Maltais 1997
Maltais 1997
Maltais 1997
1009-1020,1997
01997 Elsevier SckoceLtd
Pergamon Printed in the USA. All rights reserwd
@ 0008-8846/97 $17.00 + .00
PII S0008-8846(97)00098-7
Y. MaltaisandJ. Marchand
Centrede rechercheinteruniversitairesur le b&on
Universit6Laval,Qudbec,Canada,GIK 7P4
(Refereed)
(ReceivedMarch 13, 1997;in finalformMay 20, 1997)
ABSTRACT
The influence of fly ash and curing temperature on cement hydration and
compressive strength development of mortars was investigated. Test
parameters included type of fly ash (two different Class F fly ashes were
tested), the level of cement replacement (10, 20 and 30% by mass), and
curingtemperature(20°Cand 40”C).The mortarphysicaland microstructural
properties were determined by means of thermal analyses, compressive
strengthmeasurementsand SEM observations.Test results confirmthat fly
ash tends to increasesignificantlythe rate of cementhydrationat early age.
Data also demonstratethat an elevationof the curingtemperaturereducesthe
long-termcompressivestrengthof the referencemortar mixture.In contrast,
an increaseof the curingtemperatureseemsto have no detrimentaleffect on
the long-termcompressivestrengthof the fly ash mixtures.02997 Elsevier
Science Ltd
Introduction
1009
1010 Y. MaltaisandJ. Marchand Vol. 27,No. 7
Test Program
..
Materials,SamplePreparationand ExperimentalProcedures
TABLE 1
Chemical,Mineralogicaland PhysicalAnalysisof Cementand Fly Ash
CEMENT(%) FLYASH(%)
OXJDELS COMPOUNDCEMENT(%JFLYASH(%)
TABLE2
Fly Ash PhysicalCharacteristics
FLYASH 1
● The diameterof the various paticles rangesbetween0.5 and 20 pm. The biggest
particlesareusuallyrichin siliconandthesmrdlerareratherrichin calcium;
● The free lime (CaO)is relativelyabundant.The mean diameterof the free lime is
approximately2 pm;
. Anhydrite (CaS04), quartz and some spherical iron oxide particles were also
observed.
FLYASH2
. Theparticlediameterrangesfrom 1 to 30 pm. The diameterof most particlesrange
from2 to 10pm;
. The particlesarerichin siliciumandaluminum;
● QU@Z isalsoabundant.
1012 Y. MaltaisandJ. Marchand Vol.27,No. 7
TABLE3
MixtureCharacteristics
MIXTURE CEMENT FLYASH WATER SAND FLOW AIR
k@# k@3 kg/m3 kg/m3 % %
TIO-2O”C 530 nla 265 1325 128 3
; T104O”C 530 nla 265 1325 129 4:;
TIO-10%FA1-2O”C 477 53 265 1325 130 3.9
: TIO-10%FA14O”C 477 53 265 1325 139 4.2
5 TIO-2O%FAI-2O”C 424 106 265 1325 144 3.6
6 TIO-2O%FA1-4O”C 424 106 265 1325 148 3.4
7 TIO-3O%FA1-2O”C 371 159 265 1325 129 3.6
8 TIO-3O’7OFA1-4O”C 371 159 265 1325 14.4 2.9
