SomeThoughtsonTheChemical CompositionsofFlyAsh

ICARs17thAnnualSymposium TheUniversityofTexasAtAustin
LianxiangDu,Ph.D.,PE DepartmentofCivil,Construction&EnvironmentalEngineering TheUniversityofAlabamaAtBirmingham ElizabethLukefahr,PE TexasDepartmentofTransportation

PresentationOutline
Introduction Flyashclassifications TxDOTdatabaseonflyash Variationsofchemicalcompositionofflyash Somethoughtsonflyashclassificationbased onchemicalcompositions Summary

Introduction
Flyashorigin Challengesforsustainabledevelopment andgreenconstruction Briefhistoryofuseofflyashinconcrete

http://geoserver.cee.wisc.edu/fauga/_borders/right.4.jpg

OriginofFlyAsh
Powerplants Burningoffeed coalparticles Lightresidue capturedfromthe gaseouseffluent Heavyresidue formsbottomash

http://showmethehoney.files.wordpress.com/20 08/08/coalpowerplant.jpg

Challenges/Headaches
50%ofelectricityinUSgeneratedisfromcoal (http://www.pewclimate.org/globalwarming basics/coalfacts.cfm)
1,128.0millionshorttonsin2007(DOEreport) 32millionshorttonsofflyashin2007(only44%used) Remainingflyashstored(ponded)

Challenges/headaches Flyashcontainsheavymetals Coalashspillhighlightsconcerns aboutstorageandhandling FutureCleanAirmeasuresmay furthercomplicateflyaschemistry Ourunderstandingonflyashislimited

KingstonFossilPlantinRoaneCounty,Tennessee,12/22/2008

BriefHistoryofUseofFlyAshin Concrete
Earliest proponents powercompanies Datedbackpriorto1932 RaymondE.DavisetalatUCBerkeleyshouldbe credited(1937)
15flyashes,81cements,andabout5,000specimens Importantconclusionsstillvalidtoday
Finerparticlesizethanportlandcement Longersettimewithflyashinclusion(ClassF) Flyashreplacementupto50% LimitingLOI Lowerhydrationheat Betterdurabilityagainstsodiumsulfate

ChemicalCompositionInformation
SimilartowhatIhavetodayforflyash

Davis et al 1937

FlyAshClassifications
Howtodescribeaflyash?
ASTMC618
ClassF(%):SiO2+Al2O3+Fe2O3 >70 ClassC(%):SiO2+Al2O3+Fe2O3 <70 Whatelseinformationused?

CanadianspecificationCSAA23.5
TypeF(8 1%CaO), TypeCI(>8%and20 2%) TypeCH(>20%CaO)

Categoryapproach:behavesimilarlywheninthe samecategory Isthisapproachreasonable?

TxDOTDatabaseonFlyAsh
Reliablechemicalcompositionsofatotal of5,599flyashes(85<Sumofoxide< 105) From1992to2008 Flyashesfrom50powerplantsinsideand outsideTexas ClassFflyashes:1,608&ClassC:3,991 Alkalicontentsrecordedfrom2002with 2,087flyashes

PresentationOutline
Introduction Flyashclassifications TxDOTdatabaseonflyash Variationsofchemicalcompositionofflyash Somethoughtsonflyashclassificationbased onchemicalcompositions Summary

VariationsofChemical CompositionsofFlyAshwithTime
Compositionchangesofflyashesinonesingle powerplant(ClassC)
80 70 60

SiO2+Al2O3+Fe 2O3

OxideContents(%)

50 40 30 20 10 0 0 20 40 60 80 100 120 140 160 180 200 220

CaO

SO3

TimeLapse(months)

SimpleStatistics(notallinformation)
ClassCflyash
Variable Number Mean (%) SiO2 Al2O3 Fe2O3 Total CaO 4016 4016 4016 4016 4016 33.74 18.88 5.85 58.47 26.44 Standard Coefficient of Median Minimum Maximum Deviation (%) Variation (%) (%) (%) (%) 2.84 33.49 21.89 46.16 8.42 1.52 18.93 13.23 24.11 8.05 0.94 5.91 0.70 11.55 16.07 3.90 58.48 43.07 69.66 6.67 2.13 26.59 13.96 35.08 8.06

