Interfacial Transition Zone

in Concrete

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RILEM REPORT S
RILEM Report s ar e state-of-the-ar t report s prepare d b y internationa l technical committee s
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RILEM REPOR T1 1

Interfacial Transitio n Zone in Concrete

State-of-the-Art Report prepared by RILE M
Technical Committee 108-ICC,
Interfaces in Cementitious Composites

RILEM
(The Internationa l Union of Testing and Research
Laboratories fo r Materials and Structures )

Edited by

J, C . Mas o
LMDC, Toulouse , Franc e

Taylor & Francis

Taylor & Francis Group

L O N D O N A N D N E W YORK
Taylor & Francis

2 Par k Square , Milton Park, Abingdon, Oxon , 0 X 14 4RN

First edition 199 6

Transferred to Digita l Printing 2005

© 199 6 RILE M

ISBN 0 41 9 2001 0 X

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Publisher's Note

This book has been produced from camera ready copy provided by the individual
contributors in order to make the book available for the Workshop.
Contents

Contributors - R I L E M Technica l Committee 108-IC C i x

Preface x i

Introduction: The transition zon e - discover y an d development xii i

J. Farran

PART ON E MICROSTRUCTUR E 1

1 Characterisatio n of interfacia l microstructure 3

K.L. Scrivener and P.L. Pratt
1.1 Introductio n 3
1.2 Specime n preparatio n 3
1.3 Characterisatio n technique s 4
1.4 Feature s o f interfacial microscopy 8
1.5 Summar y 1 5
1.6 Reference s 1 6

2 Developmen t and nature o f interfacia l microstructure 1 8

A. Bentur and I . Odler
2.1 Introductio n 1 8
2.2 Concrete s 1 8
2.3 Fibre-reinforce d cement s 2 4
2.4 Conclusion s 4 0
2.5 Reference s 4 1

PART TW O PROPERTIE S O F TRANSITIO N ZON E 4 5

3 Test s to determin e th e mechanica l propertie s o f the interfacia l zone 4 7

S. Mindess
3.1 Introductio n 4 7
3.2 Problem s o f specimen preparatio n fo r the measuremen t of interfacial
mechanical propertie s 5 0
3.3 Measurement s of interfacial properties 5 4
3.4 Elasti c propertie s 6 0
3.5 Suggestion s for furthe r researc h 6 0
3.6 Conclusio n 6 0
3.7 Reference s 6 1

4 Mechanica l modelling o f the transitio n zone 6 4

P.J.M. Monteiro
4.1 Introductio n 6 4
4.2 Composit e natur e of concrete 6 4
vi Contents

4.3 A generalised continuu m theory fo r concrete 6 9

4.4 Conclusion s 7 3
4.5 Reference s 7 4

5 Micromechanic s of the interfac e i n fibre-reinforced cemen t material s 7 5

H. Stang andS.P. Shah
5.1 Introductio n 7 5
5.2 Geometrica l characterisatio n o f the interfac e 7 7
5.3 Mechanica l characterisatio n o f the interfac e 7 9
5.4 Debondin g criteria 8 9
5.5 Discussio n 9 5
5.6 Reference s 9 6

PART THRE E INFLUENC E O F TRANSITIO N ZON E ON BEHAVIOUR

OF CONCRET E 10 1

6 Influenc e o f th e interfacia l transition zone on composite mechanical

properties 10 3
J.C. Maso
6.1 Introductio n 10 3
6.2 Reversibilit y limit an d irreversibilit y mechanism s 10 4
6.3 Behaviou r beyond m e reversibility breakin g limi t 11 0
6.4 Elasti c modulu s an d Poisson's ratio 11 2
6.5 Crac k propagatio n mechanism s 11 4
6.6 Aggregat e reactivit y 11 5
6.7 Conclusio n 11 5
6.8 Reference s 11 6

7 Th e effect o f the transition zone on the transfer propertie s o f concret e 11 7

J. P. Ollivier and M. Massat
7.1 Introductio n 11 7
7.2 Transpor t propertie s an d microstructur e 11 7
7.3 Transitio n zone and permeability 12 6
7.4 Transitio n zone and io n diffusion 13 0
7.5 Reference s 13 1

8 Actio n of environmenta l condition s 13 2

F. Massazza
8.1 Introductio n 13 2
8.2 Relationshi p between porosit y and permeability 13 3
8.3 Relationshi p between porosit y and strengt h 13 7
8.4 Relationshi p between interfac e permeabilit y and strengt h 13 9
8.5 Strengt h o f concrete an d interfac e bon d strengt h 14 0
8.6 Morpholog y of the interfacia l zone 14 1
8.7 Durabilit y 14 3
8.8 Conclusion s 14 6
8.9 Reference s 14 6
 Contents vi i

9 Th e effects o f agein g on th e interfacia l transitio n zon e in concrete 15 0

M.G. Alexander
9.1 Introductio n 15 0
9.2 Effect s durin g agein g 15 2
9.3 Modificatio n of the interfacia l zon e to alte r th e propertie s o f concrete 16 9
9.4 Concludin g remark s 17 0
9.5 Reference s 17 1

Index 17 5
Contributors - RILE M Technica l Committe e
108-ICC
M.G. Alexande r Departmen t o f Civil Engineering , Universit y of Cape Town,
Rondebosch, Sout h Afric a

A. Bentu r Nationa l Building Researc h Institute, Faculty o f Civil Engineering ,

Technion, Israe l Institut e of Technology, Haifa , Israe l

J.C. Mas o Laboratoir e Materiau x e t Durabilit e des Constructions ,

(Chairman) I.N.S.A.-U.P.S . Genie Civil , Complex e Scientifiqu e d e Rangueil ,
31077 Toulouse , Franc e

M. Massa t Laboratoir e Materiau x e t Durabilit e des Constructions , Complex e

Scientifique d e Rangueil , 3107 7 Toulouse , Franc e

F . Massazz a Italcementi , Laboratorio Chimic o Centrale, Bergamo , Ital y

S. Mindes s Departmen t o f Civil Engineering , Universit y of British Columbia ,

Vancouver, Britis h Columbia , Canada

P.J.M. Monteir o Departmen t o f Civil Engineering , Universit y of California, Berkeley,

CA 94720 , US A

I. Odle r Institut e for Non-metalli c Materials, Technica l Universit y Clausthal,

Germany

J.P. Ollivie r Laboratoir e Materiau x e t Durabilit e des Constructions , Complex e

scientifique d e Rangueil , 3107 7 Toulouse , Franc e

P.L. Prat t Departmen t o f Materials, Imperia l College o f Science and Technology ,

London SW 7 2BU, United Kingdo m
Professor Pratt died during the final stages of the preparation of this
Report. A biographical note appears on the following page.

K . L . Scrivene r Departmen t o f Materials, Imperia l College o f Science and Technology ,

London SW 7 2BU, United Kingdo m

S.P. Sha h NSF Center fo r Science and Technolog y o f Advanced Cement-Based

Materials, Northwester n University , Evanston, Illinois , US A

H. Stan g Departmen t o f Structural Engineering , Technica l Universit y of

Denmark, Lyngby , Denmark
Peter L. Prat t 1927-95

Peter Pratt graduate d fro m Birmingha m University in 1948. Hi s post-graduate studies at the
Cavendish Laborator y a t Cambridge unde r Erwin Orowa n and Si r Lawrence Brag g resulte d
in th e awar d o f his PhD (1952 ) on plasticity in sodium chloride. H e worked at th e Atomic
Energy Researc h Establishment, Harwel l and lecture d at Birmingham University until 1958 ,
when h e wa s appointe d Reade r i n Physical Metallurg y in the Departmen t o f Metallurgy at
Imperial College London. H e was Professor of Crystal Physics from 196 3 to 1992 (Emeritu s
1992). H e contribute d greatl y t o th e deepe r understandin g o f th e developmen t o f
microstructure durin g cemen t hydration , an d it s relatio n t o material s propertie s an d
performance, bot h through hi s ow n work and throug h his leadershi p o f the researc h grou p
at Imperia l College, whic h had a n internationa l reputation . Throughou t hi s caree r h e wa s
awarded numerou s prizes an d honours .
Preface

