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MScthesis

SelfhealingofEngineeredCementitious
Composites(ECC)inConcreteRepairSystem

XiaHua

July2010

Graduationcommittee

Prof.dr.ir.K.vanBreugel
(CMD/Microlab)
Dr.GuangYe
(CMD/Microlab)
Dr.ir.P.C.J.Hoogenboom
(StructuralMechanics)
Ir.L.J.M.Houben
(Coordinator)

TomyparentsandXi

TABLEOFCONTENTS

ACKNOWLEDGEMENTS i

ABSTRACT ii

1 INTRODUCTION 1

1.1 Problem definition 1


1.2 Objective of the research 2
1.3 Outline of the thesis 2

2 LITERATURESTUDY 3

2.1 ReviewoftheEngineeredCementitiousComposites(ECC)material 3
2.1.1 Characteristics of ECC 3
2.1.2 Additives in ECC 5

2.2 Selfhealing in concrete materials 6


2.2.1 Introduction 6
2.2.2 Mechanisms of selfhealing 6
2.2.3 Conditionsforselfhealing 7
2.2.4 Selfhealing approaches 8

2.3 Short summary 10

3 METHODOLOGY 11

3.1 Starting point 11


3.2 Approach 11
3.3 Challenge 12

4 EXPERIMENTAL STUDY 13

4.1 Sealingmaterialandmanufacture 13
4.1.1 Introduction 13
4.1.2 Investigation of sealing materials 13

4.2 Functional performance of ECC 17


4.2.1 Introduction 17

4.2.2 Materials and mix proportion 17


4.2.3 Specimen preparation 18
4.2.4 Threepointbendingtest 19
4.2.5 Nanocomputer tomography (nanoCT) 20
4.2.6 Environmental scanning electron microscopy (ESEM) 22
4.2.7 Light microscope 23

4.3 Short summary 23

5 RESULTSANDDISCUSSION 24

5.1 RecoveredmechanicalpropertiesinECC 24
5.1.1 Loaddisplacement relation 24
5.1.2 Generalresultsofstressdeflectioncurves 25
5.1.3 Deflectionhardeningbehaviorinfluencedbythecapsules 26
5.1.4 Deflectioncapacityandrecovery 27
5.1.5 Flexural strength and recovery 28
5.1.6 Flexuralstiffnessandrecovery 30

5.2 NanoCT observation 32


5.2.1 IdentificationofmicrocracksinnanoCTimage 32
5.2.2 Openingofcapsules 34

5.3 LightmicroscopeandESEMobservations 35
5.3.1 Multiple cracking behavior 35
5.3.2 Observationofinterfacezone 36
5.3.3 Observationofcrackinside 36
5.3.4 Observationofcracksurface 37

5.4 DiscussionofpotentialofselfhealinginECC 39
5.4.1 Influencing factors 39
5.4.2 Healingefficiency 40
5.4.3 Shortsummary 41

6 CONCLUSIONS AND RECOMMANDATIONS 42

6.1 General conclusions 42


6.2 Recommendations 43

REFERENCES 44

APPENDIX 46

ACKNOWLEDGEMENTS

This research has been carried out at the Microlab of the Faculty of Civil Engineering and
Geosciences, Delft University of Technology, and continued for 8 months from December 2009
untilJuly2010. Iwishtotakethisopportunitytoexpressmygratitudetoallthosewhohelpedme
inthisresearchandsuccessfulcompletionofthisthesis,especiallythefollowingpeople:

Firstofall,IwouldliketoexpressmysincerethankstoDr.G.Yeforintroducingmetothisproject,
for his daily supervisions, discussions and constant encouragements throughout the research. I
amalsoverygratefulforhisefforttomakethisprojectgoonsmoothly.

Second,IreallyappreciateProf.K.vanBreugelandDr.P.C.J.Hoogenboomforprovidingmethe
generalsupervisions,fortheirvaluablecommentsontheresearch.

Third,IwouldliketothankPhDstudentH.Huangforhisstimulationandcollaborationonsealing
materialinvestigationandmanufacture.Duringthestudy,PhDstudentJ.Zhoualsoprovidedme
someinterestingideasandguidedmetoperformsomeexperiments.

In addition, I also thank Mr. A. Thijssen from Microlab for his assistance on the nanoCT scan
investigation and the coordinator of Structural Engineering Ir. L. J. M. Houben for his
administrationofthegraduationaspect.

Lastbutnotleast,IappreciatemyparentsandfriendsfortheirsupportandloveineverystepI
havetakenduringthetwoyearsofstudyingabroad.

XiaHua
Delft,July2010

ABSTRACT

Since the concept of high performance concrete was raised in the late 1980s, it is well known
that concrete properties have been greatly improved. However, a larger number of existing
concrete structures are suffering deterioration resulting from external or internal causes even
duringtheearlystageofservicelife.Durablerepairofconcretehasthusdrawnmoreattention.
To this end, the main objective of this research is to develop and test a novel method for
promotingtheselfhealingbehaviorinconcreterepairsystem.

A new type high performance fiber reinforced cementitious composites called Engineered
Cementitious Composites (ECC) has been developed in recent years, characterized by high
ductilityandimproveddurabilityduetothemultiplemicrocrackingbehavior.Inthisstudy,itwas
proposed that the original ECC with local waste materials was embedded with capsules to
investigate the selfhealing potential of this modified ECC material. To realize this selfhealing
concept, Super Absorbent Polymers (SAP) can be used as the water reservoir enclosed in the
capsules, and then provide available water for selfhealing process when the capsules are
ruptured by cracking. Based on this idea, the preliminary experiments, concerning sealing
materials and encapsulation procedure, were first carried out. Three ECC mixtures focusing on
the influence of capsule content and capsule size were involved. In order to induce artificial
cracks, threepoint bending tests have been used to preloaded ECC specimens to different
deflection levels. After healing for 28 days, the specimens have been tested again in the
threepointsetup.

TheexperimentalresultsrevealthattherecovereddeflectioncapacityofdamagedmodifiedECC
specimenscanarriveat65%95%ofcontrolspecimens,whichishigherthanthatofspecimens
withoutcapsule.Whiletherecoveryofflexuralstrengthandstiffnessrarelyshowimprovement.
Compared to the case of coarse capsules, the specimens with fine capsules show more
reasonableperformanceonmechanicalpropertiesincludingthedeflectioncapacity,theflexural
strength and stiffness as well as their recoveries. The nanoCT investigation confirmed that
moisture transportation took place in more than half of capsules. Under EDX observation, the
relativelyhighconcentrationofcalciumonthecracksurfacecouldbeconsideredthatthehealing
product was probably presented in terms of hydration product such as calcium hydroxide or
calciumsilicatehydrate.HowevernoapparenthealedcrackwasfoundunderESEMinvestigation,
thusitcouldbeinferredthatthehealingefficiencywasnotremarkableinthisstudy.Forfurther
research, it is suggested to investigate the contribution of the optimal capsule size and the
sufficientwatersupplementtomoreeffectiveselfhealingbehavior.

ii

1INTRODUCTION
1.1 Problemdefinition

Concrete is a strong, versatile and economical material that has been widely utilized for
constructionsovertheworld.Sincetheconceptofhighperformanceconcretewasraisedinthe
late1980s,concretepropertieshavebeengreatlyimproved.However,alargenumberofexisting
concrete structures, such as bridge decks and pavements are suffering deterioration resulting
from external and internal causes even during the early stage of service life. In the civil
engineeringsectoroftheNetherlands,prematurefailureofstructuresleadstoasituationwhere
about half the budget is spent annually on maintenance and repair. For concrete structures in
particular,90%oftherepairworksfocusonrepairofcrackscausedbyreinforcementcorrosion
[1]. Due to the brittleness of concrete, cracking is unavoidable in concrete structures. Cracking
can introduce chlorides, sulphates, oxygen, alkali or moisture into the concrete and accelerate
further deterioration of the whole system. To address this problem, the durability of concrete
repairshasdrawnmoreattention.Eventhoughthequalityofconcreterepairshasincreasedalot
inrecentyears,realizingdurablerepairsisstilldifficult.

Asstatedabove,peoplehavetriedtomakebetterandstrongermaterials,whicharecapableof
repairingcracksandrestoringtheirfunctionality.Thesematerialscanbedefined asselfhealing
materials.Thestartingpointforthisstudyisanewlydevelopedclassofhighperformancefiber
reinforced cementitious composites with called Engineered Cementitious Composites (ECC),
characterizedbyhighductility,improveddurabilityduetomultiplemicrocrackingbehaviorand
lowerfibercontent[2].Finefibersguaranteeatightcrackwidthandsignificantincreaseinstrain
capacity.ThisabilityofECCtoachievetightcrackwidthcancontributetoengageselfhealingina
varietyof environmental conditions. Therefore, ECC as a means of healing invisiblemicrocracks
canprolongtheservicelifeofstructuresmeanwhilereducethemaintenancecost.SinceECChas
severalspecialproperties,theuseofECCforconcreterepairswasproposedinthelastdecade.In
acurrentlyrunningprojectatMicrolabinTUDelft,anumberofexperimentsbasedonthebasic
ECC with local available materials have been studied. The preliminary results indicated that a
widerangeofrawmaterialscouldbeusedasthebasisfortheECClikerepairmaterials[3].

Itiswellknownthatfinecracksunderfavorablemoistureconditionshasapotentialtohealitself,
sinceselfhealingphenomenonwasfirstdirectlyobservedincrackedwaterpipesin1937[4].A
common agreement is that continued hydration of cement particles within the cracks is one of
themainreasonsfortheselfhealing.Infact,alargeamountofunhydratedcementisavailablein
most concrete and especially in those concrete with low water/cement ratio. If cracks occur in
the matrix and water flow through cracked concrete, then unhydrated cement reacts with it,
resultinginnewhydrationproducts.Thisformationandgrowthofnewhydrationproductswillfill
in the cracks. Thus, additional water supply at the locations where cracks are formed is highly
significantforsuccessfulcompletionofselfhealing.Theselfhealingcanenhancethelongterm
performanceofconcreterepairs.Forthesereasons,thisprojectstudiestheselfhealingpotential
andmechanicalpropertiesofECCmaterialbyanovelmethod.
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1.2 Objectiveoftheresearch

SincetheECCmaterialhasselfhealingpotential,themainobjectiveofthisresearchistodevelop
andtestanovelmethodforpromotingselfhealingbehaviorinECCmaterials.Theencapsulation
approach is considered as novel method of this study. More specifically, it is investigated that
whencracksruptureembeddedcapsulesinsidetheECCmixture,whetherthisactioncanrelease
healing agent (water) for further hydration of cement, without replying on external supply of
water. This study will be conducted as a preliminary study to get more insight into a
cementbasedselfhealingcoatingofoldconcreteinconcreterepairsystem.

