placed on
evated window-screening tray in a Ziploc a tray for continued curing in a fume hood.
bag. A paper towel was crumpled into a ball The final appraisal of the treatment pro-
and placed into the bag, along with the arti- cess for each button was subjective. If the
facts. The towel served to form an airspace buttons had felt waxy or had appeared to
around the artifacts. A second piece of be wet, they could have been immersed in
crumpled paper, containing cc of CT-, CR- to surface-clean the slight polymer
was then placed into the bag (fig. .). Once film that may have formed during treatment.
sealed, the bag was placed into a warming All the buttons with attached threads were
oven preset at ˚C. After hours of dipped in CR- and then carefully surface-
catalyzation, the paper containing the used dried. This made the threads more flexible.
catalyst was replaced with a new ball of pa-
per containing cc of fresh CT-. The bag
was resealed and returned to the warming
oven for an additional hours.
Care must be taken to ensure that paper
containing the CT- catalyst does not come
into direct contact with any artifacts during
catalyzation. Direct contact with the catalyst
will result in the formation of white particu-
late at the point of contact. This is polymer-
ized silicone oil, which can easily be removed
using a soft cloth once treatment is complete.
Avoiding contact, however, will eliminate the
Fig. .. Buttons draining
on a screen after polymer/
cross-linker treatment.
This procedure deals with weathered wood Where possible, the surfaces of all artifacts
and architectural materials, and with organic should be cleaned of loose debris. Most of
artifacts from dry cave sites. the time, this can be accomplished with a soft
brush or lint-free cloths. In situations where
Pretreatment dirt is heavily impacted on an artifact, how-
ever, it may be necessary to dampen the sur-
Usually, dry and desiccated wood samples faces before attempting any cleaning. After
recovered from land sites are fragile and light cleaning, sufficient time should be allowed
in weight due to water loss. Over time, the for the artifact to dry before continuing treat-
Fig. .. Buttons after ment.
completion of the While the artifact is air-drying, prepare a
Passivation Polymer suitable volume of silicone oil/cross-linker
treatment. solution to ensure total immersion of the as-
semblage throughout treatment. Be sure to
consider the potential volume of polymer
solution that will be absorbed during treat-
ment. Because dry and desiccated wood tends
to be friable, choosing a suitable polymer/
cross-linker combination is important. Ab-
sorption of the polymer will be rapid in dry
wood. Choosing a short-backbone polymer,
which is also a low viscosity polymer, will
accomplish two things. The low viscosity of
the solution will enable deep and thorough
penetration of the wood; and once polymer-
ized, the smaller polymer will ensure that the observations dictate the amount of vacuum
wood is stronger than in its pretreatment pressure that can be applied. If the diagnostic
state. attributes of the artifact are not being 29
For dry cave-site wood, PR- with a % compromised, it can remain in reduced
addition of CR- cross-linker, added by pressure treatment for several hours. Because
weight, is a perfect combination of polymers of their porosity, dried wooden artifacts
for treatment. Other polymer choices are averaging in thickness up to . inches are
listed in table .. well penetrated after this type of processing.
. If vacuum-assisted impregnation has
. Pour sufficient PR- into a container. been used, always make sure the artifact is
To this solution, add % CR- cross-linker returned to ambient pressure slowly. The
by weight and mix thoroughly. Always use a artifact should then be taken out of the
nonporous stir rod when mixing polymer vacuum chamber and, after careful removal
solutions. This will ensure that equal propor- from the Passivation Polymers solution,
tions and stoichiometry are maintained. placed onto an aluminum screen so that free-
Unless thoroughly mixed, the less viscous flowing materials can be recovered. There is
material, in this case CR-, could be no hurry to continue treatment on desiccated
absorbed by a porous stir rod, resulting in wood. The artifact can safely drain for several
an improperly prepared polymer solution. hours and, if necessary, be stored indefinitely
. Carefully place the artifact into the in solution until continued treatment can
PR-/CR- solution. Regardless of which occur.
viscosity polymer has been chosen, be careful . Before a catalyst is applied, excess
when immersing an organic substance. bulking agent needs to be removed from the
Delicate artifacts can be damaged if forced artifact’s surfaces. While many of the polymer
recklessly into a viscous bulking agent. Place solutions are sticky to the touch, they are
a piece of aluminum screen over the artifact, easily wiped from the wood surfaces using
making sure that the screen friction-fits Q-tips or clean cloths. To remove excess
against the sides of the container. This will amounts of bulking agent from cracks and
ensure that the artifact remains immersed in crevices, the artifact can be wiped with a rag
the polymer solution throughout treatment. soaked in CR-. For complex surface-
(See fig. ..) cleaning, or when all surface traces of bulking
. Dry wood needs little help to absorb a solution need to be removed, the artifact can
low viscosity polymer solution. If the be immersed in a bath of CR- then wiped
conservator feels the need for pressure with Q-tips and cloths.
treatment, proceed with caution. Very little . After the artifact has been wiped, a
vacuum will be required. During vacuum- suitable catalyst should be applied to all
assisted impregnation, use as little vacuum as surfaces as soon as possible. A list of catalysts
possible. As long as small bubbles flow slowly is supplied in table .. Catalyst’s attributes
from the wood, there is sufficient pressure to and application methods are also provided in
ensure that the polymer will penetrate the that table. CT- is the best general-purpose
artifact. If bubbling is too vigorous, reduce catalyst for treating dried wood. After
the vacuum pressure immediately. Excessive applying CT- and allowing it to sit on the
bubbling may damage delicate artifacts. Once surfaces of the wood for no more than two
bubbling appears to slow in frequency, or minutes, wipe thoroughly and quickly. Using
stop, increase the vacuum pressure and the same procedures as noted for waterlogged
maintain pressure at a point where stream- wood, continue vapor deposition by placing
type bubbling occurs. Experience and good the artifact into a Ziploc bag. Place a small
dish containing a few grams of CT- into the conservation strategies was still in its infancy,
bag and seal it shut. The catalyzation process have not fared as well.
30 will continue for up to hours. PEG was used in the treatment of wood,
If the surfaces of the wood feel damp, re- leather, paper, and other organic materials,
place the used catalyst with a dish contain- and was added to the water in which the ar-
ing fresh catalyst. CT- has a maximum tifacts were stored. Over time, the percent-
working time of hours. Once the artifact age of PEG was increased and the aqueous
feels dry, remove it from the Ziploc bag and solution permeated into the cell structure of
allow it to cure in fresh air for as long as pos- the artifact, depositing the carbowax bulk-
sible. While the artifact can remain in cataly- ing agent, which prevented cellular collapse.
zation as long as desired, the final stage of Because this preservation process was still in
fresh air curing will allow final curing and its developmental stages, conservators tended
ensure that catalyst fumes dissipate. If the to use differing percentages of PEG in treat-
wood requires spot treatment to remove ment, and in many cases, variance in post-
white particulate formed on the surfaces dur- treatment handling and curation of artifacts
ing catalyzation, use a soft cloth containing was substantial. Indeed, the pioneers of PEG
a few drops of CR-. conservation used freeze-drying in conjunc-
tion with PEG treatments. This combined
treatment strategy yielded superior finished
Reprocessing and Stabilization of artifacts that were more stable and aestheti-
PEG-Treated Wood cally correct.
But what about the hundreds of thou-
Re-treatment strategies have been of particu- sands of artifacts that were conserved with-
lar interest to conservators at the Archaeologi- out the benefit of advancements such as
cal Preservation Research Laboratory. For sev- freeze-drying and blended PEG treatment
eral decades, preservation of waterlogged strategies? Some artifacts have been lost. The
wood using polyethylene glycol has been the majority of artifacts, however, have been care-
standard treatment preferred by most conser- fully curated and re-treated over time. Early
vators. A carbowax that is miscible in water, in Ole Crumlin-Pedersen of the Danish
PEG is available in an almost infinite variety Viking Ship Museum traveled to Texas A&M
of molecular weights. A skillful conservator University to discuss the vessels in the mu-
can blend two or more molecular weights seum that had been preserved using PEG. He
of the bulking agent to attain specific and believed, as do I, that vessels preserved using
desirable traits for organic artifact preser- traditional PEG treatment methods require
vation. Like all conservation strategies, PEG additional treatment to make them as stable
treatments are always being refined; recent as possible. At Crumlin-Pedersen’s encour-
advances in archaeological chemistry have agement, re-treatment of PEG-treated wood
expanded our knowledge of PEG chemistry became a new challenge for conservators at
and its applications in archaeology. Texas A&M University. The purpose of early
Re-treatment of PEG-treated artifacts is a experimentation was not to discredit the
concept that has grown out of necessity. value of PEG in the preservation of water-
When preserved using standardized treat- logged wood. On the contrary, research ini-
ment strategies developed by Per Hoffmann, tiatives were directed at improving and
David Grattan, and others in the s and strengthening the knowledge base for using
s, artifacts treated with PEG are stable PEG in archaeological preservation. While
and well preserved. Artifacts treated in the PEG is by far the most widely used bulking
mid-twentieth century, when development of agent for the preservation of waterlogged
wood, its basic characteristics offer some chal- a saturated solution of acetone rosin, which
lenges for the long-term well-being of pre- achieves a result similar to PVA emulsion.
served wood. In the “Tongue Depressor Experiment,” 31
The posttreatment hygroscopic nature of described below, CR-, a hydrolyzable, mul-
PEG is a concern when the carbowax com- tifunctional alkoxysilane was used to expe-
pound is used for the long-term curation of dite the removal of unbound PEG from the
structurally damaged, waterlogged wooden wood. CR- self-condenses in the aqueous
artifacts. When introduced into waterlogged environment of the wood, forming a methyl
wood, some of the PEG reacts with polysac- silane polymer that is less susceptible to wa-
charides, polyphenolics, and water to form ter absorption. Results of this experiment
complex bonds that are hydrophobic in na- have shown that while PEG is an excellent
ture. The unbound PEG, located within the bulking agent for archaeological preserva-
open structures of the wood, however, re- tion, it is not a reversible process. When un-
mains hydrophilic. Accordingly, fluctuations bound PEG is removed from wood in the
in temperature and humidity result in the presence of an alkoxysilane solution, the re-
uptake of atmospheric moisture and inter- maining PEG is hydrophobic and less prone
cellular migration of the unbound PEG. In to dimensional shifting as the result of envi-
extreme conditions, the intercellular move- ronmental factors. The use of an alkoxysilane
ment of PEG stresses the weak walls of the polymer to reprocess PEG-treated wood
wood, causing shrinkage, distortion, and loss offers many advantages for the stabilization
of diagnostic artifact attributes. of waterlogged wooden artifacts. The process
Damage caused by waterlogging is sel- reduces, and sometimes eliminates, swelling
dom uniform throughout a timber. Often, that has occurred from introducing PEG into
the inner core remains in excellent condi- the waterlogged wood. After treatment, the
tion while its outer surfaces become soft and surfaces of the wood are stabilized and do
severely damaged. PEG treatments success- not require additional consolidation. All the
fully displace water in the cell structure of wood samples regained a natural wood tex-
waterlogged wood, but the bulking agent ture and color, and in all cases, the weights
alone is usually not capable of stabilizing and of the reprocessed samples were reduced.
protecting the surfaces. To stabilize badly de-
teriorated or surface-checked wood, an ap-
plication of higher molecular weight PEG Tongue Depressor Experiment
may act to consolidate the surfaces of the
artifact from abrasive damage caused by dust Nuclear magnetic resonance (NMR) analy-
and other airborne particles in the museum sis was used to investigate the chemical trans-
environment. formations that occurred when PEG was
At the conservation facilities of Parks introduced into samples of waterlogged
Canada in Ottawa, Canada, - Jade ad- wood and to characterize chemical reactions
hesive, a diluted polyvinyl acetate (PVA) resulting from the reprocessing of this wood
emulsion, is used to consolidate the checked using CR-. During reprocessing in a vat of
surfaces of PEG-treated wood.1 The substance CR-, unbound, free-flowing PEG was re-
also strengthens the surfaces of PEG-treated moved from the wood. In the aqueous envi-
timbers.2 To ensure that badly deteriorated ronment of the PEG-treated wood, CR-
wooden artifacts have resilient outer surfaces, displaced free-flowing PEG within the cell
conservators at the Archaeological Preserva- voids of the wood, hydrolyzing to form me-
tion Research Laboratory at Texas A&M Uni- thyl silane polymers. Evaluation of the repro-
versity have immersed PEG-treated wood in cessed wood indicated that swelling normally
associated with traditional PEG preservation surfaces of the silicone oil–impregnated ar-
was eliminated. In many cases, samples of tifact or as a vapor. Vapor deposition accel-
32 wood were returned to their pretreatment erates the chemical reactivity of the catalyst
dimensions. Unlike PEG-treated wood and ensures an even application to all sur-
samples, which became darker in color and faces of the artifact.
waxy in surface appearance, the reprocessed Other materials included a Pyrex gradu-
wood appeared natural in coloration and ated cylinder ( ml), a piece of aluminum
surface texture. foil to form a loose-fitting cap for the gradu-
ated cylinder, and a Despatch LFD series
Materials warming oven with computerized tempera-
ture and humidity controls.