With a view to taking stock of the subjec t an d establishing areas of future investigation , the
RILEM Technica l Committe e 'Interface s i n Cementitiou s Composites ' se t itsel f tw o
objectives: t o organize a n International Conference a t which the latest research result s coul d
be presented an d to edit a state-of-the-art publicatio n prepared by leading specialists. The first
objective wa s achieve d i n October 1992 , whe n an Internationa l Conference too k place i n
Toulouse, the proceedings o f which were published in Interfaces in Cementitious Composites
by Ε & FN Spon. Th e secon d i s achieved i n the present book .
In th e Introduction , Recto r Jacque s Farran , a pioneer i n the subject , describe s ho w th e
interfacial transitio n zone was discovered i n the early 1950s , several thousand years after the
first know n concretes an d about 200 years after the discovery - o r rediscovery - b y Apsdin
and Vicat o f the cement s tha t are th e origi n o f our modern concretes .
More an d more scientists ar e becomin g interested i n the stud y of the interfacia l transition
zone betwee n cemen t past e and aggregates. Hig h performanc e concrete s aside , i n standard
concretes thi s zone is the seat of primary defects an d the preferred path for their propagation
under mechanical , physica l an d chemica l actions . Th e defect s cause d b y suc h actions ,
working alon e o r i n combination (the latte r i s mor e usual) , ca n mak e a structur e unfi t t o
perform it s function .
To understan d thi s proble m an d als o th e conclusion s tha t ma y b e draw n fro m suc h
knowledge, i t i s necessar y t o understan d th e physico-chemica l mechanism s o f cemen t
hydration i n the immediat e vicinity o f the aggregates . Th e microstructure of the interfacia l
transition zone in hardened concret e depend s on these mechanisms. Fo r this reason, th e firs t
two chapter s o f this book are devote d to their characterization and to the experiment s use d
to stud y them.
The next two chapters ar e dedicate d to the intrinsi c properties o f the interfacia l transition
zone: mechanica l properties an d transfer propertie s relatin g to the microstructure. Although
many experiments, suc h as those for studying the microhardness o f the transition zone, ar e
now wel l established , ou r knowledge is stil l incomplete.
The fina l par t o f the boo k concerns th e influenc e of the interfacia l transitio n zone o n the
properties o f a composite, i.e . o f concrete. Althoug h this zone i s less than 15-2 0 micron s
thick, it s influence on the response of concretes t o external actions, an d consequently o n the
durability o f concrete structures , whethe r reinforce d or not, i s crucial.
Damage mechanism s unde r short-ter m mechanical action s ar e no w understood fro m th e
phenomenological poin t of view, an d althoug h we stil l nee d t o quantif y them, studie s ar e
under wa y i n various laboratories. However , study o f the behaviour o f the transitio n zone
in response to long-term actions has onl y just begun.
Since the y ar e interconnecte d i n actual concretes , th e interfacia l transitio n zones clearly
have a n important influence on the transfe r propertie s o f concretes and , a s a consequence,
on thei r durability . Her e agai n w e ar e a t th e stag e of initia l studie s an d thi s subjec t wil l
undergo significant development in the future, with very interesting results fo r practitioners.
xii Preface

The present work wil l b e a reference no t onl y fo r scientists , but als o for practitioners, wh o
will fin d inspiratio n fro m th e formulation s o f concretes and fro m a n improve d understandin g
of th e evolutio n o f concrete structures in situ. Finally , th e boo k wil l b e a significant too l fo r
both teacher s an d students .

Professor J. C. Maso
Toulouse, May 1994
Introduction: Th e transition zone - discover y
and developmen t
J. Farran
Paul Sabatie r University , Toulouse , Franc e

At th e openin g o f th e Internationa l RILE M Symposiu m o n Interface s i n Cementitiou s

Composites hel d in Toulouse i n October 1992 , the writer's introductory speech recalled th e
beginnings in Toulouse of a research programme that, even after more than 40 years, ha s not
yet covered al l aspects of the subject .
The stor y began i n 1948. Afte r th e war , Franc e wa s involve d i n the implementatio n of a
vast rebuildin g programme, particularl y in the development o f hydraulic energy. A s part of
this, man y larg e dams, undergroun d work s and power stations wer e built . Frenc h engineers
thus came into contact wit h roc k in order t o support structure s o n it, to go through it, or to
use i t in their concrete, i n a way that nobody had don e before . The y soo n discovered that ,
contrary t o wha t the y wer e taugh t o r wer e suppose d t o understan d fro m thei r
physico-mathematical training, knowledg e of the name and age o f a rock did not give them
any information on its behaviour in a technical sense (just as one cannot know an individual's
reactions whe n one know s just his age an d name) .
What struc k them particularly was th e discover y that i n the same gallery dug i n the same
very har d granite , whic h appeare d t o be stabl e an d dr y when it was built , th e wall s might
crumble i n some places after a few months, a few week s o r even a few days. A t the same
time, som e of the largest extracte d block s exposed t o the weather an d store d outsid e for us e
in concrete fo r the lining , turne d int o an incoherent clay mass. But, in other passages, these
changes di d no t tak e plac e althoug h th e roc k wa s o f exactl y th e sam e petrographi c an d
crystallographic typ e and o f the sam e chemical composition.
Apart fro m weathering , othe r extremely variable technical characteristics wer e noticed for
rocks whic h nevertheles s ha d th e sam e petrography an d mineralog y (fo r instance , drillin g
ability, 'crushability' , capability to produce hig h quality aggregates) .
Engineers wer e soon overwhelmed by the extent and economic consequences of the seriou s
miscalculations linked to the behavioural variations of the rocks, whic h at first sigh t seemed
incomprehensible becaus e the y wer e s o unexpected . So , th e engineer s turne d t o th e
geologists. Th e geologist s wer e accustome d t o the stud y o f large masse s and wer e use d t o
dealing wit h problems i n terms o f millions of years. The y were not prepared t o tackle these
localised ne w types o f problems an d indee d the y could not fin d an y appropriat e solution.
But th e crystallographers , thank s t o thei r smal l scal e methodolog y an d abilit y t o stud y
crystals u p t o th e reticula r lattic e level , prove d themselve s abl e t o detec t quickl y th e
beginnings o f change s i n th e rocks , wherea s th e engineer s notice d an d suffere d th e
consequences much later, an d ofte n too late to be abl e t o fin d a solution.
Following requests from Electricit e de France an d other large public works companies, thi s
writer wa s firs t prompte d t o stud y wit h som e o f his students , th e mai n problems o f rock
weathering, it s influencing factors, it s measurement an d rate , s o a s t o define systematicall y
what type of lining shoul d be used fo r the underground structures .
In almos t all cases, the concrete use d fo r these linings was made with aggregates resulting

Interfacial Transition Zone in Concrete. Edited by J.C . Maso . RILE M Repor t 11.
Published in 199 6 b y Ε & FN Spon, 2-6 Boundar y Row, London SE1 8HN . ISBN 0 419 2001 0 X.
xiv Introduction

quality wa s largel y dependen t o n th e stat e o f th e roc k weathering . Thes e observations ,

together wit h the study of the attachment o f watertight cement-based coating cast against rock
walls, logicall y brough t us t o examine th e problem of adherence.
These tw o researc h areas , alteratio n an d adherence , wer e obviousl y prompte d b y th e
technological demand withou t which they would probably not have been carried out. Indeed,
both studies starte d o n the building site but it must be emphasised tha t they have always been
carried ou t with th e though t and the means of the fundamenta l scientifi c research prevailing
in ou r university laboratory.
The study o f adherence carried out at the time of building the big hydroelectric works has
proved t o hav e a universa l applicatio n since user s o f al l types o f concret e hav e becom e
progressively mor e intereste d i n this characteristic dependin g o n their usage: air, maritime,
nuclear etc .
The main published results ar e recalle d here so as to make the link wit h the present work.

1 Microscopi c observation of adherence on thin plates cu t in mortars mad e from differen t

pure mineralogical species, previously vacuum-impregnated by a coloured resin, clearly
demonstrated th e determine d influenc e o f the aggregat e type (Farran , 1950) .
2 Durin g th e settin g an d hardenin g o f a define d cemen t i n contac t wit h a particula r
aggregate, som e hydrate d constituent s settl e i n a specifi c manne r i n contact wit h th e
aggregate an d th e contac t fil m typ e i s different fro m tha t o f the hydrate d cemen t mas s
(Farran, 1953) .
3 Accordin g to the cement an d aggregate type, specific reactions ca n occur at their contact
point, i n a morta r o r a concrete . Som e o f thes e reaction s ar e destructiv e an d other s
constructive, as a result of the formation of intermediate solid solutions or, even epitaxial
attachments (Farran , 1956) .
4 "Fo r the values o f the c/(c+w) ratio corresponding t o the practical field o f composition
of morta r an d concret e th e aggregate s ar e surrounde d b y a particula r paste , whic h
constitutes a transition zone between the m and th e binde r mass. Beside s a composition
difference, th e textur e o f this zone i s loose r tha n tha t o f the binde r past e mass and it s
strength i s lower. Under the action of external forces, fracture s occu r mor e ofte n inside
this zone" (Farran , 1956 ; Maso, 1967 ; Farran, Javelas , Mas o an d Perrin, 1972) .