1.3 Outlineofthethesis

Thisthesisconsistsofsixchapters.Chapter1introducesthemotivation,objectiveandoverview
of this research. Chapter 2 gives a review of the literature study about the development of
cementitiousmaterialsandselfhealingbehavior.Chapter3explainsthemethodology,including
thestartingpoint,challengeandapproachoftheexperimentalresearch.Chapter4illustratesthe
experimental setups, procedures of the research program. Chapter5 presents the results from
the mechanical tests and microscopic observations followed by the discussions concerning
influencingfactorsandhealingefficiencyoftheselfhealingbehavior.Chapter6summarizesthe
generalconclusionsandrecommendationsforfurtherinvestigation.

2LITERATURESTUDY
ThischapterintendstoreviewthepreviousworksontheECCmaterialincludingitscharacteristics
and additives in ECC. Moreover, the literature study of selfhealing phenomenon in concrete
materials including the mechanisms, the conditions and the approaches of selfhealing is
introduced.

2.1ReviewoftheECCmaterial

2.1.1CharacteristicsofECC

In the last decades, concrete with increasingly high compressive strength have been applied to
civilengineeringsincemodernbuildingconstructionsrapidlygrowtowardshighriseanddiversity.
The addition of steel fiber and powders improves a number of concrete properties. However,
most of these materials still remain brittle. In some cases, the brittleness increases as the
compressivestrengthgoesup,whichposespotentialdangersorfracturefailuresoftheconcrete.
AspeciallydesignedcementitiousmaterialtermedasEngineeredCementitiousComposites(ECC)
has been developed by Li and continuously evolved over the last twenty years. ECC is
characterized by a high ductility in range of 37%, a tight crack width of around 60 m and
relativelylowfibercontentof2%orlessbyvolume[3].Intermsofmainmaterialconstituents,
ECC has characteristics similar to regular Fiber Reinforced Concrete (FRC), including water,
cement, sand, fiber and some additives. Coarse aggregates are not used because they tend to
have negative effects on ductile behavior of the composite. So far, various fiber types and
differentcementitiousmatrixeshavebeenusedinECC,butthedetailcompositionofECCmust
obey certain principles imposed by micromechanics considerations. The most fundamental
mechanical property of ECC is of the ability to carry higher levels of loading after first cracking
whileundergoinglargedeformation.ThefibersusedinECCaretailoredtoworkwiththematrix
for the purpose of constraining localized brittle fracture and guaranteeing more uniform
distributionofmicrocracks.Duetothesliphardeningbehavioroffibers,ECCcantakeincreasing
load that generates new cracks at other sites. It can be observed from Figure 2.1 that first
cracking in ECC is followed by increasing stress accompanied by a rise in strain. This
strainhardeningbehaviorofECCissimilartoductilemetals.

Figure2.1Typesoffailuremodesincementitiousmaterials[6]
3

Thecrackwidthisanotherimportantindicator,reflectingthedurabilityofaconcretestructure.
ECC exhibits a well crack width selfcontrolled in terms of a flat steady state microcracks
propagation, see Figure 2.2. After the tensile deformation up to around 1% strain, the early
microcracksstopwideningandremainmoreorlessconstantwithcrackwidthofaround60 m .
ECC material can be tailored to form numerous closely spaced microcracks. The crack width in
ECCismuchsmallerthanthetypicalcrackwidthobservedinthereinforcedconcrete.Moreover,
the selfcontrol of crack width can be seen as intrinsic properties of ECC material, rather than
dependingonsteelreinforcementratioandstructuraldimensions[7].Figure2.2alsoshowsthe
tensilestraincapacityof5%thatisabout300500timesgreatthannormalconcrete[8].

Figure2.2TypicaltensilestressstraincurveandcrackwidthdevelopmentofECC[8]

Figure2.3Theconceptualtrappingmechanismwithloaddisplacementrelation[9]

FromtheaspectofECCconcreterepairsystem,theadvantageofusingECCasrepairmaterialis
thatthetrappingmechanismofECCcanserveasameansforenhancingthedurabilityofrepair
system.ItwasreportedthatmicrocracksemanatedfromthetipsofdefectsontheECCconcrete
interface,kinkedintoandsubsequentlyweretrappedintheECCmaterial(Figure2.3).Duetothe
rapidly rising toughness of the ECC, additional load can drive further crack extension into the
interfaceafterkinkedcrackarrest,followedbysubsequentkinkandarrest[9].

2.1.2AdditivesinECC

2.1.2.1Blastfurnaceslag(BFS)andlimestonepowder(LP)
InordertodevelopanewversionofECCwithlocallyavailablematerials,anumberofmixtures
with blast furnace slag (BFS) and limestone powder (LP) instead of fly ash and silica sand
respectivelyhavebeeninvestigatedatDelftUniversityofTechnology.Portlandcement,BFSand
LP are used to produce ECC as matrix materials, which can enhance the mechanical properties
and durability of ECC [3]. There are only a small amount of LP reacting with cement clinker or
hydration products, thus the limestone powder usually behaves as an inert filler material. The
incorporation of limestone powder and Portland cement is conducive to early compressive
strength, workability and durability of concrete. When BFS is mixed with Portland cement, it
reactswiththecalciumwhichiscalledthepozzolanicreaction.Itwasreportedthattheaddition
ofBFSleadstoalowerstrengthatearlyage,howeveritdoesnothaveanysideeffectonthefinal
compressivestrength.BesidesLP,BFSisabletoimprovethedurabilityofECCandresultsinawell
homogenous fiber distribution. The experiments with different BFS, LP contents and different
waterpowder ratios were discussed [3]. The optimal results of the ECC mix proportion with
Portlandcement,BFSandLPwereusedasareferenceinthisstudy.

2.1.2.2SuperAbsorbentPolymer(SAP)
SuperAbsorbentPolymer(SAP)isalowcrosslinkedpolyelectrolytewhichstartstoswellwhenit
comesintocontactwithwater,leadingtotheformationofahydrogel(seeFigure2.4).Attheend
ofthelastcentury,SAPaddedintoconcretewasmainlyusedtocounteractautogenousshrinkage
orselfdesiccationofcementpasteandinternalcuringagentaswell.TheapplicationofSAPcan
be attributed to its ability to absorb amounts of water a few hundred times its own weight,
releasefreewaterwhentherelativehumidity(RH)oftheconcreteporesystemdecreasescaused
bythecementhydration[10].Infact,severalstudiesverifiedthattheadditionofSAPinconcrete
not only results in a reduction of autogenous shrinkage but also modifies other microstructure
propertiesofconcretesuchasporosity,connectivityofinterfacetransitionzonebetweencement
paste and SAP, workability and durability. The main reasons inducing the change of
microstructureespeciallytheporestructures,aresummarized[11],
i.
WhenSAPisfullyfilledwithwater,itactsassoftaggregate.Whenitisempty,SAPactsasair
voidintheconcrete.
ii. NonuniformityofthedispersionofSAPduringmixing.
iii. WateruptakeofSPAchangestheeffectivewatercementratiointheearlyhydrationstage
andwaterreleasefromSAPleadscementtofurtherhydrate.

Figure2.4Dry,collapsedandaswollensuspensionpolymerizedSAPparticle[10]
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2.2Selfhealinginconcretematerials

2.2.1Introduction

Selfhealingisgenerallydefinedastheabilitytorepairorhealdamageofmaterialitself[12].In
naturalmaterials,skintissueandbonestructuresareperfectexamplesofselfhealingbehavior.
Althoughthemechanismsofhealinginnaturalmaterialscannotbecopiedexactly,someformsof
healinginconcretematerialshavebeenobservedbasedonthesimilaritytheory.

2.2.2Mechanismsofselfhealing

Selfhealing behavior in cementitious materials has been demonstrated by numerous


experimental investigations and practical experiences [7,1214]. The autogenous healing
phenomenon is that the material has the ability to seal itself without external monitoring or
human intervention. Selfhealing of cracks in concrete is a combination of the complicated
chemicalandphysicalprocesses.Uptonow,severalpossiblecausescanbeillustratedasfollows
(alsoschematisedinFigure2.5):

i.
Formationofcalciumcarbonateorcalciumhydroxide.
ii. Blockingcracksbyimpuritiesinthewaterandlooseconcreteparticlesresultingfromcrack
spalling.
iii. Furtherhydrationoftheunreactedcementorcementitiousmaterials.
iv. Expansionofthehydratedcementitiousmatrixinthecrackflanks(swellingofCSH).

i)

ii)

iii)

iv)

Figure2.5Possiblemechanismsforselfhealing[14]

Among these, most studies have indicated that the primary mechanism is attributed to the
crystallization of calcium carbonate [7,13]. This view is sustained by the fact that precipitated
calcium carbonate can often be observed at the outside surfaces of the crack as some white
residue. As one of the cement hydration products dissolved in water, the calcium hydroxide is
liberatedbetweenthecracksurfaces.Thenfreecalciumionsfromcementhydrationreactwith
carbon dioxide presented at water surface, so that selfhealed crystal is formed, grows at both
surfacesofcrackandfinallyfillsthegap.Thisprocesscanbedescribedasfollowingformulas,
6

Ca(OH)2 Ca2+ + 2OH


Ca2+ + CO32 CaCO3
AccordingtoNeville[15],selfhealingwasmainlyowingtocontinuedhydrationinhisopinionat
first.Butlaterhestatedthatthisisonlyappliedtoveryyoungconcrete[16]andbelievedthatthe
formation of calcium carbonate is the most likely cause of selfhealing. Besides, loose particles
blockingthecrackpathwasalsomentionedinsomestudiesasareasonforhealingcracks.Since
thiswasconsideredtocausethefirstfastdecreaseofwaterflowthroughthecracks[17].

2.2.3Conditionsforselfhealing

Fromtheliteraturestudy,itispointedoutthatfivegeneralcriteriashouldbesatisfiedtoensure
selfhealing.Thesenecessaryconditionstoexperiencehealingofcracksare:
i.
Presenceofwater
Allthestudiessofarstatethatthepresenceofwaterisessentialtofacilitatehealingofthecracks.
Withoutwater,itisimpossibleforthecalciumhydroxidetobeleachedoutofthebulkmaterial
intocrack[13].
ii. Presenceofchemicalspecies
Adequate concentrations of certain critical chemical species for instance carbonate ions or
bicarbonateionsandfreecalciumionsdissolvedinaflowofwater,playadirectroletoexhibit
healing mechanisms. This is readily available due to the chemical makeup of cementitious
materialsandincompletehydration[12,15].
iii. Crackwidth
Anotherimportantconditionisthecontrolledcrackwidth,whichisassociatedwiththeefficiency
of selfhealing in cementitious materials. The crack width to engage noticeable selfhealing
behaviorfallsbelow150 m andpreferablylowerthan50 m [7].Thesmallermicrocrackwidth
requireslessselfhealingproductstofillthecrackandeasiertogrowfrombothsurfacesofthe
cracktogetconnected.
iv. Waterpressure
Ifthewaterflowsgofastthroughthecrack,selfhealingwillnottakeplace.Thereforethewater
pressure should be not too large and this condition is influenced by the ratio between water
heightandthethicknessofthestructureforacertaincrackwidth[14].
v. Stablecrack
Toguaranteethatacrackisnotdamagedagain,thecrackshouldbeunderstableconditionand
thecrackwidthhastobeconstantinsteadofvariationwithtime.