ClassFflyash
Variable Number Mean (%) 55.28 22.09 6.34 83.70 8.76 SiO2 Al2O3 Fe2O3 Total CaO 1608 1608 1608 1608 1608 Standard Deviation (%) 5.51 3.03 3.39 5.93 4.22 Coefficient of Variation (%) 9.97 13.72 53.47 7.08 48.17 Median Minimum (%) (%) 55.05 21.79 5.25 83.20 9.03 37.95 14.34 0.51 70.13 0.39 Maximu m (%) 68.37 31.11 36.70 99.48 24.96

TernaryDiagramonCaOandOxideContents

70% oxide sum

20% CaO Type CH <-> Class C; Type F + Type CI <-> Class F

VariationsofCaOofFlyAsheswithTime

Class F fly ashes

Class C fly ashes

CumulativePercentofOxideContents

CorrelationsamongOxides

LinearModelsonOxideContents
Centralquestion
Howmanyoxideparametersareadequateto describetheflyash?
OtherthanClassCandClassF

Mineralsandglasscontentsnotconsidered

SASprocGLM(generallinearmodel)was usedtobuildlinearmodels

SelectedModels
SiO2=68.95930.1829*Al2O31.0955*CaO 1.2285*SO3,R2=0.9295 Fe2O3=43.99080.4625*SiO20.5322*CaO 0.4925*Al2O3+2.8485*K2O,R2=0.6883 CaO=40.80010.5724*SiO20.4964*Fe2O3+ 1.4133*MgO,R2=0.9607 Na2Onofittingmodelfound K2O=1.4304+0.03520*SiO2+0.08825*Fe2O3 ,R2=0.7381

DisappointingResult
OnlyCaOor SiO2 canbe reliably predictedby otheroxides Weneedat leastseven oxidecontents todescribe thechemical composition

PresentationOutline
Introduction Flyashclassifications TxDOTdatabaseonflyash Variationsofchemicalcompositionofflyash Somethoughtsonflyashclassificationbased onchemicalcompositions

ElementOriginsinFlyAsh
About2.8%elementmattersinfeedcoal endedinflyash(basedondatalistedabove) Mostinorganicmattersendedinflyashand bottomash Willthepossibletracingofelementsourcesin flyashhelpfulforourunderstanding?
Usingcorrelationmodels

SomePreliminaryObservations
Na2Onofittingmodel found
Possiblynotmuch contributionfrom mineralswithregular compositions Indicatethemajorsource isclayminerals

(Na+)

http://serc.carleton.edu/images/NAGTWork shops/mineralogy/montmorillonite_structur e.jpg

PotassiumOxideModel
K2O=1.4304+0.03520*SiO2+0.08825*Fe2O3 R2=0.7381 SiO2 termindicatesKelementfromclay minerals FetermindicatesthereplaceofSiinclay minerals AsurpriseofthelackofAl2O3 term
Kfeldspar(KAlSi3O8)ispossiblynotamajor sourceofKelement

IronOxideModel
Fe2O3=43.99080.4625*SiO20.5322*CaO 0.4925*Al2O3+2.8485*K2O,R2=0.6883
Ifpyrite(FeS2)andgypsum(CaSO4)areconsidered asthemainsulfursourcesinfeedcoals,the elementmatterfrompyritemustbelumpedin bottomashinsteadofflyash. Orpyriteisnotamainsourceforsulfateinflyash.

K2OvsSiO2/Al2O3 Ratios

Na2OvsSiO2/Al2O3 Ratios

Summary
ClassFflyasheshavelargervariationsthanClassC flyashes.SupportafinersystemthanASTMC618 Atleastsevenoxidecontentsneededtofully describeflyash DifferencesofClassCandClassFflyashesaremainly inCaOandSiO2 contents Al2O3 andFe2O3 contentsareverymuchsimilar Carefulaboutempiricalcorrelationsbecauseofthe varietyofdata

FurtherResearch
Abetterwaytoevaluate/rank/describlefly ashforuseinconcrete?

Questions? Thankyou!
LianxiangDu 2059348436 ldu@uab.edu