Tongue depressors were chosen for experi-
mentation because they are plentiful and Methodology
uniform in dimensions, color, genus, and
species. Several control tongue depressors Twenty waterlogged tongue depressors were
were randomly collected to assist in evaluat- randomly selected, thoroughly rinsed in run-
ing PEG-treated wood. To create a supply of ning tap water, and stored in a large jar of
waterlogged wood, hundreds of white birch freshwater. The jar was then placed into a
(Betula papyrifera) tongue depressors were vented warming oven set at a constant tem-
placed into a four-liter stainless steel con- perature of ˚C. Small amounts of water
tainer and boiled in freshwater for days. were added to the container each day to
Water was added at regular intervals to en- maintain a constant level throughout treat-
sure that the water level remained high ment. Each week, one % increment of
enough to keep all the wood pieces saturated. warmed PEG (by volume) was added,
The tongue depressors were then stored forming an aqueous solution of PEG. After
at room temperature in a large jar of water seven weeks, the warming oven was turned
with a tight-fitting screw cap. One tongue off; the tongue depressors were allowed to sit
depressor, labeled TD, was stored separately in the PEG solution for another week.
in freshwater for comparison with the con- One tongue depressor, labeled TD, was
trol sample, TD, and the PEG re-treated removed from the PEG solution, placed be-
wood, TD. Several pieces of wood were al- tween paper towels to blot free-flowing PEG
lowed to air-dry at room temperature for from its surfaces, and allowed to sit in fresh
hours. After air-drying, all samples exhibited air for hours before additional experimen-
extensive warping and shrinking. tation was conducted. The length, width,
At room temperature, PEG is a pow- thickness, and weight of TD were then re-
der. To make the task of incremental addi- corded, and NMR analysis was performed.
tions easier, a large jar of PEG was placed (The waterlogged sample, TD, and the un-
into a warming oven and warmed to a tem- treated sample, TD, were also subjected to
perature of ˚C. At this temperature, it re- NMR analysis.) TD was then immersed in
mains in a liquid state. CR- is a clear mono- ml of CR- in a graduated cylinder. To
mer that reacts with water to form silanetriol prevent rapid evaporation of the silane, the
and methanol. The silane condenses with graduated cylinder was loosely capped with
available hydroxyl groups or other silanol a three-inch square of aluminum foil. The
monomers to form siloxane resins. CT- is cylinder was placed into a ˚C vented warm-
a tin- based catalyst that remains active for ing oven for hours (fig. .). The cylinder
approximately hours in a controlled envi- was then removed from the oven and allowed
ronment. It can be applied topically to the to cool to room temperature and sit for an
additional hours. When TD was removed
from the CR- solution, it was covered with
a thin white coating of PEG. This was re- 33
moved by wiping the tongue depressor with
a lint- free cloth. The remaining CR- solu-
tion in the graduated cylinder was milky
white due to PEG extracted from the tongue
Fig. .. Graduated
depressor. This solution was poured into a
cylinder setup for repro-
flat pan and allowed to sit in a fume hood cessing of PEG-treated
for several days. wood using CR-:
Vapor deposition was chosen as the best (A) vented warming oven;
method to ensure that all surfaces of the (B) loose-fitting aluminum
wood were evenly exposed to catalyst. To cap; (C) level of CR- in
form an effective environment in which cylinder; (D) CR-
warmed vapor fumes would remain in close solution in which TD was
contact with the surfaces of TD, a tall poly- immersed; (E) TD
ethylene container with a tight-fitting lid was immersed in CR-.
used to create a containment chamber. In an
inverted position, the lid of the container
became the base of the unit. to temperatures. When immersed in warm
A Fisherbrand aluminum weighing dish CR-, PEG melts. Because it is not chemi-
with g of DBTDA catalyst was placed in cally bound to the cell walls of the wood, it
the middle of the base of the chamber. A piece migrates. This is the same reaction that would
of aluminum screen was placed over the dish be observed if the PEG-treated wood were
to act as a platform on which the tongue de- placed into warm water.
pressor could be placed during the cataly- Of interest, then, is the chemical reactiv-
zation process. Paper towels were placed on ity of CR- within the cell structure of the
top of the aluminum screen to prevent free- wood. PEG was introduced into the wood as
flowing PEG/CR- solution from contami- an aqueous solution. Accordingly, water was Fig. .. Configuration of
nating the catalyst during treatment (fig. .). bound to the PEG. It appears that H2O asso- the containment chamber
When the body of the chamber was snapped used for vapor deposition:
into place over the tight-fitting base, an ideal (A) warming oven;
environment for vapor deposition of the (B) upper body of
catalyst was created. TD was left in catalyst polyethylene chamber,
vapor deposition for hours in a warming with a small hole in its
oven set at ˚C. It was then removed from top; (C) CT- vapor
the oven and exposed to fresh air in a fume created by warming the
hood. After hours in air, TD was evalu- catalyst to _C; (D) TD
sitting on top of the
ated and samples of wood were collected for
source of catalyst;
NMR analysis.
(E) aluminum screen and
NMR spectrographic analysis showed that
paper towel, creating the
CR- was not polymerizing PEG within the platform on which TD
cell voids of the wood, as had been expected. sits; (F) aluminum
Instead, the warm solution of CR- was re- weighing dish holding g
moving the unbound PEG solution from the of CT- catalyst;
cells. PEG remains water miscible within the (G) tight-fitting base of
cells of wood. It, therefore, remains sensitive the containment chamber.
ciated with PEG had reacted with CR-, act- The preparation of TD by boiling in water
ing as part of the self-condensing reaction has been shown to alter the chemical consti-
34 that had formed new polymers within the cell tution of the tongue depressor, as evidenced
structure of the wooden tongue depressor. by the loss of the acetate resonances at and
Further NMR analysis was conducted to un- ppm in comparison with the spectrum
derstand this chemical reaction. on the control (TD). The changes in these
13
C spectra of the two birch wood tongue
1
H, 13C, and 29Si Nuclear Magnetic depressors are quite similar to those reported
Resonance Characterization by Wilson et al. for oak woods taken from
shipwrecks.4 The 13C spectral signature, along
The solid state NMR spectra were acquired with the macroscopic observations of exten-
with a Bruker MSL spectrometer oper- sive warping and shrinking upon drying in
ating at a magnetic field of . Tesla. The air, suggest that this preparation provides a
high resolution solid state 1H (CRAMPS) suitable model for the analysis of waterlogged
spectra were acquired with an MREV- pulse wood.
sequence using a microsecond -degree The 13C CP/MAS spectrum of the water-
pulse and a tau value of microseconds. The logged tongue depressor (fig. ., top) is nearly
1
H-13C cross-polarization (CP/MAS) spectra identical to that of the waterlogged tongue
with high power H decoupling and magic depressor (TD) after treatment with PEG
angle spinning were acquired with a -de- (fig. ., bottom). The spectral difference
gree pulse of microseconds, a contact time for the waterlogged tongue depressor treated
of . milliseconds, and a recycle delay of with PEG shows up in the 13C Bloch de-
seconds. cay spectrum (fig. ., top). A large resonance
Additionally, 13C spectra (Bloch decay) at . ppm is present, in good agreement
were acquired with a -degree excitation with the sharp single resonance of . ppm
pulse with high power 1H decoupling and observed in the 13C solution state spectrum
magic angle spinning using a recycle delay for an aqueous solution of PEG and with
of seconds. The 29Si spectra (Bloch decay) the broader 13C resonance at ppm for PEG
were acquired using a -degree excitation in the solid state.
pulse with high power 1H decoupling and The absence of signal or small signal in-
magic angle spinning using a recycle delay tensity observed under cross-polarization is
of seconds. consistent with significant molecular mobil-
The 13C CP/MAS spectrum for the un- ity of the PEG . Such mobility would at-
treated control tongue depressor (TD) is tenuate or average the 1H-13C dipolar inter-
shown at the bottom of figure .. The spec- action used for magnetization transfer in the
trum is consistent with a composition of experiment. This observation of the 13C reso-
cellulose, hemicellulose, and lignin.3 Both cel- nance of the PEG in the Bloch decay
lulose and hemicellulose are carbohydrates. spectrum and not in the cross-polarization
The 13C resonances of cellulose are between spectrum indicates that the PEG is still
and ppm. Hemicellulose contains ac- a very molecularly mobile species, even when
etate functional groups with resonances at absorbed within the wood. While molecular
and ppm. Lignin is a polymer of phenolic mobility sufficient to attenuate the dipolar
cinnamyl alcohols. No significant spectral interaction necessary for cross-polarization
differences were noted in comparison with need not include translational mobility, only
the Bloch decay spectrum. The 13C CP/MAS slight temperature increases above ambient
spectrum for the waterlogged tongue depres- are necessary for the PEG to migrate out
sor (TD) is shown at the top of figure .. of the wood.
TD was then treated with CR-. The 13C bond on the silicon sites with a methyl and
CP/MAS spectrum of the waterlogged two siloxy groups. The presence of hydroxyl
tongue depressor treated with both PEG groups as this fourth bond is confirmed in 35
and CR- (fig. ., bottom) is nearly identi- the solid state 1H spectrum of the polymer
cal with that of the waterlogged tongue de- (fig. .). In this spectrum, the peak at -.
pressor (TD) shown in figure . (top). The ppm shows the methyl protons on the silicon
difference is a new 13C resonance, which ap- while the smaller peak at . shows the hy-
pears at -. ppm. It should be noted that droxyl protons on the silicon. The structure
the 13C Bloch decay spectrum (not shown)
of this sample still indicates the presence of
some PEG . Inside the tongue depres-
sor, a condensation reaction has occurred.
The CR- appears to have been hydrolyzed
in the aqueous environment to the triol,
giving off methanol. The triol then self-
condensed to form a silicone polymer. The
13
C CP/MAS spectrum of the solid polymer
formed under identical conditions in the
absence of the wood is shown in the top of
figure .. The major resonance is at -. ppm
with small resonances at . and . ppm.
In aqueous solution, the 13C resonance of
PEG is at . ppm.
Though CR- is not miscible in aqueous
solution, the 13C solution state spectrum ac-
quired in deuterated chloroform shows a
Fig. .. 13C CP/MAS spectra of the control tongue depressor TD (bottom)
methoxy (–SiOCH3) resonance at . ppm
and the waterlogged tongue depressor TD (top).
and a methyl (–SiCH3) resonance at –.
ppm. This indicates that only small amounts
of PEG and methoxy groups are present with
a change in the methyl group resonance as
the polymer is formed.
No 29Si resonances were observed for the
control tongue depressor (TD). However,
figure . shows the 29Si spectra of the wa-
terlogged tongue depressor (TD) treated
with both PEG and CR- (bottom) and
of the solid polymer formed from the CR-
(top). The spectra are consistent with two types
of silicon environments, one with silicons
bearing two siloxy {H3CSi(–OSiO)2OR} groups
(– ppm) and one with silicons bearing
three siloxy groups (– ppm).
Since the 13C spectrum of the solid poly-
mer formed from the CR- (fig. ., top)
showed only a trace of a methoxy resonance, Fig. .. 13C CP/MAS (bottom) and Bloch decay (top) spectra of the water-
it is clear that the methoxy is not the fourth logged tongue depressor TD treated with PEG .
36
of the silicone polymer formed in the absence While the length of the wood remained un-
of the wood as well as within the wood is changed at . cm, its center width swelled
shown in figure .. to . cm, a .% increase. After removal
of PEG from the wood and treatment in CR-
Observations , swelling was almost completely elimi-
nated from TD. The length of TD re-
The PEG-treated tongue depressor TD was mained constant at . cm, and the width
a translucent, strong brown color (Munsell was reduced to . cm, a decrease of .%.
.YR .), and the surface texture of the The weight of TD, the control tongue de-
wood was waxy and slightly sticky. After treat- pressor, was . g. After treatment in PEG,
ment in CR-, however, the wood changed TD weighed . g, a .% increase. After
to a gray brown color (Munsell YR .). The
presence of heat and moisture during immer-
sion in CR- encouraged the flow of PEG
from the cells of the wood so that, after
the treatment, the surfaces of TD felt dry.
Additionally, the surface texture and wood
grain of TD were natural in appearance,
even though waterlogging had changed the
color.
Measurements of the control tongue de-
pressor (TD) were used to monitor dimen-
sional changes for TD at various stages of
treatment. TD measured . cm long and
. cm wide at the center. After preserva- Fig. .. Structure of
tion in PEG , swelling was noted in TD. the silicone polymer.
treatment in CR-, the weight of TD was in a fume hood for several days. Once ex-
. g, a .% decrease. posed to fresh air, the solution formed a hard,
38 Prior to treatment, temperature variations clear polymer.
affected TD. At slightly elevated tempera- The solution of CR-, PEG, and water
tures of ˚C, the surfaces of the wood were that resulted from the extraction of free-flow-
sticky; at ˚C, its surfaces were wet. After ing PEG from wood formed hard polymers
treatment in CR-, however, stickiness and when the solution was exposed to fresh air
pooling of PEG were not noted when TD for three days. There was some 13C, NMR
was exposed to elevated temperatures. The evidence to indicate that the CR- also re-
CR--treated wood remained dry without acted with some of the hydroxyl end groups
signs of warping. of the PEG, aiding in the formation of new
The surfaces of TD were slick with a thin polymers within the cell wall structures of
layer of PEG when the wood was removed the wood. Scanning electron microscopy was
from the CR- solution. After wiping with conducted on samples of wood prior to and
lint-free cloths, the wood looked more like after treatment in CR-. In figure ., the
the original color and texture of the control cell structure of the wood is not evident due
wood sample. After a few minutes of expo- to the heavy concentration of PEG. After
sure to fresh air, the surfaces of the wood treatment in warmed CR-, however, PEG
were dry, without additional color changes. that had not bonded to cell walls was elimi-
When the CR- was cooled to room tem- nated. At higher magnification, the bond be-
perature, a suspension of PEG was noted in tween PEG and interior cell walls is evident
the solution (fig. .). This solution was (fig. .).
poured into a shallow pan and allowed to sit
Conclusions
One potential by-product is formic acid.5 due to heat-induced migration. After treat-
Polymers formed in solution with CR- are ment in CR-, PEG bonded to cell walls is
more rigid in structure, and in this state, for- stable and resistant to environmental influ-
mic acid is not formed. Methanol, however, ences. One advantage to the CR- treatment
is formed in the hydrolysis of CR-. Subse- process is that, after treatment, the diagnos- Fig. .. After free-flowing
quent testing has shown that catalyzation of tic attributes and general aesthetics of the PEG is removed from the
PEG-impregnated artifacts is not necessary. wooden artifact are well preserved. Due to wood, PEG bound to the
CR- hydrolyzes in the aqueous environ- the process of degradation caused by immer- cell walls is evident.
ment to the triol. It then self-condenses to
form the silicone polymer, forming two dis-
tinct silicons illustrated in the 29Si spectra (see
fig. .). The silicon environment has a me-
thyl group and three siloxy bonds (i.e., So-
O-Si). The second silicon environment has
only two bonds. The third is formed to the
methyl group while the fourth bond is to the
hydroxy group as in the 1H spectra (see fig.
.). Polymerization can be accomplished
without catalyzation. The use of catalysts
should not be ruled out, however. Additional
experimentation is needed to determine if
catalyzation acts to strengthen or enhance the
polymers created by combining PEG with
CR-.
Repeated testing has shown that immer-
sion in heated CR- removes unbound PEG
from the cells of waterlogged wood, probably
sion in water, CR-- treated wood does not with large canons is the sabot, a wooden, flat-
have the same coloration as the nonwater- based attachment that allowed better posi-
40 logged control wood samples. The wood, tioning of the ammunition and fuse within
however, is dimensionally stable after treat- the breech of a gun. In this case study, I ex-
ment in the silane. Because unbound PEG amine an effective process developed at the
has been removed from the cell structure, the Archaeological Preservation Research Labo-
wood is lighter in weight. ratory to stabilize the wooden components
After several days’ exposure to fresh air, of a composite artifact initially preserved
the CR-/PEG solution resulting from ex- using polyethylene glycol.
traction of PEG from TD had formed into a The two sabots delivered to the lab were
hard, clear polymer. CR- self-condenses to part of an assemblage of Civil War spheri-
form this polymer, with or without PEG. At- cal shot cases recovered from Mirror Lake
tempts at dissolving the polymer in water, al- near North Calais, Vermont. These shot cases
cohol, or acetone have not been successful, and were intact when recovered, but the flat-based
the polymer is not affected by fluctuations in wooden sabots had been separated from the
temperature or humidity. Additional experi- cast iron components for conservation pur-
mentation is needed to determine if the CR- poses. First, each of the shells was considered
polymer, which had bonded to the cell walls live, necessitating that each be defused. Sec-
of the wood, strengthens the artifact. Prelimi- ond, it was determined that the component
nary results indicate this may be the case. parts required separate conservation and that
Because unbound PEG flows freely from the each part would need close monitoring in wet
artifact during treatment in CR-, cell inte- storage. Figure . is a more modern ex-
riors and voids within the wood remain un- ample of an assembled spherical shot.
clogged. Removal of free-flowing PEG results Inspection of the two wooden artifacts
in a reduction in weight of the wooden arti- indicated that, even three years after treat-
fact. This reduces physical stress on the wood. ment, both remained wet to the touch and
The resultant polymers do not fill cell struc- surprisingly spongy. Because both sabots
tures and voids within the wood, making ad- were very wet, it was impossible to section
ditional re-treatment possible, if needed.