2.2.4Selfhealingapproaches

With the developments of smart materials, several innovative approaches of selfhealing have
beenpromotedinrecentyears.Thecoreoftheseapproachesiscapableofcontinuouslyoffering
materials or energy. For another, an ideal healing agent is supposed to continuously sense and
respondtodamage,andrecoverthematerialperformancewithoutadverseaffectingthematrix
materialproperties[18].Severalapproachesbasedonthisprinciplecanbediscussedbelow.

2.2.4.1Encapsulation
Themicrocapsulescanbedefinedasparticles,sphericalorirregular,inthesizerangeofabout
50 nm to 2000 m or larger, and composed of an excipient polymer matrix (shell or wall) and
incipient active polymer (core substance) [19]. The microencapsulated approach of
incorporation of healing agent was demonstrated by White [12], and Figure 2.6 illustrates this
autonomic healing concept. When the crack ruptures embedded microcapsules, the healing
agentisreleasedintothecrackplanethroughcapillaryaction.Thenthehealingagentcontacts
theembeddedcatalyst,triggeringpolymerizationthatbondsthecrackfacesclosed.However,a
successfulcompletionofthehealingprocessisnoteasilyrealizedsinceitcombinesacomplexset
ofrequirementsonstorage,rupture,release,transportandhealing.Furthermore,somestudies
indicated that specific problems in terms of the size of microcapsules and surface morphology
significantlyinfluencedthehealingefficiency[12].

i)

ii)

iii)

Figure2.6Basicmethodofthemicrocapsuleapproach:i)cracksforminthematrix;ii)thecrack
rupturesthemicrocapsules,releasingthehealingagentintothecrackplanethroughcapillary
action;iii)thehealingagentcontactsthecatalyst,triggeringpolymerizationthatbondsthecrack
facesclosed[12].

2.2.4.2Hollowglassfibers
Theuseofhollowglassfibers(Figure2.7(A))follows thesimilarconceptasthemicrocapsules.
Glass is a typical brittle material, once the glass fibers break, the healing agents flow into the
matrixcracksandhealthemsothatthemechanicalpropertiesofconcretecanberegainedtoa
certainextent.Thekeyadvantageofhollowfibersapproachisthatthefiberscanbeplacedatany
location depending on the operational requirement to deal with specific failure threats (Figure
2.7(B)).Inordertoquicklyandeasilyseetheinternaldamageincompositematerials,adamage
visualenhancementmethodwasdesignedbyPangandBond[12].Intheirwork,thefibersfilled
withhealing agent were mixed with fluorescent dye to monitor the healing process (Figure 2.7
(C)).

(A) (B)

(C)

Figure2.7(A)Hollowglassfibers;(B)hollowglassfibersembeddedincarbonfiberreinforced
compositeslaminate;(C)damagevisualenhancementincompositelaminatebythebleeding
actionofafluorescentdyefromhollowglassfibers[12]

Li [20] utilized hollow glass fibers embedded in ECC material to investigate the feasibility of
passive smart selfhealing via experimental tests. The sensing and actuation mechanisms were
validatedbyobservationofESEMandtheeffectofrecoverywasvalidatedbyregainingofflexural
stiffness.Healsoconcludedthatthestudyofthebiomimeticselfhealingtechniquepresentlywas
stillintheexperimentalstage,andplentyofissuesremainsuchashowtoeffectivelyfillandplace
thehollowglassfibersinlargescaleapplications.

2.2.4.3Bacteria
On the otherhand, it is found that bacteria incorporated in the concrete matrix as selfhealing
agent probably catalyzes the autonomous repair of cracks [21]. Basically, bacteria of the genus
bacillus were used for the biological production of calcium carbonatebased minerals. Such
bacteria added in the cement matrix prior to casting should keep viable for prolonged periods.
Onceintegratedintheconcretematrix,itshouldbeabletoproduceamountsofmineralsneeded
toplugorsealfreshlyformedcracks.Inthissense,integratedbacteriawouldthusrepresentan
internal selfhealing agent which autonomously decreases matrix permeability upon cracks
formation.Thescenarioisschematicallyshowninthefollowingfigure.

Figure2.8Scenarioofcrackhealingbyconcreteimmobilizedbacteria.Bacteriaonfreshcrack
surfacebecomeactivatedduetowateringression,starttomultiplyandprecipitatemineralssuch
ascalcite,whicheventuallysealthecrackandprotectthesteelreinforcementfromfurther
externalchemicalattack[12].

2.3Shortsummary

From the above literature study, it is known that the ECC material itself has healing potential
primarilyforthefinecracks.Ontheotherhand,theselfhealingprocesscanbeonlyrealizedin
thepresenceofwater,thusitisproposedtouseSAPbasedonitshighcapacityofabsorptionasa
watercarrierinthemixturetorealizetheselfhealingofECC.Thedetailedmethodologywillbe
introducedinthenextchapter.

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3METHODOLOGY
3.1Startingpoint

Theideaofthisresearchcomesfromanembeddedcapsulesapproachtorepairmaterialitself.
Two starting points were proposed in this study to realize the selfhealing process in concrete
repairsystem.Asmentionedintheintroduction,thefirststartingpointistouseECCmaterialin
studyingthehealingpotential.BecauseECCexhibitsthehighstraincapacityandtightcrackwidth
control,thoseuniquepropertiescanpromotetheoccurrenceofselfhealing.Thesecondstarting
point is related to the saturated SAP, here SAP is considered as a water carrier enclosed in
capsulessinceitisabletoabsorbalargeamountofwater,andthewaterreleasedfromSAPhas
thefunctionofpromotingthefurtherhydrationofthecement.

3.2Approach

Thecorequestionofthisthesiscanbesimplystatedaswhetherwatercanbereleasedfromthe
embedded capsules thereby promoting selfhealing in ECC material. The first task is to find a
proper way to seal the saturated SAP. To realize healed cracks in laboratory conditions, the
capsulesarerupturedbyinducingartificialcracksforreleasingwater.Finally,mechanicaltestand
microscopicobservationwillbecarriedouttoassessthequalityofselfhealing.Theoverviewof
thisapproachcanbeillustratedinthefollowingFigure3.1.

Figure3.1Basicapproachoftheselfhealingconcept

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3.3Challenge

Fromtheapproachpresentedintheprevioussection,therearethreemainchallengesinvolving
sealing material and manufacture, cracking pattern during preloading and selfhealing
observation,whichwillbediscussedasbelow,
iv.

Sealingmaterialandmanufacture
Thesuitablesealingmaterialshouldtrytomeetasetofrequirementonphysical,chemical
features and mechanical properties at the same time. For instance, it is expected to has a
stablecapacityofwaterstorage,andbesensitivetocrackswhilstitisaskedforagoodbond
strengthbetweenthesealingmaterialandthematrix.Ontheotherhand,themanufacture
of capsules could be difficult without rolling machine. Since dry SAP powders used in this
experimenthasasmallparticlesizeof300 m indiameter,afterswellingitbecomessofter,
suchthatitisdifficulttobegatheredtoformaball.

v.

Crackingpatternduringpreloading
The second challenge is to determine the crack propagation through the capsules. In this
research,thecapsuleconsistsofsaturatedSAPparticlesasthecoreandsealingshellasthe
outersurface.WhenthecapsulesareincorporatedintoECC,thebondstrengthatinterfacial
transition zone (ITZ) between the sealing shell and the cementbased matrix needs to be
strongerthanthestrengthofcapsuleitself,toensuretheartificialcrackspropagatethrough
thecapsulesinsteadofpassingaroundthecapsules.ThiscanbeillustratedinFigure3.2.

Cementbasedmatrix

Sealingshell

ITZ

SaturatedSAP

Figure3.2IdealpatternofthecrackpassingthroughSAP

vi.

Selfhealingobservation
Sincethemechanicaltestuntilfinalfailurewilldamagethespecimen,howtomonitorthe
internal crack pattern in the case of ensuring the integrity of specimen, that is another
problemforthisstudytoassessthequalityofselfhealinginECCmaterial.

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4EXPERIMENTALSTUDY
4.1Sealingmaterialandmanufacture

4.1.1Introduction

Since further hydration can only be realized in the presence of water or solution, SAP particles
canbeintroducedasawaterreservoirincementitiouscomposites.Inordertocausethecapsules
toreleasetheentrainedwaterattherighttime,theoutersurfaceofsaturatedSAPneedstobe
sealed by a protected layer. In this research, the ideal sealing material can be defined as that
which meets the following three requirements. The first is to appear impervious to leakage of
water before inducing the microcracks. Second, this material should be sensitive to cracking,
allowing the broken of capsules occurs at a certain level before arriving at ultimate strength of
ECCmaterial.Lastrequirementistheproperinterfacialbondstrength.Thisstrengthofinterface
betweenthecapsuleandthematrixrequiresbeingstrongerthanthestrengthofthecapsule,to
guarantee that cracks can propagate through the capsules rather than around them. Thus high
bond strength at the interface is one of the important factors contributed to cracks passing
throughthecapsules.

Besides the intrinsic properties of sealing material, the diameter of capsule and the surface
morphology also highly influence capsule cracking behavior. Normally the use of capsules
embedded in composite materials has a negative effect on the mechanical properties such as
strengthandductility,especiallywhenthediameterisrelativelylargercomparedtothespecimen
size,thisdisadvantageshouldthereforebeminimizedinthisresearch.

4.1.2Investigationofsealingmaterials

4.1.2.1Selectionofsealingmaterials
Inthisexperiment,twosealingmaterialswereprepared:paraffinwaxandepoxycementmaterial.
Thereasonfortakingadvantageofwaxisthatthewaxgenerallyhasanexcellentwaterresistant
property, stable chemical characteristics. But it is a brittle material that cannot be mixed via a
mixer.Moreoverthebondcapacityofwaxcouldberelativelyweakerduetothesmoothsurface.
Inthisresearch,keepwateravailableforselfhealingbehavioristhecrucialrequirement.Another
alternative is to use the epoxycement material, since the watersoluble epoxy blended with a
number of cement can maintain better compatibility with the surrounding matrix. The
compositionofthisepoxycementispresentedinAppendixA.

4.1.2.2Encapsulationprocedure
Asabovementioned,thesizeofcapsuleisnotallowedtobelarge.Herethecapsulesusedinthis
experiment were made into two groups with an average diameter of 8mm and 5mm, called
coarse capsule and fine capsule respectively. The complete procedure of sealing saturated
SAPparticles isshownin Figure4.1.Inthefirststep,everysinglesaturatedSAPparticlewitha
13

smallsizecouldbemoreeasilygatheredandshapedintoaballwhenCEMI52.5Nwasutilizedto
formasurfacecover.Tofinishthisprocess,thesaturatedSAPparticlesweresievedby2.4mmsize
ofsieve,toseparatethemfromtheexcesscement.Itisimportanttocontroltherateofshaking.
Iftheamountofcementisless,thethinsurfacecoverwouldnotform.However,excesscement
will absorb more water from saturated SAP particles. To maximize the contained water inside
capsules,onemethodofavoidingwaterlosswastocuretheseballsinwateratatemperatureof
20 C for 7 days, in order to achieve the hydration of cement and keep the SAP particles fully
absorbingwater.Afterwards,theoutsurfaceofballwassealedbyashellofwaxorepoxycement,
respectively.Forthefirstcase,paraffinwaxwasheatedupto105 C andthenkeptaballinto
thishotsolutionfor2seconds.Finally,waxmicrospherewasobtainedfromrapidcoolingofthe
suspensionofmoltenwaxdropletsanditwascuredunderroomcondition.Forthesecondcase,
5wt%epoxyand100wt%cementwasmixedbyhandandthenrolledaballintheepoxycement
pasteuntilsmooth.Afterthis,theballwascuredinRH100%at20 C for7days.Insuchaway,
saturatedSAPparticlesweremadeintotwotypesofcapsules(Figure4.2).