TABLE4
Non-evaporableWaterContents
f’ MIXTURE TIME
7h IOh 26h 3d 14d 28d 42d
1 TIO-2O”C Wn(t)lc 0.0355 0.0885 0.123 0.168 0.192 0.182
2 TIO-4O”C Wn(t)/C 0.0~87 0,0900 0.1290 0.157 0.178 0.207 0.218
3 TIO-10%FA1-2O”C
Wn(t)/C+FA - 0.0409 0.0869 0.124 0.159 0.145 0.181
Wn(t)/C - 0.0454 0.0966 0.138 0.177 0.161 0.201
4 TIO-10%FAI-4OOC
Wn(t)/C+FA0.0710 0.0889 - 0.157 - 0.192 -
Wn(t)/C 0.0789 0.0990
5 TIO-20%FAl-20°C
Wn(t)/C+FA - 0.0344 o.oio2 ::;1: o.i49 ::?:; o.i59
Wn(t)/C 0.0430 0.1002 0.148 0.186 0.198 0.199
6 TIO-20%FAl-40°C
Wn(t)/C+FA0.0j77 0.0833 0.1225 0.150 0.179 0.154 0.189
Wn(t)/C 0.0721 0.1041 0.1531 0.188 0.223 0.193 0.236
7 T10-30%FA1-20°C
Wn(t)/C+FA - 0.0354 0.0739 0.105 0.145 0.142 0.158
Wn(t)/C 0.0506 0.1055 0.150 0.207 0.203 0.226
8 TIO-3O%FA]-4OOC
Wn(t)/C+FA0.0;71 0.0838 0.1170 0.141 0.170 0.168 0.166
Wn(t)/C 0.0816 0.1197 0.1670 0.201 0.244 0.240 0.237
9 T10-20%FA2-20°C
Wn(t)/C+FA - 0.0352 0.0746 0.100 0.132 0.141 0.136
Wn(t)/C - 0.0440 0.0933 0.125 0.165 0.176 0.170
10 TIO-20%FA2-40°C
Wn(t)/C+FA0.0555 0.0781 0.1242 0.132 0.163 0.177 0.171
Wn(t)lc 0.0694 0.0976 0.1552 0.165 0.203 0.221 0.213
Vol.27, No. 7 CURINGTEMPERATURE,FLYASH,HYDRATION,STRENGTH 1013
................................. : ............................................
05
time (d)
FIG. 1.
Non-evaporablewater contentfor fly ash 1 and 2 for an isothermalcuring at 20°C (a) and
400C(b),
TABLE5
Increasein Non-evaporableWaterContent*at Early Days
.
1014 Y. MaltaisandJ. Marchand Vol. 27,No. 7
TABLE6
CompressiveStrengthResults
ff MIXTURE TIME
IhIOh 26h 3d 7d 14d 28d 35d 42d
1 TIO-2O”C -2.3 17.2 26.6 37.8 43.9 45.0 49.0 51.0
2 TIO-4O”C 7.1
13.4 26.2 35.3 38.9 40.7 42.8 - 44.7
3 Tlo-lo%FAl-20°c 1.7 15.5 27.5 31.5 39.3 48.7 51.7 53.6
4 TIO-10%FA1-4O”C10.5 15.9 27.0 28.1 - 41.0 45.0 - 46.9
5 TIO-2O7OFA1-2O”C 1.0 14.0 18.7 28.2 41.1 45.9 52.3 53.2
6 TIO-2O%FA1-4O”C4.5 9.6 22.5 28.6 39.2 42.2 50.5 - 55.0
7 TIO-3O%FA1-2O”C 0.8 9.0 20.5 28.8 34.1 39.9 43.0 46.5
8 TIO-3O%FA14O”C 3.9 9.0 22.7 29.9 - 47.9 52.1 - 55.2
9 TIO-2O7OFA2-2O”C 1.5 13.6 20.1 30.8 33.8 39.9 44.1 45.9
10 TIO-2O%FA2-4O”C5.6 11.7 22.5 26.2 37.3 41.5 49.0 - 50.6
w“ (t) W105”C
~= E = {1- y+s-cx (z- y)}- (l+s) (1)
where
Wn(t)/C+ FA = non-evaporablewaterexpressedin a unitmass of binderbasis;
W1o~.c = mms of the sampleafterheatingat 105”C;
WIOCWC = massof the sampleafterheatingat 1000°C;
x = 105son igitionof the-sand;
Y= losson ignitionof tie cement;
s = samlhinderratio;
c= fly as~inder ratio.