The interfacia l zone, thu s identified , seeme d therefor e t o hav e a particularl y important,
even determining role, on several mai n characteristics o f concrete (mechanica l strengt h and
frost resistance , fo r example). In fact, durin g recent years , man y research works have been
conducted o n this subject an d their authors gathere d i n Toulouse for the 199 2 Symposium to
discuss their points of view an d to examine th e curren t situation.
Besides numerou s point s o f agreement , a divergenc e i s t o b e note d relate d t o th e
designation o f thi s zone , tha t wa s originall y called , afte r a lon g terminologica l debate,
'transition aureole ' (Farran , Javelas , Mas o an d Perrin , 1972) , puttin g aside, afte r carefu l
consideration, expressions suc h as 'interfacia l zone' o r 'contac t zone ' tha t many people now
seem to prefer. Lexicologist s and etymologists in Greek and Latin would sa y that an aureol e
is golden (from th e Latin aureus), plan e and circular. I t was long used b y painters t o encircle
the hea d o f Jupiter's descendant s and the n the So n o f God's head ; it s usage was sparingl y
extended t o the Saint s onl y centuries later .
Bearing in mind this rather classica l definition i t is clear tha t the term is not really suitable
for ou r field o f activity - merely because it is not the mos t golden part o f the concret e - far
from it!
 Introduction x v

Nevertheless th e usage became more widespread amongs t scientist s wh o called the 'aureole '
the seat of any ne w formation arising from th e meeting of two materials inducin g a reaction
when comin g into contact. Metallurgist s speak about a n aureol e i n relation to weldin g and
geologists hav e use d th e concep t o f 'aureol e o f metamorphism ' t o distinguis h rock s o f
progressive variabl e types forme d when an eruptive massif an d a sedimentary massi f meet.
And here the word 'aureole ' cover s th e four meanings o f complete encircling, o f interaction,
thickness an d gradien t o f composition , wherea s th e wor d 'zone ' seem s t o th e write r t o
convey a lot less than these four essentia l ideas .
But let us sto p this analysis o f terminology. The problem is neither insignificant , nor eve n
marginal, but it is only semantics and changes nothing in the physico-chemical or mechanical
reality. Nevertheless , havin g observed an d described i t in the first plac e i n 1953, we wished
to explain the decision , i n 1972, t o call th e subjec t o f our concerns the 'transitio n aureole' .
The mai n thing s whic h remai n t o b e don e ar e t o broade n th e knowledge , t o asses s th e
different characteristics , t o stud y th e propertie s an d th e consequence s on th e behaviou r o f
cementitious composites , particularl y during their technological applications .
Many researcher s hav e worked and ar e stil l workin g o n this subject , wh o participated in
the Internationa l Symposium in 1992 to debate this question and t o examine th e state of the
current knowledge . Considerin g th e numbe r an d th e qualit y o f th e participants , i t wa s
pleasing, bu t no t surprising , t o not e tha t th e researc h pat h tha t ha s bee n opene d look s s o
promising.
On a personal note , I wa s gla d t o b e abl e t o tel l th e participant s ver y sincerel y tha t w e
were deepl y touche d tha t Toulous e ha d bee n selecte d t o organiz e th e Symposiu m an d w e
were ver y gratefu l fo r their participation. The wor k o n this topic has no w reached anothe r
milestone wit h th e completio n of this RILE M Report .

References

Farran, J . (1950 ) Bulletin de la Societe d'Histoire Naturelle de Toulouse, T.85-1950, p. 338 .

Farran, J. (1953 ) Comptes-rendus des seances de I'Academie des Sciences, Paris T.237-1953,
p. 73 .
Farran, J . (1956 ) Thes e d e Doctorat , Toulouse , i n Revue des Materiaux de Construction,
Paris, No s 490, 49 1 and 492.
Maso, J.C . (1967 ) These de Doctorat , Toulouse , i n Revue des Materiaux de Construction,
Paris, No s 647 , 64 8 an d 64 9 (1969).
Farran, J. , Javelas , R. , Maso , J.C . an d Perrin , B . (1972 ) Comptes-rendus des seances de
I'Academie des Sciences, Paris, T.275-1972 , p . 1467 .
 PART ON E

MICROSTRUCTURE
1

Characterisation of interfacial
microstructure
Karen L . Scrivener and Peter L. Pratt

1.1 Introductio n

It ha s lon g been appreciate d tha t th e microstructur e o f cemen t paste i n the vicinit y o f a n

aggregate particl e i n mortar o r concret e differs fro m tha t furthe r awa y fro m th e aggregat e
and fro m tha t i n neat cement paste containing no aggregate. However, th e interfacia l region
is an integra l part o f the whole microstructure s o i t is difficult t o characterise the distinctive
features o f thi s region . Ideall y the interfacia l zon e i n real concret e shoul d b e studied , bu t
only a limited number o f techniques, mostl y developed fairl y recently , can be used to do this.

1.2 Specime n preparatio n

1.2.1 COMPOSIT E SPECIMENS

In th e 1950s , Farra n (1956 ) developed a model composite specime n t o study th e interfacia l

zone specifically. This specimen, whic h has sinc e been used extensively, consist s of cement
paste cast against a flat (usuall y polished) block of aggregate. The specime n ca n then eithe r
be spli t alon g th e interfac e o r cu t perpendicula r t o i t exposing th e past e i n the interfacia l
zone. Th e microstructur e o f the past e side of the interfac e ma y b e characterise d b y X-ray
diffraction (XRD ) o r surfac e analytica l techniques as discusse d below.
Despite th e obviou s advantage s o f thi s mode l interfacia l specimen , i t differ s fro m rea l
concrete i n three importan t respects:

1. Only one piece of aggregate is present so the microstructure o f the paste can adjus t ove r
an effectively infinit e distance without encountering anothe r aggregate particle as would
be th e cas e in concrete ;
2. A n extensive flat (an d polished ) surfac e wil l facilitat e the formatio n of a fil m o f wate r
or mor e extensiv e bleedin g a t the interface ;
3. Th e aggregat e is not present during the mixin g o f the paste . Th e presence of aggregate
during th e mixin g o f concrete may hav e a significan t effect o n the past e by increasin g
local rate s of shear an d ma y allo w the aggregat e to acquir e a coating o f cement grain s
as i t moves through the paste.

Later variants o f this model composite specime n includ e the sandwich of paste between tw o

Interfacial Transition Zone in Concrete. Edited by J.C . Maso . RILE M Repor t 11 .

Published i n 199 6 b y Ε & FN Spon, 2- 6 Boundar y Row, Londo n SE1 8HN. ISB N 0 419 2001 0 X.
4 Characterisation of interfacial microstructure

flat piece s o f aggregat e use d b y Xi e Pin g et al. (1991 ) fo r measuremen t o f electrical

conductivity o f the interfacia l zone .
The thir d differenc e betwee n th e mode l and rea l concret e ma y b e overcome , i n part a t
least, b y mixing the aggregate together wit h the paste, placing it in a mould and then pouring
the past e ont o it . Mitsui, L i and Sha h (1991 ) used thi s techniqu e wit h a smal l cylindrical
piece of aggregate placed upright in a larger cylindrical mould. This composite specimen was
used fo r push-out test s to characterise th e mechanical properties o f the interfacia l zone .

1.2.2 REA L CONCRETE

If rea l concret e i s to be studie d ther e ar e thre e mai n possibilities for specime n preparation
depending o n the characterisatio n techniqu e t o be used .

Bulk comparisons
The pore siz e distributio n o f concretes an d mortars a s a whole may be compare d wit h tha t
of nea t paste, b y mercury porosimetry, magnetic resonanc e relaxation analysis (MRRA ) o r
impedance spectroscopy . Fro m these comparisons th e effec t o f the interfacia l zon e o n the
overall por e siz e distributio n ma y b e determine d bu t the spatia l distributio n o f porosity in
relation t o the position of the paste-aggregate interfac e ca n onl y b e inferred.