Figure4.1Flowchartoftheencapsulation
14

(A)SaturatedSAPparticles (B)Shapedbycementcover

(C)Sealedbyparaffinwax (D)Sealedbyepoxycementpaste

Figure4.2Manufactureofthecapsules

4.1.2.3Evaluationofsealingeffect
Toinvestigatethesealingeffectoftwodifferentmaterials,10groupsofcapsulesforeachsealing
material were cured under room condition (RH 70% at 23 C ) and the mass losses of these
capsules due to the evaporation were measured. The weight of capsules was recorded within
threeconsecutivedaysafterencapsulationprocedure.

Figure 4.3 demonstrates the results of water loss in the capsules against time for two sealing
materials respectively. As seen in Figure 5.1 (A), the curves of remaining water seem to
approachahorizontal.Thelowestpointstillkeepswaterinsideabove99%byweightafter3days
curinginair,whichmeansalmostnowaterlossfromthecapsules.Whileitcanbeobservedin
Figure 5.1(B) that, when the capsules sealed with epoxycement paste, the mass of remaining
water decreases rapidly within the first 24 hours and finally the average weight percentage is
approximately below 85%. Compared with sealed with paraffin wax, there is a relatively large
water loss in the capsules when using epoxycement paste. Thus paraffin wax was preferred as
thesealingmaterialinthelaterexperiment.

15

105

Remainingwater(%)

104
103
102
101
100
99
98
97
96
95
0

20

40

60

80

Time(h)

(A)Capsulessealedbyparaffinwax,curingat23 C RH70%
105

Remainingwater(%)

100
95
90
85
80
75
0

20

40

60

80

Time(h)

(B)Capsulessealedbyepoxycementpaste,curingat23 C RH70%
Figure4.3Comparisonofmasslossofcapsulessealeddifferentsealingmaterials

16

4.2FunctionalperformanceofECC

4.2.1Introduction

Thischapterfocusedonproposingtheexperimentalprogramandsetupsusedinthisresearch.
To study the functional performance of healed ECC, the overview of the experimental program
can be designed as following steps. After preparation of ECC specimens embedded with the
capsules, the principal task is to introduce cracks to these specimens. For this end, the ECC
specimens are under threepoint bend to form cracks inside. After healing for 28 days, the
specimens will be tested again in threepoint bending. Meanwhile, the reference without
capsules is parallel tested for comparison. The crack pattern and the healing products can be
observed by NanoCT, environment scanning electron microscopy (ESEM) and light microscope
techniquestoverifywhethertheselfhealingphenomenontakesplace.

4.2.2Materialsandmixproportion

As mentioned above, various modified ECC incorporating local waste materials have been
developedtooptimizeECCmixproportionandinvestigatetheselfhealingproperties.BFSasthe
maincementreplacementmaterialintheNetherlandsshowsapotentialofpozzolanicreaction
but these reactions need to be activated by the hydration products of Portland cement. In mix
design, the Portland cement and BFS were used as cementitious materials, and the limestone
powderwasconsideredasinertfillermaterial.Inthisthesis,onemixtureofECCwaschosenasa
referenceandothertwomixturesofECCmixedwithblendingadditionalcapsulescomparedwith
thereference.AsshowninTable4.1,threemixtureswerepreparedinallforcomparisonpurpose,
includingM1M3.M1withoutcapsuleswasatrialmixtureasthereference,M2andM3contains
the same capsule content of 2% of cement weight, but with capsule size of 8mm in diameter
(coarse capsule) and 5mm in diameter (fine capsule) respectively. The water to binder ratio,
water to powder ratio and superplasticizer content were therefore constants to reach similar
workabilityforeachmixture.Thedetailsforthematerialpropertiesandthecompositionofeach
mixture are presented in Appendix B. In all mixtures, the polyvinyl alcohol (PVA) fiber with a
lengthof 8mmanda diameterof 40 m was used withthe contents of 2% by total volume. In
order to control the amount of water inside capsules and prepare the specimen better, the
weightofsaturatedSAP(showninAppendixB)wasconvertedintothenumberofcapsules,see
AppendixC.

17


Table4.1MixproportionofECC(byweight)
Mix

CEMI Limestone

BFS

Number

42.5N

Powder

M1b

1.2

M2c

1.2

M3d

1.2

Water Water/powdera

Saturated

SAP
0
0.02
(0.46%byvolume)
0.02
(0.23%byvolume)

Super

PVAfiber

ratio

plasticizer

(byvolume)

1.092

0.26

0.030

2%

1.092

0.26

0.030

2%

1.092

0.26

0.030

2%

Remark: aPowderincludescement,BFSandlimestonepowder
bMixturewithoutcapsules(reference)
c

Mixturewithcapsulesizeof8mm(coarsecapsule)

Mixturewithcapsulesizeof5mm(finecapsule)

4.2.3Specimenpreparation

The ECC specimen preparation followed the procedure described in [3]. In the first place, the
solid materials, CEM I 42.5, BFS and limestone powder were mixed with a HOBART mixer for 2
minutes at low speed. Then water and superplasticizer were added at low speed mixing for 1
minute,followed by high speed for 2 minutes. At last, the PVA fiberswere added at low speed
andthesamplewasmixedathighspeedforanother2minutes.InthecaseofECCspecimenwith
capsulesinside,thecapsulesweremainlyarrangedinthecenterregionofthespecimenwithin
the stacking sequence to increase the opening probability of capsules. The distribution of the
capsulesembeddedinECCspecimencanbeillustratedinFigure4.4.Becausethecapsuleswere
notstrongenoughtoresistthemixingprocess,theywereaddedintothespecimenlayerbylayer
byhandinthefinalstep.After1daycuringinmouldscoveredwithplasticsheet,thespecimens
werecuredundersealedconditionatatemperatureof20 C foranother27or55daysbefore
testing. The specimens with the dimension of 160mm 40mm 40mm were carefully ground
withP120sandpapersbeforethemechanicaltest.

Capsule
Specimen
Profile

Top

Front

Figure4.4Distributionofcapsulesembeddedinthespecimen
18

4.2.4Threepointbendingtest

Inthisresearch,thethreepointbendingtestwasthemainmethodtoinduceartificialcracksand
alsocharacterizethemechanicalpropertiesofthemodifiedECCmaterial.
4.2.4.1Experimentalsetup
AsseeninFigure4.5,thesupportspanofthreepointbendingtestsetupis110mmandtheload
islocatedinthemiddleofthespecimen.Theconfigurationofthreepointbendingtestsetupis
explained more in Appendix D. Two linear variable differential transducers (LVDTs) are fixed on
bothsidesofthesetuptomeasuretheverticaldeformationatmidcrosssectionofthespecimen.
The test was conducted under deformation control at a constant speed of 0.01 mm/s. At least
two measures were done for each mixture, and the flexural strength and deflection were
calculatedbasedontheaverageresultsofthesemeasures.

Figure4.5Threepointbendingtestsetup

4.2.4.2Experimentalprogram
AsshowninFigure4.6,theoverallprogramforthreepointbendingtestincludesthreedifferent
schemes for each mixture, resulting in nine combinations in total. In order to roughly estimate
howmuchdeflectionispreloadedto,thesamplesfromschemeAwasbendeduntilfinalfailure
at first to derive the flexural stressdeflection relation. Based on the results from scheme A
(reference), the preloaded levels of schemes B and C were then determined. The deflection of
1.0mmwasselectedsinceitisapproximatelyequaltohalftheultimatestrength.Meanwhilethe
deflectionof1.3mmiswellbelowultimatedeflectionofthemixture.ForschemesBandC,the
samples were cured in sealed condition at 20 C for 28 days and preloaded to the specified
deflectionlevels,afterwards,thepreloadedsampleswerefurthercuredundersealedcondition
foranother28daysbeforetesting.

19

Remark: X stands for M1, M2, and M3 respectively. Therefore, 3 mixtures and 3 schemes for each
mixture,resultingin9combinationsintotal.
Figure4.6BendingtestprogramofECCmaterial

4.2.5Nanocomputertomography(nanoCT)

4.2.5.1Experimentalsetup
ThenanoCTinstrumentisbasedonthesamegeneralprincipleasothermicroCTsystems,while
the improvement of nanoCT is that it provides the focal spot size in the submicron range and
capable of resolving image features as small as 200nm, thereby achieving stable and ultra
highresolutionimages.TheprincipleofnanoCTsystemisdepictedinFigure4.7.Itcanbeseen
thatthesampleisplacedontheobjectstagebetweenXraysourceandarraydetector.Whenthe
sample is rotated within the xray cone beam, the CT scanner firstly acquires the complete
geometryofthecomponentbygeneratingaseriesofxrayimages.TheresultingXrayabsorption
image including information about sample features for instance the position and the density is
projectedontothedigitaldetector,whichwillbeavailableforthenumerical3Dreconstructionof
thevolumedata.Thisoutputisa2DXrayimage,wheredifferencesingrayscalesreflectchanges
in density of the sample. Darker regions correspond to a material of lowdensity such as pores
whilstlighterregionscorrespondamaterialofhighdensitysuchascement.Afull3Ddatasetis
createdbycollecting2Dimagesthougha360degreesrotation,thenthesevolumetricdataare
reconstructedtovisualizeavirtual3Dvolume.

The NANOTOM is a very compact laboratory system, which is particularly suit for the 3D
inspectionofsmallandcomplexsamplessuchasmineralsamplesandcompositematerials,etc.
Thesamplesizeisallowedto120mmindiameter,150mminheightand1kginweight.Basedon
3D analysis with submicrometer resolution, any internal difference in material, density and
porositycanbemeasured.Hencethissystemisperfecttoolforexaminationofthesamplesfor
internalcracks,inclusionsandporosityandmore.Ontheotherhand,theNANOTOMincludesthe
software package for system control, data acquisition, image analysis and realistic 3D
visualization,toensureoptimumimagequalityandhighvolumereconstructionspeeds.Software
20

ImageJ(freelicense)wasappliedtogenerate3Dimageandfurtheranalyzethecrackingpattern.