Because of the self-condensing nature of
CR-, resulting in the formation of poly-
mers, catalyzation is not necessary. In the case
of the waterlogged tongue depressors, the use
of topical and vapor deposition catalyzation
does not appear to adversely affect the end
results of CR- treatment.
and visually identify the genus and species to a / water/PEG mixture. Following
of the wood used for construction. Accord- treatment, the sabots were surface-wiped and
ingly, the decision was made to attempt this then freeze-dried to remove excess moisture.
identification after the wood had been re- Upon completion of the preservation pro-
treated. Sabot B was in better condition than cess using PEG, it was evident that it would
sabot A, which had numerous cracks around be impossible to reassemble the wooden
the upper edge of its concave surfaces and a bases with their conserved components, due
central hole and crack running through the to the hygroscopicity of the wood. Sabots A
base. In both cases, raised wooden grain along and B are illustrated in figure ., and the
the tangential plane suggested that, at some exterior surface texture of the sabots is illus- Fig. .. The exterior
point, the specimens had been partially de- trated in figure .. surface of one sabot.
hydrated, causing shrinkage and slight dis-
tortion of the surface wood. As E. E. Astrup
has noted, the problem of shrinkage is ex-
pected because of evaporation of residual
water within a treated specimen and the re-
sultant decrease in the volume of PEG.6
Conservation notes for the two artifacts
indicated that both sabots had been mechani-
cally cleaned with dental instruments. Each
artifact was then rinsed in a % bath of hy-
drochloric acid to remove iron stains prior
to rinsing in a % solution of hydrogen per-
oxide with % ammonia in deionized water
to remove organic stains. After additional
rinsing, the sabots were treated in a blend of
and PEG, which was slowly increased
Prior to re-treatment, each of the sabots aluminum foil cap was placed over the top
was weighed, measured, and photographed of the cylinder. Then the TD, immersed in
42 to record all aspects of the artifacts for com- solution, was placed into a vented warming
parative analysis following re-treatment. Be- oven set at .˚C for hours (fig. .). The
cause neither sabot appeared to be perfectly sample was then removed from the oven and
round, two sets of diameter measurements allowed to stand at room temperature for
were recorded. The position of the first mea- hours before it was taken out of the CR-
surement was recorded, and a second diam- and surface-wiped with a paper towel. In-
eter reading was taken at degrees to the spection of the cylinder revealed that a large
first. Tracings of the top and bottom surfaces volume of free-flowing PEG had been ex-
of the sabots were made to assist in monitor- tracted from the tongue depressor. As the CR-
ing potential dimensional changes that may solution cooled, PEG remained in suspen-
have resulted from re-treatment. Dimen- sion, appearing as a fluffy white substance.
sional data appear in table .. The last step in the process of re-treating
the PEG-treated TD was to initiate vapor
Test Process in Preparation for catalyst deposition, using a tin-based cata-
Treating the Sabots lyst to complete the polymerization process.
To accomplish this, a closed environment was
An initial experiment was conducted to de- needed to contain catalyst fumes in close as-
termine the efficacy of an alkyl silane for re- sociation with the tongue depressor. A con-
moving free-flowing PEG from the cellular tainment chamber was constructed out of a
structure of waterlogged wood. This type of one-quart polyethylene pail placed in an in-
cross-linker is commonly used in the Re- verted position so that its tight-fitting cover
search Laboratory as a cross-linking agent for served as the flat base of the unit. A catalyst
the purpose of polymerizing dimethyl silox- tray was created using an aluminum sample
ane, hydroxyl-terminated polymers. It has tray with mesh aluminum screen placed over
proved potentially useful for treating chemi- it. The screen formed a platform on which
cally bound PEG within the cell wall struc- the sample rested and was positioned above
tures of wood, reducing the hygroscopicity the catalyst tray during catalyst vapor deposi-
of the remaining PEG. tion processing. Several paper towels were
To illustrate the general results from re- placed on top of the screen to prevent free-
peated experimentation, a single waterlogged flowing PEG from dripping into, and contami-
tongue depressor (TD), treated with PEG nating, the catalyst. Fifteen grams of CT-
, was taken from its PEG solution and were added to the catalyst tray, and the TD was
wiped with a paper towel to remove pooled positioned on the screen with the body of the
PEG from all its surfaces. The sample was containment chamber properly fitted over it
then placed into a graduated cylinder con- (fig. .).
taining ml of fresh CR-. A loose-fitting Once assembled, the unit was placed into
Sample Top Width (in cm) Base Width of Rim (in cm) Height (in cm) Weight (in g)
Sabot A 11.505 (1st reading) 9.72 (1st reading) 4.882 2.662
11.026 (2d reading) 9.75 (2d reading)
Sabot B 10.986 (1st reading) 10.00 (1st reading) 4.65 2.622
10.984 (2d reading) 9.73 (2d reading)
solution into a milky colored solution as a
result of the PEG in suspension, which had
been removed from the tongue depressor. 43
Instead of remaining dark brown, the tongue
depressor was a light gray brown. The re-
treatment color was very similar to the color
of the control samples. Prior to re-treatment,
the PEG-treated tongue depressor had
swelled to a size slightly wider than the con-
trol tongue depressor. After re-treatment, the
tongue depressor had returned to its origi-
nal width.
Re-treatment of PEG-Treated
Waterlogged Wood
Fig. .. Configuration of the containment The methods used to preserve sabots A and
chamber used for catalyst vapor deposition: B were the same as those outlined for the
(A) vented oven; (B) loose-fitting cap; tongue depressor above. Sabot B was placed
(C) graduated cylinder; (D) CR- solution; into a large plastic container and immersed
(E) tongue depressor. in a sufficient volume of CR- to ensure that
there was approximately ½ inch of CR-
covering the uppermost portion of the arti-
a vented warming oven set at ˚C. The fact. A loose-fitting top was positioned over
sample remained in catalyst vapor deposition the container, and the artifact in solution was
for hours. Following treatment, the sample placed into a well-vented warming oven set
was removed from the oven and transported at ˚C. The artifact was left in treatment for
to a vented fume hood and opened. After the . hours.
TD was allowed to sit in fresh air for several Sabot A had extensive cracks that extended
days, it was placed into a vented warming through its sides and base. To determine if
oven and heated to ˚F for a few hours. the presence of a catalyst in the cross-linker
Throughout the heating process, no dimen-
sional changes or sweating were noted.
four sections. Due to its waterlogged state, shipwreck, La Belle. Each piece of wood was
the plank was very fragile. Sectioning was roughly carved and slightly tapered in shape.
accomplished using a long scalpel blade. Fig- After desalination in freshwater baths for
ure . illustrates the dimensions of the months, treenails were surface-dried with
group wood samples. paper towels and then weighed, measured,
and photographed (figs. . and .). Six-
Materials—Group 3 Waterlogged Treenails teen of the treenails were then placed into a
series of four ethanol baths, followed by a
Fig. .. Waterlogged Group samples were treenails extracted series of four acetone baths, each lasting two
treenail before air-drying. from the timbers of a seventeenth-century weeks. Eight of the treenails were picked ran-
domly and immersed in CR-. Eight were
immersed in Q-. The remaining two
treenails were air-dried for hours in a
vented warming oven to determine percent-
age of water content.
Materials—Chemicals
1
Fragmentation precluded posttreatment length and width measurements.
2
Fragmentation precluded exact posttreatment length measurement; the value is an
approximation.
initial cleaning and desalination, the treenails Group wood samples treated with CR-
were found to be less spongy than the sec- alkoxysilane polymers experienced only
tions of plank, and the wood was noticeably slight changes in posttreatment weight,
harder. Many of the ends of the treenails had length, and diameter compared to the group
either been broken or splayed under the force Q--treated wood. After treatment, the
of being removed from the ship’s timbers. mean weight of CR--treated treenails was
. g, a reduction of .%. Treenails pre-
served using Q- polymer had a mean
weight of . g after treatment, a reduction
of .% (table .). Group treenails pre-
served using CR- had a mean reduction in
length of .%. The change in length was
greater for Q--treated treenails, with a
mean posttreatment length of . mm.
Fig. .. Group wood
This represents a shrinkage of .% shrink-
after treatment. W1, oven-
age (table .). Similarly, the mean change
dried wood; W2, CR--
in diameters for the group , CR--treated
treated wood; W3,
Q--treated wood; nails was substantially less than the mean
W4, air-dried wood in change in diameter for Q--treated tree-
vented fume hood. Note nails. The posttreatment mean diameter for
the comparatively lighter CR--treated wood was . mm, a reduc-
color of W2. tion of .%. Q--treated treenails had
a mean loss in posttreatment diameter of as well as the availability of nonwaterlogged
.% (table .). control samples, make the group wood
The most noticeable difference between samples invaluable for experimentation. Be- 57
the CR-- and Q--treated treenails was cause of inherent inconsistencies of water-
in coloration. In all cases, the CR--treated logged archaeological wood, similar compara-
wood was much lighter in color. Q-- tive data cannot be derived for archaeological
treated wood tended to be darker, with fewer samples.
wood grains and surface features visible. Air-dried group wood samples experi-
enced a mean weight loss of .%, a mean
Discussion reduction in sample width of .%, and a
mean reduction in length of .%. All the
NMR spectral analysis, ESEM analysis, and samples were warped and twisted after air-
empirical data indicate that the structural drying.
integrity of the group tongue depressors CR--treated group wood samples were
was sufficiently degraded that the wood generally well preserved. Mean reduction in
samples can be used to evaluate preservation length was .% after treatment. Mean re-
treatments for waterlogged timbers from duction in width was .%. These figures
shipwrecks. Group wood samples also pro- may seem high, but a comparison of the post-
vide a reasonably homogenous source of treatment dimensions of the CR--treated
wood that allows quantifiable and qualita- samples shows that they are nearly identical
tive analysis of the efficacy of consolidants to the untreated, control depressors, indicat-
being tested for use in conserving water- ing that the treated wood was restored to
logged wood. Regularity of size and species, dimensions nearly identical to those of the
Leather
Preservation
L
eather recovered from archaeological lubricates collagen fibers and prevents shrink-
sites presents a variety of challenges for age. Accordingly, PEG treatments based on
the conservator. Regardless of their the incremental addition of PEG to an aque-
condition, leather artifacts reveal something ous solution in which the artifact is immersed
about the technology and craftsmanship used have been the most common means of pre-
in their creation. Tool marks may indicate the serving waterlogged leather. In combination
level of skill of the cobbler. Wear marks may with freeze-drying technology, PEG treat-
help characterize the occupation and affluence ments have been very successful in preserv-
of the owner. ing the diagnostic attributes of waterlogged
leather artifacts.
Mold, mildew, fungi, and exposure to ul-
Archaeological Leather traviolet light and airborne contaminants
such as sulphur dioxide all act to undermine
Whether from a terrestrial or marine site, ar- the integrity of leather. Singly, or in combi-
chaeological leather is affected by numerous nation, these factors complicate the process
environmental factors that act to compromise of stabilization. The often delicate condition
its general stability. Leather recovered from of archaeological leather necessitates that all
land sites may be brittle if the relative humid- destructive mechanisms be neutralized prior
ity (RH) is less than %. Often, embrittled to treatment. In most cases, archaeological
leather will crack and shrink excessively. In leather requires some degree of cleaning be-
dry and desiccated leather, collagen fibers, fore conservation procedures are undertaken.
which are polymers made up of amino acids, Badly deteriorated leather, however, may be
may become rigid due to a lack of moisture. too friable to clean, and it may therefore be
These artifacts need careful rehydration to impossible to remove stains without causing
prevent continued cracking and deteriora- extensive damage. In such cases, it may be
tion. Dressings and topical applications of best to focus on stabilizing the leather.
lanolin and cedarwood oils have been used
to lubricate leather. To regain flexibility in dry Variables to Consider
leather, conservators have used glycerol, sor-
bitol, or a wide range of molecular weights Many factors need to be considered before
of PEG. attempting to conserve leather. These factors
Wet leather also requires careful treatment may be beyond the abilities of the conserva-
to prevent surface drying and hardening of tor to determine but nonetheless play a role
collagen fibers. Excessive hydration may lead in the state of deterioration affecting archaeo-
to the loss of tannins. In their absence, water logical leather. Determining genus and spe-
cies of the animal may be important when treated hide. Vegetable tanning processes pro-
trying to assess the degree of flexibility and duce polyphenols, which readily form hydro-
color desirable in a preserved piece of leather. gen bonds with carbon atoms associated with 61
The degree of use wear may also be an im- available hydroxyl groups within the leather.
portant consideration. Apart from being di- For this reason, vegetable tanned leather, in
agnostic features of the artifact, extensive many cases, deteriorates rapidly as hydro-
scuff marks and surface abrasion may help lyzation interrupts the chemical equilibrium
determine a suitable treatment strategy. of the leather. Bark from oak trees is still com-
Artifact association or proximity is an- monly used for noncommercial tanning of
other consideration when developing a con- hides; indeed, the bark and roots of many
servation strategy for leather. Archaeological plants have tannins that are effective in sta-
leather closely associated with large deposits bilizing proteins.
of organic materials may be heavily degraded For the most part, twentieth-century
due to fungus and decay, whereas leather in leather was tanned using chromium tanning
close association with iron artifacts may be processes; it is sometimes called mineral
heavily concreted or impregnated with min- tanned leather. Chromium salts, which act
erals and oxides. to reinforce collagen molecular chains, also
Initial means of tanning used to preserve give leather a chemical resistance to many
the leather may be a factor in an artifact’s state agents of decomposition including molds
of deterioration. This may also help deter- and fungi, as well as airborne contaminants
mine viable treatment strategies for preserv- producing sulfuric acid. In comparison, veg-
ing the artifact. The earliest suspected means etable tanned hides are more susceptible to
of preparing animal hides were concerned airborne contaminants since the cross-linking
with slowing the processes of putrefaction. of proteins is not as complete as the chemi-
Besides hides, other organs including the cal transformation and stabilization induced
stomach and bladder were utilized. Brain tan- by chromium processing, which makes hides
ning was also common. In many cases, the somewhat hydrophobic.
