i

The Microstructureof Concrete

KARENL. Scnrvexen, Imperial College

The great tragedy of science: the slaying ol a

beautiful hypothesisby an ugly lact.

Thomas Huxlev

The various aspects which contribute to the microstructure of concrete are

consideredand illustrated,from the microstructureof the anhydrouscementto the
microstructureof mature concrete. At each strge the importanceof quantitative
characterizationand methodsof achievingthis cre discussed.

Introduction
At somelevel the behavior of every material is relatedto its microstructure. The
understanding of theserelationships betweenstructureand propertiesforms the basis
of materialsscience. Microstructureencompasses a wide rangeof structurallevels,
from the atomic scale to that of the engineering component, and includes all
discontinuitiesinside and betweenphages,such as dislocations,grain boundaries,
phase interfaces, pores, and cracks.' A complete characterization of the
microstructureof a multiphasematerial must also entail quantitativeinformation
about the relative proportions of the phasesand their distribution in space. The
relative lack of successin developing rnigrostructure/property relationships.for
concreteis due, in no small part, to the lact of good microstructuralcharacterization.
In microstructural terms, concrete is an extremely complex system of solid
phases,pores, and water, with a high degree of heterogeneity. This heterogeneitl
ian be considered on several leveli. lt the simplest level, concrete consistsof
aggregateparticles,distributed in a matrix of cementpaste. On a more detailedlevel,
thJ paste itself is a mixture of unreacted cement, hydration products, pores, and
water and at a still finer level thesephasesthemselveshavecomplex microstructures.
In this chapter, various aspeits of the microstructure of concrete will be
consideredin anattimpt to provide a coherent picture. As an introduction, a brief
description of the chemistry and structure of ihe solid phasesin cement pastesis
given, followed by a short survey of the physical methods used to study
microstructure. Initiatly, the components of the concrete microstructure are
consideredseparately:thi microstruciure of anhydrouscement;the developmentof
l microstructurb auting the hydration of cemLnt paste; the microstructure of

Materials Scienceof Concrete t27

aggregares;ano the rntertace betweencement pasteand aggregates.To arrive at a
completecharacterizationof concretemicrostructure,these componentsmust be
integ,rated,
but this is an areain which much work needsto be done and only a few
commentscan be made. For conciseness, it has been possibleto cover only the
microstructuraldevelopmentof concretesat near ambienttemperatures.
Solid Phasesin Cement Paste
Anhydrous cement powder is a combination of oxides of calcium, silicon,
aluminum, and iron (plus small amounts of other oxides). The four principal
mineralsfound in ordinaryportlandcementarealite,impuretricalciumsilicate(C3S);
belite, impure dicalciumsilicate(CzS);and the aluminateand ferrite phaseswhich
haveaveragecompositions of c3A and c4AF, respectively.Thesemineralsreactwith
water to give a variety of hydrates. The calcium silicatesreact to give calcium
hydroxide and calcium silicatehydrate and the aluminateand ferrite phasesreact
with the added calcium sulfate to give two groupsof product referred to as AFt and
AFm .
Calcium hydroxide (CH) is the only hydration product to have a well-defined
stoichiometryand crystal structureand normally forms as massive,relativelypure
crystalswith a euhedralhexagonalhabit.
The calcium silicate hydrate in cement paste is a gel which shows no long-
rangecrystallinity. Its compositionis uncertain(and possiblyvariable)with a C/S
ratio of about 1.7 to 2.0; consequentlyit is usually written as C-S-H. The short-
rangeorder of this phaseis probablyrelatedto the layer structureof the cry5lalline
ca l c iums ilic at ehy d ra te s -1 .4
n m to b e rmo ri te(C 5 S^H n) 4n! j enni te(C ' S 6H 1r).2.r
Thi s
phaseappearsto adopt a wide rangeof morphologiris,*-o somebasedon ihin sheets
which may give fibrillar or honeycombstructuresat early ages,otherswith a more
compactstructureforming at later ages.
The term AFt denotes the phasesrelated to ettringite-calcium aluminum
trisulfate(CaA . 3CS . 32HzO)with the F indicatingthe poss-ible substitutionof iron
for aluminum in the structure. This phaseforms when the concentrationof sulfate
ions in solutionis relativelyhigh and hasa morphologyof hexagonalrods.
_ The AFm phasesare isostructuralwith calcium aluminum monosulfate(CrA .
C S.l 2H2O ) . I n ad d i ti o nto p o s s i b l es u b s ti tu ti o nof al umi numby i ron, hydroxl de,
carbonate,or chloride ions may replacethe sulfate. Thesephaseshave a hexagonal
plate morphology.
Techniques for Studying Microstructure
There are many techniqueswhich have been usedto study microstructure;they
can be divided broadly into two categories. Indirect or bulk techniques give
information on averagefeaturesof the whole microstructure. Examplesof indirect
techniquesare thermogravimetry(TG) and X-ray diffraction (XRD), which can be
used to determine the amounts of certain phasesin the sample. Methods used to
obtain information about the pore-size distribution, such as mercury intrusion
porosimetry (MIP) and methanolabsorption,are also indirect techniquesas they give
no information as to how the pores are arranged in space. The other group of
techniquesis direct or microscopicaltechniqueswhich provide information about
the way in which the componentphasesare arrangedin the microstructure.
r2 8 Materials Scienceof Concrete
_d|[,
I ne advantageol the lndirect techniquesrs that they provide information in a
quantitativeform so that different samplescan be comparedobjectively. In contrast,
information derived from direct techniquesusually takesthe form of images. Images
are extremelyvaluablein conveyinga vivid impressionof the microstructure.but
comparisons between different samples are more subjective and rely on the
experienceand interpretation of the observer. As most of the findings presented
here have beenobtainedby microscopytechniques,their applicationto the study of
the microstructureof cementand concretewill be discussedin more detail.
optical microscopy has been widely used in the study of cement and concrete.T
The useof suitableetchantsmakesit pQlsibleto study the distributionof anhydrous
phasesin clinker and cementpowder.6'vIn hydratedpastesand concretetiere is
little contrastbetweenthe phasesin reflectedlight. However, in thin sectionsthe
refractivepropertiesof different phasesand the useof fluorescentresincan indicate
cementand aggregatetype, the presenceof mineral admixtures,the w/c ratio. the
quality of compaction,and the presenceof alkali silica reaction(e.g.,Refs. l0 and
I l ).
Ultimately, the resolutionof optical microscopyis limited by the wavelengthof
light and for detailed microstructuralstudieselectron microscopymust be used. As
cement is nonconducting,and due to the presenceof water, the preparationof
cement pastesand concretesfor electron microscopyposesproblems. The possible
effects of drying on the microstructureand the selectivityof different preparation
techniquesmust be consideredwhen interpretingelectronmicrographsof cement
pastes.
Fracture surfaces provide a relatively simple means to observe the three-
dimensionalarrangementof hydrationproducts. Thesesurfacescan be imagedby
secondaryelectronsin the scanningelectronmicroscopewith fairly good resolution
(arl0 nm). While providing much useful information, the microstructureobserved
using this techniqueis that of cementpastewhich hasbeendried and exposedto the
high vacuum of the electron microscope. Given the amorphousnature of the
hydration products,it is likely that somealterationin their morphologywill occur
during specimenpreparation. Also, only fracture pathsare revealed,so that weak
areas of the microstructure predominate. In young pastes the fracture path is
interparticular,showingonly the outer surfaceof the hydration products. In older
pastesthe fracture surface is dominatedby areasof cleavedcalcium hydroxide,
which has grown in the originally water-filled spaceto engulf the other hydration
products. After hydrationfor longerthan one day it becomesincreasinglydifficult
to assessthe extent to which fracture surfaces are representativeof the bulk
microstructure.
Undried cement pastescan be examinedif the areaaround the specimencan be
isolatedfrom the high vacuum in the electro_n microscopecolumn. In the AEI EM7
I MeV high-voltage electron microscope(HYEM) there is a comparatively large
space between the objective pole pieces, which permits the incorporation of an
environmental cell. Two types of environmental cell have b_e^e1^ used to study the
hydration of cement in tha HVEM. Double and coworke.sl2'I3haue studiea the
hydration of cement in a window-type cell, at a high water/cement ratio. With this
type of cell, the resolution is limited by the presenceof windows and furt[gr by the
large excessof water in the paste. f-he cell used by Jenningsand Pratt" and by
Scrivenero and Scrivener and Prattr) has pairs of differentially pumped open
apertures. Pressuresof up to 300 r can be maintained in the cell with water-
saturatedgasesand better resolutioncan be obtainedthan with the window-type cell.
Using this technique, much information can be gained on the morphology of
Materials Scienceof Concrete t29
hydration products in the undried state and the way in which their morphology Ftg. 1. Mlcrostructure of e
changeson drying. However, due to the method of specimenpreparation it is still commerclelclinker (bse lmege).
only the outer surfacesof the hydrating grains which can be observed. Light-grry crystels of ellte rnd
Ion-beam thinned sectionsallow t-hqs^t^ructure to be viewed in crosssection in darker rounded crystels of belite
the transmissionelectron microscope.6'1s-20 The brittlenessof cement pastesand cen bc seenin e metrix of the
concretes makes the preparation of electron-transparent sections by ion-beam Interstitiel pheses-ferrlte (light)
thinning very difficult and young pastesmust first be impregnatedwith Lpoxy resin. and eluminate (derker). Porosity
The use of scanningtransmissionelectron microscopy(srEM) minimizes damageto (bleck) cen elso be seen.
the cement by the electron beam. Fairly extensiveelectron-transparentareascan be
obtained with careful thinning; neverthelessa certain amount of selectivity is
inevitable.
Another techniqueusesbackscatteredelectronimagesof polishedsections.With
thick polished sections, large cross-sectionalareas can be observed by SEM.
However, they do not show good secondary electron contrast. Using a pair of
backscatteredelectron(bse)detectors,imagescan be producedin which the intensity
is dependenton the averageatomic number of the scannedarea. Thus, in polished
unetched sections the anhydrous material, massive calcium hydroxide, other
hydratio.n^products, porosity, and aggregateparticlescan be distinguishedfrom one Fig. 2. Scanning electron
another.o'rrThe contrastbetweenthesecenstituentsis sq-fficientto allow quantitative mlcrogreph of rnhydrous cement
image analysisof their total area and size distribution.z The form and distribution gnins showlng the wide reoge of
of the hydration products observableis comparablewith, though of lower resolution particle slzes. Small lrthlike
than, that seenin the STEM of thin foils. However, bse imagesmay be taken over crystalsof calclum sulfate can be
a large cross-sectionalarea, eliminating the selectivity of ion-beam thinning usedto seenon the surfacesof the larger
prepare STEM specimens. grains.