Figure4.7SchematicrepresentationofnanoCTsystem

4.2.5.2Experimentalprogram
As mentioned in Chapter 3.3, the important advantage of nanoCT is that the nondestructive
technique can show the internal crack pattern meanwhile keep the integrity of the specimens.
Therefore,nanoCTwasusedtoviewthathowthecrackspropagatedwithinECCmaterialinthis
research.TheexperimentalprogramisshowninFigure4.8,thenanoCTonlyaimsatasituation
thatthespecimencontainscapsules.Thescanningwascarriedoutwithinthespecifiedlocation
(Figure 4.4) where all the capsules were distributed. In order to study the internal differences
before and after healing, the images from the same position and the same scan direction are
guaranteed for each specimen. On the other hand, the images from front, top and profile
direction(Figure4.4)areconducivetoobservethehealedcracksfrommultipledirections.

Figure4.8NanoCTprogramofthepreloadedECC

21

4.2.6Environmentalscanningelectronmicroscopy(ESEM)

4.2.6.1Experimentalsetup
Environmental scanning electron microscopy (ESEM) was preferred in this study to analyze the
qualityofselfhealingproductsformedinsidethecrack.Thistechniquecanprovideinsightinto
thechemicalcompositionofhealingproductsandthereforeidentifytheselfhealingbehaviorin
ECCmaterial.TheESEMretainsallperformanceadvantagesofaconventionalSEM(Figure4.9),
moreovereliminatesthehighvacuumconstraintonthesampleenvironment.Theelectrongunat
the top of the column creates a electron beam, and then the electrons are accelerated and
focusedbyaseriesofmagneticlensesandapertures.Asetofscanningcoilsdeflectstheelectron
beam in a scanning pattern over the sample surface and the objective lens offers the final
focusing. The interactions between the beam electrons and the sample atoms will generate a
variety of signals in forms of secondary electrons (SE), backscattered electrons (BSE) and
characteristicXrays,andemergingsignalscanbedetectedandreconstructedintoavirtualimage
displayedonthemonitorscreens.

Figure4.9Schematicofascanningelectronmicroscopy

4.2.6.2Samplepreparation
Toobservethecrackinside,samplesfromM2andM3series(withcapsules)after28dayscuring
wereexaminedunderESEM.Sinceitisdesiredthatcomponentsinsidethecapsulecanbeclearly
seen, the sample was not impregnated with a lowviscosity epoxy. Sample preparation for BSE
imaging followed the steps below. At first, the specimen was cut into a small piece with the
dimensionof20mm 20mm 30mm,andthenwasgroundwithsandpaperfromp300p4000for
about half minute each. During the grinding process, ethyl glycol was used instead of water in
order to keep its probable products integral. For the case of EDX (Energy dispersive Xray
spectroscopy),samplesweredealtwithbyasmallchiseltomaintainthefractalsurface.

22

4.2.7Lightmicroscope

AsshowninFigure4.10,atransmittedlightmicroscopeLeicaMZ6withcoldlightsources(CLS150)
wasusedinthisstudytoobservethetypicalcrackpattern.Thismodularstereomicroscopecan
create brilliant threedimensional images of spatial object and Leica cold light sources provide
stronglightintensityevenwithinsmallspace.Inaddition,theCLS150hasbeenspeciallyadapted
forautomatedcontrolofthenewtransmittedlightbaseviathepowerfulsoftwareofLAS(Leica
Application Suite). Through the serial interface, brightness and the electronic shutter can be
controlledusingthecomputer.

Figure4.10Lightmicroscope

4.3Shortsummary

At the beginning of this chapter, the preliminary experiment for investigating two sealing
materialswasintroduced.Basedonusingtheparaffinwaxasthesealingmaterial,themechanical
testingprogramandseveralmicroscopicobservationswerepurposedandintroducedtoexplore
thefunctionalperformanceofhealedECC.Thenextchapterwillpresenttheexperimentalresults
anddiscussions.

23

5RESULTSANDDISCUSSION
5.1RecoveredmechanicalpropertiesinECC

Several techniques have been used in examining selfhealing behavior. In this section, the
selfhealinginECCisevaluatedfromthepointofviewofmechanicalproperties.

5.1.1Loaddisplacementrelation

Thedisplacementcontrolledthreepointbendingtestrecordstheloaddisplacementrelationship.
OneexampleofloaddisplacementcurveatthreedifferentstagesofloadingisgiveninFigure5.1
(A).Asindicated,thereisaninitiallinearelasticpartuptothefirstcrackstrength.Thefollowing
isofthepropagationofcracks,moremicrocracksareformedanddevelopedinthespecimenbut
theloadingcontinuestoincreaseduringthisstagewhichiscalledhardeningandthematerialis
stillcapableofresistinghigherlevelsofloadinguptoamaximum.Afterthepeakloadisreached,
the applied load becomes to go down, a single macrocrack has appeared and the material has
startedtosoften.

Comparedwiththecontrolsamplesbendeduntilfinalfailure(schemeA),thepreloadedsamples
(schemes B and C) have different stages, as described in Figure 5.1 (B). When the desired
preloadinglevelisarrivedthespecimenthenisunloaded.Afterhealingperiod,thespecimenis
reloadedunderthreepointbendingtestagain.Becauseofreopeningofthecracksresultedfrom
thepreloadingstage,theloaddisplacementcurveofreloadingpresentsdifferencesinterms of
deflection,stress,andstiffness,whicharediscussedfurtherbelowrespectively.Thecalculationof
conversionfromloaddisplacementrelationstressdeflectioncurveisexplainedinAppendixD.

Load(kN)

Softening

Propagationofcracks
Linearelastic

Displacement(mm)

(A)Controlsamples(schemeA)

24

Load(kN)

Unloading
Preloading

Reloading

Displacement(mm)

Curingfor28days

(B)Preloadedsamples(schemesBandC)
Figure5.1Comparisonofloaddisplacementcurvesfordifferentschemes

5.1.2Generalresultsofstressdeflectioncurves

To represent the typical feature of different mixtures and schemes, the general results of
stressdeflection curves from threepoint bending test are presented in Figures 5.25.4. For
comparison of mechanical properties in Figures 5.6, 5.7 and 5.9, the value shown in column
charts were calculated based on the average results of at least two experimental results, after
removal of the maximum and minimum. All results in Figures 5.25.4, 5.6, 5.7 and 5.9 were
derivedfromthestressdeflectioncurveswhicharegiveninAppendixE.

M1series(nocapsule)

16

SchemeA
SchemeB
SchemeC

Bendingstress(MPa)

14
12
10
8
6
4
2
0
0

Deflection(mm)

Figure5.2BendingstressdeflectioncurvesofM1series

25

M2series(coarsecapsule)

16

SchemeA
SchemeB
SchemeC

Bendingstress(MPa)

14
12
10
8
6
4
2
0
0

Deflection(mm)

Figure5.3BendingstressdeflectioncurvesofM2series

M3series(finecapsule)

16

SchemeA
SchemeB
SchemeC

Bendingstress(MPa)

14
12
10
8
6
4
2
0
0

Deflection(mm)

Figure5.4BendingstressdeflectioncurvesofM3series

5.1.3Deflectionhardeningbehaviorinfluencedbythecapsules

Figures5.5showsthebendingstressdeflectioncurvesofseriesM1M3underschemeA(control
scheme). Asexpected,M1(nocapsule)presentatypicaldeflectionhardeningbehavior,which
characterized by a straight, linear part up to first cracking, then followed by a bent over and
consequent plateau curve until final failure. When comparing the linearelastic curves between
reference(M1)andothertwomixtures(M2andM3),itcanbeobservedthatoncelinearpartof
M2andM3(withcapsules)ends,ashorterbendoverpartisfollowedbyadecreaseofflexural
stressatarapidrate,whichimpliesfinalfailuretakesplacequickly.Thusoneconclusioncanbe
drawnthatthecapsuleshaveanegativeeffectondeflectionhardeningbehaviorofECC.

26

SchemeA(bendtofinalfailure)

16

M1
M2
M3

Bendingstress(MPa)

14
12
10
8
6
4
2
0
0

Deflection(mm)

Figure5.5Comparisonofdeflectionhardeningbehaviorfromdifferentmixtures

5.1.4Deflectioncapacityandrecovery

Inthisstudy,deflectioncapacityisaconcerntoevaluatetheselfhealingbehaviorinECCmaterial.
Deflection capacity is defined as the deflection which corresponds to the maximum bending
stress(flexuralstrength).Andtherecoveryofthedeflectioncapacitycanbecomputedaccording
tothefollowingformula:

Normalizedvalue = (

schemeY control
)deflectioncapacity (1)
control

whereschemeYstandsforschemeA,schemeBandschemeC,control=schemeA

Figure 5.6 (A) provides the results of the deflection capacity for three mixtures under three
schemes.It is found thatM3 (fine capsule) has a higher deflection capacitycompared withM2
(coarsecapsule).Inmostcases,thedeflectioncapacityofM3undereachschemeexceedsthatof
the corresponding parallel scheme of M2. The possible reason is that the properties of matrix
suchastoughnessinECCarechangedtomoreextentbythecapsuleswithlargesize.

AsshowninFigure5.5(B),M2andM3(withcapsules)bothclearlyrevealthedesirablerecovery
of deflection capacity in schemes B and C. The preloaded samples from M2 and M3 (with
capsules) can reach about 70%90%, 80%90% of its control deflection capacity, respectively.
WhilethereferencefromM1(nocapsule)onlyarrivesat60%80%thatofthecontrolspecimen.
Moreover,therecoverylevelofM3(finecapsule)isslightlyhigherthanM2(coarsecapsule),and
this is another support for that the large capsule size exerts more reduction of deflection
capacity.

It also can be observed from Figure 5.6, scheme B (bend to 1.0mm deflection) shows higher
values of deflection capacity as well as its recovery, compared with scheme C (bend to 1.3mm
deflection). From the selfhealing point of view, the results reflect that the selfhealing tend to
occurinsmallcracks.
27

Deflectioncapacity(mm)

SchemeA

SchemeB

SchemeC

0
M1

M2

M3

Mixturedesignation

(A)Deflectioncapacity
140%

Normailizeddeflectioncapacity

120%

SchemeA

SchemeB

SchemeC

100%
80%
60%
40%
20%
0%
M1

M2

Mixturedesignation

M3

(B)Normalizeddeflectioncapacity
Figure5.6Comparisonofdeflectioncapacityanditsrecoveryfromdifferentmixtures

5.1.5Flexuralstrengthandrecovery

Therecoveryofflexuralstrengthcanbecalculatedasfollowed:

Normalizedvalue = (

schemeY control
(2)
)flexuralstrength
control

whereschemeYstandsforschemeA,schemeBandschemeC,control=schemeA

The recovery of flexural strength is shown in Figure 5.7. It is noticed that the flexural strength
fromM1(nocapsule)underallschemesexceedstheperformanceofM2andM3(withcapsules).
This indicates that the capsules inside the specimen will reduce the flexural strength of ECC
composite due to the disturbance of fiber, matrix and fibermatrix interface properties. When
comparedthedifferencebetweenthemixtureswithcapsulesinside,theflexuralstrengthofM3
28

(fine capsule) under three schemes is higher than that of M2 (coarse capsule), especially for
schemeCshowninFigure5.7(A).Fromtheviewofnormalizedflexuralstrength(Figure5.7(B)),
thevaluesfromM3(finecapsule)nearlyremainatalevelof100%ofcontrolvalue,whichalmost
arrivesatthesamerecoverylevelofM1(nocapsule).Theseseemtoindicatethatsmallcapsule
sizeattainsbeneficialinfluenceonflexuralstrengthanditsrecoverycomparedwithlargecapsule
size.