brains of the animal were considered suffi- Regardless of the method used for tanning
cient to tan the whole useable hide of the leather, hides share one common character-
animal. Smoking and close skinning tech- istic. Collagen fibers, which are fibrous pro-
niques, which removed thick layers of fat, teins that give leather its flexibility, require
were also commonly used to prepare hides. natural lubrication for the hide to remain
By removing the thick layers of subcutane- supple. These same fibers require chemical
ous tissue or using smoke to cure tissues, restructuring to prevent breakdown of the
hides could be effectively preserved. fibers and putrefaction. Hydrolyzation acts
Historic period hides and leather were also to break down collagen chains, thus reduc-
commonly prepared using vegetable tanning ing a skin’s ability to remain supple once
methods. This incorporated the use of natu- water has been removed from the hide. Wa-
ral tannins found in the bark and roots of terlogged leather usually becomes increas-
numerous plants. Hides were soaked in baths ingly soft as the process leaches tannins and
of bark and water in order to infuse them fats from its matrix. Accordingly, determina-
with tannins that combine easily with col- tion of the physical state of deterioration can
lagen and proteins. Tannins replace water in be difficult. High pH levels may indicate the
the hide and reinforce side chain structures, presence of oxides in degraded leather. Nu-
essentially cross-linking protein molecules, merous tests can be made on wet leather.
making them stable. They are effective anti- Generally, these tests measure characteristics
oxidants and help maintain flexibility of the or qualitative aspects. Regardless of the state
of the artifact, leather removed from a wet Many inexperienced conservators hold the
environment must remain wet until treated. tip of the air scribe at too sharp an angle,
62 which directs the force of the stylus directly
into the artifact. By working at a shallow
Cleaning angle to the line of the artifact, the force of
the stylus is deflected, reducing stress. With
Waterlogged leather recovered from ship- practice, an air scribe or pneumatic chisel can
wreck sites can pose many challenges. Leather be operated with finesse, allowing very fine
from these sites may be covered with con- and detailed mechanical removal of con-
creted deposits, which are the product of creted materials from leather and other deli-
oxidation of metals. Concreted material and cate artifacts.
impacted soil on leather from land sites
should be removed carefully using soft
wooden dowels and brushes. In some cases, Chemical Cleaning
leather may be too soft and fragile to clean. It
is best to treat these artifacts with a minimum Numerous organic acids can be used to re-
of cleaning and handling. Often, additional move corrosion and stains on leather recov-
cleaning can be successfully accomplished ered from marine environments. Citric acid,
after conservation, when the leather is in a oxalic acid, disodium EDTA, tetrasodium
more stable state. EDTA, ammonium citrate, and dilute hydro-
To prevent structural damage to badly chloric acid (–%) are a few of the most
deteriorated leather, cleaning should be con- common treatments. Citric acid is a slow and
ducted using a soft brush, while the artifact gentle acid; hydrochloric acid tends to work
is submerged in freshwater. Leather in good more quickly. Whatever means are employed
condition can be cleaned by placing it on a to remove corrosion, concretion, and stains
clean working surface and using a gentle, di- from leather, it is essential to extensively rinse
verted flow of water to keep it wet. This al- the artifact in fresh running water baths af-
lows the conservator to inspect the artifact ter treatment. If chemicals are not completely
more closely. A direct flow of water on leather flushed from the matrix of the leather, there
should never be used since this may cause is a risk of chemical reactivity among tannins,
irreversible damage due to erosion and pit- fats, collagen fibers, and the acids and neu-
ting of the artifact’s surfaces. tralizing agents used to treat the artifact. Ac-
While it is best to remove concretion cordingly, chemical cleaning of waterlogged
from the surfaces of leather using soft or desiccated leather is often not the first
wooden tools, heavier areas of concretion choice of many conservators.
can be removed using an air scribe. With a
gentle touch, using the vibration of the sty-
lus to break apart hard deposits, this instru- Treatment of Leather
ment can be more effective for removing
thick, concreted materials than wooden It is difficult and risky to attempt conserving
dowels. Care must be taken, however, since archaeological leather by controlled drying
these same vibrations can undermine the or freeze-drying methods without the aid of
artifact’s integrity. It is often better to hold a a replacement bulking agent to maintain the
small piece of leather or place it on a soft artifact’s physical attributes. As water is re-
bedding of cloth to absorb vibrations from moved from the artifact, collagen fibers are
the air scribe. This will substantially reduce drawn together, causing hardening, shrink-
stress on the artifact. age, and disfigurement. To prevent these
problems, water within the matrix must be bacteria. Use of organic solvents, however,
displaced with a suitable bulking agent that displaces water within the matrix of the
will enable the artifact to withstand the dry- leather. Loss of water as a lubricant in the 63
ing process. Over the last few decades, PEG leather results in stiffness. In some circum-
has been widely used for the treatment of stances, this is useful during treatment since
leather. Through incremental additions of it adds a degree of rigidity to the artifact, pre-
PEG to water, the cells and voids in the ma- venting damage or loss of information due
trix of leather can be sufficiently supported to disarticulation. The state of deterioration
and lubricated to prevent the shrinkage and and the need for internal stabilization are
hardening that occur as the result of drying. prime considerations when deciding on a
Anyone who has ever worked with wet treatment strategy for leather.
leather has observed that the artifact remains Treating waterlogged leather with PEG
soft and supple while immersed in water. followed by freeze-drying to remove water
When moved to a bath of organic solvent, from the artifact has proved to be a highly
such as ethanol, the leather becomes stiffer successful conservation strategy. Because
and harder to manipulate. This change in PEG is soluble in water, it is an attractive
malleability occurs as water is replaced by the treatment method for leather. To a lesser de-
solvent. Progressive dehydration has been gree, PEG is soluble in methanol. Because of
successfully used to conserve some wet leather this, badly deteriorated leather can be stabi-
artifacts. By taking the artifact through a se- lized in a solution of water and alcohol, which
ries of baths, starting with ethanol and work- helps to give the leather some degree of ri-
ing up to fresh baths of acetone, it is possible gidity. At the Preservation Research Labora-
to dehydrate leather into a relatively stable tory, treatments usually involve incremental
state. additions of PEG to water to form an aque-
The problem with such treatment strate- ous solution in which the leather remains
gies, as Cronyn notes, is that there is a chance immersed until a high enough percentage of
of shrinkage and distortion in the artifact.1 PEG is introduced into the matrix of the
Degree of degradation, biological activity, leather to allow controlled, slow air-drying.
rate of water-solvent exchange, variance in Lower molecular weight PEGs (PEG
surface tension, and chemical reactivity with to ) are clear and somewhat viscous at
insoluble deposition on the surfaces of the room temperature. These products are ideal
artifact will affect dehydration and prepara- for use in room temperature treatment of
tion of the leather for continuing conserva- leather. After reaching –% concentration
tion work. of PEG in water, the artifact can be removed
from the solution, surface-dried of excess
solution, and allowed to slowly air-dry in a
PEG/Air-Drying Treatments controlled environment. Controlled drying
will prevent excess pooling of PEG on the
While immersed in water, the fibers of leather surfaces of the artifact. Surface deposition
are supple and flexible. This works to the of PEG can be removed by daubing the
advantage of the conservator during treat- affected areas with a damp, lint-free cloth.
ment since the leather object is relatively Surface pooling, however, may be an indica-
easyto work with as compared to leather tion of more serious problems affecting the
stored in alcohol or water/alcohol solutions. stability of the artifact. If the leather is al-
Often a mixture of alcohol and water are used lowed to dry too quickly or if temperature
for the long-term storage of leather since such and humidity are not regulated, PEG will
solutions inhibit the growth of fungi and migrate to the surfaces of the artifact and,
over a short period of time, shrinkage may long-term controlled storage in a standard
occur. Controlled, slow air-drying will pre- freezer. Humidity control is limited using a
64 vent most of these complications. Generally, conventional freezer system; nonetheless, ice
however, as much as % shrinkage has been crystals sublimate as gases, resulting in a sta-
associated with the PEG treatment of water- bilized artifact. With more elaborate freeze-
logged leather. drying systems, the vacuum, temperature,
and relative humidity can all be monitored
and regulated. Controlled environment pro-
Freeze-Drying PEG-Treated Artifacts cessing and monitoring of humidity allow the
conservator to determine when the treatment
Generally, there is no steadfast rule for de- process is complete.
termining the percentage of PEG that should The use of larger and more elaborate
be added to water to pretreat leather before freeze-dryers allows the conservator more
freeze-drying. Experience is the best guide control over the processing of artifacts (fig.
since state of degradation, possible fungal .). Artifacts are usually frozen for a period
problems, and presence of oxides all affect the of time at very low temperatures (–˚C)
potential for preserving leather. Conservators prior to placing them into a freeze-dryer.
use a wide range of pretreatment strategies Drying can then be accomplished in many
in preparation for freeze-drying. In the case ways. Low-temperature freeze-drying takes
of badly deteriorated leather, a % or higher a longer period of time, while near room tem-
aqueous solution of PEG may be necessary perature processing will be completed com-
to stabilize the artifact. Leather in good con- paratively quickly. Many successes have been
dition may require a lower percentage pre- reported using ultralow and near room tem-
treatment. perature methods, so it is best to experiment
Aqueous solutions of PEG may require the with a particular assemblage of equipment
use of biocides to control biological activity, to determine how to reliably obtain consis-
especially at lower percentages. Because it is tent results. Regardless of which strategy has
impossible to accurately assess the ramifica- been prescribed for an assemblage of arti-
tions of their use to control microbial activ- facts, low vacuum is maintained throughout
ity, they should be closely monitored and processing.
applied sparingly. Many biocides are mildly Other processes have been successful for
toxic, and some people have a mild reaction the treatment of wet leather. J. M. Cronyn
when they come into contact with these reported success in using freeze-drying pro-
agents. Ortho-phenylphenol, commonly cessing with PEG in -methylpropanol.2
known as Dowicide , has been widely used Several nonpolar solvents, such as toluene
since it appears to be an effective deterrent to and kerosene, have also been reported to give
microbial activity. Tests indicate that it is less good results. Because many of these solvents
of a biological hazard than other commer- are flammable, care must be taken in their
cially available biocides. use. Be aware that changes in pressure and
After pretreatment, pooled PEG must be dispersion of fumes will alter the explosion
carefully removed from the surfaces of the point of some solvents.
leather before freeze-drying. This will ensure In recent years, PEG has fallen into disfa-
that the freeze-drying process is uniform. All vor with many conservators because of
conservators seem to have a freeze-drying changes in environmental laws, which vary
strategy that works well for their range of from one country to another. Disposal of
artifacts and levels of expertise. Many arti- PEG has become an issue for many labora-
facts have been successfully preserved using tories since the introduction of too much
PEG solution into a community septic sys-
tem can stop microbial activity, thereby effec-
tively halting the processing of waste water. 65
In the early stages of experimentation with
PEG, the material was considered environ-
mentally friendly and safe for laboratory use.
Today, conservators realize that, in large
quantities and at the higher level of concen-
tration used for the treatment of artifacts,
precautions need to be taken when handling
PEG. Certainly, protective clothing, goggles,
and limited exposure to PEG fumes are man-
datory.
Most organic artifacts are hygroscopic. Many chemical reactions are slowed or in- 73
Waterlogging processes act to break down the hibited by keeping organic materials at lower
fibrous structures of leather as well as remove temperatures. Temperatures must never be so
natural lubricants that protect fibers from low, however, that changes in humidity cause
hydrolysis. Hydrolysis increases the amount problems with condensation. It is important
of water in the matrix of the leather, which to keep artifacts at a constant, cool tempera-
ultimately must be replaced with an agent ture below the melting point of the bulking
that can stabilize the leather without its los- agents and consolidants used to treat the as-
ing physical integrity. Relative humidity is an semblage. PEG-treated artifacts are most vul-
important consideration for the storage of nerable to temperature changes because as
leather since elevations in humidity can pro- temperatures are decreased, the relative hu-
mote microbial activity and new problems midity increases, causing potential problems
in the stabilization of the artifact. in the stability of the artifact. Artifacts pre-
Maintaining a constant relative humidity served using Passivation Polymer technologies
in a display environment will prevent ab- are substantially more stable and are unaffected
sorption and release of moisture from by changes in temperature. Although stability
leather. In many cases, leather treated with is increased, however, good practice dictates
PEG can swell if relative humidity is too high that all artifacts be treated with the same con-
(% or more). The miscibility of PEG- cerns for safety and stability.
treated leather encourages beading and sur-
face pooling of the bulking agent as mois- Light
ture in the surrounding environment is
absorbed into the leather. Ideally, maintain- Exposure to light is one of the most poten-
ing a constant relative humidity is best for tially dangerous problems for artifacts in
artifacts, and it is a costly environmental fac- museums. Ultraviolet light causes oxidation
tor to ignore. RH is computed using the fol- and sets a number of chemical reactions in
lowing simple equation: motion that are not fully understood. Many
of the consolidants and adhesives used in the
Amount of H2O in air X 100 = preservation of leather are sensitive to light
Relative Humidity Maximum H2O air and, over a short period of time, become
can hold at a specific temperature brittle or lose their desired characteristics.
CHAPTER 5
74
Composite
Artifacts
C
omposite artifacts are generally made of wicker basket, heavily concreted with iron
two or more contrasting materials. Ex- oxides and iron shot, which was recovered
amples include iron cannon balls out- from La Belle.
fitted with iron straps and a wooden base
called a sabot, and knives recovered from the
shipwreck La Belle consisting of hard wooden Case Study: Preservation of a
handles that contain sections of iron knife Composite Artifact Containing
blade. Basketry and Iron Shot
Often each component in a composite ar-
tifact requires a different treatment strategy. The silty bottom of Matagorda Bay has cre-
If this is the case, disassembling the artifact ated the ideal anaerobic environment in
into component parts may be essential for which the large assemblage of artifacts from
preservation. Two complications arise when La Belle have been well preserved. When re-
disassembly is required. Waterlogged artifacts covered, the wicker basket and iron shot were
are usually structurally compromised. Even indistinguishable, since oxides from the cast
the most precise job of disassembly may re- iron balls had combined with minerals and
sult in breakage or damage to one of the com- sediments to create a large formless block,
ponents. Also, when components are treated commonly referred to as a concretion. Apart
separately, they are exposed to treatment- from the general outline of a few of the larger
related structural changes that may inhibit shot, the only distinguishable feature was a
posttreatment reassembly. Wooden compo- large wooden barrel stave encrusted to the
nents, for instance, are more prone to swell- flattest surface of the concretion.
ing during preservation. During treatment, Once the stave and layers of concreted
badly deteriorated iron may be prone to sur- material were removed, the flattened outer
face spalling, resulting in the loss of metal. surface of a wicker basket was visible. Addi-
Even the most gifted conservator will en- tional removal of encrustation revealed that
counter problems in treating some compos- a bar shot was also concreted to the top sur-
ite artifacts. face of the block. Before an initial evaluation
One cannot overstress the point that sili- could be made, a pneumatic chisel was used
cone oils preservation techniques are not a to remove the bar shot from the outer sur-
cure-all for the conservation of all artifacts. faces of the artifact. Radiographs and me-
These technologies, however, do offer some chanical cleaning of a small area of the
benefits for the preservation of delicate arti- concretion’s flattest surface indicated the
facts concreted together with heavy iron ar- outline of one side and the base of a basket.
tifacts. Such is the case of a waterlogged From the X-rays, the basket appeared to be
intact but heavily permeated with oxides and lease of very low molecular weight silicone
concreted material. compounds during setting.1 In creating a
Inside the basket, small shot were clus- successful facing compound for the treat- 75
tered, held in place by impacted sediments ment of painted plasters, Pulga concluded
and concreted materials (fig. .). The shot there was a direct link between the amount
ranged in size from . to . cm in diameter. of staining that occurred and the porosity
Because the outer surface of the basket ap- of the organic material being treated.2 Pulga
peared to be intact, the decision was made to and others have noted that shorter setting
clean the thin layer of encrustation encasing times reduce the release time of siliceous
this outer surface. To minimize damage to compounds and, therefore, reduce the risk
the fragile wicker basketry, a rubber cast of of staining. Since the basketry was thoroughly
the bottom was made. During treatment, this stained with minerals and surface concretion,
cast would act to support and protect the potential staining caused by siliceous com-
basketry while the shot were mechanically pounds during treatment was determined to
cleaned and removed from the interior of the be minimal.
basket.
