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10/5/2016 5.

3TheHydrationReactionsinConcrete

5.3TheHydrationReactions
Eachofthefourmaincementmineralsreactsatadifferentrateandtendstoformdifferentsolidphaseswhen
ithydrates.Thebehaviorofeachofthesemineralshasbeenstudiedbysynthesizingitinitspureformand
hydratingitundercontrolledconditions,andthesereactionsarediscussedinthissection.Itshouldbenotedthat
duringtheactualcementhydrationprocessallthemineralsdissolveintothesameporesolution,andthusthe
solidhydrationproductsareassociatedwiththeporesolutionasawholeratherthanaparticularcementmineral.
However,theindividualreactionsprovideagoodapproximationoftheoverallhydrationbehaviorofcement.

Hydrationofthecalciumsilicateminerals(C3SandC2S)
Tricalciumsilicate(C3S)isthemostabundantandimportantcementmineralinPortlandcements,contributing
mostoftheearlystrengthdevelopment.ThehydrationofC3Scanbewrittenas:

5.1

where1.7CSHxisthecalciumsilicatehydrate(CSH)gelphaseandCHiscalciumhydroxide,whichhasthe
mineralnameportlandite.Thevariablexineq.5.1representstheamountofwaterassociatedwiththeCSHgel,
whichvariesfromabout1.4to4dependingontherelativehumidityinsidethepasteandonhowmuchofthe
waterassociatedwiththeCSHisconsideredtobepartofitsactualcomposition.Thestateofwaterincement
pasteandinCSHgelisdiscussedfurtherinSection5.6.ThekineticsofhydrationofC3Saresubstantially
similartothoseofPortlandcementasawhole(seeFigure51).Muchofthereactionoccursduringthefirstfew
days,leadingtosubstantialstrengthgainsandreductionincapillaryporosity.
Thedicalciumsilicatephase(C2S)reactsaccordingto:

5.2

ThehydrationproductsarethesameasthoseofC3S,buttherelativeamountofCHformedisless.C2Sismuch
lesssolublethanC3S,sotherateofhydrationismuchslower.C2Shydrationcontributeslittletotheearly
strengthofcement,butmakessubstantialcontributionstothestrengthofmaturecementpasteandconcrete.

Hydrationofthecalciumaluminate/ferriteminerals(C3AandC4AF)
Thehydrationofthealuminateandferritemineralsissomewhatmorecomplexthanthatofthecalciumsilicate
minerals,andthereactionsthattakeplacedependonwhethersulfateionsarepresentintheporesolution.C3A
ishighlysoluble,evenmoresothanC3S.IfC3Aishydratedinpurewater,calciumaluminatehydratesform.
Thereactionsequenceis:

5.3

wherethefirstreactionisveryrapidandthesecondreactionoccursmoreslowly.Thefinalreactionproduct,
C3AH6,iscalledhydrogarnet.Theinitialreactionissorapidthatifitisallowedtooccurinaportlandcement
pasteitwouldreleaselargeamountsofheatandcouldcausethepastetosetwithinafewminutesaftermixing,
anundesirableconditionknownasflashset.Thepurposeofaddinggypsum(C H2)toPortlandcementisto
preventthisfromhappening.Thegypsumisalsohighlysoluble,rapidlyreleasingcalciumandsulfateionsintothe
poresolution.ThepresenceofthesulfateionscausestheC3Atoundergoadifferenthydrationreaction.The
reactionofC3Aandgypsumtogetheris:

5.4

whereC6A 3H32isthemineralettringite.Sinceallportlandcementscontaingypsum,eq.5.4isthemain
hydrationreactionforC3A.Smallamountsofhydrogarnetformedbyeq.5.3cansometimesbefoundincement
pastes,however.IfthegypsuminthecementreactscompletelybeforetheC3A,thentheconcentrationofsulfate
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10/5/2016 5.3TheHydrationReactionsinConcrete

ionsintheporesolutiondecreasesdrasticallyandtheettringitebecomesunstableandconvertstoadifferentsolid
phasewithlesssulfate:

5.5

wherethenewreactionproduct,C4A H12,iscalledmonosulfoaluminate.Mostcementsdonotcontain
enoughgypsumtoreactwithalloftheC3A,andasaresultmostoralloftheettringiteisconvertedto
monosulfoaluminatewithinthefirstdayortwoofhydrationviathereactionofeq.5.5.