On the other hand, it should be note that the flexural strength of M2 (with capsules) under
scheme C (bend to 1.3mm deflection) exhibits a sharp reduction, and is recovered only about
60% of the control specimen. This may be explained that the flexural strength was already
reachedduringthepreloadingstageforthecaseof1.3mmdeflectionlevel.Asinglemacrocrack
waslikelytobegeneratedandthiscanbefurtherconfirmedbythemicroscopicobservationin
thelatersection.

20

Flexuralstrength(MPa)

18

SchemeA

SchemeB

SchemeC

16
14
12
10
8
6
4
2
0
M1

M2

Mixturedesignation

M3

(A)Flexuralstrength
140%

Normailizedflexuralstrength

120%

SchemeA

SchemeB

SchemeC

100%
80%
60%
40%
20%
0%
M1

M2

Mixturedesignation

M3

(B)Normalizedflexuralstrength
Figure5.7Comparisonofflexuralstrengthanditsrecoveryfromdifferentmixtures

29

5.1.6Flexuralstiffnessandrecovery

Stiffness measurement was used to monitor the extent of selfhealing within preloaded ECC
specimens. In this research, the flexural stiffness is the equivalent slope of initial linearelastic
stageofflexuralstressdeflectioncurveasshowninFigure5.8,stiffnessanditsrecoverycanbe
calculatedbythefollowingformulasrespectively:

Stiffness = tan =

(3)
[MPa / mm]
L

schemeY control
(4)
Normalizedvalue = (
)flexuralstiffness
control

whereschemeYstandsforschemeA,schemeBandschemeC,control=schemeA

16

Bendingstress(MPa)

14

Flexuralstrength

12
10
8

Linearelasticstage

4
2

0
0

0.4*Flexuralstrength
1

Deflection(mm)

Figure5.8Stressdeflectioncurveforstiffnesscalculation

Figure5.9presentsthecomparisonofflexuralstrengthanditsrecoveryfromdifferentmixtures.
FromFigure5.9(A),itcanbeseenthattheflexuralstiffnessfromM1(nocapsule)undercontrol
schemeAisrelativelylowercomparedwiththatofM2andM3(withcapsules)underthesame
scheme.Thisisasexpected,thecapsulesbehaveasthenormalaggregates,andtheirpresence
increasestheflexuralstiffnessofECC.However,thistrendisreversedinpreloadedschemesBand
C,M1(nocapsule)hasslighthigherstiffnessthanM3andM2(withcapsules)inmostcases.This
isprobablybecauseoncethecracksformedduringthepreloadingstage,thereislittleresistance
toloadandtendtocauseareductionofstiffness.

BycomparingtherecoveryofflexuralstiffnessfromFigure5.9(B),thelevelofstiffnessretained
ofM3(finecapsule)isnotremarkablethanthatofthereferenceM1(nocapsule),butithasan
enhancementcomparedwithM2(coarsecapsule).Itcanbeconsideredthatfinecapsuleleadsto
more reasonable recovery compared with coarse capsule since fine capsules has relatively less
influence on the matrix toughness and fibermatrix interface properties. This finding is also
supportedbythedeflectionandflexuralstrengthrecoveryasdescribedearlier.

30

30

Flexuralstiffness(Mpa/mm)

SchemeA

SchemeB

SchemeC

25
20
15
10
5
0
M1

M2

Mixturedesignation

M3

(A)Flexuralstiffness
140%

Normailizedflexuralstiffness

120%

SchemeA

SchemeB

SchemeC

100%
80%
60%
40%
20%
0%
M1

M2

Mixturedesignation

M3

(B)Normalizedflexuralstiffness
Figure5.9Comparisonofflexuralstiffnessanditsrecoveryfromdifferentmixtures

31

5.2NanoCTobservation

5.2.1IdentificationofmicrocracksinnanoCTimage

Asmentionedbefore,inordertocheckhowthecracksdevelopintheinterfacezonebetweenthe
capsuleandthecementbasedmatrix,thecrackpatternbeforeandaftercuringwasinvestigated
with nanoCT scan. First of all, Figure 5.10 illustrates the components of the ECC material
represent in the nanoCT 2D images according to the greylevel histogram. The pore and void
insidethecapsulearepresentedbythedarkest,whilethelightestcorrespondstocementbased
matrix and the medium gray is an indication of the capsule. Due to the similarity of density
between the paraffin wax and the SAP, the wax shell and the saturated SAP particles are very
difficulttobedistinguishedinthisgraylevelimage.

Capsule

Matrix

Voidinside

Crack

SaturatedSAP

Pore

Figure5.10Explanationof2DnanoCTimages

On the other hand, how the cracking actually propagates (passing through or around capsules)
seemsdifficulttobeobservedfromthese2Dimages.However,thedifferenceinsidethecapsule
before and after curing can provide an insight into the moisture transportation aspect. Here it
could be assumed, that capsules after 28 days curing are generally divided into two types:
opened and closed. Two examples in Figure 5.11 compare the difference between two images
beforeandaftercuringatthesamelocationofthespecimen.Itisclearlyseenthattheopened
capsulecanbeconsideredasintermsofanobviousenlargementofdarkregioncomparedwith
theinitialimage.Onthecontrarythereislittlechangeintheclosedone.Theconclusioncanbe
made fromthe opened capsule isthatthe water is already released from the capsules andthe
moisturetransporttakesplaceduetorelativehumidity(RH)gradient.

32

8mm

Opened

Closed

(A)Beforecuring_28daysold Aftercuring_56daysold

8mm

Opened

Closed

(B)Beforecuring_28daysold Aftercuring_56daysold
Figure5.11TwoexamplesforcomparisonofnanoCTimagesbeforeandafter28dayscuring

In order to further verify whether the opening of capsules is induced by the cracking, it is
interesting to check the crack pattern by 3D reconstruction view. Figure 5.12 corresponding to
abovetwoexamplesshowsthat,someapparentcrackingpatternsarerevealedonthewaxshell
oftheopenedcapsule,anditcanbeseenfromtheclosedcapsule,thereisalsocrackingpattern
ontheshell.Thereforeitcannotbeestablishedthatoncethecrackspassthroughthewaxshell
the water will be released from the capsules, this may occur due to the dense structure of
paraffinwaxandthesmallerpreloadedlevel.Basedonabovereasons,theusefulinformationcan
beinferredfromthis3Dviewisthatthecapsuleswiththewaxshellispossibletobeopenedby
thecracking.

33

Opened
Opened

Closed
Closed

(A) (B)
Figure5.123Dviewofthecrackingpattern

5.2.2Openingofcapsules

Inthissection,theopeningpossibilityofcapsuleswillbediscussed.Allcapsuleswhichmightbe
openedbythecracksfromthepreloadedspecimens(schemesBandC)ofM2,M3series(with
capsules) were checked based on the principle of opened and closed. Figure 5.13 gives a
summaryofopenedratioofcapsules,andpointoutthattherearemorethan50%capsulesbeing
openedduringthepreloadingstageinthisresearch.Morestatisticalinformationissummarized
inAppendixF.

100%

Openedratioofcapsules

90%

SchemeB

SchemeC

80%
70%
60%
50%
40%
30%
20%
10%
0%
M2

Mixturedesignation

M3

Figure5.13Summaryofopenedratioofcapsulesinpreloadedspecimens

34

5.3LightmicroscopeandESEMobservations

5.3.1Multiplecrackingbehavior

The multiple cracking behavior of ECC is one of the distinct differences from normal concrete.
Becauseofthefiberbridgingeffect,thecrackscanprogressivelyopen.Whenthecementbased
matrixstartstocrack,thefiberswillslipoutthematrix.Withthematrixcrackextends,thefibers
canbecompletelypulledoutfromthematrix.Asaresultofthisprocess,theECCisabletotake
the increasing load and forms new cracks at other sites. Figure 5.14 obtained by the light
microscopeshowsthetypicalcrackpatternofmultiplecrackingbehavior.Thebridgingeffectof
fibersobservedunderESEMisalsoshowninFigure5.15.

200m

Figure5.14TypicalcrackpatterninECCspecimen

Figure5.15FibersbridgingeffectinECCspecimen

35

5.3.2Observationofinterfacezone

Besides,thecrackpathattheinterfacebetweenthecapsuleandthecementbasedmatrixwas
also studied by ESEM technique. One thing is clear from the Figure 5.16: when the crack
propagatesacrossthewaxshell,thecrackwidthappearssmallerthanthatofdevelopinginthe
matrix. This is most probably associated with the characteristic of paraffin wax with a dense
laminatedstructure.Insomecases,thecracksgoaroundinsteadofpassingthroughthecapsules,
seeFigure5.17.Thisiscausedbytheweakerbondstrengthattheinterfacezonecomparedwith
thatofthecapsuleitself.

Waxshell
Crackpath
onthewaxshell
Crackpath
Matrix

Figure5.16Crackpatternonthewaxshell
SaturatedSAP
Waxshell

SaturatedSAP

Passthrough
Around
Matrix

Figure5.17Interfacebetweenthecapsuleandthematrix

5.3.3Observationofcrackinside

Another main purpose of ESEM observation is to investigate whether there is healing product
being formed inside the cracks. Figure 5.18 explains what is crack inside and crack surface
separately. For M2 and M3 series (with capsules), the failed specimens from schemes B and C
(preloaded) were used to prepare samples for ESEM observation. Unfortunately, no apparent
healing product for instance calcium carbonate crystals with prismatic shape was found within
the cracks. However, as shown in Figure 5.19, calcium hydroxide in the shape of hexagonal
plateletcanbeobservednearthecracksurface.

36

Crack

UnderESEM

Crackinside:

Cut
UnderESEM

Cut
Cracksurface:

Figure5.18Illustrationofcrackinsideandcracksurface

Figure5.19Preloadedsampleafter28dayscuring

5.3.4Observationofcracksurface

Finally,SemiquantitativechemicalcharacterizationbyEDXofthepreloadedECCspecimensusing
anESEMwascarriedouttorevealthecompositioninsidethemicrocracks.Onesamplecutfrom
crosssection of the crack and another sample with normal crosssection (noncrack) from the
same specimen as a reference for comparison purpose (Figures 5.20 and 5.21). Table 5.1
summarizestheresultsofweightpercentageofelementcalciumatthespecifiedlocation.More
detailedinformationislistedinAppendixG.Itcanbeseenthatthecalciumcontentatthecrack
surface accounts for more percentage (10% larger) than that of the calcium at the noncrack
surface. Another evidence is of the elemental mapping (MAPing) by EDX analysis as shown in
Table 5.1 and Figure 5.22. As mentioned in Chapter 2.2.2, the healing products could be
presentedintermsofthreesubstances,includingcalciumcarbonate(CaCO3),calciumhydroxide
(Ca(OH)2) and calcium silicate hydrate (CSH). In this research, it could be explained that the
specimenwascuredinsealedcondition,theavailablecarbondioxide(CO2)dissolvedinwateris
little, such that it is difficult to form the calcium carbonate. Hence, the high concentration of
calcium could indicate that the healing product is probably hydration product, such as calcium
hydroxideorcalciumsilicatehydrate.