60. .
1?
g50
a
k ..................~.......................................~..................................
6
time (d) time (d)
FIG. 2.
Influenceof fly ash 1 and 2 on the compressivestrengthdevelopmentof mortars cured at
20°C(a) and 40°C (b).
Vol. 27,No. 7 CURINGTEMPERATURE,
FLYASH,HYDRATION,
STRENGTH 1015
TestResults
Discussion
..-
VO1.27, No. 7 CURINGTEMPERATURE,FLYASH,HYDRATION,STRENGTH 1017
FIG.3
Fly ash 1 after28 daysat 20”C(6000X).
the results of a previous study where the influence of fly ash 1 on the consumption of
Ca(OH)zwas foundto be insignificantduringthe firstweeksof curing(16).
If fly ash does not react duringthe first days of curing,test resultsclearly indicatethat it
cannotbe consideredas a totally“inert”material.Despitevery littlepozzolanicactivity,the
presence of fly ash appears to increase the mortar non-evaporablewater content at early
days. This is particularlytrue for fly ash 1 which contributedto markedlyincreasethe non-
evaporablewater content of the mixture. Such a phenomenonhas also been observed in
previousstudies (6-9). Many authorshave attributedthis increaseto an accelerationof the
early cementhydrationin presenceof fly ash.
It shouldbe emphasizedthat conflictingreportshave been publishedon the influenceof
fly ash on the kineticsof cementhydration.In somecases,the presenceof fly ash particles
has been foundto retardthe earlyhydrationof cement(17, 18).However,there existnumer-
ous experimentalevidenceswhichdemonstratethat fly can contributeto acceleratethe reac-
tion of cement at early days (6-11). As underlinedby many authors, the study of the fly
ash/cement reaction processes is complicatedby the fact that the chemical and physical
propertiesof fly ash tend to differ markedIyfrom one sourceto another.Even within one
source,individualgrainsare highlyvariablein nature.
According to many authors,the acceleratingeffect of fly ash on the cement hydration
mechanismsis mainlyphysicalin nature(6-11).In many cases,the additionof fly ash tends
to increasethe number of fine particlesin the system.The presenceof these fine particles
contributesto increasethe densityof the matrix.The replacementof cementparticlesby fly
ash is alsobelievedto increasethe availablespacein the floe structurecreatedby the cement
grains. Finally, the fine particlesprovide additionalnucleationsites for cement hydration
productssuchas C-S-H,portlanditeand ettringite.
In the present study,the use of fly ash shouldnot have had any significantinfluenceon
the packingdensityof the matrix.The physicalpropertiesof the two fly ash are very similar.
Furthermore,the two materialshavegradingcurvescloseor coarserthanthat of the canadian
1018 Y. MaltaisandJ. Marchand vol. 27,No. 7
FIG.4.
Fly ash 2 after42 daysat 20”C(1500X).
CSA type 10 cement. Apparently,the effect of fly ash on the hydrationcannot be solely
explainedby the “fiie particleeffect”.
Accordingto Takemotoand Uchikawa(11),the accelerationof cementhydrationin pres-
ence of fly ashes is mainlyrelated to the preferentialadsorptionof calciumions on the fly
ash particles.Thisphenomenoncontributesto decreasethe calciumion concentrationin the
liquidphase which subsequentlyfavorsthe dissolutionof calciumphases from the cement
grain. Although the assumptionof Takemotoand Uchikawa cannot be confirmed on the
basis of our results, it is probable that the accelerationof the early cement hydration is
mostly related to an alterationof the pore solutionchemistry.As emphasizedby Luke and
Glasser(19), the aqueousphasecompositionof fly ash mixturesis governedby the balance
of a numberof competitiveprocesseswhichmay occurat differentrates.For instance,it has
been shown that the influenceof fly ash on the early hydrationof cement is influencedby
the relativevolubilityof the sulfateand alkalisourcesof the cementand by the solublealkali
content of the ash itself. It is probable that the fly ashes used in the present study
(particularlyfly ash 1)havecreatedfavorableconditionsfor the hydrationof cement.