Fracture surfaces
A fractur e pat h throug h concret e wil l pas s throug h severa l interfacia l regions , runnin g
parallel t o the interfac e i n some places and across it in others. Stud y of the fracture surfac e
in the SEM allows the microstructure of these regions to be examined. This technique is very
useful fo r qualitative characterisation, but , because the crack path favours weaker region s of
the microstructure, fracture surface s ar e unrepresentativ e o f the concrete a s a whole.

Cut and polished sections

Sections through bulk specimens prepare d b y mechanical cutting should be representative of
the bul k i f they ar e larg e enough . Cu t and polished sections ca n be examined in the optica l
microscope (thi n sections) o r at higher resolution in the SEM with back scattere d electrons .
Despite their advantages over fracture surfaces , i t is still not possible to determine the angle
at which the plane of the section intersects th e paste aggregate interface. Generally this angle
of intersectio n wil l no t b e a righ t angl e s o th e apparen t widt h o f th e interfacia l zon e i s
expanded. I t is also possible to prepare thi n sections o f the interface by ion beam milling for
examination i n the transmisisio n electron microscope (TEM) , althoug h with thi s technique
only smal l regions ca n be examined.

1.3 Characterisatio n technique s

1.3.1 X-RA Y DIFFRACTIO N (XRD )

X-ray diffractio n i s a valuabl e techniqu e fo r studyin g the interfacia l regio n i n composite

specimens. Th e technique developed by Grandet and Ollivier (1980a, 1980b) has been widely
used t o stud y th e orientatio n of calciu m hydroxide crystals i n the interfacia l zone . Thi s
technique entails splitting the composite specimen along the interface; an X-ray diffractometer
 Characterisation techniques 5

trace of the cement past e side of the interfac e i s then taken, a layer of paste is ground away
and anothe r XR D trace taken. I n this way informatio n is built up abou t calciu m hydroxide
and othe r crystallin e component s o f th e microstructur e a t increasin g distance s fro m th e
interface. Th e penetration of X-rays into cement paste will be of the order o f 10 μπι or more
so there wil l b e a degree of overlap between result s fro m successiv e layers .
The mos t widesprea d applicatio n of this technique i s to stud y th e orientatio n of calcium
hydroxide in the interfacial zone. Fo r randomly oriented calcium hydroxide crystals the ratio
of intensitie s fo r the peak s at 4.90 A , fro m th e {0001 } basal planes, an d a t 2.62 8 A , fro m
the {1011 } plane s shoul d b e 0.74 . Thu s th e rati o R = (Ι ιοοο}/Ι{ΐοιΊ})/0.74 i s take n a s a
{

measure o f the degre e t o whic h th e C H crystals ar e preferentiall y oriented . Man y studies

have used this method t o indicate that calciu m hydroxide in the interfacia l zone tends to b e
oriented wit h it s basal plane paralle l to the interfac e (c-axi s perpendicular) .
Recently th e interpretatio n of results obtaine d wit h thi s technique ha s bee n questioned. I t
has bee n pointed out (Diamond, 1988) that only crystals oriente d with the {0001 } or {1011}
planes paralle l t o th e interfac e wil l contribut e t o th e peak s measure d b y thi s technique .
Detweiler et al. (1988 ) have studied th e complete distributio n of CH crystal orientations on
pole figure s an d obtaine d result s consisten t wit h thos e obtaine d b y th e Grandet/Ollivie r
technique. Yua n et al. (1988) used rocking curves to study the degree of preferred orientation
and obtaine d result s qualitativel y simila r t o thos e obtaine d wit h th e Grandet/Ollivie r
technique.
Results obtaine d b y Ziir z an d Odle r (1987 ) indicat e tha t th e orientatio n index o f calcium
hydroxide change s wit h hydratio n time, water/cement rati o and othe r factor s i n a way tha t
appears t o b e inconsisten t wit h th e usua l interpretatio n o f thi s index . I n particular , th e
(Ι{ΐοοο}/Ι{ΐοϊΐ}) P k intensit y rati o wa s foun d t o declin e wit h progressin g hydration , an d
ea

preferred orientatio n was als o detecte d b y thi s metho d i n bulk cement pastes . I n a recen t
presentation, Mas o (1991 ) suggeste d tha t th e orientatio n inde x migh t b e mor e correctl y
interpreted a s a measure of the size of calcium hydroxide crystals i n the interfacial zone, bu t
this interpretation would no t appear to explain the result s obtaine d b y Ziir z an d Odler . I t is
possible tha t calcium hydroxide crystals may tend to become oriented with their basal planes
parallel t o th e interfac e durin g polishing, and thu s tha t th e orientatio n index i s i n part a n
artefact o f the preparatio n process . Suc h reorientation would be mor e likel y t o occur whe n
the microstructure was less dense (i.e. close to the interface, a t high water/cement ratio s and
at shorter hydratio n times) and when the crystals wer e larger. Suc h an effect would , i n part,
explain the result s o f Ziirz an d Odle r and the view s of Maso and Grandet . However , whe n
the cement past e was impregnate d wit h resin before usin g the Grandet/Ollivier technique (in
an attempt t o avoid reorientation of the C H crystals durin g polishing) very similar results t o
the un-impregnated past e were obtaine d (Monteir o and Scrivener , 1991) .
The progressive polishin g technique ha s als o been used to estimate th e variatio n of weight
fraction o f calcium hydroxide and ettringit e with dept h (Monteir o and Mehta , 1985) . Only
semi-quantitative result s ca n b e obtaine d a s th e interna l standar d metho d canno t b e used .
However, i t seem s clea r tha t th e proportio n o f bot h C H an d ettringit e increas e i n th e
interfacial region .

1.3.2 SURFAC E ANALYSIS (XPS , SIMS)

Composite specimen s offe r th e possibilit y of characterisin g th e microstructur e o f cemen t

paste immediately adjacent t o the aggregate with a range of surface analytica l techniques .
6 Characterisation of interfacial microstructure

X-ray photoelectro n spectroscop y (XPS) , otherwis e know n a s electro n spectroscop y fo r

chemical analysi s (ESCA) , involve s th e us e o f sof t X-ray s unde r hig h vacuu m t o ejec t
photoelectrons fro m atom s near the surface o f solid materials. Typical depths of investigation
are 5-1 0 ran an d a chemical analysis o f the surfac e laye r can be obtained by measuring th e
kinetic energ y o f the photoelectrons. Th e technique ha s bee n used t o measure C/S ratio s in
C S an d cement powder s whic h change rapidly durin g the firs t minute s of hydration.
3

Secondary io n mass spectrometry (SIMS ) involves bombarding the surface wit h a beam of
high energ y ions , causin g subsurfac e displacemen t cascades . Secondar y ion s emitted fro m
the surface a t the end of the cascade are analysed i n a mass spectrometer. Lo w primary beam
currents ar e necessar y fo r good surface analysis . Moder n instruments using a microfocused
beam, rastere d acros s the surface , ca n produce chemica l maps wit h a latera l resolution o f
0.2 μπ ι and an analysis dept h of only a few nanometres .
Very littl e wor k o n mortars or concretes ha s bee n reporte d although the techniques coul d
be used t o study the composition of surface layer s and near-surface layer s of aggregates and
of fibre s either before mixin g o r after extractio n from th e hardene d material.