Displacement Mechanism
Materials and Chemical Sequence
Cordage
and Textiles
T
hroughout history, cordage in one form monoxide (CO) greatly affect cordage and
or another has been made from the textiles. Storage and display of artifacts in
natural fibers of plants and animals. close proximity to parking garages should
Cotton, flax, jute, hemp, grasses, silk, wool, therefore be discouraged. Airborne soot cre-
hair, and strips of animal hides have been ated from incomplete combustion of fossil
used to make rope. These materials have been fuels may chemically react with fabrics. Par-
woven, braided, or spun together to create ticulate contaminants lodge between fibers,
threads for sewing and weaving. causing wear and physical damage.
Artifacts made of cotton and flax are Singly, or in combination, these factors
greatly susceptible to fungi and bacteria in and ever-present microorganisms act to un-
humid conditions and are seldom recovered dermine an artifact’s tensile strength and pli-
from archaeological excavations. Other arti- ability. Generally, textile conservation should
facts made using animal fibers, which are be left in the hands of specially trained con-
primarily proteins, are better able to survive servators. Accordingly, most of this chapter
because they are less prone to destruction by is devoted to the preservation of waterlogged
bacteria. All cordage and textiles, however, are rope. One case study, however, discusses the
affected by exposure to light. Natural dyes will preservation of tar-coated canvas associated
fade quickly if an artifact is left in direct, with a gudgeon strap from a vessel that sank
bright sunlight. The ultraviolet spectrum of during the earthquake of in Kingston
normal light will accelerate deterioration of Harbor, Jamaica.
the artifact, often reducing its pliability. Air-
borne pollutants interact with dyes and natu-
ral fibers. Care should be taken to ensure that New Techniques for the Preservation
artifacts are not stored in modern cabinetry of Waterlogged Rope
constructed using particleboard and urea-
based finishes. Off-gases from these materials To help illustrate new techniques of preserv-
interact with the natural fibers of the artifact ing waterlogged rope, I discuss rope recov-
and some chemicals commonly used in their ered from La Salle’s vessel, La Belle, which
preservation. sank off the Texas coast in . Among the
Other forms of air pollution can affect organic materials found on the vessel were
museum displays and long-term curation of lines from the rigging and coils of rope that
artifacts. Fumes from automobile emissions had been stored in her hold. Conservators
are dangerous to organic artifacts. Hydrocar- have been faced with the formidable task of
bons, nitrogen oxides (NOX), and carbon preserving the large amount of hemp rope
recovered from the vessel, which includes film; the film is then heat-sealed to produce
segments more than . m long. Especially a formfitting jacket in which each rope
82 challenging to the conservators is the anchor sample remains throughout treatment. The
line of the vessel, consisting of a continuous packaged rope is attached to a piece of
section of rope more than m long. The Masonite, which acts to support the rope, and
diameter of these sections of rope ranges then treated with PEG. After treatment, the
from . to . cm, after conservation. Al- rope is placed into a large freeze-drying unit
though most of the recovered rope appeared and freeze-dried at –˚C with a % rela-
to be in pristine condition during excavation, tive humidity.
microscopic analysis indicated that most of After freeze-drying, the rope sample is re-
the fibers were thin and visibly degraded; moved from the Masonite/polyethylene bag
microbial action had caused the fibers to de- structure and allowed to sit in fresh air. Rope
cay while significant water saturation had specimens treated with the Frankfurter
further weakened them. method often require additional treatment
with applications of polyurethane in ethyl-
acetate.2 This is necessary because the rope is
Silicone Treatment Strategies often extremely delicate after processing. Rope
treated with the Frankfurter method retains
The Texas A&M Archaeological Preservation its pretreatment color and the individual
Research Laboratory technique for stabiliz- fibers, yarns, and strands that comprise the
ing waterlogged rope with silicone oils in- rope are well preserved. Like other success-
volves a displacement of the water trapped ful treatments for severely deteriorated wa-
in the rope fibers with acetone, followed by terlogged rope, this process is generally not
the replacement of the acetone with a hy- reversible due to two factors. First, the appli-
droxyl-ended functional polymer and cross- cation of polyurethane in ethylacetate is gen-
linker. The polymer-impregnated rope is erally not reversible. More important, how-
then cured by exposure to a catalyst, which ever, is the fact that most treated rope samples
is applied either topically or as a vapor. I sug- are very friable and desiccated after treat-
gest that the preservation of the treated rope ment, making additional treatment difficult.
is a result of both surface consolidation and
penetration of hydroxyl-ended polymers
with cross-linking agents added. The poly- Treating Waterlogged Rope in a
mer-rich matrix of the artifact is then treated Nonpolar Suspension Medium
with a tin-based catalyst, which completes the
polymerization process. Experiments conducted by the National Mu-
seum Conservation Laboratories have also
demonstrated that treating waterlogged rope
Frankfurter Method of Rope with PEG in a volatile, nonpolar solution such
Preservation as ether or kerosene enables the individual
fibers to “float” during treatment, facilitating
Conservators at the National Museum Con- thorough impregnation of the PEG within the
servation Laboratories in Brede, Denmark, rope’s matrix. The use of suspension medi-
routinely use a technique for conserving wa- ums in PEG treatments results in rope speci-
terlogged rope that they refer to as the mens that lack the matted appearance of rope
“Frankfurter method.”1 This process in- treated with PEG alone; the resulting rope,
volves encapsulating waterlogged rope be- however, is extremely fragile and very suscep-
tween sheets of perforated polypropylene tible to environmental changes.
Incorporating the Use of Nonpolar proposed hybrid silicone treatment process
Suspension Mediums and Elements of (Si- and Si-), while the third sample (WL)
the Frankfurter Method into “Tradi- would be allowed to air-dry at room tempera- 83
tional” Silicone Treatment Strategies ture for a -hour period.
The samples were rinsed in fresh running
Experiments conducted with silicone oil water for two days to ensure the removal of
treatments at the Archaeological Preservation soluble salts. The samples were then placed
Research Laboratory have demonstrated that on a sheet of glass for additional manual
treating waterlogged rope that has not been cleaning. During this process, the samples
enclosed in some form of permeable mate- were positioned beneath a constant, gentle
rial results in a specimen that tends to un- flow of tap water to keep the rope wet while
ravel slightly during treatment. We believed debris was flushed from its surfaces. Like the
the polypropylene jacket used in the Frank- majority of rope from the assemblage, the
furter method would provide a permeable samples were partially covered with black
membrane that would facilitate chemical and dark brown sulfide stains. These stains
transfer and also serve to protect the physi- resulted from the fact that the cotton cloth
cal integrity of the artifact during treatment. in which the rope had been transported
Furthermore, after observing the results of from the site to the laboratory had decayed
experiments conducted by the National Mu- en route. Most of these stains were removed
seum Conservation Laboratories on the use by lightly rubbing the affected areas with a
of suspension mediums in the treatment of cotton swab. No attempts were made to re-
waterlogged rope with PEG, we anticipated move deeply set stains by chemical means,
that the use of a suspension medium during as it was feared that additional chemical ad-
the polymerization of waterlogged rope ditives would interfere with the conserva-
would alleviate the slightly matted appear- tion process.
ance commonly observed after silicone oil Each sample that was to undergo silicone
treatments that do not involve the use of a treatment was placed between two sheets of
nonpolar suspension medium. perforated polyethylene film, which is scored
with uniform holes that allow water, acetone,
and silicone oil to freely diffuse (fig. .).
Case Study: La Belle Rope These sheets of polyethylene film were then
heat-sealed, creating formfitting, ventilated
The following procedure is but one example bags in which the ropes would remain
of the use of preservation polymers in rope throughout the initial stages of treatment.
conservation. For researchers in the field of Ziploc vegetable bags are an ideal source of
conservation, exploration with other silicone perforated polyethylene film; they are readily
preservation polymers and cross-linkers is available and easily sealed to form a pouch,
recommended in order to determine the re- using either a heat-sealing appliance or a
sultant attributes of varying combinations of small soldering iron and brown paper.
these invaluable materials. Each encased rope was placed into a bea-
The majority of rope recovered from La ker containing ml of fresh acetone, and
Belle was transported to the Texas A&M Uni- the beaker was set in a vacuum chamber. At
versity Preservation Research Laboratory, room temperature, a vacuum of . Pa
where it was stored in freshwater until treat- ( Torr) was applied to the samples to in-
ment. Three rope samples of similar length duce rapid displacement of the water with
were taken from a single continuous coil. Two acetone. The samples initially bubbled rap-
of these samples were to be treated by the idly as air and acetone were driven from the
than PR-. Because of the porosity of the
waterlogged rope, larger molecular weight
84 polymers such as PR- are expected to eas-
ily permeate the matrix of the rope samples.
Due to its increased viscosity, PR- acts as
a consolidant by keeping loose strands
together; furthermore, rope that has been
treated with PR- tends to be more flexible
after treatment than rope treated with smaller
molecular weight polymers. A blend of these
two silicone oils was used for this experiment
to ensure that the finished product main-
tained a degree of flexibility as well as inter-
nal rigidity and physical strength. CR- %
by weight was added to the PR-/PR- sili-
cone oil solution. CR- is a highly efficient
Fig. .. Waterlogged rope internal structures of the rope. After approxi- cross-linker that has been shown to work well
encased between sheets of mately minutes, the rapid bubbling ceased, with silane polymers.
Ziploc vegetable bag and smaller, more infrequent bubbles were After placing the dehydrated ropes in clean
material prior to water/ observed escaping from the ropes. The beakers, a sufficient amount of the silicone
acetone displacement. samples were then removed from the water- oil/cross-linker solution was added to each
laden acetone and placed into clean beakers beaker in order to immerse the samples in
containing ml of fresh acetone. Each bea- solution. Aluminum mesh was securely fixed
ker was returned to the vacuum chamber and over the packaged ropes to prevent them
a vacuum of approximately . Pa ( from floating to the surface of this viscous
Torr) was applied. Once the bubbling ceased, mixture. A vacuum of . Pa ( Torr)
the ropes were removed from the vacuum was applied to the samples in solution for
chamber and allowed to sit at ambient pres- minutes to ensure that the acetone present
sure and room temperature. in the rope fibers would vaporize rapidly, fa-
The next phase of treatment was to ex- cilitating a thorough penetration of silicone
change the acetone with an appropriate sili- oil solution throughout the artifacts. During
cone/cross-linker solution. The polymer and the initial stages of vacuum treatment, large
cross-linker were specifically chosen to pro- bubbles were observed escaping from the
duce a desired texture and strength. To main- ropes. After minutes, this rapid bubbling
tain flexibility in the treated rope samples, diminished and sporadic, small bubbles rose
two hydroxyl-ended silicone oils were from the artifacts.
blended together in a : solution, by The packaged ropes were then taken out
weight. The lighter of the two polymers was of the vacuum chamber and allowed to sit
PR-, which is a low viscosity hydroxyl- in solution at ambient pressure and room
ended fluid.3 Repeated experimentation in- temperature. After hours the samples were
dicates that lighter molecular weight silicone removed from the silicone oil/cross-linker
oils such as PR- tend to penetrate easily solution and from their perforated polyeth-
into organic materials such as rope; once po- ylene bags. The samples were placed on an
lymerized, however, they tend to produce a aluminum screen to allow drainage of ex-
rigid artifact. cess free-flowing silicone oil solution. After
PR- is a slightly more viscous hydroxyl- hour the surfaces of the ropes appeared to
ended fluid with a larger molecular weight be reasonably dry, and the artifacts were
placed in beakers containing ml of fresh of deterioration caused by waterlogging, as
CR- cross-linker. Immersion in CR- af- well as to compare the results of the silicone-
ter bulking the samples with a silicone oil/ treated rope against an untreated specimen, 85
cross-linker solution is helpful in removing an additional sample of rope from the same
additional silicone oil solution from the ex- coil was weighed, measured, and allowed to
ternal surfaces of the rope. During the im- air-dry at room temperature in a vented fume
mersion process, the rope surfaces were hood for hours.
wiped with a soft brush to facilitate removal
of excess silicone oil solution. After five min- Results and Discussion
utes of immersion and surface preparation,
polymerization was initiated by exposing the The silicone oil–treated rope samples felt
rope sample to a tin-based catalyst. slightly stiff, but were stable and aesthetically
The samples were placed into loose, per- pleasing compared to the sample that was
forated polyethylene bags, and the bags were simply allowed to air-dry. The individual fi-
heat-sealed shut. Each package was sus- bers, strands, and ply of the silicone-treated
pended with two wooden clothespins from rope samples were easily distinguishable
wooden dowels. These dowels rested on the after treatment and did not become matted
top edges of a small vat containing kerosene or compressed. The high degree of visible
with CT-, % by weight (fig. .). The open detail in the silicone-treated samples was sur-
structure of the mesh bag evenly exposed the prising because these features were indistin-
surfaces of the rope to the kerosene/catalyst guishable in a waterlogged state. And while
solution. With the samples suspended in the it may be impossible to determine the origi-
solution, the vat was placed into a vacuum nal color of the waterlogged rope, the post- Fig. .. Rope sample
suspended in kerosene/
chamber, and a vacuum of . Pa ( treatment coloration of the silicone-treated
CT- solution:
Torr) was applied. After minutes under samples was acceptable, ranging from a pale
(A) clothespins; (B) dowel
vacuum, the valves of the chamber were to medium brown. (See tables ., ., ., and
spanning the length of the
locked, and the rope was left suspended in ..) Figure . is a photograph of sample Si- vat; (C) perforated
the solution overnight. The following morn- . Prior to treatment, this sample was loosely polyethylene bag;
ing, the vacuum chamber was returned to twisted. Following treatment, no discernible (D) silicone-impregnated
ambient pressure, and the samples were re- changes were observed in the twist or physi- rope suspended in mesh;
moved from the kerosene/catalyst solution. cal dimensions of either silicone oil–treated (E) vat containing
The rope was removed from the perforated rope sample. kerosene/CT- solution.