Microstructure of Anhydrous Cement

An account of the microstructuraldevelopmentof concrete must start by

consideringthe microstructureof the startingmaterials.The microstructtlreof the
most important of these,anhydrouscement, is determined by the microstructureof
the clinker producedin cement kiln and the way in which the clinker breaksup
during grinding. The resultingproduct is quite different, in both appearanceand
reactivity, from a simple mixture of monomineralic grains of the four main
anhydrousminerals.
An "ideal' clinker microstructureconsistsof crystalsof alite and belite (which Flg. 3. Backscetteredelectron
are solid at the firing temperature)in a matrix of interstitial phaseswhich solidify lmage of polishcd sectlon of
from the melt during cooling. The alite crystals have a hexagonal habit, while the enhydrous cement greins
belite crystals tQnd to-be lounqed. In the interstitial material, the alirminate and dlspersedln resln. It cen be seen
ferrite phises ma! bt{ifte$ divided and intergrown. The details of the that most of the gralns ere
microstructure,such as the shapeand distribution of the phases,will depend on the polyminerrlic.
physical and chemical characteristicsof the raw mix (fineness,homogeneity,and
chemicalcomposition)and the exactconditionsof burning and cooling of the clinker.
Nevertheless, the general features described above can be identified in most
commercialclinkers, such as that shown in Fig. l. This clinker also showsextensive
cracking, which commonly occurs due to thermal stressesduring cooling.
Clinker is ground with gypsum to give a powder with a wide range of particle
sizesfrom less than I pm to about 100 pm. Secondaryelectron imagesof cement
powder by SEM (Fig. 2) give someimpressionof this size distribution and show the
agglomerationof many smaller grains on the surface of the larger grains. Such
imagesalso reveal fine particlesof gypsum spreadover the grain surfaces.