1.3.3 BUL K POR E SIZ E DISTRIBUTIO N

Several technique s ma y be used t o compare th e por e structur e i n cement paste wit h tha t in
concretes an d mortars . Winslo w an d Li u (1990 ) compare d th e por e siz e distribution ,
measured usin g mercury intrusion porosimetry (MIP), of a plain cement paste with that same
paste in mortar an d i n concrete. Fo r mature specimen s the y foun d tha t th e paste in mortar
and concret e wa s mor e porou s tha n th e correspondin g plai n past e an d th e bul k o f th e
additional pore volume, presumably i n the interfacial zones, wa s i n pore sizes larger than the
threshold por e diamete r fo r th e plai n paste . Thi s i s interestin g bu t b y itsel f difficul t t o
interpret because the analysis i s based upon an oversimplified geometrica l model of pores as
spheres or cylinders. A paper b y Snyder et al. (1992 ) overcame thi s by using concepts fro m
percolation theor y t o interpre t th e MI P measurements fro m mortar s containin g increasing
sand contents. Th e pore size distribution, normalised per gram of cement, showe d a dramatic
change betwee n 45 % an d 48 % i n th e volum e fractio n o f san d (Fig . 1.1) . This , the y
concluded, indicate d that the interfacia l zone s became linked together , o r percolated, int o a
continuous pathway. They developed a continuum computer simulation model based on hard
cores and soft shells , using some 10,000 aggregate particles. From this they concluded that
the thickness o f the interfacial zon e whic h best explained the experimental MIP results wa s
15-20 μπι.
Two othe r sophisticate d physica l technique s ar e availabl e fo r th e stud y o f porosit y i n
cement paste : magneti c resonanc e relaxatio n analysi s (MRRA ) an d comple x impedanc e
spectroscopy. Unlik e MIP, both must be used without drying the specimens because they rely
on the presence of water i n the pores; bot h are promisin g in the informatio n the y can give
about th e natur e o f th e porosity . MRR A make s us e o f th e differenc e i n nuclea r spi n
interactions betwee n proton s i n bul k por e wate r an d thos e encounterin g a liquid-soli d
interface. Fo r a range o f pore sizes inhomogeneously distributed over distances greate r tha n
a fe w μπι, Halperin (1989) has show n that th e invers e Laplac e transfor m o f th e nuclea r
magnetic resonance (NMR) relaxation profile i s simply related to the distribution of the local
surface/volume ratios; this is equivalent to the local pore size distribution. He and co-workers
used this technique to study porous rocks and ceramics an d are no w looking at cement paste.
The second technique, complex impedance spectroscopy , i s valuable for studying changes
 Characterisation techniques 7
0.20

0.001 0.0 1 0. 11 1 0 10 0 5 0 0

P o r e d i a m e t e r (/vm )

Fig. 1.1 . Mercury intrusion porosimetry for mortars with varying sand contents (from Snyder et al.,
1992). Note the large difference in pore size distribution between mortars with sand contents of 0.448
and 0.486 by volume.

in a high conductivity phase, like pore water, embedded in a low conductivity matrix like the
hydration product s o f cement. Maso n an d co-worker s hav e applie d it both to a rang e o f
ceramic materials and to the curing of cement pastes (Scuderi et al, 1991 ; Christensen et al.,
1992). Th e importan t feature o f this technique i s that i t enables the resistanc e o f the bul k
material t o b e separate d fro m th e electrod e resistanc e unambiguousl y by measurin g th e
impedance ove r a range o f frequencies. Th e value of the real impedance at the minimum in
the imaginary impedance between the electrode ar c an d the bulk arc give s the dc resistanc e
of th e bulk material . Fro m thi s it is easy to obtain the dc conductivity of the bulk material.
By expressin g th e por e flui d fro m th e specime n i n a press, th e conductivit y o f the liqui d
phase can be measured separately . Th e difference between the conductivity of the free liqui d
and the liquid in the specimen gives a direct measure of the connectivity and tortuosity of the
microstructure. Christense n et al. (1992 ) have reporte d systemati c measurement s o f these
conductivities fo r a cement paste , findin g reasonabl e agreemen t wit h compute r simulation .
Beaudoin, a t the Engineering Foundation Conference i n Potosi in 1992, reported the results
of applyin g the technique to study the development of the interfacia l zon e i n mortars.

1.3.4 OPTICA L MICROSCOP E

Details o f the spatia l distribution of the porosity and of the phases in the hardened past e in
the interfacia l regio n can be see n with a n optical microscop e at a resolution limited b y the
wavelength o f visible light , typicall y a fe w microns. Examination in transmitted polarised
light of thin sections, prepared by cutting, grinding and polishing, is a well-known technique
for concrete . Fluorescen t resin s ar e frequentl y used t o fil l th e larger pores an d in this way
an indication of the water/cement ratio, th e original mix design and the homogeneity of the
porosity ca n be obtained.
8 Characterisation of interfacial microstructure

1.3.5 ELECTRO N MICROSCOPE

The transmission electro n microscope (TEM ) offer s increase d resolvin g power o f the orde r
of nanometres , becaus e o f th e shorte r wavelengt h o f th e bea m o f electrons , bu t th e
preparation o f goo d thi n foils , transparen t t o th e electrons , i s tim e consuming . Fo r th e
highest resolution of the details of interfacial microstructure the TEM technique is necessary.
Scanning electro n microscop y (SEM ) has bee n use d i n two different mode s of imaging:
secondary electron imaging to study fracture surface s where topographica l features produc e
the contrast i n the image and the large depth of focus is valuable, and back-scattered electron
imaging t o stud y flat polishe d surface s wher e difference s i n back-scatterin g coefficient ,
dominated b y atomi c numbe r differences , produc e th e contrast . Becaus e bac k scattere d
electrons ar e generated fro m deepe r in the specimen the resolution of the image is not as high
as i n the TEM , bu t the preparation o f the specime n i s much simpler. Detector s fo r energy -
dispersive an d wave-lengt h dispersiv e X-ra y analysi s enabl e chemica l composition s t o b e
determined i n regions excite d b y th e electro n beam . Th e scannin g instrument s produc e a
digitised imag e whic h ca n be store d o n disc o r transferred directl y to image processing an d
image analysin g systems . I n thi s wa y gradient s o f microstructura l compositio n ca n b e
determined t o characterise th e interfacia l region (Scrivener an d Gartner, 1988 ; Scrivener et
al., 1988 a Scrivene r et al., 1988b) .

1.4 Feature s of interfacia l microstructure

There ar e tw o main components t o the microstructur e of the cement past e in the transition
zone. Firs t there i s the thi n laye r of products whic h for m directl y on the aggregate surface ,
typically only a micron or so in thickness. Thi s includes the products from an y reaction there
may be between th e aggregate and the cement paste . In addition to this layer directly at the
interface, ther e i s th e muc h large r regio n of paste i n which th e presenc e o f the aggregat e
particle affect s th e origina l packin g o f th e cemen t grain s which , i n turn, determine s th e
subsequent development of microstructure. Thi s region may extend some 50 μπι or more out
from th e aggregat e surface .

1.4.1 LAYE R O N AGGREGATE SURFACE

The natur e o f the surfac e laye r ha s bee n the subjec t o f much debate. Barne s et al. (1978 ,
1979) used secondar y electro n imaging of fracture surface s t o study the layer whic h formed
when cement paste was cas t against a glass slide and subsequentl y th e surfac e laye r formed
on aggregates in concretes. The y characterised thi s as a 'duplex' laye r of calcium hydroxide
on the aggregate side and C-S-H on the cement paste side. The calcium hydroxide component
is sometime s referre d t o a s a n epitaxia l layer, bu t thi s i s a misnomer . Th e ter m epitaxial
implies a crystallographi c orientatio n relationship betwee n th e produc t an d substrate , bu t
similar layers have been reported on glass and polythene which are non-crystalline (Yuan and
Guo, 1987) . However, any aggregate surface, whethe r i n concrete o r in a model specimen ,
provides a n idea l heterogeneou s nucleatio n sit e fo r th e precipitatio n o f eithe r calciu m
hydroxide or C-S-H. Javels et al. (1974 , 1975 ) and Zhang et al (1988) , using TEM o f ion-
thinned specimens from mortar, and Scrivener and Pratt (1986), using back-scattered electro n
 Features of interfacial microstructure 9

(bse) imagin g o f polishe d surfaces , note d a simila r thi n laye r forme d directl y o n th e
aggregate surface bu t identified this as C-S-H. If a layer of CH does form par t of the surfac e
layer it is certainly well under a micron in thickness an d so could not be detected b y analysis
of characteristic X-ray s in the SEM, or by the XRD technique of Grandet an d Ollivier. More
recently Monteir o and Osterta g (1989 ) hav e reporte d th e result s o f grazin g angl e X-ra y
scattering o n the cement past e side o f a composite specime n spli t a t the interface , thi s gave
a clear patter n fo r CH with n o sig n of any broad peak fro m C-S-H .
The presence o f CH could, of course, depen d o n the natur e o f the specime n preparatio n
and the size o f the aggregate particles. Studies by Ping and Beaudoin (1991) of the electrical
conductivity of concretes show a strong influence of the size o f the aggregate on parameters
related t o the microstructure . A large, singl e piece o f polished aggregate probably favour s
the formatio n of a continuous laye r o f water a t the surfac e whic h woul d i n turn favou r th e
formation o f CH . Wherea s i n mortars , use d fo r mos t o f th e microscopi c studies , larg e
concentration gradients i n the pore solutio n around aggregate particles woul d b e les s likel y
and consequentl y C-S- H would b e mos t likel y t o precipitate o n the aggregate surface .