polyethylene bags and placed on several pa-
per towels, which absorbed the kerosene/
cross-linker and silicone oil solutions from
the artifacts. Immediately following removal
from the kerosene/cross-linker solution, the
surfaces of the cordage were covered with a
thin, slippery coating of silicone. After the
rope was exposed to fresh air for a few min-
utes, droplets of fully cured polymer were
observed on one end of the samples. These
were easily removed using a soft, lint-free
cloth. After the rope was allowed to air-dry
in a vented fume hood for hours, the sur-
faces of the samples appeared dry and very
natural in texture. To determine the degree
Posttreatment Strength ing. To prevent slippage with the other
samples, the second silicone-treated rope
86 After one week of air-drying, the silicone oil– sample (Si-) and the untreated sample (WL)
treated rope and the comparably sized sample were mounted into the load frame using
of untreated rope (WL) were taken to the wedge grips only after being outfitted with
Texas Engineering Experiment Station, Test- epoxy potted ends. This is a more complex
ing Machinery and Repair Laboratory at mounting process that requires that the ends
Texas A&M University for tensile strength of the rope be cemented into a cone-shaped
testing. We believed these tests would pro- epoxy base prior to mounting in the frame.
vide insight into the strength characteristics The use of these potted ends eliminated slip-
of polymer-treated rope. Tensile strength page and resulted in more reliable data.
testing was conducted with a kip ( kip = Tensile strength testing has demonstrated
lbs tensile strength) MTS servohydraulic that rope preserved in silicone oil is consider-
frame, which measures the maximum load- ably stronger than rope that has been allowed
breaking point of materials. To more accu- to air-dry. When tested, the rope section WL
rately measure the maximum load-breaking failed at . lbs tension, and the sections of
point of low-potential tensile strength mate- rope treated with silicone oils, Si- and Si-,
rials such as the fragile, treated La Belle rope failed at . lbs and . lbs, respectively.
fibers, a kip load cell was mounted into the Table . lists the data acquired from this ten-
jaws of the kip machine. sion test. As a result of waterlogging, which
Data control and acquisition were re- deteriorated and weakened individual fibers
corded using Gardner Systems software. of the rope, the strands that make up the rope
Time, distance, and pounds force were mea- failed at different times in each of the samples.
sured for each sample. In each test, tensile The sawtooth graphs in figures ., ., and
strength testing continued until the sample . represent the tension and breaking points
failed. Rope (Si-), treated with silicone oils, of the fibers, strands, and plies of the rope
was mounted in the load frame using wedge samples. Although posttreatment strength
grips. This sample slipped once during test- may not be an important factor in the deci-
Table . Measurements and Percentage Changes for Air-Dried Rope Sample WL
Table . Texture, Integral Strength, and Color of Air-Dried Rope Sample WL
Pretreatment Posttreatment
Texture Soft-mushy Brittle
Integral strength Fragile Friable
Color 10YR-2/2 very dark 5YR-6/2 → 5YR-5\2
brown → 10YR-2.1 black pinkish gray
Table . Measurements and Percentage Changes for Silicone-
Treated Rope Samples
87
Measurement Mean % Change
Length of rope (in cm)
pretreatment 14.308 14.228 –1.118
posttreatment 14.148
Width Si- (in cm)
pretreatment 0.9280 .922 –1.293
posttreatment 0.9160
Width Si- (in cm)
pretreatment 0.9380 .932 –1.386
posttreatment 0.9250
Weight of rope (in g)
pretreatment 16.597 11.499 –61.438
posttreatment 6.400
Pretreatment Posttreatment
Color 10YR-2/2 very dark brown → 10YR-6/3 pale brown → 10YR→
10YR-2.1 black 4/3brown
Flexibility Limp, almost formless, individual Dry, individual strands visible, slightly stiff
strands indistinguishable
Note: Color determined using Munsell Soil Color Charts, Macbeth Division, Kollmorgen
Corporation, Baltimore, Md., 1975 ed., p. 26.
sion to conserve rope by a particular method, chemical transfer and also helped protect the
it is beneficial to know that silicone oil– physical integrity of the artifacts during treat-
treated cordage is more internally stable and ment. Rope treated without being enclosed
stronger than rope not treated with silicone in some form of permeable material, such as
oil. a perforated polyethylene bag, tends to un-
ravel slightly during treatment.
Effectiveness of Incorporating Nonpolar Silicone oil–treated rope treated without
Suspension Mediums and Elements of the a nonpolar suspension medium such as kero- Fig. .. Silicone oil–
Frankfurter Method into “Traditional” sene usually results in an artifact with a treated rope Si-.
Silicone Treatment Strategies
hours. In addition, artifacts treated with sili- Silicone oil treatments, like treatments
cone oils do not require special curation and that require applications of polyurethane in
the dimensional attributes of the artifact ethylacetate, are not reversible; this is not to
seem to be accurately preserved. As Vera de say, however, that rope treated with silicone Fig. .. Accelerated
la Cruz Baltizar has observed, silicone oil– oil cannot be re-treated. In the past, several weathering machinery
treated samples appear to be dimensionally fragile leather and canvas artifacts preserved used for testing silicone
stable with good coloration.4 Repeated test- with lower centistoke silicone oils have been oil–treated artifacts.
ing of the hybrid silicone oil treatment
described above at the Archaeological Pres-
ervation Research Laboratory consistently
yields waterlogged rope specimens that are
aesthetically pleasing and dimensionally
stable.
Accelerated aging tests and data supplied
by Dow Corning Corporation continue to be
encouraging regarding the long-term stabil-
ity of silicone oil–treated artifacts. Eight sili-
cone oil–treated samples were subjected to
an extended test in an accelerated weather-
ing machine (fig. .). The samples were
exposed to four months of continuous, al-
ternating cycles of hours at high humidity
(%) and high temperature (˚C) with a
UV light, and hours at a lower humid-
ity (%) and temperature (˚C) with no
light exposure. The tested sample data (in-
cluding overall dimensions, color, and sur-
face integrity) were comparable to data for
silicone oil–treated specimens that had not
undergone accelerated weathering.
re-treated, using more viscous polymers to metal plate could be treated using appropri-
add additional strength and stability. More ate conservation strategies with the idea that,
90 important, waterlogged rope appears to re- once completed, the gudgeon assembly could
spond well to treatment using silicone oils. be documented and reconstructed on paper.
Although silicone oil processes will not ad- Microscopic analysis of the canvas indi-
dress all archaeological conservation issues, cated that the backing had been made from
the field of archaeological conservation can cotton canvas material that had been crudely
benefit from ongoing research into silicone cut to follow the shape of the gudgeon plate.
oil treatment techniques. Two squared holes were present in the sec-
Based on experimentation to date, I con- tion that was to be treated using silicone oils.
cur with Baltazar’s observations that silicone These holes lined up with the remains of two
oil preservation is a promising technique for large bolts that would have been used to fas-
the consolidation and preservation of many ten the gudgeon plate to the hull of the ves-
waterlogged materials.5 The added strength sel. The warp of the fabric was counted at
and elasticity characteristics associated with strands per inch while the weft averaged
the silicone oil process used for this experi- strands per inch. Variances in warp and weft
ment may have important implications for counts, as well as the generally uneven shape
the structural well-being of some artifacts. of the strands, suggest that this was probably
Continuing research at the Archaeological a common, though sturdy, material.
Preservation Research Laboratory is focused Once removed from the back of the gud-
upon these issues. geon, the canvas was placed into a vat of fresh
tap water, and the surfaces of the cloth were
lightly cleaned, using fingertips to remove
Case Study: Preservation of Waterlogged loose debris and concretion. The canvas was
Canvas from Port Royal initially placed into a vat of acetone, which
successfully removed traces of pitch embed-
Among the wide range of artifacts recovered ded in the weave of the fabric. After several
from underwater excavations at Port Royal, rinses of freshwater, which were used to re-
Jamaica, was an interesting section of a gud- move salts and any remaining acetone from
geon from a vessel. Because the Port Royal the fabric, the canvas was placed into a %
site is covered by a deep silt layer, many or- solution of hydrochloric acid in water to aid
ganic artifacts have been recovered that in the removal of rust stains and minute
would not have survived, or at least be as well specks of concretion. After treatment, the
preserved, at a land site. Artifact PR - cloth was immersed in several freshwater
is such an object. When recovered, the gud- baths to remove any remaining acid. The can-
geon plate was heavily concreted, looking vas was then briefly placed into a % solu-
more like a long rock than a piece of ship’s tion of hydrogen peroxide to remove heavy
equipment. sulfide stains. The fabric was again rinsed in
During initial phases of conservation, we freshwater.
were delighted to note that a long strip of The goal of the entire cleaning process was
canvas had been used as a backing behind to remove sufficient pitch and staining to
the gudgeon plate, along with a thick layer of enable the polymer to penetrate the cloth but
pitch. After the outer layer of concreted ma- not enough to disturb their function as di-
terial had been removed from the artifact, it agnostic attributes of the canvas. The clean-
was a relatively simple task to slowly sepa- ing process complete, the fabric was placed
rate the canvas backing from the back sur- into an acetone bath to dehydrate the mate-
face of the plate. Once removed, the cloth and rial in preparation for silicone bulking. To aid
in the removal of any remaining water, the containing grams of catalyst was placed
container holding the fabric in acetone was into the containment chamber, and the pro-
placed into a vacuum chamber and a vacuum cess was continued for an additional 91
of Torr was applied until all bubbling hours.
ceased. At this point, all remaining water had After two days of polymerization, the fab-
been removed from the artifact. The canvas ric felt slightly damp, but had retained the
was then quickly placed between two sheets look and feel of cotton canvas material. The
of lint-free paper and blotted to remove some warming oven was turned off, and the fabric
of the acetone in the fabric. was left in the containment chamber at room
After blotting, the canvas was placed into temperature for an additional hours. Af-
a large beaker containing mg of PR- ter a total of three days, the fabric was re-
silicone oil. A mesh screen was placed on top moved and allowed to air-dry undisturbed
of the fabric in solution as a means of keep- on a sheet of white paper.
ing the cloth suspended in solution through-
out the bulking process. The beaker was then Observations
placed back into the vacuum chamber, and
as before, a vacuum was applied to the fabric The processes used for removing embedded
for hours. Vigorous bubbling ceased after concretion and stains from the cotton can-
minutes and no bubbles were noted after vas are conventional conservation processes
hour of applied vacuum. The fabric was al- that are widely used in the treatment of stable
lowed to sit in solution and slowly returned fabrics. Care was taken to thoroughly rinse
to ambient room temperature, where it re- the artifact prior to bulking with silicone oils;
mained for hours. the effects of interaction between these ma-
Fig. .. Containment
Before the fabric was removed from the terials are not known. The porous nature and chamber configuration
silicone solution, a warming oven was pre- loose weave of the fabric suggested there illustrating the canvas
heated to ˚C. As in many of our other ex- would be no difficulty in the dehydration and material sitting on an
periments, a containment chamber was cre- subsequent bulking of the material with sili- aluminum screen above
ated by placing an inverted polypropylene cone oils; this meant that using the longer a tray containing CT-
pail with a tight-fitting lid into the warming process of applying a vacuum to the fabric catalyst.
oven. In the center of the lid (acting as the
base of the chamber), we placed a flat dish
containing grams of CT- catalyst. A large
mesh screen covering the dish served as a
platform on which the fabric could be placed
for exposure to warm catalyst fumes (fig. .).
After much of the free-flowing silicone was
removed by suspending the canvas over a
stainless steel dish and allowing excess sili-
cone to drip from the material, the fabric was
placed between two sheets of newspaper and
lightly pressed to remove additional oils. The
fabric was then placed onto the screen in the
containment chamber, where it was exposed
to catalyst fumes for hours. After hours,
the catalyst had become hard and crusty as a
result of silicone oils dripping into the dish,
forming polymerized material. A new tray
acetone baths prior to silicone bulking would
have removed more of the staining and pitch
92 from the fabric. These, however, are diagnos-
tic attributes of the cloth, indicating some-
thing about the mounting of the gudgeon
strap to the vessel. Accordingly, dehydration
time was closely monitored to ensure that
these stains were not removed.
After treatment, the fabric was both flex-
ible and stable. Indeed, five years after treat-
ment, flexibility and physical integrity of the
canvas remain unchanged (fig. .). Placing
the treated canvas on sheets of white paper
Fig. .. Posttreatment in a freezer-mounted vacuum chamber to was the simplest means of determining the
view of the canvas after drive off acetone was not necessary. degree of polymerization that had occurred.
catalyzation. Pre-and posttreatment traces of the out- After it sat on paper for one week, no oil spots
line of the canvas material, as well as mea- were noted. If polymerization were incom-
surements taken from the edge of the mate- plete, the points of contact between the can-
rial to the edges of the nail holes, indicated vas and paper would be oil stained. Since no
that no determinable shrinkage occurred stains were noted, this was a good visual in-
in the fabric. More extensive treatment in dicator that polymerization was complete.
CHAPTER 7
93
Glass
Conservation
I
n ancient times, artisans combined secret variety poses a considerable challenge for
ingredients, which they heated to high archaeological conservators.
temperatures to form a wide range of col- The basic component of glass is silica
ors of glass. They used ash and varieties of (SiO2), which, unlike quartz, is a randomly
plants to make flux, which helped in meld- arranged network of crystalline structures.
ing their complex chemical compositions. The presence of additional elements such as
The chemical processes in a marine environ- oxides (R2O) or potash (K2O) act as fluxes,
ment that act to deteriorate glass are as com- which by their nature affect some silicon-
plex and varied as the processes of making oxygen bonds. Unattached oxygen atoms are
it. In this environment, organic components negatively charged and, as Cronyn has ob-
of ancient glass are easily leached out of its served, loosely hold monovalent cations
matrix through a series of complex reactions, within the spaces of the network.2 Because
rendering the glass unstable. these bonds are weak, the cations migrate
Despite the fact that glass has been made within and out of the network in close asso-
for more than years, scientists know little ciation with water. The proportion of silica,
about the development of the glassmaking flux, and other stabilizing agents within glass
process and the myriad combinations of ma- is infinitely variable. These proportions affect
terials used by artisans to create glass the character and quality of glass. Addition-
throughout history. Archaeologists have re- ally, the combination of these elements will
covered an incredible variety of glass from determine the melting point of the glass. The
terrestrial and underwater excavations. From coloration of glass depends on the state of
analysis of these artifacts, we know that a oxidation-reduction of the artifact as well as
wide variety of raw materials can be com- mixtures of ions and the presence of addi-
bined to produce raw glass. tives, which can accentuate or diminish color.
Although there is significant debate about The basic composition of nearly all an-
the fundamental nature of glass, Robert Brill cient glass consists of a soda-lime-silica mix-
of the Corning Glass Museum considers it to ture with substantial impurities added to the
be a “state of matter that combines the rigid- mixture from raw materials. In medieval
ity of a crystal with the largely random mo- Europe, the source of silica was sand and, in
lecular structure of a liquid.”1 He has observed some cases, crushed stones. Limestone and
that hundreds of thousands of forms of glass burned shells were a common source for the
have been made; the term “glass” therefore is lime component of glass. Mesopotamian tab-
a generic term used to loosely describe an lets also specify that “ground red shells from
endless series of chemical variations. This the sea” were a good source for lime.3 As the
Roman Empire expanded, so did the spread minute amounts of manganese are added to
of technologies related to glassmaking. This make the glass clear, but potash glass is less
94 influenced English glassmaking and the tech- clear than soda glass. Most early glass is green
nologies used during the colonial period of because of iron impurities in the materials.