r30 Materials Scienceof Concrete Materials Scienceof Concrete l3r

 Paste
The distribution of phaseswithin the cement grains can be studied in polished Developmentof Microstructure During Hydration or cement
sectionsprepared from samplesof cement dispersedin epoxy resin. Examination
During hydration, cementpastechanges, flom a fluid mixture of cementpowder
of suchsectionswith backscattered electronsby SEM (Fig. 3) indicatesthat fracture iO. itt" r"actions ihich occur are exothermic and the overall
through the alite crystalsdominatesthe grinding procels,.with little evidenceof ana *"t"r T" i iiglO tof From
fracture alongthe interphaseboundaries.Almost all grainslarger than 2 to 3 pm are IrJn."ss of tne rEactionian UestuOieaby isothermalconduction calorimetry.
i'ff;ilirat;Ji:rti"t-.*rution rurr" fo. an ordinary portland^cement, various
polymineralic and on the surfacesof the larger grains only small areasof interstitial
;di,-o|h)^i;.;;;;; ue iOentirieo, which will be usedas a basisfor describingthe
materialsare exposed,betweenareasof alite. Relatively greater proportionsof (ttre times indicatedare intendedonly as a generalguide
,oliiort.u"iural development
aluminateand ferrite phasesare exposedon the surfaceof smallergrains,as their Uy a variety of factors including temperatureand admixtures):
formation is more likely to involve fracture through the interstitial material. ffi-;tii U"
"fi."t"O
At present,mostcementsare characterizedsolely by their surfaceareaand oxide -I (about 0 to 3 hours). on mixing, a large amount of heat is evolved; the
composition. The surfacearea is generallydeterminedby permeabilitymethods. iate of heat evolution then decreasesrapldty to a minimum after about 3
Suchmethodsgive a much lower valuefor the surfaceareathan absorptionmethods hours. This initial period, during which the cementremainsfluid and
(suchas BET), becauseblockedchannelsare not accessible to the moving air stream. workable, is often referred to as the induction period'
Surfaceareameasurements give little informationaboutthe particle-sizedistribution, II (about 3 io 2a hours). During this period some 30%of hydration occurs'
which is of great importance in determining the packing of the cement grains in which is reflected by the maior peak in the rate of heat evolution.
paste and concrete. Laser diffraction methods can be used to measure the size III (24 hours onward). After iUout Z+ hours the rate of heat evolution
distribution;the result for a typical cementis shown iUFig.4. declines,although hydration rnay continue indefinitely'
From the oxidecomposition,the Boguecalculationamay be usedto estimatethe I (0 to 3 Hours)
relative proportions of the major phases. This calculation assumesthat complete
pasteduring
reaction occurs in the kiln and takes no account of any solid solution between the It is particularly difficult to examinethe microstructureof cement
phasesor of the presenceof minor oxides,and may give quite inaccurateresults. Moit'of the mixing water is present as free water. If this water is
this ;;;J.
Quanti-tptlye X-ray diffraction can be usedto measurethe proportionsof the clinker ia."-""di" that specimenscan bJexamined in the electronmicroscope,fundamental
phases--^ and accuraciesof l% are claimedfor this methodif a suitablerangeof ;;;;s;i" the microstructure may occur. Even apart from an-y-.damage causedby
ii"ir"e. the time taken for specimen preparation makes it difficult to follow the
standardsis used.zoAnalysesof clinker can alsobe obtainedby optical microscopy
using a point-countingmethodon polishedand etchedsectionsof clinker. ir6"iEit nvOiationaccuiately.Theseproblemsmakeexaminationof specimens
As illustratedin Fig. 3, the distributionof phaseswithin the cementgrainscan "itfte
i,iifi"'.,ipii"i;;it";, in the environmentalbell of the HVEM, an especiallvvaluable
be
be seen in bse images of polished sections. If these images are analyzed in ;";h;GG for stuOylngthe early hydration- Using this technique,specimenscan
conjunctionwith dot mapsfrom energydispersiveX-ray analyses of the saqg areas, examinedas little as l0 minutesafter mixing.
Severalworkers have repo-r1g{.the appearanceof a gelatinouslayer on the surface
the relative amounts of silicate and interstitial phases.canbe measured.4' This
of cementsoon after mixing.6'13'la'2e Mictog.aphsof undried cement taken in the
techniquecan be extendedto assess the relativeproportionsof the phasesexposedon
the surfacesof the grains,which might be expectedto determinethe initial reactivity environmentalcell (Fig.5ishow an indistinct layer of produ_cton.the surfacg
of the cement. Preliminarystudieshaveshown that thesesurfaceproportionsmay Similar early produci ttasbeenobservedduring the hydration 9f C-3Awith 8yp6s1lm'--
differ significantly from the bulk values. Other studiesusing secondaryion mass In the hydration of C3S,the early formation of product has also been notecl'"'"^but
spectroscopy (SIMS)haveshown^thatthe surfacesof the cementgrainsmay contain in this c.se the product appeais to have a somewhat different morphology of
grains,,the
high proportionsol impurities,4 which might alsoaffect the rea-ctivity. iifofiating fifrt.' Consideringthe polymineralic nature of cement
gefatinoui layer observed in tie hydration cement is probably. an amorphous
Proper characterizationof anhydrouscement is an important first step in -of
understanding differences in the reactivity of cements and the properties of the iottoiaat product, rich in alumina and silica, but also containingsignificant amounts
concretesmade from them. of calcium and sulfate, iftiE""i composition varying with the composition of the
of AFt can alreadv
;;J;;itG ii"in i"ri"d". Outsioethis ielatinous layer, small rods
be seen afiei as rittr" .t lO .inutes hvd-ration(Fig. 5) and after abpP.t"83l,.b"tijh;;;
rods can be clearly seen on dried fracture surfaces (Fig' 6)'""''
environmentalcell thev can be observeddispersedqn the carbon support film at some
a
distance from the rutf".i of the hydrating grain,$ indicating that they form by
N
;
o through-solution mechanism. when cement paste is- dried,. the gelatinous layer
.a
cottapiis and shrinks il[; to the surface of ttre grai-ns. It is difficult to identify
tftii J.oOucton fracture;rfaces, althoughindicqtipnsof somegelatinou-s-product can
tre seenin ion-beamed thinned sections-(Fi8. 7).o't The AFt rods also fall back onto
the surface of the grains, although the denJity of rods is probably still related to the
comjosition of ttre'unOeilyinggiain. After somethree hours hydration, the amount
as
of C-S-H formed h suiiiiirn-t ior this phaseto be identifip{qp fracture surfaces
small spiky outcrops on the surfaceof the grains (Fig' E)'"-"*
20

Fig. 4. Particle-sizedistributionfor r typical cementobtainedby laserdiffraction.

133
r32 MaterialsScienceof Concrete Materials Scienceof Concrete
 'ij
Fig. 5. (Left) cement pastehydratedfor l0 min'in the environmentalcell of
the HVEM. The surfacesof the grains have e gelatinousappearanceand seyeral
short rods of AFt can also be seen.
Tig.6_._(Right) Dried fracture surfacein the SEM of cementpastehydratedfor
I h. Many rods of AFt can be seen.
f!q.:. (Left) Ion-beemed thinned sectlon of cement peste hydrated for 2 h
(srEM). Product with e gelatinousrpperrrnce can be seen with some AFt rods.
Iig, 8. (Right) Fracture surface of 3-h-old paste. Spiky outcrops of dried
C-S-H can be seen.mong the AFt rods.
'The w7c ratio of sll the pastesillustrated is 0.5 unlessotherwise stated.
t34 Materials Scienceof concrete
It (3 to 24 Hours)
The end of the induction period is marked by the rapid growth of both C-S-H
and CH. In the undried state, C-S-H has a filmy, foil-like morphology, (Fig. 9),
which dries to a fibrillar morphology(diamondtype I) where there is plenty of space,
and to a honeycombmorphology (diamond type II) where spaceis more restricted.
(The presence of foreign ions such as Cl- may also affect the morphology of
C-S-H.) Small grains of cement(which probably contain only alite) hydrate rapidly
to give rosettesor spherulitesof C-S-H (Fig. l0).
In ion-beam thinned sections(Fig. ll), it can be seenthat the C-S-H shell is
separatedfrom the unde;[ying grain. This separationcan be observedafter as little
as five hours hydrationo't' and is thought to occur becausethe C-S-H nucleates
outside the gelatinouslayer formed earlier, on a framework of AFt rods. The space
which is observedin dried sectionsis most likely filled with a highly concentrated
or possiblycolloidal solution in the wet state,although the discontinuity betweenthe
hydrate shell and core cag also be seen in undried samples examined in the
environmentalcell (Fig. l2)." The growth of C-S-H betweenthe cementgrainsbonds
the paste together, causing the paste to set after about 3 to 4 hours of hydration.
After about 12 to l8 hours, this bonding is strong enough for fracture to occur
through the hydrate shells,such that the separationbetweenthem and the anhydrous
core can be seen on fracture surfaces(Fig. l3). Such separiltedshells, which are
completely hollow in some cases,were first noted by Hadleys on fracture surfaces
Flg. 9. (Left) One-day-old paste in the environmentalcell of the HYEM. The
C-S-H which formed through solution during the major heat evolution peak has
e morphology of crumpled foils; some rods of AFt can also be seen.
Ftg. f 0. (Rlght) Fracture surface of one-day-old paste in the SEM. 'Rosettes'of
dried ftbrillar C-S-H (diamond Type I) and long rods of AFt from the secondary
reaction of the aluminate phasecan be seen.
Materials science of concrete 135
 l-ig. ll. Ion-besm thinned
section of e l2-h-old oaste
(STEM). Shells of hydration
product can be seen rround. but
separated from, the dark
enhydrous cores. Rosettes from
the hydration of small grains and
some hollow shells of C-S-H can
also be seen.
Fig. 12. Undried, one-day-old
paste(environmentalcell,
HVEM). Although this is not e
cross-section,there is e region of
low-densitymaterial visible
betweenthe hydrete shell and
core.
Fig. 13. Partially reacled grain
of anhydrous cement with e
separated shell of hydretion
product revealed on the frecture
surface of a one-day-old paste.
Rods of AFt and plates of AFm
can be seen between the shell and
core.
and such phenomenaare often referred to as'Hadley grains.' During fracture, large
anhydrouscores may fall out, to leave large hollow ihetts. Howevlr, on poiistrJo
sections,while it can be seenthat practically all grains have separatedhydraie shells
(Fig. l4), the separationbetweenshell and core is seldom moie than about I pm.
The separationbetweenthe reactinggrain and the C-S-H product indicatesthat
the formation of the latter occurs by a through-solution mechanism. At this stage
the shell is very open and porous and ions migrate through it, leading to the growih
of C-S-H on the outer surface of the shell and increasingthe sepaiation b6tween
shell and core.
r36 Materials Scienceof Concrete
Fig. 14. Backscatteredelectronimageof e polishedsectionof a l2-h-old paste.
A large massof calcium hydroxide(light gray) crn be seen. This has grown
around many of the hydrating grains. In this pasterlmost sll of the cement
grains have separatedhydrate shells.
The calcium hydroxidewhich is producedby the reactionof the silicatephases
is depositedas massivehexagonalcrystalsin the spaceoriginally occupiedby the
water. In bse imagesthis phasecan be seenas extensivelight-gray areas(Fig. l4).
The numberof nucleationsitesappearsto be smalland the crystalsmay engulf some
of the smallercementgrainsas they grow.
After about l6 hours,a renewedgrowth of AFt occurswith long rods growing
through the C-S-H layer (Fig. l0). Thesemicrostructuralchangescorrespondto the
shoulder on the main heat evolution peak which is sometimesobserved in
calorimetric .u.lres.6'27'35The chemical changesresponsiblefor this secondary
reactionof the aluminatephaseare probablyrelatedto the reactionof the alite. This
reaction of the aluminate phasemay lead to larger local separationsbetweenthe core
and its hydrateshell.
At the end of the main heatevolutionpeak, all grainssmallerthan about 5 pm
will have completelyhydrated. Many of thesewhich originally containedsome
aluminatephasewill leavehollow shellsof hydrationproduct.
m (24 Hours Onward)
As the hydrate shell thickens, it becomeslesspermeableand continuing reaction
of alite leadsto deposition of C-S-H on the inside of the shell. As the volume of
C-S-H formed is greater than that of the alite which reacts,this processdecreases
the separationbetweenshell and core. If the grainsare large enough,this separation
disappearsafter about sevendays hydration, by which time the shell is about E pm
thick (Fig. l5). Further hydrationof alite is very slow, with changebeingobservable
only on the scaleof years. There is evidenceto suggestthat th-igperiod of hydration
occurs by a topochemicalmechanism,as suggestedby Taylor." In old pastes,three
regigrs of C-S-H product can be identified in the relicsof fully hydrated grains(Fig.
t6).37 The outermostof theseis a thin layer (sl pm) of nouter"C-S-H which formed
through solution, in the originally water-filled space,during the major heatevolution
peak.-Inside this is a layer, about E pm thick, which formed through solution while
Materials Scienceof Concrete r37
:

1t

Fig. 17. Fracturesurfac,eof e r4-day-ord paste. The

edgeof a hydratesherl
runs diegoneilvacrossthe microgreph-.--oo'ii"inner_surrece
preresof AFmcanbescen..ours-ide'i-lie (top"reft) many
space. (CourtesyA. Ghose.)
in"ii iri-,itil;ililiril ,r. por"
Fig' 15. Partiallv hvdratedgrein in a 69-dav-ord
paste (bse imageof porished
section)'Ar rheoureredgeor rne rriorate;'L"ii;ffi;r;;of'.il;r,c-s-H
formedduringthe maintti"q.";"!ril9-1-;;;k;""
be seen."i;ri;. thi; is e rayerof
c-s-H formedthrouehsorurioniniiili'i-},.'r.p"ration
within this leyer,arongthe bottomed-ge-oiirr" between sheilandcore.
grain,is e roundedcrystatof
uureactedbelite. At thc top right edge"is i.gi6'o
(Courtesy oi'uor"""tlJ-r-"-..itu.
of K. D. Baldie.) "

Fig. 18. Fracturesurfaceof_aone-day-ordwhite

5oloaluminatebv oXDA). cement(63% arite, 27o/oberite,
rh;;irili"i"-prr"..,
to the formatioi oi targ6 efm unresrricredby ferrite, has read
pt"t.il--'- '"'
Inside the shelr. the concentrationof surfa.tein
sorutiondrops rapidry as the
aluminate phasereacts. This resultsin ttre .eaction
or iuitr,ii.iuriin"t, phasewith
anv AFt present on the inside of the shelr tJ giui
(ignoring any substitution of iron): ;i;;;;;;n;^io tr,. reaction

2CrA+ caA. 3cS. H3z* 4H* caA. cS . Hlz (t)

Fig' 16. Relic of fuilv reactedgrain In e 23-year-ord
paste(bse image). In The heat produced by this reaction is sometimesviqi.bre
additlon to the two regionsor E-s--ri-ii.iiiri"a as a row, broad peak in the
in Fig. 15, rhere is an inner
region formed by e tof,ocheri"al ;;h;is;. 3t9 9f heat evolution, as noted by prar and Gt ose.35- it e Ji.""t'.-on"""rsion of AFt
t-oAFm in the absenceof aluminate phasedoesnot
appear to occur in cement. on
fracture surfaces,AFm_maybepgserveoinsiae tne
hydration shelrsand AFt outside
in-the samespecimen Gii.'tii.e'n -iro*"r.ilir
rhe concentrationof sulfate ions in
the hydrate shell was separat!dfrom the anhydrous solution drops before th; hydrate J"rt r,"r. thickened
product, occupying spaie.originallv.tiiriJ6-i core. This is almost all "innern and partially isolated the
anhydrousgrains, much rarg-erpratesof ,tFm-may
the anhydious-ir"i"l"rr," innermost be formed irrilugirout the paste,
region is also "inner' oroductl in ttris casi i6rmeo as hasbeenobservedin somJtuhite cements*t ict'contai"
by a topochemicalor sorid state ;;?u;;i;;;il; ifits:ls).d
mechanism. The be.litephaseappe.arsto take rittre part in the earry rrvci"ir""
_ .
-regions *action. Smail
-Aiier'auout
of belite within alite may be left unreacted
rrie. rsi. l4 days,

r3E Materials Scienceof Concrete

Materials Scienceof Concrete
t39
the syrfa_ce!of_be.[iteparticles revealedon fracture surfaces show signs of local
reaction (Fig. l9),rr although there is still relatively little hydration pro?uct visibte
around the particle after severalmonths (Fig. 20). This reaction appearsto occur
preferentially along the twin boundaries. ln a 23-year-old paste,t-h; belite grains
have completely hydr,qted,although the original limellar oi the twin structure is
preserved (Fig. 2l)." This strongly sugge!-tsthat hydration has occurred
topochemically,as originally suggested by Funk$ and McConnell.3e
_ The ferrite phaseappearsvirtually unreactedin bseimagesof polishedsurfacqs
(Fig. 22), even in pastesmany yearsold. close examinationof s 23-year-old paste3T

Fig. 19. Belite crystal reveeled

on lhe fracture surface of e l4-
dry-old paste, showing signs of
locel rerclion. (Courtesy A.
G ho s e . )
Flg.22. R e l i c o f l a r g e g r a i n s i n e o n e - ye a r - o l d p a sl e l n w h l ch th e fe r r l te p h a se
( w h l t e ) l s a p p a r e n tl y u n r e a cte d ( b se i m a g e ) .

Fig. 20. Backscattered electron

image of belite crystal in e 3-
month-old paste showing
preferential reaction along the
twin planes.
{
\

',.:. ;
* t't
Fig. 21. Relic of fully reacled
belite crystal in 23-year-old
paste. The original twin lamellas
cen still be identified (bse image).
, !9rq ,
F l g . 2 3 . S u m m a r y o f m i cr o str u ctu r a l d e ve l o p m e n t fo r a g r a i n o f ce m e n t. ( a )
U n h y d r a t e d se cti o n o f p o l ym i n e r a l i c g r a i n ( sca l e o f In te r sti ti a l p h a se l s sl i g h tl y
e x a g g e r a t e d ) . ( r ) - 1 0 m i n . So m e C 3 A ( a n d /o r Fss) r e a cts w l th ca l cl u m su l fa te
I n s o l u l i o n . Am o r p h o u s, a l u m i n a te - r l ch g e t fo r m s o n th e su r fa ce e n d sh o r t AFt
rods nucleate at edge of gell and in solution. (c) -10 h. Reaction of C3S to
produce nouler" product C-S-H on AFt rod nelwork leaving -l trrmbelween graln
surface and hydrated shell. (d) -18 h. Secondary hydration of C3A (rnd/or Fss)
produclng long rods of AFt. C-S-H inner product starls to form on Inside of
shell from continulng hydration of C3S. (e) 1-3 days. C3A reacts with any AFt
l n s l d e s h e l l fo r m i n g h e xa g o n a l p l a te s o f AFm . C o n ti n u l n g fo r m a ti o n o f "l n n e r "
product reduces separation of anhydrous grain and hydrated shell. (f) -14 days.
Sufflclent "lnner" C-S-H has formed to fill In the space between grain and shell.
The "outer" C-S-H has become more fibrous. (8) -years. The remalnlng
a n h y d r o u s m a te r i a l r e a ci s b y a sl o w so l i d sta te m e ch a n i sm , to fo r m a d d l ti o n a l
"lnnern product C-S-lI. The ferrlte phase rppesrs lo remaln unreacted.