Test resultsclearlyindicatethat the influenceof fly ash on the early cementhydrationhas
to be consideredin the elaborationof any model aimingat reliablypredictingthe physical
propertiesof concrete.In that respect,the modeldevelopedby De Larrard(4) is probablythe
one which is the more adaptedto accountfor the influenceof fly ash on the concretecom-
pressive strengthdevelopment.In De Larrard’smodel,the contributionof fly ash is taken
into accountthrough a cement equivalentfactor and a time-dependentpozzolanicactivity
coefllcient.The modelreadilyaccountsfor the influenceof the type and the amountof fly
ash on compressivestrength.
60 i
I :
............................................. ,
.$
.1
............
.....................................................
2oyoFAl ~:
0
20 25 30 35 40 20 25 30 35 40
Temperature(“C) Temperature(“C)
FIG. 5.
Influenceof temperatureon thecompressivestrengthdevelopmentof mortars.
the curingtemperatureis much lessdetrimentalfor fly ash mixturesand that it can, in certain
cases,even have a beneficialinfluenceon the long-termcompressivestrengthof the material
(see Figure5). As can be seen in Table6, an elevationof the curingtemperaturefrom 20”C
to 40°C has contributedto increasethe long-termcompressivestrengthof all fly ash mix-
tureswith a replacementlevelof 20°Aand 300A.
The effects of high curingtemperatureson long-termcompressivestrengthof OPC con-
crete have been the subjectof much attentionin the past decades.Accordingto many stud-
ies, the negativeeffects of high curingtemperatureare directlyrelated to modificationsof
the microstructureof the OPC cementpaste (13, 20, 21). Other authorshave also attributed
the detrimentalinfluenceof high curingtemperaturesto the significantdifferencebetween
the thermal expansioncoefficientsof the variousphases present in the material (22). Ac-
cording to these authors,the increasein the volumeof water and air due to a rise in tem-
perature is prevented by the rigid skeleton of the hardening cement paste. This induces
significantstresseswhichcontributeto the formationof microcracks.
The beneficialinfluenceof an elevationof the curingtemperatureon the long-termcom-
pressive strength of most fly ash mortars can probably be explainedby the fact that the
pozzokmicreaction is, like most chemicalreactions,significantlyinfluencedby the tem-
perature(6, 14,23).Accordingto Fraayet al. (23),the relativetemperature-sensitivity of the
fly ash hydrationprocesscan be explainedby the factthat the dissolutionof fly ash particles
is directlyaffectedby the pH levelof the porewater solution.Theseauthorsshowedthat the
OH- ion concentrationincreasessignificantlywith temperature.The hydrationof fly ash is
thus acceleratedby an elevationof the curing the temperature.Furthermore,accordingto
Berry and Malhotra(24),oncethe pozzolanicreactionhasbeen initiatedby heat, it will carry
on even if the temperatureis reduced.It appearsthat oncethe surfaceof fly ash particleshas
been dissolved,hydrationis mucheasier.
The beneficialinfluenceof an elevationof the curingtemperatureon the long-termcom-
pressivestrengthof fly ash concreteis particularlyinterestingfor precastconcreteproducers
which regularlyrely on steamcuringto acceleratethe mechanicalstrengthdevelopmentof
their products.Althoughfly ash tendsto slightlyreducethe 24-hourcompressivestrengthof
the mixturescuredat 40”C,it globallycontributesto increasethe long-termvalues.
1020 Y. MaltaisandJ. Marchand Vol. 27,No. 7
Conclusion
● Testresultsindicatethat if fly ash doesnot reactduringthe fust daysof curing,it cannot
be consideredas a totally “inert” material.Despite very little pozzolanicactivity,the
presenceof fly ash appearsto increasethe mortarnon-evaporablewater contentat early
days.