Jamaica. The alkali lowers the melting point of the
Numerous factors complicate attempts to sand and the flux facilitates the mixture of
understand the processes of devitrification the components. As long as the original glass
that affect archaeological glass. First, the in- mixture is kept in balance, the resulting glass
teraction of water with glass, especially sea- will be stable. Problems arise when an ex-
water, causes chemical instability. Association cess of alkali and a deficiency in lime (cal-
with other materials within an archaeologi- cium oxide is used as a stabilizer) are used
cal site can complicate the chemistry of glass, in the mixture, for the glass will be especially
since oxides and minerals may interact posi- susceptible to attack by moisture. A relative
tively or negatively with the degradation pro- humidity (RH) higher than % can be dan-
cesses of the glass. In addition, the sediments gerous. Old glass with –% sodium or
in which the glass is buried profoundly affect potassium may begin to weep and break
the degradation process. These and other fac- down. This is often called glass disease.
tors account for the wide range of colors and In all glass, the sodium and potassium
degrees of degradation observed within the oxides are hygroscopic; therefore, the surface
Port Royal glass assemblage, consisting of of the glass absorbs moisture from the air.
hundreds of bottles, known as onion bottles; The absorbed moisture and exposure to car-
sections of window pane, often with lead bon dioxide causes the NaO2 or NaOH and
caming attached; and fragments of small the KO2 or KOH to convert to sodium or
ointment bottles. potassium carbonate. Both NaCO2 and KCO2
Glass is usually the most stable of archaeo- are extremely hygroscopic. At an RH of %
logical materials, but it can undergo some and above (and in some cases as low as %),
complex disintegration—especially seven- drops of moisture appear on the glass sur-
teenth-century glass. Ideally, glass should face. In water, especially saltwater, the Na and
consist of –% silica, –% alkali or K carbonates in unstable glass can leach out,
soda ash (sodium carbonate) or potash (po- leaving only a fragile, porous hydrated silica
tassium carbonate, usually derived from (SiO2) network. This causes the glass to craze,
wood ash), and –% flux lime (calcium crack, flake, and pit, giving it a frosty appear-
oxide). Soda-lime glass is the most common ance. In some cases, an actual separation of
glass throughout the history of glassmaking, layers of glass from the body occurs. Fortu-
and the modern equivalent is approximately nately, glass from the nineteenth century or
–% silica (SiO2), –% soda (Na2CO3), later seldom manifests such effects. Problems
and –% lime added as a stabilizer. Soda are rarely encountered on glass found at sites
glass is characteristic of southern Europe, dating from this period. Pearson discusses
where it is made from crushed white pebbles glass deterioration and reviews the various
and soda ash derived from burnt marine veg- glass conservation procedures.4
etation. Soda glass, often used for the manu- Currently, the decomposition of glass is
facture of cheap glass, is twice as soluble in imperfectly understood, but most glass tech-
water as potash glass. nologists agree that glass decomposition is
Potash glass is more characteristic of in- due to preferential leaching and diffusion of
land Europe, where it is made from local alkali ions (Na and K) across a hydrated po-
sands and potash derived from wood ash and rous silica network. Sodium ions are removed
burnt inland vegetation. A little salt and and replaced by hydrogen ions, which diffuse
into the glass to preserve the electrical bal- simple rinsing and removal of incidental
ance. The silicates are converted into a hy- stains (especially lead sulfide staining on any
drated silica network through which sodium lead crystal) or calcareous deposits is envi- 95
ions can diffuse out. Glass retrieved from an sioned. The main problems will be related
acid environment often appears laminated, to gluing pieces together and possibly some
with an iridescent film formed by the leached restorations. All the problems likely to be en-
silica layers. The alkali that leaches out is neu- countered are discussed thoroughly in Con-
tralized by the acid and fewer hydroxyl ions servation of Glass by Roy Newton and Sandra
are available to react with the silica. This Davison.5
causes the silica layer to thicken and become Submersion in seawater will cause glass to
gelatinized as the alkali leaches out. Glass become unstable. If left untreated, the arti-
excavated from an alkaline environment is fact will deteriorate. A technique described
less likely to have laminated layers because by Plenderleith and Werner is representative
an abundance of hydroxyl ions are available of a range of conservation strategies that are
to react with the silica network. Normally, a effective for stabilizing archaeological glass.6
protective layer does not form on glass ex-
posed to alkaline solutions. The dissolution . Wash the artifact thoroughly in running
of the glass proceeds at a constant rate. The tap water.
alkali ions are always extracted in excess of . Soak it in distilled water.
the silica, leaving an alkali-deficient layer that . Immerse the artifact in two baths of
continually thickens as the deterioration alcohol to dry quickly. This treatment will
moves deeper into the glass. retard the disintegration and also improve the
There are considerable differences of opin- appearance of the glass. It does not, however,
ion regarding the preservation of unstable always stop the breakdown of the glass.
glass. Some conservators believe the only . If applicable, apply an organic lacquer—
treatment should be to keep the glass at low PVA, Acryloid B-—to impede the disinte-
RH so that it cannot react with any moisture. gration.
While a RH environment of % is ideal for . Store the artifact in a dry environment
archaeological class, the range can be ex- with the relative humidity no higher than
tended to % if the glass is stable. The weep- %; others say –% is ideal. The Corning
ing or sweaty condition is sometimes made Glass Museum keeps incipient crizzled glass
worse by the application of a surface lacquer stored at –% RH. RH % is the critical
or sealant, which traps humidity in close as- point at which KCO3 becomes moist.
sociation with the affected glass. No resin seal-
ants are impervious to water vapor and the The above treatment does not attempt to re-
disintegration continues under the sealant move any of the glass corrosion products,
until the glass falls apart. Other glass conser- which often result in layers of opaque glass
vators try to remove the alkalinity from the and which can be removed with various acid
glass to halt the deterioration. treatments. The decision to remove surface
When it comes to eighteenth- and nine- corrosion products that often mask the color
teenth-century sites, we are on much more of the glass must be made on a case-by-case
secure ground. Most, if not all, of the glass basis. Removal of corrosion products can
found from this period was produced from a significantly reduce the thickness of the walls
stable glass formulation, with few problems and sometimes weaken the glass object. In-
arising other than normal devitrification. discriminate removal of surface corrosion
Since the glass is impervious to salt contami- products can weaken, blur, or alter surface
nation, no conservation treatment other than details. The corrosion layers of a glass object
can be deemed a part of the history of the Consolidating Waterlogged Glass Using
object and thus a diagnostic attribute. They Passivation Polymers
96 should not be removed without good reason.
Another useful method for halting devitri-
fication is treating waterlogged glass with
Devitrification silicone oil, which, when polymerized, forms
a complex layer and bond with the remain-
Devitrification is a natural process that oc- ing matrix of the glass. As noted in the
curs in siliceous material. In flint and obsid- Plenderleith and Werner process, the first
ian, this process provides the basis for obsid- steps must include extensive washing, first in
ian hydration dating. The surface of any glass tap water and then distilled water, to remove
from any time period usually becomes hy- soluble salts and debris. After rinsing, the
drated, especially soda glass. Devitrification following steps have proved effective in con-
occurs when the surface of the glass becomes solidating small glass artifacts with silicone
partly crystalline as it absorbs moisture from oils.
the atmosphere—and from being submerged First, it is essential to drive off water from
in water. As the glass becomes crystalline, the the artifact. This can be accomplished by us-
surface becomes crazed and flakes from the ing two baths of alcohol and allowing the
body. Devitrified glass has a frosty or cloudy, glass to remain immersed in each bath for
iridescent appearance. Pane glass is especially hours. For processes utilizing silicone oils,
susceptible to this process. To prevent further additional dehydration using fresh indus-
devitrification and to consolidate the crazed trial-grade acetone is beneficial. To prepare
surface, a coating of PVT or Acryloid B- is glass for treatment with a silicone oil solu-
applied. Any of these surface adhesives will tion, the most effective means of water/ac-
smooth out the irregularities in the pitted, etone exchange is to use vacuum to assist in
crazed surface of the glass, making it appear driving off water in the waterlogged glass.
more transparent by filling in the small cracks Acetone is more volatile than alcohol, which
and forming optical bridges. Merely wetting assists in removing water and alcohol from
glass will cause it to appear clearer for the the glass object.
same reason. Used in conjunction with a vacuum
chamber, the process of acetone/silicone oil
displacement is much more efficient than al-
Removal of Sulfide Stains from Lead cohol/silicone oil displacement. When a
Crystal vacuum is applied to glass in treatment, the
boiling point of acetone within the matrix
Leaded glass, which includes a wide variety of the glass is lowered, causing remaining
of stemware and forms of lead crystal, can acetone to be rapidly driven from the glass.
become badly stained by lead sulfide. Glass This creates a void, enabling silicone oils to
that is normally clear will emerge from ma- replace water and acetone that have been re-
rine and anaerobic sites with a dense black moved from the artifact.
film on its surfaces. A –% solution of
hydrogen peroxide is used, as with ceramics,
to remove these sulfide stains. Besides stain An Effective Silicone Oil Treatment
removal, strengthening of glass artifacts with Strategy
a consolidating resin is often required. Frag-
ments can be reassembled with a good glue The following is a simple and effective pro-
or, if necessary, an epoxy such as Araldite. cess for treating small glass artifacts. It is
essential that most of this work be con- screen over the glass will prevent it from
ducted in a well-ventilated fume hood or moving during treatment. Place the glass in
work area. Rubber gloves should be worn to solution into a vacuum chamber and slowly 97
prevent long-term chemical contact with apply a vacuum. Almost immediately, small
bare skin. Older vacuum pumps, which have bubbles will begin emerging from the artifact.
all-metal components, are more desirable As acetone is driven from the artifact, silicone
than newer pumps when working with ac- oil will displace it. A vacuum of Torr
etone; vapors escaping into these pumps will (. Pa) is sufficient to assist penetration
not damage any internal parts. If a modern of the consolidant into the matrix of the
pump is used, a Dewar flask, gas traps, and glass. After allowing the glass in solution to sit
dry ice must be used to prevent acetone at Torr (. Pa) vacuum for
fumes from damaging the plastic compo- minutes, slowly return the artifact in solution
nents in the pump. to ambient pressure. Allow the artifact to sit
in solution for an additional hour before
. After immersing the artifact in a handling (fig. .).
container of fresh acetone, place the con- . For the last phase of treatment, two
tainer in a vacuum chamber. Slowly increase small beakers are needed. The first beaker
the vacuum in the chamber. Initially, there should be filled with sufficient CT- catalyst
will be a profusion of large bubbles (fig. .). to immerse the artifact. An equal volume of
Over a short period of time, rapid bubbling CR- cross-linker should be poured into
will subside, though smaller bubbles will the second beaker. Once the cross-linker-
continue to be visible. At this point, acetone and catalyst-filled beakers have been
and remaining water are being driven from prepared, the artifact should be carefully
the artifact. The valves of the vacuum removed from the polymer/cross-linker
chamber should then be locked off and the solution and placed into the beaker contain-
artifact allowed to sit in the solution for at ing the CR- cross-linker. Allow the artifact
least hour. to sit in this solution for a few minutes. It
. While water/acetone exchange is taking should then be carefully removed and
place, a suitable consolidant should be allowed to sit on lint-free cloth for a short
prepared. For heavily crizzled glass, PR- has period of time. It is difficult to give an exact
proved to be an excellent polymer. Enough time frame for allowing the artifact to drain,
PR- should be poured into a clean, dry but usually two or three minutes is sufficient.
container to ensure that the artifact will be After draining, the artifact should be placed
completely submerged during treatment. For in the CT- catalyst for a short period of
small artifacts, plastic-coated paper cups are time. Monitor this phase of treatment
useful and convenient. To this volume of carefully. After a few seconds, a zone of
PR-, add a % addition of CR- (by chemical reactivity will be noticed around
weight). This solution needs to be mixed the artifact. Generally, the artifact is left in
thoroughly, using a nonporous stir rod. Rapid the catalyst for the same period of time as it
mixing will result in bubbles in the solution. was treated in the CR- solution. It should
These can be removed, if desired, by placing then be removed, very lightly surface-wiped
the polymer solution into a vacuum chamber with lint-free cloths, and the processes of
and applying a slight vacuum. immersion in CR- and CT- should be
. Once the polymer solution is ready, repeated, at least one more time. For most
carefully and quickly remove the artifact from artifacts, two or three immersion cycles are
the acetone and immerse it in the PR-/CR- sufficient to create a stable, consolidated end
solution. A small piece of aluminum product (fig. .).
. After treatment, the CT- catalyst needs
time to work. Some experimentation is
98 required but, generally, only a very light
surface-wiping of the artifact is required to
remove free-flowing silicone oil solution
from its surfaces. The glass should then be
placed into a well-ventilated environment
and allowed to air-cure for several hours
before handling. It is possible to touch
completed artifacts within a few minutes, but
for a complete cure, the process may take as
long as hours. For larger artifacts, or in
cases where additional contact with an active Fig. .. The glass bead in solution during the
catalyst may be desirable, the finished artifact acetone/polymer displacement process.
and a cloth with several drops of CT- can
be placed into a glass jar with a tight-fitting
lid. When the jar is tightly sealed, the artifact with a uniform, satin finish. If this doesn’t
will react with the catalyst fumes, causing remove pooled silicone from the artifact, use
additional or more rapid polymerization. the edge of a soft wooden dowel or tooth-
pick to gently mechanically clean the poly-
Posttreatment Aesthetics mer from the artifact’s surface.
After treatment, the glass may require addi- Analysis of Polymer-Treated Glass
tional cleanup to remove surface deposits of
silicone. In most cases, pooled silicone can Analysis of silicone-treated glass indicates
be easily removed with a soft cloth. For larger that a complex, consolidating coating has
surface pooling, wipe the artifact surface with been formed on the surface of treated glass.
Fig. .. Rapid bubbling a soft cloth containing a few drops of CR- Chemical analysis of the glass also indicates
during the acetone cross-linker. This is usually sufficient to re- that silicone polymers are present in all the
dehydration process. move surface polymer and leave the artifact test sites within the core of the sample. Fig-
ure . is a cross section of a piece of treated
glass. Three distinct layers are visible in the
cross view.