140 MaterialsScienceof Concrete MaterialsScienceof Concrete t 4l

L
has revealed two distinct regions in the iron-rich areas. It is possiblethat there is
some leaching of calcium and aluminum from the outer layer to leave amorphous,
hydrous ferric oxide. If the interstitial phasesare intimately mixed, the reaciion of
aluminate phasewill probably be restricted.
. Th9 developmentof microstructure for a large grain of cement is surnmarized
in Fig. 23. After the first day or so, the net movehent of ions during the hydration
processis very small. This fact was noted by Taylor and Newburyao from their
electron microprobe study of a cementpastewhich had been cured for 23 years. In
bse.images,of.this(Fig. 24) and other mature pastes,the relics of originai cement
grains can be identified. Ne.vertheless, the continued growth of calciuir hydroxide
and some c-s-H in the originally water-filled space has gradually reduced the
volume and connectivity of the large pores.
In terms of microstructuraldevelopment,fly ashstartsto react only after several
days hydration, although impurities, such as alkali sulfates,in the fly ash may affect
the hydration of the cement earlier. Nevertheless,deposition of C-S-H and AFt
from the reaction of the cement may be observed on the surflce of the fly ash
particles, almost immediately,.inthe environmentalcell (Fig. 25)al and after several
hours on fracture surfaces.'o''" After severaldays the dissolutionof the glassyphase
can be seenon fracture surfaces,where the crystalline material in someof the larger
particles has been exposed(Fig. 26).* Rims of hydration product can also be seen
around the fly ash particles on fracture surfaces and in bse images of polished
sections(Fig. 27).
Fig. 25. Cement/fly esh paste
(70/30\, hydreted for l0 min
(TEM environmentel cell).
Product cen bc seen on the
cemeot greins and deposited on
the surfaces of the spherical fly
ash particles.

Fig.26. Large particle of fly ash

on the frecture surface of a 28-
Fig.24. Microstructureof a 23-year-old paste(bse image). This pasteis fully day cement/fly ash paste.
reactedapart from the bright regionsof ferrite phase;thesehelp to identify tire Reaction of the glassy phase in
relics of the original grains which now mainly consistof denseinner' c-s-H. the fly ash has exposed some
Among the relics can be seentortuousregionsof calcium hydroxideand a crystalline material. (Courtesy of
mixture of other hydration products(dark gray) and porosity(black). Y. Halse.)

Effect of Mineral Replacementson Microstructure

Various minerals are often used in concrete as partial replacementfor cement.
These minerals have some capacity to hydrate, usually reacting with calcium
hydroxide, to give space-filling product and thus refining the porosity of the paste.
The most widely usedmineral replacementsare fly ash,blast-furnaceslag,and silica Fig. 27. Backscatteredelectron
fume. The fly ash is generally used at replacementlevels of up to about 30%. For imageof a 69-day-old cement/flY
slag replacements, levels at around 40% and around 70% are used for different ash paste. Severalparticles of fly
applications. With thesetwo mineralsthe developmentof microstructureof the paste esh ere visible in a massiveregion
during hydration is only slightly modified from the pattern previously described. of calcium hydroxide, some of
The replacementlevelsfor sitica fume are much lower, typically around i096,but the whlch show signs of reaction.
effects on the microstructural developmentare much more drlmatic.
Fly ash is a by-product of coal burning in power stationsand consistsof small
spherical particles with a similar particle-size distribution to anhydrous cement.
About 80% of a fly ash is a reactivesilica glasscontaining calcium, aluminum, iron,
and other minor oxides. The crystalline content is typically mullite, ferrite, and
quart?. In cement paste,the glassycomponentof the fly ash undergoesa pozzolanic
reaction with the calcium hydroxide produced by the cement to give C-S-H.

t42 Materials Scienceof concrete Materials Scienceof concrete r43

Fig- 28. (Left) Backscatteredelectronimageof cement/slagpaste(30/20)
hydrated for one day. A large massof calcium hydroxide hii grown around r
collectionof angular slag grains. (Courtesyof M. p. Cook.)
Ftg. 29. (Right) Partially hydratedcementgrain (top) and sleg grain (bottom) in
an 8-month-old cement/slagpaste(60/40). The different grey level of the
hydration rims indicatestheir different composition(bse image).
Blast-furnace slags have a glass content of about 90% glass of typical
composition:35%SiOz,45%CaO, l0% Al2O3,8% MgO, and small amounrsof-other
oxides.Althoughslagshavesomeinherenthydraulicity,an activator(suchascalcium
hydroxide)is neededand the slagplayslittle activepart in the early microstructural
development. However, it doesappearto have someeffect on the distribution of
calcium hydroxide. In bse imagesof slag/cementpastes(Fig. 28), it is noticeable
that large massesof cH have grown around the slag particles. over a period of
severalmonthsthe slagslowly reactsand the amountof calciumhydroxidedecreases.
In old pastes,reactionrims can be seenaround the slagparticles(Fig. 29); theseare
darker (with a lower averageatomicnumber)than the hydrationproductaroundthe
cementgrainsand conlginsignificantquantitiesof Mgo. Suchlayershavealsobeen
noted by Tanakaet al."' Analytical work by Harrison et al.6 sug,gests that theserims
are composedof C-S-H mixed on an atomic scalewith another product, possibly a
hydrated magnesiumaluminate of the hydrotalcite group.
Silica fume consistsof very small particles(s0.1 pm) of amorphoussilica. The
high surface area of the fume meansthat it reactsmuch more rapidly than fly ash
or slag. As it is very difficult to dispersethe silica fume, superplasticizersare ahvays
added to such mixes in practice. Severalworkers have noted that the microstructure
of pastescontgiq[ng silica fume is very different from that developedin ordinary
cementpastes,'"* having a denseamorphousappearance.The bse imageof a mature
cement silica fume paste(Fig. 30)4villustratesthis densemicrostructure. Despitethe
useof superplasticizer,someclumps of fume are still present(theseare marked Si in
the micrograph). Somelarge cementgrains appearto have hydrated to leave hollow
pores containing unreacted ferrite phase. The reasonsfor these differences in
microstructural developmentare not fully understoodat present. Silica fume also
appearsto have a profound influence on the microstructureof the interface between
cement past and aggregate,which will be discussedsubsequently.
t44 Materials Scienceof Concrete
Fig. 30. Polishedsectionof a maturecement/silicafume paste(85/15). Clumps
of silice fume cen be identified (Si). No massiveregionsof celcium hydroxide
can be seen. Some of the large pores ere associatedwith the hydration of cement
grains to leavehollow shells of hydration product.
Characterization of the Overall Paste Microstructure
In the previoussectionsthe developmentof microstructurewasdescribedmainly
in termsof the localchangeswhich occur aroundindividualgrainsof cementduring
hydration. The resultingmicrostructurefor a given pastewill dependon:
l. The phasespresentand their distributionwithin the grains.
2. The grain-sizedistribution.
3. The amountof reaction(relatedto age,moisturestate,and temperature).
4. The water/cementratio.
The first two are determined by the anhydrous cement powder, whose
characterizationhas already beendiscussed.The grain size, in conjunction with the
degreeof reaction, is particularly important in determining the distribution of the
C-S-H product in the microstructure. As previously indicated, grains smaller than
about 5 pm (about 6 wt% of the total) will hydrate completelyduring the major heat
evolution peak to give "outernC-S-H in the originally water-filled space. Grains
betweenabout 5 and l5 pm (about 30 wt%) will have reactedafter about sevendays
to give "outer'and 'through solution, inner" C-S-H. Only the cores of grains larger
than about l5 pm will then eventually hydrate to give "solid state, inner'C-S-H.
The water/cementratio determinesthe amount of water-filled spacein the fresh
cement pastes;for tw/c of 0.5 this is about 60%. At early agesthe effect of the w/c
ratio on the appearanceof fracture surfaces is quite dramatic (Figs. 3l and 32).
After l8 hours, the fracture of the cementpastewith w/c = 0.5 is almost completely
interparticular(Fig.3l), whereas,in the pastewith w/c = 0.3, the closerspacingof
the cement grains meansthat more bonding hasoccurred and there is more fracture
through the shells,revealing more anhydrouscoreson the fracture surface(Fig. 32).
At later agesthe effect of w/c ratio on the microstructure is lessobvious.
Materials Scienceof Concrete t45
 -"*'