1.4.2 PAST E AFFECTED B Y PRESENCE O F AGGREGATE

The early wor k o f Farran (1956 ) noted the lowe r density o f the paste around the aggregate.
Increased porosit y aroun d aggregat e particles ma y als o b e observe d b y optical microscopy
in thi n section s o f concrete impregnate d wit h fluorescen t dye , althoug h a distinct interfacia l
zone i s no t obviou s i n goo d quality , lo w water/cemen t rati o concretes . Suc h qualitativ e
observations hav e been confirmed by quantitative analysis o f back-scattered electro n image s
(Scrivener an d Gartner , 1988 ; Scrivene r et al., 1988a , 1988b) , whic h show s tha t th e leve l
of porosit y steadil y increase s fro m a 'bulk ' leve l som e 20 μπι from th e interfac e t o nearly
twice thi s leve l i n a 3 μπι-wide ban d adjacen t t o th e interface . Thi s technique ca n als o b e
used t o determine th e gradients i n unreacted cement , calciu m hydroxide and other hydration
products. Typica l plots fro m a one day ol d concrete ar e show n in Fig. 1.2. Th e gradient in
porosity is reflected in the distribution of the unreacted cemen t whic h increases steadily fro m
near zero adjacen t t o the interface t o a 'bulk ' leve l about 20 μπι out. The amount of calcium
hydroxide als o increase s to about twic e its bulk valu e a s th e interfac e i n approached .

1.4.2.1 Packing of cement particles at the interface

From th e gradien t o f unreacted cemen t i t is clear tha t th e initia l distributio n o f the cemen t
grains aroun d th e aggregat e particl e i s th e principa l facto r i n determining the subsequen t
microstructure. The aggregate is effectively a wall against which the cement grains must pack
themselves. Thi s effect i s shown for an idealised 2-dimensional case with monosized circular
particles i n Fig. 1.3 . Eve n thoug h th e particle s ar e touching , the amoun t o f empty spac e
approaches 100% as the 'wall ' i s approached. I n a 3-dimensional case of monosized spherical
particles there may appear to be a 'film ' o f empty space at the interface even though particles
are touching , Fig. 1.4 . I n concrete, th e situatio n is further complicate d by the fac t tha t th e
cement grain s hav e a wide range of sizes ranging from les s than 1 μπι up to 10 0 μπι or so .
To loo k a t th e initia l packin g of cement particle s i n a concrete i t would b e necessar y t o
examine a section of concrete befor e i t is set, whic h i s not practical. Escadeillas an d Maso
(1990) have attempted t o stud y concrete s a s nea r t o this initia l stat e as possibl e b y freeze -
drying an d resin-impregnatin g fres h concrete . Thi s qualitativ e stud y indicate d a zon e of
disturbance aroun d the aggregate some 20 μπι thick, i n which more small particles and voids
10 Characterisation of interfacial microstructure

^ U D C O ^ r O C ^ C O O ^ O L O C O C > C N i u - ) r ^ - C D C > J - ^ - r - ^

D i s t a n c e f r o m a g g r e g a t e (μιτι )

Fig. 1.2 . Distributio n of microstructural constitutuent s i n the interfacial regio n o f a 1-day-ol d

concrete.

Fig. 1.3. Hypothetica l packing of monosized circle s against a 'wall' i n two dimensions. Eve n though
the circles are touching, the fraction of space occupied by the circles approaches zero as the interfac e
is approached.
 Features of interfacial microstructure 1 1

Fig. 1.4. Hypothetica l two-dimensional section of monosized spheres packed against a 'wall' i n three
dimensions. Soli d circles indicate profiles in plane of section while dotted lines indicate maximum
cross-sections. Shade d area represents region at the interface which appears to be devoid of particles.

were observed. Th e initial distribution of grains in the interfacial region can also be deduced
from relic s and Hadley grains i n a mature paste (Scrivener and Gartner, 1988) . This indicates
that small particles predominate close to the interface wit h larger particles lying further out.
A mor e quantitativ e approach i s to calculate th e initia l distributio n o f anhydrous cemen t
from th e microstructural gradients measure d i n hardened pastes . This can be done fro m th e
analysis o f concrete s hydrate d fo r 1 day, 2 8 day s an d 1 year b y Crumbi e and Scrivene r
(1993). T o do thi s i t has t o be assume d tha t al l the hydratio n products othe r tha n calcium
hydroxide are deposited very close to the anhydrous cement from whic h they form. Althoug h
there i s considerable evidenc e tha t C-S- H forms through solution (including th e deposition
of C-S- H on aggregate surfaces ) thi s assumption i s probably valid t o a first approximation
as th e mobilit y o f silicat e species i n solution is low . The initia l distributio n o f anhydrou s
material s o calculated is shown along with th e equivalent original water/cemen t rati o in the
interfacial regio n in Fig. 1.5 .
If th e aggregate particles are present durin g mixing the cement grain s may become grade d
around the aggregate, wit h smal l particles packing close to the interface and larger particles
tending t o settl e furthe r away . Thi s would b e expected t o reduce th e gradient s i n porosity.
Evidence of this grading can be deduced fro m the gradients of anhydrous (unreacted ) cemen t
measured afte r differen t amount s o f hydratio n (Fig. 1.6) . Eve n a t 1 da y th e degre e of
reaction at the interfac e i s higher than that in the bulk, indicatin g that the cement grain s in
this region are smalle r and so have reacte d mor e completely. The gradient measured i n the
concrete cure d fo r 2 8 day s suggest s tha t th e preponderanc e o f smal l particles i n the firs t
20 μπι from th e interfac e lead s to a concentration of larger particle s beyond thi s zone an d
that only beyon d about 40-50 μπ ι is the particle size distributio n similar to that in the bulk.
After curin g for one year the gradient of anhydrous cement indicate s that the effective width
of th e interfacia l regio n is at least 5 0 μπι confirming th e long-rang e effect o f the aggregate
'wall' o n the packing of the cement grains .
Similar results to those obtained in real concretes wer e found by Garboczi and Bentz (1991)
when the packing of cement grain s aroun d aggregate particles was simulate d in a computer
model.
12 Characterisation of interfacial microstructure

50

40

30

20

10

10 20 3 0 40 50
1.2
D i s t a n c e f r o m a g g r e g a t e (μηη )

1.0
ο
CO
0.8
ο

0.6
c
_'cp
0.4
6

0.2

10 2 0 3 0 40 50

D i s t a n c e f r o m a g g r e g a t e (//m )

Fig. 1.5 . Calculate d initia l distribution of anhydrous cemen t and effective water/cemen t rati o in the
interfacial zone.

1.4.2.2 Effect of aggregate type

Grandet an d Ollivie r foun d tha t th e degre e o f orientatio n o f calciu m hydroxid e i n th e
interfacial zon e was affecte d b y th e mineralogica l nature o f the aggregat e used. However ,
Crumbie (1994 ) foun d tha t th e typ e o f aggregat e ha d relativel y littl e effec t o n th e
microstructural gradient s measure d by imag e analysi s i n real concretes.
Comparison o f as-received aggregates with polished aggregates indicates slightl y narrowe r
interfacial zone s when the aggregat e surface i s rougher. Suc h differences probabl y occu r a s
rough particle s wil l hav e a greate r tendenc y t o acquir e a 'coating ' o f smal l cement grain s
during mixing . I n th e cas e o f som e syntheti c lightweigh t aggregates wit h ver y uneve n
surfaces thi s may resul t i n quite significan t amelioration of the microstructural gradient s i n
the interfacia l region (Ben Othman et al , 1988) . Wu et al. (1988 ) have developed speciall y
precoated aggregat e particle s an d foun d significan t improvemen t i n mechanical propertie s
when these are use d in concrete .

1.4.2.3 Effect of mix design

Crumbie (1994 ) foun d tha t factor s relate d t o the mi x design ha d som e modifying effect o n
the packin g o f cement particles an d hence on the microstructura l gradient s i n
 Features of interfacial microstructure 1 3

1 da yc 2 8 day sx 1 yea r

25τ

0 1 0 2 0 3 0 4 0

σι
Ω
0.2 -

0 J Η - « , , ,

0 1 0 2 0 3 0 4 0 5 0

Distance fro m aggregat e {μπι)

Fig. 1.6 . Distributio n of unreacted cemen t and calculated degree of reaction for concretes aged Id,
28 d and 1 yr .

the interfacia l zone. Lo w water/cement ratio s an d high aggregate/cement ratios appeared to

promote efficien t packin g of cement particle s a t th e aggregat e and s o minimised the widt h
of th e interfacia l zone . Highe r water/cemen t ratio s an d lowe r aggregate/cemen t ratio s
permitted rearrangemen t o f th e cemen t grain s ove r greate r distance s resultin g i n wider
interfacial zone s in which microstructural gradients ar e shallower . However, the proportion
of th e microstructural constituents i n th e firs t 5 μπι o r s o adjacen t t o th e aggregat e wa s
relatively unaffecte d b y mix design.