Reconstruction
Location of Sample
Crust
Outer Edge .44 3.09 4.69 69.97 5.74 9.17 2.96 2.21
Inner Edge .41 4.88 1.96 73.50 4.07 6.11 7.13 1.07
Glass Core
Outer Core .65 1.33 .89 53.14 7.76 30.96 3.62 .74
Inner Core .53 1.15 .74 52.89 8.26 31.63 3.12 .97
102
A
with other artifacts. The surface crust is effectively. Inspection of several bottles indi-
hydrophilic, containing amorphous silica cated the consolidant only partially pen-
compounds. The core of the glass is highly etrated the outer surfaces of the glass. Because
hydrated, resulting in a complex matrix that the consolidant did not form an effective bar-
is difficult to stabilize. rier on the surface of the core glass, deterio-
The general instability of the Port Royal ration was not halted. Additionally, the
onion bottles may be due, in part, to the vis- consolidant did not seem to act as an adhe-
cosity of PVAC V and its inability to bond sive between layers of flaking glass, which
may have caused the high rate of surface de-
terioration. Lower viscosity consolidants may
penetrate throughout the matrix of an arti- 103
fact but fail to act as an adhesive between the
crust and core, resulting in poor consolida-
tion of the glass.
Note: For all samples, cross-linker was 3% CR-20; catalyst was CT-32.
Observations
have been possible in part because of the pounds may penetrate into the glass well but, Fig. .. Microscopic
highly degraded state of the cork. Micro- characteristic of their size, they should not (X ,) view of silicone
scopic observations and X-ray microanaly- offer as much mechanical strength and cohe- oil–treated waterlogged
sis determined that voids and cell structures sive bonding ability within the matrix of the cork.
of both materials were heavily bulked with devitrified glass. Unlike the end surfaces of the
silicone. The solid state of the silicone within cork, which are visible and feel slightly rub-
these structures further indicates the effec- bery to the touch, the interior and exterior
tiveness of the processes of cross-linking and surfaces of the onion bottle glass feel dry and
catalyst polymerization. natural in texture. In both materials, PR- has
The process of bulking these artifacts us- acted to fill cellular voids, as well as cracks and
ing an additive process in which cross-linking cavities, and seems to be an excellent optical
agents were added to PR- ensured the most bridge since it is not shiny or unnatural in
complete bulking possible. It would be inter- appearance. Several thin coats of Krylon
esting to replicate this experiment using clear spray were applied to the outer surfaces
lighter molecular weight siloxanes such as PR- of the bottle neck, acting as an additional seal-
. Because of their smaller size, these com- ant against environmental exposure.
CHAPTER 8
112
I
vory and bone artifacts have been recov collagen), and the main inorganic materials
ered from nearly all excavations con are calcium phosphate associated with car-
ducted by Texas A&M University and the bonates and fluoride. Viewed under a micro-
Institute of Nautical Archaeology. Excava- scope, bone has a coarse grain structure made
tions of the seventeenth-century submerged up of collagen fibers with lacunae or voids
city of Port Royal, Jamaica, which perished throughout. A crystalline inorganic material
in a catastrophic earthquake in , have un- called hydroxyapatite surrounds these col-
covered bones in cooking pots from meals be- lagen fibrils, providing strength to the bone.
ing prepared at the time. Skeletal remains of The chemical structure of hydroxyapatite is
young children who perished when they were generally listed as Ca10(PO4)6(OH)2.
trapped indoors have also been recovered. Bone and ivory are anisotropic, meaning
Excavations carried out by the Texas His- that their collagen fibrils and associated
torical Commission on the vessel La Belle structures have directional properties. Bone
have led to the recovery of the bones of at and ivory artifacts have different mechanical
least two sailors. Buried in the anaerobic en- and strength characteristics along their
vironment of Matagorda Bay, off the south lengths, widths, and thicknesses. Accordingly,
Texas coast, these remains were so protected artifacts made of these materials are struc-
that a large volume of brain matter was well turally weakened when they are altered and
preserved in the cranium of one victim. Small used for manufacturing purposes. As the
pieces of cartilage were also recovered, and structural layers are removed or altered, as
generally, the skeletal remains were in excel- in the case of carvings, the support mecha-
lent condition. While skeletal materials of- nism of the bone is weakened.
ten survive well in marine environments, An important component of ivory is den-
bones recovered from land sites may be in tine, which is very hard and dense. When
poorer condition, depending on soil acidity, viewed through a microscope, this matrix
pH, and the presence of water. looks very compact in cell structure with very
few voids. Characteristically, ivory appears
to have a network of lenticular areas, which
Basic Structural Differences result from the intersection of a system of
striations radiating out from the center and
The structure and function of the components increase in number as the tusk grows. As ivory
of bone are complex. From an archaeological ages or becomes waterlogged, this radiating
perspective, however, the major organic com- pattern may appear similar to growth rings
ponent of skeletal materials is ossein (protein in a tree.
Prolonged immersion in water will cause Equipment Setup for Very Fragile
hydrolysis of the ossein, resulting in poten- Bone and Ivory
tial warping and deterioration of an artifact. 113
Care must be taken with heavily degraded ar- In The Conservation of Antiquities and Works
tifacts to prevent loss of diagnostic attributes of Art Plenderleith and Werner described a
due to collapse of the cellular structure. Inor- simple vacuum chamber system (fig. .).
ganic salts and hydroxyapatite making up the Instead of a vacuum pump, they suggested
rest of the structure are affected by acidic con- using a water pump system to supply slight
ditions. Over time, waterlogged bone and vacuum to achieve thorough impregnation
ivory absorb organic and inorganic salts. of a bulking agent into the porous structure
Desalination, therefore, is an important of an artifact.1 This system works well in situ-
phase in treatment of artifacts from saltwa- ations where the use of a high efficiency
ter environments. If salts are not removed, vacuum pump may be too powerful and po-
artifacts may become distorted and, in some tentially hazardous for delicate artifacts. This
cases, suffer from surface exfoliation as crys- form of water-driven vacuum treatment is
talline structures form during air-drying. slow but highly effective for the treatment of
Bone and ivory recovered from terrestrial bone and ivory artifacts that are small, thin
sites are affected by acidic soil. Hydroxyapa- walled, or both. Many of the artifacts pro-
tite dissolves in acidic conditions, leaving cessed at the Archaeological Preservation Fig. .. Configuration for
unsupported anisotropic collagen fibrils to Research Laboratory are more robust. These water flow vacuum
shrink and warp as the artifact is air-dried. artifacts can be safely processed using a sys- processing of delicate
In alkaline conditions, the organic collagen tem similar to that proposed by Plenderleith artifacts: (A) desiccator/
hydrolyzes and is often attacked by bacteria and Werner but substituting a high volume, vacuum jar with valve;
(B) beaker containing
and other microbial activity. This often re- electric vacuum pump (fig. ., F). Because
artifact and either acetone
sults in the hydroxyapatite becoming brittle. of the presence of volatile vapors resulting
or polymer solution;
Thus bone recovered from alkaline soils may from solvent dehydration, a double gas trap
(C) in-line vacuum gauge;
be structurally unstable and very crumbly. assembly (C) immersed in a container of dry (D) in-line trap to catch
Passivation Polymers have proved to be ice or liquid nitrogen (D) acts to efficiently solvent or polymer
useful for the preservation of bone and ivory freeze gases escaping the vacuum chamber. solution; (E) hose con-
from marine and terrestrial sites. Three case Note also that the vacuum gauge (E) should nected to running water
studies are presented in this chapter. The first be placed in line after the gas trap assembly source; (F) sink with
is an example of consolidating friable bone to prevent damage from solvent vapors. drain.
from a land site. The second study illustrates
a successful process for preserving delicately
carved ivory from nautical excavations at
Tantura Lagoon in Israel. The last case study
illustrates the successful processes used to pre-
serve large sections of elephant tusk from ex-
cavations of a Dutch East Indiaman, Vergulde
Draeck, which sank off the coast of Western
Australia in .
Before discussing preservation strategies
for bone, however, I examine various equip-
ment configurations and how each may be
used for the treatment of archaeological bone
and ivory.
114
Fig. .. Equipment Case Study: Consolidating Friable Bone quickly rinsed in a gentle stream of tap wa-
configuration using high ter to remove additional dirt and dust from
efficiency vacuum pump: Dry, desiccated bone is generally easy to con- its surfaces. After rinsing, it was left in a fume
(A) desiccator/vacuum jar solidate using Passivation Polymers. The hood for hours to air-dry. The bone and
with valve; (B) beaker bone sample brought to the research labora- its foil wrapper were then gently immersed
containing artifact and tory had been recovered from excavations of in a beaker of acetone for approximately
either acetone or polymer
the well-defined Clovis occupation strata at hour to ensure that dehydration was com-
solution; (C) in-line gas
the University of Texas Gault site during a plete. Because the bone fragments were too
traps embedded in dry ice;
(D) Dewar flask with dry field school excavation conducted by Texas fragile to remove from the foil, sections of the
ice; (E) manometer; A&M University. After large clumps of soil bone were first treated with a topical applica-
(F) vacuum pump. were removed with a soft brush, the bone tion of the polymer/cross-linker solution.
fragments were stored in aluminum foil. Fig- Because of its viscosity, CR-, was selected
ure . illustrates the bone’s fragmented sur- for consolidation purposes. A % addition of
faces. CR- by weight was thoroughly mixed with
Before treatment, the fragmented bone, CR- to create a suitable volume of polymer/
supported by the aluminum foil wrapper, was cross-linker solution to consolidate the bone.
Expanding
the Conservation
Tool Kit
A
ll case studies and research discussed cavity of the concretion is. But devising ap-
to this point have been directed at the propriate conservation strategies using tradi-
preservation of organic substances by tional radiographs is difficult when dealing
displacing water and salts with polymer and with large, complex artifacts. More important,
resins that, once polymerized, ensure the it is extremely difficult to clean the cavities of
preservation of diagnostic attributes of or- intricate artifacts sufficiently to allow the flow
ganic artifacts. Silicone oil technologies are of resins used in the mold-making phase of
useful for other aspects of artifact preserva- conservation.
tion as well. Combining computerized to- Iron artifacts recovered from marine en-
mography (CT) data and computer-aided vironments fall into three basic categories.
design (CAD) modeling software, technicians The first group is concreted artifacts in which
can create three-dimensional models of ar- no metal remains. The second group com-
tifacts using laser driven polymerization of prises solid metal artifacts deeply imbedded
each “slice” of CT data. The process permits in concretion due either to partial surface
nonintrusive investigation and recording of disintegration or to close proximity with
complex artifacts. other artifacts that have deteriorated. The last
CT and CAD technologies can be espe- group, consisting of concreted metal objects
cially useful in the preservation of iron ob- in which only some of the metal remains, are
jects from marine environments. When ex- the most challenging artifacts. In all three
posed to water, the natural tendency of iron cases, the conservation process is often hin-
is to revert to oxides. In a marine environ- dered by the inability of traditional radio-
ment, oxides, sediments, and salts combine graphs to supply sufficient data to give the
to form a hard outer surface as deterioration conservator a complete view of the artifact
of the metal progresses. The buildup of con- concealed within the concretion. Delicate
cretion also acts to preserve the original form details of a three-dimensional artifact are also
of the artifact. In many cases, little to no iron often impossible to distinguish in two-
will remain while wood closely associated dimensional film prints. During casting and
with the artifact may be preserved in perfect, removal of the outer layer of concretion with
waterlogged condition. pneumatic chisels, fine details of an artifact
Traditionally, conservators use radio- may be missed unless the conservator can
graphs to look inside the concreted mass. In distinguish surface features and act quickly
doing so, they can devise a conservation strat- enough to prevent destruction and loss of
egy for the artifact, based on the determina- internal features.
tion of what iron remains and how clean the The advent of stereolithographic (STL),
rapid-prototype technologies represents a concreted artifacts that could be easily
new set of tools for better diagnosis and handled and x-rayed; and we found a com-
120 modeling of artifacts prior to commencing pany willing to work with us to create rapid
conservation. This technology affords many prototype reproductions of the artifact.
benefits for the archaeological conservator. CT technology is a nondestructive means
Three-dimensional imaging of a complex of looking inside a concreted artifact. The
artifact allows the conservator to view the machinery, working with high energy X rays,
artifact from an infinite variety of angles and produces two-dimensional slices of the cross
perspectives. Through the use of three- section of an artifact. Each slice is between
dimensional CAD programs, a radiographic . inches and . inches, depending on
view of an artifact can be manipulated and the resolution needed. Thinner slices produce
rotated until the conservator has the infor- higher resolution images. Naturally, produc-
mation necessary to commence conservation. ing a complete image requires many more
To attain similar views of the interior of a slices when done in high resolution. Scan-
concretion with conventional methods is time- ning time is therefore longer and all related
consuming and often less accurate, based on costs are higher. Creating a CT image requires
the limitations of the diagnostic machinery. compiling a series of slices, which when com-
CT-STL analysis of an artifact allows the con- plete allow the operator and conservator to
servator to create an exact replica of the arti- evaluate the integrity of the artifact inside the
fact in resin prior to treatment of the origi- concretion. Each slice is a discrete set of data
nal artifact. A three-dimensional model is an about one particular section of the artifact.
invaluable aid to anyone who must clean en- When the CT scanning process is complete,
crustation from delicate features of an arti- data that have been stored on disk during the
fact. Additionally, the ability to create a resin scanning must then be processed using spe-
cast replica of the artifact being treated is an cial software that renders the slices, creating
insurance policy. If something goes wrong a three-dimensional image. Programs such
during treatment, the presence of the replica as MIMICS (Materialise’s Interactive Medi-
may serve to retrieve data that might other- cal Image Control System) are widely used
wise be lost. for the purpose of aligning and correcting
individual scanned images. Once scanned
images are prepared, additional software is
Computerized Tomography and the required to transform the data into an inte-
Stereolithographic Process grated image that is usable on rapid proto-
typing instruments.
Stereolithography is literally three-dimensional The stereolithographic machinery is
printing. I have not attempted to explain the unique. It consists of a large vat of photo-
stereolithographic process and associated curable resin, mirrors, a UV laser assembly,
equipment, because for archaeological pur- and an elevator assembly that is precisely
poses, understanding potential applications driven through the vat (fig. .). As image data
for the process is far more important than are processed, the laser assembly scans the
understanding the mechanics of the technol- layer of the part being modeled. As one layer
ogy. Essentially, three main components were is completed, the elevator assembly drops
brought together to do reproductive model- slightly to allow the laser to draw the next
ing of encrusted artifacts: a local hospital section of artifact information onto the first
donated time and personnel to obtain com- layer (fig. .). The process continues until
puterized tomographic (CT) images of what all the layers have been re-created. The cast
is inside an encrustation; we identified heavily is put into an oven for curing of the resins
before touch-up work can be completed.
Depending on the size of the artifact, the
rapid prototyping system can take several 121
hours.
Case Study: Scanning an Encrusted
Artifact—CT Scanning Used as a Diag-
nostic Tool
differ in size, appropriately sized vertebra can Stereolithographic prototyping can also be
be manufactured to make the fossil remains used to fill in gaps of an artifact assemblage
complete for display purposes. Because the for display purposes. If for instance, a par-
fabricated vertebrae are made of resin, they ticular Clovis point is missing in an assem-
can be dissimilarly colored to illustrate that blage, a replica artifact can be made from a
they are replacement parts or, when desired, borrowed artifact. Depending on the resolu-
colored to look like real bone. tion of the original CT scans, reproductions
123
Notes
125
Index