Fig. 31. Fracturesurfrce of cementpastewith w/c = 0.5, hydrated for 18 h.

The fracture hes beenpredominsnllyinterparticular.
0.a
o w/COll o
o Yrcoat o lY/co{t
r w/C Oll

0.2

I
z dot
0.1
0.1

0.q 0.0+
0:l 0.2 O:l 0.0 o;2 o:3
f" ANr.o P,*"

fig. 33, Analysisof microstructuralconstituentsin cementpaste. (a) Bse image

Fig. 32. Fracluresurfaceof cementpastewith w/c = 0.3, hydratedfor lg h. In
this case there has been more fracturi through the hydreie ih"llr, revealingthe
separationbetweentheseshellsand the anhydiouscores.
from 28-day-paste;(D) gray-levelhistogram,showingpeaksfor: anhydrous
material (AN), calcium hydroxide(CH), and other hydration products;(c)
anhydrousmaterial;(d) calcium hydroxide;(e) porosity;(f) comparisonof
anhydrousmaterial measuredby imageanalysis(ia) and by losson ignition
(LoI); (g) comparisonof porosityfrom imageanalysisand methanotabsorption.

Given these various. factors, quantitative descriptions are necEssaryfor
rnicrostructural characterization. The simplest meani of quantification'is to
determine the relative proportions of the Constituentsp.esent. The gray-level
contrastbetweenthe microstructuralconstituentsin bseimagesmakesit p6ssi'btefor
them to be discriminated by an automatic image analyzer,is illustrated in Fig. 33.
This method can be used to measurethe quantlties of anhydrousmaterial, missive
calcium hydroxide, other hydration products,and pores. If a sufficiently large area
is-analyzed, the quantities determined will be rlpresentative of the -uutt-paste.
Although the same quantities can be measured by indirect techniques, sivera!
techniquesmust be usedto measureall the constituenis. A study by Scriveneret a1.22
showedthat measurementof the amountof unreactedanhydrousmaterial by analysis
iqragesgives comparableresultsto valuesmeasuredby loss on igniiion (rig.
of .b..se
33(/). The measurementsof porosity by the imageanalysisrnethodwere lower iha-n
thoseobtained by methanolreplacement,owing to ttre timitea resolution (0.5 pm) of
the bse-imagesat the magnification used (x 400). Nevertheless,there was good
proportionality between the two setsof measurementsfor pastesat a wide range of
agesand w/c ratios (Fig. 33(g)). It should also be possibleto determine the ambunt
of calcium hydroxide by this method, but, becauseof the unevendistribution of this
phase,measurementsmust be made over a larger area than was done in this study.
The importance of the analysisof bse imageslies in the potential it offers for
obtaining quantitative descriptions of the distributions ol the microstructural
constituents. The choice of suitable parametersto characterizea distribution must
be considered carefully and the best strategy will depend on the nature of the
distribution and the end purpose of the characterization. It is also important to
understandthe stereologicalproblemsinvolved in trying to derive information about
three-dimensionaldistributions from the study of two-dimensional sections.
The anhydrousmaterial existsas discreteparticles. In this casethe distribution
of particle sizesmight be suitable for some applications,while for others the total

t46 MateriatsScienceof Concrete Materials Scienceof Concrete t47

surl'acearea of the grains or the uniformity of their distribution in spacemight be
3#
wffi
a more appropriate description of the microstructure.
In contrast,the poresin cementpasteare not discreteand the connectivity of the
pore spacehas an important influence on such properties as permeability. In this

y4
casethe pore-sizedistribution and connectivity measuredin two-dimensionalsections
may bear little or no relation to the three-dimensionalpore structure. For some
purposes,characterizationof the.pore surf?^cermaybe more appropriate and here
* +tEilt
conceptssuch zrsfractals may be important.ru'
The distribution of calcium hydroxide posessimilar problemsdue to the tortuous
shape of the crystalline masses. Here the density of nucleation sites might be an
important parameter,which could be estimatedby analysisof nearest-neighbor
distances.
*#w
It is clear that there is much to be done in this area, but with appropriate basic =
work it should be possibleto establishways of characterizingthe microstructureof
cement paste,which will further the understandingof its behavior. -j*
Fig. 34. Photographs of (c) gravel and (D) crushed granite. (Courtesy of A. K.
Crumbie.)
Aggregates

A very wide range of aggregatesis used in the production of concrete.

!mpirically, severalfactorshavebeenestablished as affectiggthe workability of the
fresh concreteand the durability of the hardenedstructure." Thesefactorsmay be
summarizedas follows:
Physical characl.eristicsof the aggregateparticles: the particle-sizedistribution
(gradingXthe particleshape;the surfacetexture of the particles.
Impurities and contaminants: Clay, silt, and dust; organic matter; mica, chalk,
shell;sulfatesand chlorides;metallicimpurities,in particularlead and zinc oxides.
Mechanicaland chemicalstability: mechanicalstrength;susceptibilityto reaction
with alkalis;soundness with respectto freezingand thawing.
During the early stagesof hydration,the aggregate doesnot play an activerole
in microstructuraldevelopment. Thus, in the absenceof significant amountsof
impurities or contaminants,the physical propertiesof the aggregateare of most
importance. In particular, the grading of the aggregatewilt affect the packing of the
particlesin the concreteand the surfaceareaof aggregatewhich must be coveredby
cement paste. It is difficult to characterizefeatures such as particle shape and Fig. 35. Micrograph of sand particles ln the SEM (bar = 196 U.1.
texture in a quantitative manner; in particular, a surfacemay be describedas rough
on severaldifferent scales.
Examples of two commonly used aggregatesare shown in Figs. 34(a) and (b). Cement Paste/AggregateInterface
The aggregatein Fig. 34(c) is a natural gravel aggregate;the particles are generally
rounded and have a wide rangeof surfacetextures. The other agg,regate is a crushed
granite rock. In this casethe particlesare angular and the surface is fairly uniform. The interface betweencementpasteand aggregatecannot be studied in isolation
The speckledappearanceindicatesthe polymineralic natureof this aggregate.Figure as it existsonly as a localizedregion in the microstructuresof concretesand mortars.
35 showsthe surfaceof a fine aggregatesandtaken by SEM; someparticlesare fairly This makes microscopical techniques well suited to the study o-f. this region.
smooth, while others are pitted. Examinationsof fracture surfages(e.g.,Ref. 53) and polishedsurfaces)"by SEM, and
Over periods of severalyears,someaggregatesmay undergo chemical reaction. ion-thinned sectionsby TEMr"rd haveall been reported. However, becauseof the
The most seriousof thesereactionsis the aggregatealkali reaction (AAR), in which difficulties in obtaining quantitative information from microscopicalstudies,many
componentsof the aggregatereact with alkalis in the cement paste to give a gel, worker;(e.9., Refs.55-60) have usedthe "model'concretespecimen,developedby
which may imbibe water and swell, causingcracking in the concrete. The AAR is Farranot to study the interface. In this specimen,cement paste is cast onto a large
most commonly causedby the presenceof amorphousor microcrystallinesilica in the flat piece of aggregate.After a suitableperiod of hydration, the specimencan then
aggregate,but has also been reported with carbonateaggregates. be fractured at the interface and the surfacesso producedexamined by SEM. The