Reactions5.4and5.5arebothexothermicandcontributetotheheatofhydrationofcement.Theearly
hydrationofC3Atoformettringiteviaeq.5.4isquiterapidthisisamajorcontributortothestage1kinetics
showninFig5.1.AswiththeearlyCSHformation,thisseparatestheC3Aparticlesfromtheporesolution,
slowingtheirdissolution.Afteraperiodofseveralhourstheearlyformingettringiteconvertsto
monosulfoaluminateviaeq.5.5,allowingtheC3Atoundergorenewedrapidhydration,withkineticsthatare
roughlysimilartothemainhydrationpeakofC3S(stages3and4).WhentheC3Aishydratingwithinacement
paste,thissecondperiodofreactionoftencreatesashoulderinthedecelerating(Stage4)rateperiodjustafter
themainpeak(notshowninFig.5.1).
Theferritephase(C4AF)reactsinasimilarfashiontotheC3A(eqs.5.15.5),butmoreslowly.Oneimportant
differenceisthatsomeofthealuminuminthereactionproductsissubstitutedforiron.Theamountofsubstitution
dependsonmanyfactorsincludingthecompositionoftheC4AFandthelocalconditionsinthepaste.A
convenientwaytorepresentthesereactionsis[1]:

5.6

5.7

where(A,F)indicatesaluminumwithvariablesubstitutionofiron,and(F,A)indicatesironwithvariablesubstitution
ofaluminum.The(F,A)H3isanamorphousphasethatformsinsmallamountstomaintainthecorrectreaction
stoichiometry.Becauseofthesubstitutediron,themainreactionproductsarenotpureettringiteand
monosulfoaluminate,althoughtheyhavethesamecrystalstructure.Instead,cementchemistshavegiventhem
thenamesAFtandAFm,respectively,wherethemindicatesmonosulfate(onesulfateion)andthetindicates
trisulfate.InaportlandcementpastewheretheC3AandC4AFareintimatelymixedtogether,itcanbesafely
assumedthatthealuminumbearingreactionproductsarenevercompletelyfreeofiron,andsothetermsAFm
andAFtaremorecorrect.However,aswiththetermsalite(impureC3S)andbelite(impureC2S),thisisabit
moreconfusionthanmanypeoplearewillingtodealwith,andthusthetermsettringiteandmonosulfoaluminate
arecommonlyusedtorefertothesephasesincementpastes.

Reactionwithadditionalsulfateions
Asnotedabove,mostportlandcementsdonotcontainenoughaddedgypsumtofullyhydratetheC3Aand
C4AFviareactions5.4and5.6toformettringite.Oncethegypsumisconsumed,theettringitereactswiththe
remainingC3AandC4AFtoformanewlowersulfatephasecalledmonosulfate(reactions5.5and5.7).Thusin
amatureportlandcementpasteitisnormaltofindmonosulfateandlittleornoettringite.
However,ifanewsourceofsulfateionsbecomesavailableintheporesolution,thenitbecomes
thermodynamicallyfavorabletoformettringiteagain,justasitwasinitially.Thiswilloccurattheexpenseofthe
existingmonosulfate:


5.8

whereitisunderstoodthattheAsiteswillcontainsomeF.Thegypsumontheleftsideofeq.5.8representsthe
equivalentamountofdissolvedion,asnosolidgypsumneedforminthepaste.
Reaction5.8ismorethanjustatheoreticalpoint:infact,itisalltoocommonforsulfateionspresentinground

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10/5/2016 5.3TheHydrationReactionsinConcrete

water,seawater,andsoiltodiffuseintoconcrete,allowingthereformationofettringitetoproceed.Thisoccurs
primarily,butnotexclusively,inconcretebelowgroundlevel,suchasbuildingfoundations.Theproblemwiththis
phenomenonisthatreaction5.8isexpansive,meaningthattheettringiteoccupiesalargervolumethanthe
monosulfateitreplaces.Thusexpansivestressesarecreatedthatcancausecrackingandotherdeterioration.
Unfortunately,thisisactuallyonlythefirststepinthesulfateattackprocess,asonceallofthemonosulfateis
consumedotherchemicalreactionscanoccurthatfurtherweakenthecementpaste(assumingacontinued
ingressofsulfateions).WewilldiscusssulfateattackfurtherinChapter12,andconcludethisdiscussionby
mentioningthatthebestwaytominimizethedamagingeffectsofsulfateattackandsimilarchemicalattack
processesistousealoww/ctokeepthepermeabilityoftheconcretelow.

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