. Test resultsclearlyconfirmedthat an elevationof the curingtemperaturecontributesto
reducethe long-termcompressivestrengthof OPCmixture.
● Data also indicatethat an increaseof the curingtemperatureis much less detrimentalfor
fly ash mixturesand that it can, in certaincases,evenhave a beneficialinfluenceon the
long-termcompressivestrengthof the material.
References
1. E.J. Sellevoldand F.F. Radjy, First InternationalConferenceon the Use of Fly Ash and Other
MineralBy-ProductsIn Concrete,ACI SP-79,p. 677,Montebello,Canada(1983).
2. S.E.HedegaardandT.C. HansenjMaterialsand Structures25,273 (1992).
3. F. DeLarrardand R. Le Roy, FourthCANMET/ACIInternationalConferenceon Fly Ash Silica
Fume,SlagandNaturalPozzolansin Concrete,SP-132,965,Istanbul,Turkey(1992).
4. F. De Larrard,Fitlh InternationalConferenceon Fly ash, Silica Fume, Slag, and Natural Pozzo-
kmsin Concrete,ACI SP-153,p. 99, Milwaukee,USA(1995).
5. T.C. Hansen,Cementand ConcreteResearch,20, 193(1990).
6. A. Xu, Ph.D.Thesis,ChalmersUniversityof Technology,G6teborg,Sweden(1992).
7. H.F.W.Taylor,Cementchemistry,AcademicPress,London,U.K., 475pages(1990).
8. S. Diamond,Q. Shengand J. Ole~ MaterialsResearchSocietySymposiumProceedings,137,437
(1989).
9. A. XWS.L.SarkarandL.O.Nilsson,Materialsand Structures,26,414 (1993).
10. M. Kokubu, Fifth InternationalCongress on the Chemistry of Cemen6 p. 75, Tokyo, Japan
(1968).
11. K. Takemotoand H. Uchikaw~ SeventhInternationalConferenceon CementChemistry,4, 2/1,
Paris,France(1980).
12. V.S.RarnachandranandC.M. Zhang,11Cemento,83, 129(1986).
13. Y. Maltais,M.SC.Thesis(in French),Universit+Laval,Qu6bec,Canad~ 185pages.(1996).
14. J. Bijen and H. Pietersen,Advancesin Cement and Concrete,EngineeringFoundation,p. 292
(1995).
15. K.O. Kjellsen,Ph.D.Thesis,NorwegianInstituteof Technology- Divisionof BuildingMaterial,
Norway,223pages.(1990).
16. M. Pigeonand J. Marchand,Report GCS-96-05(in French),Universit6Laval, Qu6bec,Canad~
196pages.(1996).
17. L Jawed, and J.P. Skalny,Effectsof Fly Ash Incorporationin Cementand Concrete,MRS Sym-
posiumProceedings,60 (1981).
18. A. Ghoseand P.L. Pratt,Effectsof Fly Ash Incorporationin Cementand Concrete,MRS Sympo-
siumProceedings,82 (1981).
19. K. Lukeand F.P.Glasser,MaterialsResearchSocietySymposiumProceedings,65,73 (1985).
20. M. RegourdandE. Gautier,B&on198,387,83 (1980).
21. K.O. Kjellsen,R.J.DetwilerandO.E.Gjarv,CementandConcreteResearch21, 179(1991).
22. J. Alexanderson,Proceedingsof the SwedishCementand ConcreteResearchInstitute,135pages,
Stockholm(1972).
23. A.L.A.Fraay,J.M. BijenandY.M.deHaan,CementandConcreteResearch,9,235 (1989).
24. E.E. Berryand V.M.Malhotr~Fly ash in concrete.Supplementary
CementingMaterialsfor
Concrete,p. 37, CANMET(1987).