l4E Materials Scienceof concrete Materials Scienceof concrete r49

L.
 !rg. J6. Leyer of product
deposited on rggregrte surfece in
four-dey-old mortrr.
Fig. 37. Microstructureet edge
of sendgrein In one-day-old
mortr. There is e layer of C-
S-H productelong the surfaceof
aggregete.
9fin
Fig. 38. Contact zone betweeu
calcite and cementpaste,ion-
beem-thinnedsectionof r one-
year-old sample. (CourtesyJ-P
Ol l i vi er.)
Fig. 39. Area of frecture surfece
in e one-day-old mortar, edJacenl
to en aggregeteperticle. Beyond
the surface leyer (some of whlch
edhered to the eggregatedurlng
fncture) can be seen 'rosettes'of
C-S-H from the hydration of
small cementgrains and long rods
of AFt.
Itl r5 0 Materials Scienceof Concrete
llI
tll
Concentrationand orientation of phasesin the tnterta9lau:egtoncan also DeanalyzeO
by the techniquedevelopedby Grandetand Ollivier,r)-r' which involvessuccessive
abrasion of the cement paste side of the interface and examination of the phases
Dresenton the surface by X-ray diffraction. This type of specimenalso facilitates
microstructural examination by SEM, when it is fractured along the interface. As
a model for concretethere are severaldisadvantagesto this specimenconfiguration.
First, the surface of the aggregateis flat and often polished;second,the aSSregate
is not presentduring the mixing process,and third, there is a considerablethickness
of paste in contact with the aggregateas opposed to the narrow bands of paste
between aggregateparticles in concrete.
Microstructuralstudiesindicatethat a thin layer of hydration product (sl pm
thick) forms on the -slrfaceof the aggregate.From their studiesof cementpastecast
againstglassslides,o'Barneset al. suggestedthat this is a duplex layer with a thin
film of calcium hydroxide adjacent to the aggregatesurface surrounded by a layer
of C-S-H. However, Scrivenerand Pratt! found no evidenceof the calcium
hvdroxide film in their study of mortarsexaminedas fracture surfaces(Fig. 36) and
as polishedsectionswith bse(Fig. 37). Even with the higherresolutionpossiblewith
transmissionelectron microscopy,there appearsto be only qSlr.nplelayer of product
in contact with the aggregatein the work of Javelset al.""o (SeeFig. 3E.) The
depositionof this product layer does not entail any chemical reaction with the
aggregate,which merely actsas a nucleationsite. However,at later agesthere may
bi1 chemical reqgt_i^on betweenthis layer and somecarbonateaggregates,producing
a strongerbond.r6'or
Beyondthis layer of product there is a regionof high porosity which is known
as the naureole de transition.' This arisesbecausethe largeanhydrouscementgrains
cannot pack ctoseto the aggregateparticles. In compositespecimensthis region is
charactirizedby the prefeired orientationof calcium hydroxide with--th-e^ c axis
parallel to the aggregatesurface,and by inc.easedconcent;ationsof AFt55-s8which
extend some 50 pm into the cement paste. On fracture surfacesof concretesand
mortars,this region can be seenthrough openingsin the surfacelayer where it is
incompleteor hasremainedattachedto the aggregate particle(Fig. 39). In this region
there are many "rosettes"of C-S-H from the hydrationof small grainsand a large
number of long AFt rods. In bse imagesof polishedsections,the distribution of
cementgrainsJan be observeddirectly or deducedfrom relics in maturespecimens.
Figure 4-0showsthe interfacial region in a one-day-old mortar. There are few large
griins close to the interface and, in this case,therl appearsto be a concentrationof
imall grains in the crevicesof the aggregateparticles,which probably accumulated
as the-mortar was mixed. The numiioul small grains close to the interface lead to
many hollow hydration shellsbeing observedin this interfacial region which can still
be sien in mature specimens(fig.4f ). It is perhapsno coincidencethat Hadley first
observedhol-lowhydration stretti (Hiatey grains) while studying interfacial regions
il-;;n;;"t..5{ ns-oiscussea eailiet, t'treie tenas to be a higher proportion of
interstitial phasesexposedon the surfacesof smallergrains,which-would accountfor
trte rrigii c,in..nir"tion oi nrt observed in this teglon. In. bse image::.crystary-9f
calciuit hydroxide can be seen in the interfacial region (e.g., Fig. 40), but tt ts
difficult to identify any preferred orientation.
Materials Scienceof Concrete
l5l
Fig. 40. (Left) Backscatteredelectronimageof interfacial zoneof a one-day-
old mortar. There are few large cementgrainscloseto the aggregatesurface.
There are many hollow shellsof hydration productin the interfacial region. In
the crevicesof the aggregatesurface,small grainsof cementhave accumulated
during mixing, leadingto more product in theseregions. Severalmassiveregions
of calcium hydroxide(light gray) are also apprrent with e range of orientations.

Fig. 4l. ( Right ) H i g h -m a g n i fi c a ti o nb s ei ma g eof the i nterfaci alregi oni n a l 0-

week - oldc om po s i tes p e c i m e n(R e f. 6 5 ). E v e ni n thi s maturepaste,hol l ow shel l s
of hydration product from the reactionof small grainscan still be seen. Fig. 42. Measurement of microstructural gradients in the interfacial region. (c)
Bse image with aggregate particle at the top of the micrograph; (6) porosity detected
As the microstructuralconstituentscan be distinguishedin bse images of in cement paste; (c) black lines indicate the bands in which the microstructural
polishedsectionsof concretesand mortars,this techniquecan be usedto characterize constituents are measured.
the microstructureof the interfacial region quantitativelyin real concretesand
mortars.With an automaticimageanalyzer,the relativeamountsof the constituents
can be 4gasuredin bandsspreadingout from the aggregate surface,as illustratedin
Fig. 42.* However, with random sectionsof concrete,the angle at which the
aggregatesurface intersectsthe plane of the sectionis unknown, and the normal
distancefrom the aggregatesurface to a point in the sectio_q can only be estimated.
In order to avoid this problem, Scrivenerand Gartneror preparddspecimensin
which single pieces of aggregateswere cast into blocks of cement paste. Sections
were then cut from thesespecimens,normal to the aggregatesurfaces. Thesesections o g t ro c o o t ro o o o
were analyzedby the techniquedescribedabove,averagingthe resultsfor eachband
over l0 fields covering about 200 pm length of the aggregatesurface. With this ll!
lll
number of fields there was considerablescatterin the results. but there was a clear rrrrr artt

decreasein the amount of anhydrous material and increasein the porosity in an

interfacial zonesome 30 to 50 pm deep (Fig. a3). A slight increasein the amount of
calcium hydroxide close to the interface was also observedbut this was not signifi-
cant with regard to the scatterin the results. In terms of simulating concrete,these
specimenshave an advantageover composite specimenswhich use a flat piece of
aggregate,by having an unpreparedaggregatesurface. However, the aggregateis Ftg. 43. Microstructuralgradientin the interfacial regionof 10-week-old
still not presentduring mixing. The accumulationof small particlesat the aggregate compositespecimensexaminedby Scrivenerand Gartner (Ref. 65). The results
surfaceseenin Fig. 40 indicatesthat the movementof aggregateparticlesthrough the plotted ere the averagemeasurements from 10 fields in each of three different
pasteduring mixing has an effect on the microstructureof the interfacial zone. aggregates. (a) Anhydrous material, (D) porosity.