37

3
1

Figure5.20ESEMimagesofcracksurface

Figure5.21ESEMimagesofnoncracksurface(reference)

Table5.1SummaryofCalcium(Ca)weightpercentage
Sample

Location

CaWt%

42.05

Crack

42.51

surface

48.87

38.66

Noncrack

33.06

surface(reference)

34.68

AverageWt%

43.02

33.87

(A)Analysisarea (B)Distributionoftheelementcalcium
Figure5.22MAPinganalysisonthecracksurface
38

5.4DiscussionofpotentialofselfhealinginECC

5.4.1Influencingfactors

In this research, six mechanical indicators are involved: deflection capacity, flexural strength,
stiffness and their normalized values. Two factors (capsule content and capsule size) were
designedtoexploretheselfhealingpotentialofECCmaterial,andtheyarediscussedasbelow,

vii. Capsulecontent(nocapsule&withcapsules)
AsmentionedinChapter4.2.2,theECCspecimenswithoutcapsule(M1)andwithcapsules(M2
andM3)weretakenintoaccounttoinvestigatehowthecapsulesinfluencethehealingproperties.
When comparing the magnitude of deflection capacity between M1 (without capsule) and M2
and M3 (with capsules) at each parallel scheme, the reference M1 (without capsule) always
exceedstheperformanceofM2andM3.Thesametrendalsooccursinmostcasesoftheflexural
strength and stiffness. This can be explained that, the capsule itself behaves as the normal
aggregate, and the presence of aggregates disturbs the matrix properties especially the fiber
distributionoftheECCcompositeandhasnegativeinfluencesonthemechanicalproperties.

However, from the results of recovered mechanical properties, it is noticed that the deflection
capacity from the specimens with capsules (M2 and M3) can recover about 65%95% from
controlspecimens,whichishigherthanthatofthereferencespecimenswithoutcapsule(M1).
While, there is a slight reduction from aspect of flexural strength recovery expect M2 (coarse
capsule)underscheme3(bendto1.3mmdeflection)thatiswithasignificantdrop.Inthiscase,
thespecimenwasalreadypreloadedtoasinglemacrocrackandofferedlittleresistancetoreload.
In addition, approximately 60% in average of flexural stiffness is regained for specimens with
capsules(M2andM3),thisrecoverylevelismuchlower(about20%)thanthatofthereference
withoutcapsule(M1).Hence,thereisanenhancedrecoveryofdeflectioncapacitybutareduced
recoveryofflexuralstrengthandstiffnessmoreorless,anditmaybeexplainedthatthewater
released from the capsules is partially contributed to promote the selfhealing of cracks in this
research.Furtherdiscussionofhealingefficiencywillbepresentedinthenextparagraph.

viii. Capsulesize(coarsecapsule&finecapsule)
From the literature study, it is suggested that the size range of microcapsule is from 50nm to
2000 m or larger [19]. Butmanufacture of microcapsules is difficult in this research dueto no
availablerollingmachineatthattime.Insuchacase,M2withcapsulediameterof8mm(coarse
capsule)andM3withcapsulediameterof5mm(finecapsule)weredesignedinthisresearch,to
comparetheinfluenceofcapsulesizeontheperformanceofECC.ItisclearfromFigures5.5,5.6
and5.8thatsmallcapsulesizeshowshigherdeflectioncapacity,flexuralstrength,stiffnessaswell
astheirrecoveryforalmostallthecasescomparedwithlargercapsulesize.Forthecrackpattern,
itcanbeseeninFigure5.22thatwhenthecapsulesaremadeinlargesize,oncethepreloadingis
slightlylargerthanacertainlevel,theECCspecimentendstogenerateasinglemacrocrackand
lessnewcracksareformedafterreloading.Incontrast,thespecimenwithsmallcapsulesizehas
39

more even distribution of multiple cracks. Thus small capsule size has more benefits on
mechanicalpropertiesandmechanicalrecoveryandcrackingpatternsinceitchangesmatrixand
fibermatrixpropertiestoalessextent.

Macrocrack

Coarse_1.0mm Fine_1.0mm Coarse_1.3mm Fine_1.3mm


(A) 28daysold(beforereloading)

Coarse_1.0mm Fine_1.0mm Coarse_1.3mm Fine_1.3mm


(B) 56daysold(afterreloading)
Figure5.22ComparisonofcrackpatternforM2(coarsecapsules)andM3(finecapsules)under
schemeB(preloadedto1.0mm)andschemeC(preloadedto1.3mm)

5.4.2Healingefficiency

Althoughitwasindicatedthattherecoverylevelofdeflectioncapacitywasenhancedwhilethe
recovery of flexural strength and stiffness had a reduction more or less compared with the
reference. Even though the high concentration of calcium on crack surface was found via EDX
analysis,basedonthis,itcouldbeconsideredthatthehealingproductwaspresentedintermsof
calciumhydroxideorcalciumsilicatehydrate.Butnoapparenthealedcrackwasobservedunder
ESEM, maybe since the product was too little and the healing efficiency was low. Here the
possiblereasonsofthatarediscussedinthissection.

Thecrucialreasonoflowhealingefficiencyisthattheamountofavailablewaterisnotsufficient.
Herethehealingefficiencycanbeexplainedintermsofmoisturetransportationinthepreloaded
ECCspecimens.Inthisstudy,whenthecapsuleisopened,themoistureisfirstlydesorbedform
theSAPparticlesandmovestothecracksurface.Itcanbeassumedthatthecrackisimmediately
in high humidity environment (RH 99%), then the moisture movement takes place by diffusion
40

whichisdrivenbythehumiditygradient.AccordingtoHuang[24],thenumericalsimulationwas
establishedtoshowtherelationshipbetweenthedistanceofmoisturetransportintothemortar
andthetime,seeFigure5.23.Itindicatesthatthemoisturewillmovefarawayfromthecrack
surfaces with the increase of curing time. Similar to that, in this study it was confirmed that
moisture had moved to the crack surface, but when the water supply is limited, the moisture
contentleftonthecracksurfacesistoolittletoproducemorehealingproductsinshortcuring
period. Thus the sufficient water supplement is essential for desirable healing efficiency. The
amountofwaterforfurtherhydrationofunhydratedcementwillbeinvestigatedinthefurther
research.

Since the moisture transportation can be considered as the function of time, the curing time
becomesanotherfactorinfluencingthehealingefficiency.However,whentheamountofwateris
sufficient,thecuringtimeisnotadecisivefactorforselfhealing.

50
45
40
35
30
25
20
15
10
5
0

8h

Z (mm)

8h

2h

2h
1h
0.5h

1h
0.5h
crack

20

40

X (mm)60

80

100

Figure5.23Waterpenetrationdepthincrackedcementitiousmortarduringwettingprocess[24]

5.4.3Shortsummary

Backtothecorequestion,whethertheselfhealingoccursinthemodifiedECCmaterial?Itcanbe
viewed from two aspects. On the one hand, both capsule sizes (coarse capsule with 8mm in
diameterandfinecapsulewith5mmindiameter)usedinthisresearch,arerelativelylargefrom
theview of microscale. The capsulesact as theaggregates embeddedinto ECC, and thus their
influence on the mechanical properties of ECC cannot be ignored. As discussed above, the
capsule itself has a negative effect on the micromechanics. However on the other hand, it is
expectedthatthecapsulescanprovidewateravailabletohealthecracks.Thiscouldenhancethe
mechanicalproperties.Thereforeasanaccessofthewatersupply,thecapsuleexertsapositive
effectonmechanicalproperties.Thesetwoaspectsseemtobecontradictory,thatcouldexplain
whytheenhancementaswellasthereductionwerepresentedinthisresearch.Fromtheviewof
healingproduct,itcouldbesaidtheselfhealingoccurduetoalittlehealingproductpresentedas
the high concentration of calcium, but this behavior is not apparent. It can be inferred that
optimize the capsule size will be contributed to minimize the negative effect and provide
sufficientwaterwillpromotemoreeffectiveselfhealingbehavior.

41

6GENERALCONCLUSIONSANDRECOMMENDATIONS
6.1Generalconclusions

Inthisthesis,theselfhealingpotentialoftheECCmaterialbymeansofavailablewaterreleased
from the capsules containing the water saturated SAP has been investigated. Based on the
experimental results of mechanical test and microscopic observation, the following conclusions
canbedrawn,

Themassofwaterisalmostnotinfluencedbythecuringtimewhentheparaffinwaxisusedas
sealingmaterial.Duetoitsbettercapacityofwaterstoragecomparedtothatofepoxycement
paste,theparaffinwaxwaspreferredasthesealingmaterialinthisresearch.

Recovery of mechanical properties are regarded as the indicators of the selfhealing efficiency.
Therecoveryofdeflectioncapacity,flexuralstrengthandstiffnesswereexaminedinthisresearch.
Therecovereddeflectioncapacitywasenhancedwhiletheimprovementonflexuralstrengthand
stiffness were rarely shown. It could be considered that the selfhealing efficiency was not
remarkable,sincethemechanicalpropertieswerenotsignificantlyimproved.

TheECCspecimenswiththesmallcapsulesizeof5mmindiameterhavepreferableperformance
inmechanicalpropertiesandtheirrecoveryaswellasincrackpattern.Similartonormalconcrete,
the mechanical properties of a cementitious material are highly influenced by the capsule size.
Basedontheresults,thesmallercapsulesizeisconducivetotheselfhealingbehavior.

Under nanoCT technique and ESEM observation, it could be confirmed that moisture
transportation took place in more than half of capsules. Sufficient water supplement plays a
majorroleonpromotingtheselfhealing process.Inthisresearch,thelowefficiencyofhealing
wasthusmainlyattributedtotheinsufficientwatersupply.

Theobservedhealingproductprobablyisofthehydrationproductsuchascalciumhydroxideor
calcium silicate hydrate. This finding indicates that the selfhealing phenomenon probably
occurred.Unfortunatelynoapparenthealedcrackwasobserved,itcouldbeconcludedthatthe
crackswerelikelytoundergotheselfhealingprocess,butitisnotaveryeffectivehealinginthis
research.

42

6.2Recommendations

Several feasible improvements and further research to realize the selfhealing of cementitious
materialsinconcreterepairsystemcanbegivenasfollowing,

i.

Alternativesealingmaterial

Asdiscussedbefore,asuitablesealingmaterialisnotonlycapableofstoringwater,butalsohas
high bond strength at the interface between the sealing material and the cementitious matrix.
The capsule is considered as the weakest element in the composite and the interface bond of
sealingmaterialdirectlydeterminesonthecrackpattern,whichinfluencesthereleaseofhealing
agent.Thusselectionofapropersealingmaterialiscrucialasabasisforfurtherstudy.

ii.