1.4.2.4 Differences in interfacial microstructure above and below aggregate

If significan t settling occurs i n the concrete befor e setting , the smaller cement particles tend
to pil e up on top of large aggregate particles (whose movement amongst the cement particles
is impede d b y thei r size). Similarl y ther e wil l ten d t o be fewe r cemen t particle s belo w the
aggregate. Thi s wil l resul t i n a n effectivel y lowe r water/cemen t rati o abov e aggregat e
particles an d an effectively higher water/cement rati o below. Such effects wer e reporte d by
Hoshino (1988) and were noted to be more significant at higher overall water/cement ratios .
14 Characterisation of interfacial microstructure

In th e wor k of Crumbie (1994) there wa s relativel y littl e difference i n the microstructural

gradients measure d abov e an d below aggregate particles at an overall water/cement rati o o f
0.4. A t the highe r water/cement rati o of 0.6 th e gradient i n anhydrous cemen t wa s steepe r
above th e aggregate particles and shallowe r below.

1.4.2.5 Redistribution of hydrates within the interfacial zone

If th e amoun t o f anhydrous materia l reacted an d th e amount s o f CH and C-S- H formed at
different distances fro m the aggregate are compared, the redistribution of hydrates withi n this
zone can be investigated. Such a comparison involves several assumptions an d will be subject
to errors. However , Fig. 1.7 shows some results fro m th e work of Crumbie (1994) in which
the genera l trend s ar e though t to b e valid . Thi s figur e show s amount s o f CH an d C-S- H
calculated a s bein g i n excess o f th e amount s expecte d i f all the hydratio n products wer e
precipitated i n the immediat e vicinity o f the anhydrou s cemen t fro m whic h they formed . It
is apparent tha t there i s a fairly large-scal e redistributio n of calcium hydroxide. Due to the
greater availabilit y o f space clos e t o th e interfac e th e growt h o f crystals i n this regio n is
relatively unrestricted. Calcium and hydroxide ions diffuse from paste further away from th e
aggregate leadin g t o a relativ e exces s i n the firs t 1 0 μπι adjacen t t o th e interfac e an d a
relative deficit i n the next 40 μπι or so. Significan t redistribution has occurred already afte r

D i s t a n c e f r o m a g g r e g a t e (//m )

Fig. 1.7 . Calculated 'excess' deposition of products, above those formed from the cement originally
present, i n the interfacial zone.
 Features of interfacial microstructure 1 5

1 day of hydration and has considerabl y increase d b y 28 days. Furthe r curing from 2 8 days
to 1 year result s i n little furthe r change presumably owin g t o the reduced diffusio n rate s of
ions through a more compact structure . Ver y roughl y speaking, hal f th e CH in a 3 μπι band
adjacent t o the interface i n a mature paste has forme d from th e reaction of anhydrous phases
outside thi s region.
The redistribution of C-S-H is less marked due to the lower mobility o f silicate species in
solution. The calculation assumed that there was negligible redistribution in the one day paste
although this assumption is probably not entirely valid. Afte r 2 8 days there i s a slight excess
of C-S- H in the firs t 5 μπι nearest to the interface an d this excess increases somewha t afte r
curing fo r 1 year. However , i n a mature past e only abou t 20 % o r s o o f C-S-H in a 3 μπι
band adjacen t t o the interfac e ha s forme d fro m th e reaction of material outside thi s region.
The ne t effec t o f this redistributio n of hydrates i s t o ameliorat e th e gradien t i n porosity
initially se t u p b y th e packin g o f th e anhydrou s particles . However , th e interfacia l zone
continues t o hav e a highe r porosit y tha n th e bulk . Thi s i s mainl y the resul t o f th e initia l
packing but is also contributed to by the phenomenon o f one-sided growt h noted by Garboczi
and Bent z (1991) . I n the bul k paste , por e spac e ma y becom e fille d wit h hydrate s b y th e
migration of species into that space from al l directions, and on the scale of several micron s
there i s no redistribution of hydrates. Clos e to the interface, however, hydrates mus t migrate
from th e cemen t past e side . Thi s phenomenon result s i n an increase d porosit y i n the firs t
5 μπ ι or so adjacent t o the aggregate, above an d beyond that arising from th e packing effect.

1.4.2.6 'Width' of interfacial zone

The packin g o f unreacted cemen t grain s aroun d aggregat e particle s result s i n a regio n of
affected microstructur e o f a widt h o f similar order o f siz e t o th e larges t cemen t particles .
However, th e widt h o f the zon e i n which th e porosit y i s noticeabl y different fro m tha t of
bulk past e i s probabl y les s tha n 2 0 μπι ( a media n siz e fo r cemen t grains) . Transpor t
properties depen d criticall y o n th e degre e o f connectivit y o f th e por e structure , whic h
evidence fro m MI P an d impedanc e measurement s suggest s i s mos t affecte d withi n thi s
narrower zone .
When ver y fin e particle s ar e present , suc h a s silic a fum e o r eve n iner t particles suc h a s
carbon black, these pack preferentially close to the aggregate and there i s little or no increase
in porosity in the interfacia l region (Scrivener et al., 1988a) .

1.5 Summar y

•I n fresh paste s a thin laye r o f hydration products precipitate s o n aggregate particles. In

compact an d well mixe d systems such a s goo d quality, lo w water/cement rati o concret e
this layer is essentially C-S-H . In composite specimens or at higher water/cement ratios ,
where bleeding may occur, calcium hydroxide may precipitate on the aggregate surface ,
especially o n the lowe r surface .
• Beyon d this surface laye r the interfacia l microstructure is essentially determine d b y th e
packing o f cement grain s agains t th e aggregate 'wall' .
• Packin g i s largel y determine d b y th e particl e siz e distributio n of th e cemen t paste .
However, th e water/cemen t ratio , aggregate/cemen t ratio , mixin g an d settlin g o f th e
concrete pla y a role.
• Thi s packing o f the cemen t grain s result s i n microstructural gradients extendin g some
50 μπι from th e interfac e int o the cement past e in which:
16 Characterisation of interfacial microstructure

- th e amount o f anhydrous cemen t decrease s as th e interfac e i s approached ;

- th e amount o f porosity increases;
- th e amoun t o f CH increases and may become oriented;
- th e amoun t o f ettringite increases.

•I n matur e paste s th e majo r chang e i n porosit y i s confine d t o 15-2 0 μπι aroun d th e

aggregate, reflectin g the effects o f One-sided' growt h of hydrates a s wel l a s packing.
• I n this thinner interfacial zon e th e connectivity of the pore structur e appears to increas e
as wel l a s th e amoun t o f pore space . As a consequence this region is of significance in
determining th e transport propertie s an d durability o f concrete.