r52 Materials Scienceof Concrete Materials Scienceof Concrete 153

 the type ot'specimenconfiguration,and especiallythe presenceof the aggregate
Concrete (ogg/cem 4:1)
zgdoys w/c = O,1 during mixing, may affect the gradientsof microstructurein this zone.
ANHYDROJS Do"--
o
o
Effect of Silico Fume on the Interface

There is considerableinterestin the incorporationof silica fume in mixes to

o
s- oroduce high-strength concrete. This replacementmaterial appearsto have a
brofound effect on the microstructureof the interfacial region, consistentwith the
microstructure observed in silica fume/cement pastes. Figure 45 shows the
microstructureof the interfacial zone in a concretecontaining silica fume; the
tO eenerallydenseappearance of the microstructureis apparent. Howeverfairly large
distffie lrm intsloce pm 6ores are still present in the form of hollow hydrate shells. In contrast to the
iquivalent paste,the silica fume was well dispersedin the concrete,due to crushing
or shearing-b-etween the aggregate parlicles,and no clumpingof the silica fume was
ANHYDROUS
observed."'o' Scrivenerand Bentur*t analyzedmicrostructuralgradientsof the
Otr_
toooooooootroootroo
interfacial zones in high-strength concretes with and without silica fume. The
cradient in the amount of anhydrous material was in both casessimilar to that
5bservedin the other studiesdescribed(Figs. 43(a) and 44(a)). This is consistent
with the view that the particle-sizedistributionof the cementdeterminesthe width
E
e
&
PORO
SITY of the interfacialzone. The porositygradientwas much shallowerin the concrete
o
c containingsilica fume, as indicatedby the appearance of the micrograph(Fig. 45);
rllrlrlaatrll
4
z this suggeststhat the small particlesof silica fume accumulatein the interfacial
aatttr l r l l tl l l tr r r r regionduring mixing.

b) c)
Overall Microstructure of Concrete
F ig .44 . Micro stru c t ur al gr adient s in t he int er f ac i a l r e g i o n o f 2 8 - d a y - o l d
The microstructureof concreteis that of a compositematerial, composedof
concretes, average of 50 fields. (a) Anhydrous material, (D) porosity, (c)
aggregate,cementpaste,and the interfacebetweenthem.The complexitybehindthis
standard errors. statementcan be appreciatedby observingthe sequence
of micrographsshownin Fig.
46, eachof which was takenof the samearea,at about four timesthe magnification
Des pit et he pro b l e mo f th e u n k n o w na n g l eo f i ntersecti on
of the aggregate w i th
the plane of the section,it might be possibleto apply this method to concreteif ,4
largenumberof areasare analyzed.To investigatethis possibility,Scriveneret al.m
looked at the variability of the resultswhen a large number of fields, selectedin a
nuniform randomnmanner, are analyzed. Some of the results from this work are
shown in Fig.44. In thesegraphs,the distancesfrom the aggregatesurfacemeasured
in the plane of the sectionhavebeenestimatedfrom the averageangleof intersection
of the aggregatesurfaceswith a random section. The proportionsof the constituents
changesmoothly and the standarderrors for the measurements are all around l0% of
the measuredvalues. From this preliminary study it appearsthat this method could
be developedas a meansof characterizingthe interfacial zone in real concretesand
used to investigatethe effect that factors such as mix designor direction of casting
have on this region.
All the quantitativestudies,both on compositespecimensand in concretes,
indicatethat the width of the interfacialzoneis between30 and 50 pm. From Fig.
4 it can be seenthat only about l5 to 20%of anhydrousgrainsare larger than 50 pm. Fig. lS. Interfacial region of silica fume concrete. The microstructureis dense
This seemsto indicate that the essentialfeature determining the interfacial zone is and there lre no clumpsof silica fume as seenin the cement/silicafume paste
the packingof the anhydrouscementgrainsagainstthe "wallnof aggregate.However, (Fig. 30). The hydrati,onof somesmall cementgrainshas lefi someenclosidpores.

MaterialsScienceof Concrete r55

154 Materials Scienceof Concrete

>-.
 the picture there is very little anhydrous material present. At x 400 the

rill
Fig. 46. Microstructure of concrete(180 days): (c) nomlnal magnlfication (NM) x
rl ?5. A large particle of granite eggregateand seieral sma[ part'iclesof send cen
be seenIn e matrix of cement pasie. lr; NM x 100; the dis;ibutioo or
cemen-tin the paste cen "ohio-i*,
!e seen-morecleerly. There is very littte anhydroui
material in the narrow-ribbon of paste betwlen two sand giains to the right of
the microgrrph. (c) NM x 400; distribution of the catciui hydroxide an-dlarge
pores in the cement paste can now be seen. (d) NM x 1600 microstructure
betweentwo partielly reected cement grains. (e) NM x 6000 detaired
mlcrostructure of hydration products.
microsttucture of the paste can be seen in more detail and the distribution of the
larger pores can be seen. The next micrograph (x 1600)shows the microstructure
between two hydrating cement grains and the final micrograph (x 6000) gives an
impressionof the morphologyof the hydration products.
The characterizationof the concretemicrostructureentails the characterization
of the cement paste and the paste/aggregateinterface, which have already been
discussed.In addition, the distribution of the aggregateparticles and the incidence
of features such as air voids and bleeding must be considered. In the caseof real
concrete structures, the microstructure may vary throughout the cast section. In
particular it is essentialto take accountof the microstructureof the material near the
surface,whic! p-laysa crucial role in protectingthe reinforcingsteel.
Kreijger""* discussedthe phenomenonof the concrete skin, which occurs
wheneverconcreteis poured againsta barrier or is leveledflat. This skin consistsof
an outer layer of cementpastesome0.1 to 0.3 mm thick, beneathwhich is a 3 to 5
mm thick layer of mortar. The water/cementratio alsovariesin thesesurfacelayers.
In addition, the gradients will also occur in the mois.t^u;p
stareof this layer as water
evaporatesfrom the surface,as discussedby Parrott."'''u Theseeffects will produce
microstructuralgradientsextendingsome50 mm into the concrete.
The fact that these phenomenaproduce variations of microstructure in space
indicatesthat quantitativemicroscopy(both opticaland with backscattered electrons)
can play an importantrole in characterizing and understanding the surfaceregionof
concrete.
The microstructureof concretecontinuesto changethroughoutits life, due not
only to continuing hydration but also to the effects of the environment. In
particular,the ingressof othercompoundssuchascarbondioxide may haveprofound
effects on the microstructure.The diffusion of such compoundswill also produce
gradientsin the microstruc-ture.I^nenvironmentssuch as seawater,severaldifferent
ionic species(e.g.,Cl-, SO?-,Mg2+)diffuse at different ratesand the gradientsthey
producemust be consideredindividually.
Despite these many complexities,"good" microstructuralcharacterizationof
concrete is not an unrealistic goal. In qualitative terms, the way in which
microstructuredevelopsduring the hydrationof cementand concreteis fairly well
understood. What are needed now are more quantitative descriptionsof the
microstructure,which can be relatedto its behavior.They will not necessarily entail
completequantification of every detail, but only by understandingthe overall context
can useful methodsof characterizationbe established.
Acknowledgments
The author would like to thank Dr. K. D. Baldie, Ms. M. P. Cook, Ms. A. K.
Crumbie, and Prof. P. L. Pratt for helpful discussionsand the Warren ResearchFund
of the Royal Society for financial support.

of the precedlngone (as indicated ttre white boxes). At the lowest magnification
(nominally x 25) a_largeparticle of-by
lranite aggregateand severalsand gra'inscan be References
seen in a matrix of cement paste. At a nom-i-nal-magnification oC 16o tne bright
anhydrouscement corescan be seenmore clearly. T-heirdistribution " is uneuen;io. lE. Hornbogen,
'On the Microstructure of Alloys,' Acta Metall., 32, 615-27
example,in the narrow ribbon of pastebetweenthe two sand grains on the right of (t984).

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l6l
Materials Scienceof Concrete
160 Materials Scienceof Concrete

ill