Next:Solidspercolation:setUp:MainPrevious:BasicConcepts

CementPaste
Wenowspecificallyconsiderthemicrostructuretransportpropertyrelationshipsincementbased
materials.Webeginwithcementpaste,asthisisthematrixmaterialfortheconcretecomposite,anditis
difficulttounderstandthebehaviorofacompositewithoutfirstunderstandingthematrixphase.Laterwe
willconsidermortarandconcrete,compositesmadefromcementpasteathigherlengthscales,and
individualphasesofcementpastelikeCSH,handledatlowerlengthscales.
Thestartingpointforcementpaste=cement+water,cementpowder,isobtainedbygrindingcement
clinker.Thecementclinkerismanufacturedbyfiringmixturesoflimestoneandclay,whichcontain
aluminateandferriteimpurities.Afterextractionfromthekiln,gypsum(calciumsulphatedihydrate)is
addedtomoderatethehydrationprocess.Aftergrindingtogethertheclinkerandgypsum,thecement
powderconsistsofmultisize,multiphase,irregularlyshapedparticlesgenerallyranginginsizefrom
lessthan1mtoabout100m,withanaveragediameterofabout1520m.
Figure2showscrosssectionalimagesoffourdifferentportlandcements.Theseimageswereobtainedby
firsttakingabackscatteredelectronscanningelectronmicrograph,whichdeterminedtherankingofthe
averageatomicnumberofeachphaseviathegrayscale

Figure2:ShowingprocessedandsegmentedSEMimagesoffourkindsofportlandcementparticles.
Eachphaseinthecementisidentifiedbyauniquecolor.Therandommicrostructuraldifferencesbetween
particlesinthesamecement,andbetweenparticlesindifferentcements,isreadilyapparent.
contrast.XraybitmappingwasalsocarriedoutusingtheSEMinordertodeterminerelativeatomic
abundanceofimportantelementslikecalcium,silicon,aluminum,sulfur,andiron.Bycombiningthex
rayandbackscatteredelectronimages,theprincipalchemicalphasesofthecementparticlescouldthen

determined[10].Figure2clearlyshowsthatevenbeforehydrationtakesplace,thecementpowderis
itselfarandomcomposite,withevenmostparticlesthemselvesbeingmultiphasecomposites.
Whenthecementismixedwithwater,hydrationreactionsoccurwhichultimatelyconvertthewater
cementsuspensionintoarigidporousmaterial,whichservesasthematrixphaseformortarandconcrete.
Thenominalpointofhydrationatwhichthisconversiontoasolidframeworkoccursiscalledtheset
point.Thedegreeofhydrationatanytimeisthevolumefractionofthecementthathasreactedwith
water,andisoftendenotedbythesymbol.Theratioofwatertocementinagivenmixtureisspecified
bythewatertocementratio(w/c),whichistheratioofthemassofwaterusedtothemassofcement
used.Anordinaryconcreteusedinbuildingsusescementpastewithw/c 0.5.Newerhighperformance
concretesoftenhavew/cratiosof0.3orlower[11].
Thevariouschemicalandmineralphaseswithinthecementpowderhydrateatdifferentrates,depending
ontheirsizeandcomposition,andinteractwithoneanothertoformvariousreactionproducts.Some
productsdepositontheremainingcementparticlesurfaces(surfaceproducts)whileothersformas
crystalsinthewaterfilledporespacebetweencementparticles(poreproducts).Forsimplicity,and
becauseitstillcorrectlycapturesthemainfeaturesoftheporestructure,cementpastecanbethoughtof
asconsistingoffourphases:1)unreactedcement,2)surfaceproducts(likeCSH),3)poreproducts(like
CH=calciumhydroxide),and4)capillaryporespace.Surfaceproductsgrowoutwardfromthe
unreactedcementparticlesandcontainconnected(percolated)gelpores,whileporeproductsare
generallypolycrystallineandfullydense,withnoconnectedpores.Thecapillaryporesaretheremaining
waterfilledspacebetweensolidphases,leftoverafteragivendegreeofhydrationtakesplace.Capillary
poresgenerallyrangefromabout0.01to0.1micrometersinsize,inareasonablywellhydratedcement
paste(>0.5),althoughinearlyhydration,theycanrangeuptoafewmicrometersinsize.
Whileimagesofbothinitialandhydratedcementmicrostructurescanbeexperimentallyobtainedintwo
dimensions,acquiringquantitativethreedimensionalinformationismuchmoredifficult.Itisforthis
reasonthatcomputermodelsofthe3Dmicrostructuraldevelopmentofcementpastehavebeen
developed.
Theactualprocessofcementhydration,forthepurposesofmodellingthedevelopmentof
microstructure,canbebrokendownintothreeparts:1)materialdissolvesfromtheoriginalcement
particlesurfaces,2)diffuseswithintheavailableporespace,and3)ultimatelyreactswithwaterandother
dissolvedorsolidspeciestoformhydrationproducts.Therefore,inordertosimulatethemicrostructure
developmentofhydratingcement,thephysicalprocessesofdissolution,diffusion,andreactionmustbe
simulated.Eachoftheseprocessesmaybeconvenientlysimulatedusingcellularautomatontyperulesas
hasbeenpreviouslydescribed[12,13].Figure3showsfourstepsofsimulatedhydrationforaC3S
cementpastein2D.TheoriginalparticleshapesaretakenfromabackscatteredSEMimage.Theimages
havebeencolorizedaccordingtothemajorphasesofportlandcement[12].


Figure3:ShowingfourstagesofhydrationinamicrostructuralmodelofC3Shydration.Thedegreesof
hydrationare:topleft0,topright20%,bottomleft50%,bottomright87%.Red=unreactedcement,
blue=CH,yellow=CSH,andblack=porosity.
Thisbriefdescriptionofthechemicalhydrationprocess,whichisthebasisofthemicrostructural
formationofcementpaste,ofcourseglossesoveranumberofchemicaldetails,manyofwhicharenot
clearlyunderstood[12].However,thissimpledescriptionissufficienttobeabletogoonandinvestigate
thevariousimportantpercolationthresholdsthatoccurincementpaste.

Solidspercolation:setpoint
Capillaryporespacepercolation
CSHpercolation
Cementpasteporesize
DiffusivityofCementPaste
CHpercolation:Leaching

Next:Solidspercolation:setUp:MainPrevious:BasicConcepts