1.6 Reference s

Barnes, B . D . , Diamond, S. an d Dolch, W . L . (1978 ) Th e contact zon e betwee n Portlan d cement past e and
glass "aggregate " surfaces , Cement and Concrete Research, Vol . 8 , pp . 233-44 .
Barnes, B . D . , Diamond , S . an d Dolch , W . L . (1979) Micromorpholog y o f th e interfacia l zon e aroun d
aggregates i n Portlan d cement mortar , Journal of the American Ceramic Society, Vol . 62 , pp . 21-4 .
Ben-Othman, B . , Scrivener , K . L . and Buenfeld , N.R . (1988 ) Permeabilit y an d microstructur e o f
lightweight aggregat e concrete , presente d a t Institute of Ceramics , Annua l Convention , Durham, April .
Christensen, B . J . , Mason , T . O . , Jennings , H . M . , Bentz, D.P . an d Garboczi , E . J . (1992 ) Experimental
and compute r simulatio n result s fo r th e electrica l conductivit y o f Portlan d cemen t paste , Advanced
Cementitious Systems: Mechanisms and Properties, Material s Research Society, Vol . 245 , pp . 259-64 .
Crumbie, A . K . (1994) Ph D Thesis, Universit y of London.
Detweiler, R . J ., Monteiro , P . J . M . , Wenk , H.-R. an d Zhong, Z. (1988) Texture of calcium hydroxide near
the cemen t paste-aggregat e interface , Cement and Concrete Research, Vol . 18 , pp . 823-9 .
Diamond, S . (1988 ) persona l communication , cite d i n Detweile r et al. (1988) .
Escadeillas, G . C . and Maso , J . C . (1990) Approac h o f th e initia l stat e i n cemen t paste , morta r an d
concrete, Advances in Cementitious Materials, (ed . S . Mindess) , American Ceramics Society , Cerami c
Transactions, Vol . 16 , p p 169-84 .
Farran, J . (1956) Contributio n mineralogique a Γ etude d e Γ adherence entr e le s constituant s hydrate s de s
ciments e t le s materiau x enrobes , Revue des Materiaux de Construction, No s 490-491 , pp . 155-7 ,
No. 492 , pp . 191-209 .
Garboczi, E . J . an d Bentz, D . P . (1991 ) Digita l simulatio n o f th e aggregate-cemen t past e interfacia l zon e
in concrete , Journal of Materials Research, Vol . 6 , No . 1 , pp . 196-201 .
Grandet, J . an d Ollivier , J.-P . (1980a ) Nouvell e method e d'etud e de s interfac e ciments-granulats ,
Proceedings of the 7th International Congress on the Chemistry of Cement, Edition s Septima , Paris ,
Vol. Ill , pp . V I I . 85- 9
Grandet, J . and Ollivier, J.-P . (1980b) Orientatio n des hydrate s a u contact de s granulats , Proceedings of
the 7th International Congress on the Chemistry of Cement, Edition s Septima, Paris , Vol . Ill , pp . V I I .
63-8.
Halperin, W . P . , D'Orazio, F . , Battacharaja, S . an d Tarczon, J . C . (1989 ) Magneti c resonanc e relaxatio n
analysis o f porou s media , Molecular Dynamics in Restricted Geometries, (ed s J . Klafte r an d J . M.
Drake), Joh n Wiley an d Sons Inc. , chap. 11 , p . 311 .
Hoshino, M . (1988 ) Differenc e o f th e w/ c ratio , porosit y an d microscopica l aspec t betwee n th e uppe r
boundary an d th e lowe r boundar y o f th e aggregat e i n concrete , Materials and Structures, Vol . 21 ,
pp. 336-40 .
Javels, R . , Maso , J . C . and Ollivier , J.-P . (1974 ) Realisatio n d e lame s ultra-minc e d e mortie r pou r
observation direct e a u microscop e electroniqu e pa r transmission , Cement and Concrete Research,
Vol. 4 , pp . 167-76 .
Javels, R . , Maso , J . C , Ollivier, J.-P . an d Thenoz , B . (1975 ) Observatio n direct e a u microscop e
electronique pa r transmissio n d e l a liaso n pat e d e ciment-granula t dan s de s mortie r d e calcit e e t d e
 References 1 7

quartz, Cement and Concrete Research, Vol . 5 , pp . 285-94 .

Maso, J . C . (1991) presentatio n a t 3r d Europea n Conferenc e o n Microscop y o f Buildin g Materials ,
Barcelona, September .
Mitsui, K . L i, Z . and Shah, S.P . (1991) A new metho d of characterising properties of the paste-aggregat e
zone, Presente d a t Material s Researc h Societ y Symposium , Advance d Cementitiou s Systems :
Mechanisms an d Properties.
Monteiro, P . J.Μ an d Mehta, P . K. (1985) Ettringite formatio n at the aggregate-cemen t interface , Cement
and Concrete Research, Vol . 15 , pp . 378-80 .
Monteiro, P . J . M . an d Ostertag , C P . (1989 ) Analysi s o f th e aggregate-cemen t past e interfac e usin g
grazing incidenc e X-ra y scattering , Cement and Concrete Research, Vol . 19 , pp . 987-8 .
Monteiro, P . J . M . an d Scrivener, K . L . (1991 ) unpublishe d work .
Ping, X . , Beaudoin , J.J . an d Brousseau , R. (1991 ) Fla t aggregate-Portlan d cemen t past e interfaces : I
Electrical conductivit y models, Cement and Concrete Research, Vol . 21, No . 4 , pp . 515-22 .
Ping, X . an d Beaudoin , J . J . (1991) Effec t o f aggregat e siz e o n th e transitio n zon e propertie s a t th e
Portland cemen t past e interface , Cement and Concrete Research, Vol . 21 , No . 6 , pp . 999-1005 .
Scrivener, K . L . and Pratt , P . L . (1986 ) A preliminar y stud y o f th e microstructur e o f th e cemen t
paste-aggregate bon d i n mortars , Proceedings of the 8th International Congress on the Chemistry of
Cement, Ri o de Janeiro , Vol . I l l , pp . 466-71 .
Scrivener, K . L . an d Gartner , E . M . (1988 ) Microstructura l gradient s i n cemen t past e aroun d aggregat e
particles, Bonding in Cementitious Composites, (ed s S . Mindes s an d S.P . Shah) , Material s Research
Society, Vol . 114 , pp . 77-86 .
Scrivener, K . L . , Bentur , A . an d Pratt, P . L . (1988a ) Quantitativ e characterisation of th e transitio n zone
in hig h strengt h concretes, Advances in Cement Research, Vol . 1 , pp . 230-9 .
Scrivener, K . L . , Crumbie , A . K . an d Pratt, P . L . (1988b ) A study of the interfacial regio n between cemen t
paste and aggregate i n concrete, Bonding in Cementitious Composites, (ed s S . Mindes s and S.P. Shah) ,
Materials Researc h Society , Vol . 114 , pp . 87-8 .
Scuderi, C . A . , Mason , T . O. and Jennings, H . M . (1991) Impedanc e spectra of hydratin g cemen t pastes ,
Journal of Materials Science, Vol . 26, pp . 349-53 .
Snyder, K . A . Winslow , D . N . , Bentz , D.P . an d Garboczi , E . J . (1992) Effect s o f interfacia l zon e
percolation o n cemen t base d composit e transpor t properties , Advanced Cementitious Systems:
Mechanisms and Properties, (ed s F . P . Glasse r et al), Material s Researc h Society , Vol . 245 ,
pp. 265-70 .
Winslow, D . N . an d L i u , D. (1990 ) Th e por e structur e o f past e i n concrete , Cement and Concrete
Research, Vol . 20 , pp . 227-35 .
Wu, X . , L i , D . , Wu, X. an d Minshu, T . (1988 ) Modificatio n of interfacia l zon e betwee n aggregat e an d
cement paste, Bonding in Cementitious Composites, (ed s S. Mindess and S.P. Shah), Material s Researc h
Society, Vol . 114 , pp . 35-40 .
Yuan C . Z . and Guo , W . J . (1987 ) Bon d betwee n marbl e an d cemen t paste , Cement and Concrete
Research, Vol . 17 , pp . 544-52 .
Yuan, C . Z . , Min , Z . W. an d Jiang, L . (1988) Determination of preferred orientatio n degree o f portlandite
by usin g rockin g curve of diffractio n line, Materials and Structures, Vol . 21, pp . 329-35 .
Zhang, X . , Groves, G . W . and Rodger, S.A. (1988 ) Th e microstructure o f cemen t aggregat e interfaces ,
Bonding in Cementitious Composites, (ed s S . Mindes s an d S.P . Shah) , Material s Research Society ,
Vol. 114 , pp . 89-95 .
Ziirz, A . an d Odler , I . (1987 ) X R D studies o f Portlandit e present i n hydrate d Portlan d cemen t paste ,
Advances in Cement Research, Vol . 1 , No . 1 , pp . 27-30 .
References

Introduction: The transition zone -

discovery and development

Farran, J. (1953) Comptes-rendus des seances de I'Academie

des Sciences, Paris T.237-1953, p. 73 .

Farran, J . (1956 ) These de Doctorat , Toulouse , i n

Revue des Materiaux de Construction, Paris, No s 490, 491
and 492.

Maso, J.C . (1967 ) These de Doctorat , Toulouse , i n

Revue des Materiaux de Construction, Paris, No s 647, 64 8
and 649 (1969).

Farran, J. , Javelas , R. , Maso , J.C . an d Perrin , B .

(1972) Comptes-rendus des seances de I'Academie des
Sciences, Paris, T.275-1972 , p . 1467 .