Alternativewaterreservoir

Liapor particle is a promising candidate for carrying water instead of SAP. It has a high water
absorptioncapacity(30%40%byweight)andtheparticleisroughlysphericalwithadiameterof
110mm.Therefore,itcanbemadeintoasmallcapsule.Asknown,thecapsulesizesignificantly
influences the mechanical properties of the composite. Moreover, control of capsule size is
essential to the uniform distribution of capsules and the probability of capsule opening. The
applicationofliaporneedstobestudiedfurther.

iii.

Encapsulationprocedure

Fromthepointofviewofproducingthecapsules,Itisimportanttofindaneffectivemethodto
manufacture capsules quickly and easily. A rolling machine (Figure 6.1) is suggested in future
study.Thisrotarybarreltumblerresultsineconomic,quietandefficientoperationfortumbling
smallparts[25].

Figure6.1Rotarybarreltumbler

iv.

Effectivehealingagent

Currently, sodium silicate used as the microencapsulated healing agent was embedded in a
concretemixture[26].Thesodiumsilicatereactswiththecalciumhydroxideandformsagellike
material (calciumsilicahydrate) that will heal the crack and block the pores. The advantage is
thatthegelhardensinaboutoneweekandtherecoveryofthestrengthcanreach26percentof
its original strength. It is believed that a more effective healing agent can contribute to the
selfhealingprocess.
43

REFERENCES

[1] M.G.Grantham,Diagnosis,inspection,testingandrepairofreinforcedconcretestructures,M.
G.Associates,1999,p.35
[2] Li V.C., Kanda T., Engineered cementitious composites for structural application, ASCE J.
MaterialsinCivilEngineering,1998,Vol.10,No.2,p.6669
[3] Zhou,J. Qian, S. Ye, G. Breguel, K van and Li, V.C., Development of Engineered Cementitious
Composites with Limestone Powder and Blast Furnace Slag, submitted to Materials and
Stuctures,2009
[4] Huan He, Zhangqi Guo, Piet stroeven, Martijn Stroeven, Lambertus Johannes Sluys,
Selfhealingcapacityofconcretecomputersimulationstudyofunhydratedcementstructure,
ImageAnalStereol2007,p.137143
[5] Tsuji M., Okuyama A., Enoki K. and Suksawang S., Development of new concrete admixture
preventingfromleakageofwaterthroughcracks,JCAProc.OfCement&Concrete52,1998,
p.418423
[6] Li V.C., Engineered Cementitious Composites (ECC) Tailored Composites though
Micromechanical Modeling, Fiber Reinforced Concrete: Present and the Future, Canadian
SocietyofCivilEngineers,1998,p.6497
[7] YingziYang,MichaelD.Lepech,EnHuaYang,VictorC.Li,Autogenoushealingofengineered
cementitious composites under wetdry cycles, Cement and Concrete Research 39, 2009, p.
382390
[8] Mustafa Sahmaran, Victor C. Li, Durability properties of microcracked ECC containing high
volumesflyash,CementandConcreteResearch39,2009,p.10331043
[9] Toshiro Kamada, Victor C. Li, The effects of surface preparation on the fracture behavior of
ECC/concreterepairsystem,CementandConcreteComposites22,2000,p.423431
[10] RomildoD.ToledoFilho,EugeniaF.Silva,AnneN.M.Lopes,Effectofsuperabsorbentpolymers
(SAP)ontheworkabilityofconcrete,RILEMTCSAPChapter5,2009
[11] Guang Ye, Klaas van Breugel, Effect of SAP on the Harding Process of Binder Paste and
MicrostructureDevelopmentinConcrete(Porosity,morphology,connectivity),RILEMTCSAP
Chapter6,2009
[12] S. van der Zwaag (ed), Self healing materials: an alternative approach to 20 centuries of
materialscience,2007
[13] S. Qian, J. Zhou, M.R. de Rooij, E. Schlangen, G. Ye, K. van Breugel, Selfhealing behavior of
strain hardening cementitious composites incorporating local waste materials, Cement and
ConcreteComposites31,2009,p.613621
[14] E.Schlangen,FractureMechanics,CT5146LectureNotes,DelftUniversityofTechnology,2007
[15] A.Neville,PropertiesofConcrete,1995,p.328
[16] A.Neville,AutogeousHealingAconcreteMiracle,ConcreteInternational,2002,p.7682
[17] Nynke Ter Heide, Crack healing in hydrating concrete, Master thesis, Delft University of
Technology,2005
[18] Dong Yang Wu, Sam Meure, David Solomon, Selfhealing polymeric materials: A review of
recentdevelopments,Prog.Polym.Sci.33,2008,p.479522
[19] R.Arshady(ed),Microspheres,microcapsulesandliposome,Vol.1:preparationandchemical
44

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[21]

[22]
[23]
[24]

application,CitusBooks,1999
Victor C. Li, Yun Mook Lim, YinWen Chan, Feasibility study of a passive smart selfhealing
cementitiouscomposite,CompisitespartB,1998,p.819827
Henk M. Jonkers, Arjan Thijssen, Gerard Muyzer, Oguzhan Copuroglu, Erik Schlangen,
Application of bacteria as selfhealing agent for the development of sustainable concrete,
EcologicalEngineering,2009
HaoliangHuang,GuangYe,KlaasvanBreugel,Numericalsimulationonmoisturetransportin
crackedcementbasismaterials,2010
McMASTERCARR,http://www.mcmaster.com/#barreltumblers/=7yvslm
SusanWilson,CosteffectiveselfhealingconcretedevelopedatURI,2010

45

APPENDIXAMixproportionofepoxycementmaterial

Mixproportion
CEMI

Epoxy

52.5N[g]

[g]

20

0.6135

Hardener
[g]
0.7730

Epoxy/hardener

Water

Water/cement

Epoxy/cement

ratio

[g]

ratio

ratio

1:1.26

5.6135

0.300

0.05

46

APPENDIXBMixdesignofECC

MaterialpropertyandmixproportionofM1
Component

Density
3

Mixproportion

Weight

MaterialpropertyandmixproportionofM2

Volume
3

Diameter

[g/cm ]

(byweight)

[g]

[cm ]

[mm]

Portlandcement

3.15

550

175

BFS

2.85

1.2

660

232

2.70

1100

407

Water

1.00

1.092

601

601

Superplasticizer

1.17

0.030

16.5

14

PVAfiber

1.30

37.1

Limestone
powder

SaturatedSAP

insidecapsule
Numberof

capsules
Capsulesize

(byvolume)
0
(byCEMweight)
0
(0%byvolume)

Water/powder

ratio

Total

0.02

0.26

Component

Mixproportion

Weight

Volume
3

Diameter

[g/cm ]

(byweight)

[g]

[cm ]

[mm]

Portlandcement

3.15

550

175

BFS

2.85

1.2

660

232

2.70

1100

407

Water

1.00

1.092

601

601

Superplasticizer

1.17

0.030

16.5

14

29

PVAfiber

1.30

37.1

29

11.0

6.7

Limestone
powder

SaturatedSAP

insidecapsule
Numberof

capsules

Capsulesize

0.02
(byvolume)
2%
(byCEMweight)
25
(0.46%byvolume)

Water/powder

ratio

2964

1457

Total

47

Density

0.26

2975

1465

MaterialpropertyandmixproportionofM3
Component

Density
3

Mixproportion

Weight

Volume
3

Diameter

[g/cm ]

(byweight)

[g]

[cm ]

[mm]

Portlandcement

3.15

550

175

BFS

2.85

1.2

660

232

2.70

1100

407

Water

1.00

1.092

601

601

Superplasticizer

1.17

0.030

16.5

14

PVAfiber

1.30

37.1

29

11.0

3.3

Limestone
powder

SaturatedSAP

insidecapsule
Numberof

capsules
Capsulesize

(byvolume)
2%
(byCEMweight)
50
(0.23%byvolume)

Water/powder

ratio

Total

0.02

0.26

2975

1461

48

APPENDIXCConvertingtheweightofSAPintothenumberofcapsules

Basically,capsulesinthesameserieswerecontrolledtobethesimilarsizeaccordingtodifferent
requirementsofcapsulesize(M2:diameterof8mm,M3:diameterof5mm).Duringthemaking
processofcapsules,saturatedSAPparticleswereshapedintoaballbyathincoverofcement,and
lesscementwasremainedespeciallyaftercuringtheminwaterfor7days.Ontheotherhand,dry
SAPpowdercanabsorbamountsoffreewatermanytimesthanitsownweight.Basedonabove
twopoints, the weight of cement coverandSAP particles can be assumedto beneglected, the
weightofballisthereforeconsideredastheweightofwateronly.Asaresult,thecalculationof
saturatedSAPwith2%weightratioofcementinAppendixB,meanstheamountoffreewater
neededforhealing,whichisrepresentedbyWwater.

Thissectioninterpretsthathowtoconverttheamountoffreewaterintothenumberofcapsules.
First, the saturated SAP particles after shaping by cement cover and 7 days curing in water is
calledaball,andtheweightofaballactuallyistheweightofwaterasexplainedabove.Inorder
toinvestigatetheweightofaball,100ballsweredividedinto10groupsandeachgroupincluded
10balls.Eachgroupofballswasweighedbyelectricbalance,andthentheaverageweightofone
ball (Wball) can be evaluated. Due to accidental errors, it was proposed that the number of
capsulesfordifferentmixtureswasmultipliedbyamagnificationfactor1.1,thenitfollowsthat:

Ncapsules = 1.1

Wwater
Wball

Thefollowingtablegivestheexperimentalresultsandcalculationofthenumberofcapsulesfor
twodifferentmixtures.

Experimentalresultsandcalculationofthenumberofcapsules

Capsulesize

M2:diameterof8mm

M3:diameterof5mm

Group

WeightofsaturatedSAP[g]

WeightofsaturatedSAP[g]

0.8694

0,4101

0.8793

0,4310

0.7360

0,3874

0.8945

0,4363

0.8121

0,4102

0.7475

0,3976

0.6763

0,4227

0.7698

0,3830

0.7271

0,4039

10

1.0014

0,4701

Average

0.8113

0,4152

Wball

0.0811

0,0416

Wwater

11.0g

11.0g

Ncapsules

149.14 150

291.40 300

Ncapsulesperspecimen

150/6=25

300/6=50

49

APPENDIXDThreepointbendingtestconfigurationandbendingstresscalculation
F
Specimen
h=40mm

L=55mm

A
110mm
160mm

b=40mm

Testsetup SectionAA

M=F/2*L

Momentdiagram

Bendingstressatmidspan: =

M
(F /2)*L
(F /2)* 55
=
=
= 0.002578125F[kN mm2 ] = 2.578125F[MPa]
2
2
W (1/6)*b *h (1/ 6)* 40 * 40

50

APPENDIXEBendingstressdeflectioncurves

M1b(preloadedto1.0mm_28daysold)

M1a(nocapsule_28daysold)
M1a1

12

M1a2

10
8
6
4

14

M1b1

12

M1b2

6
4

10

12

10

M1c1
M1c2
M1c3
M1c4

14
Bendingstress(MPa)

14

Bendingstress(MPa)

Bendingstress(MPa)

M1c(preloadedto1.3mm_28daysold)
16

16

16

8
6
4
2

Deflection(mm)

Deflection(mm)

0
0

2
Deflection(mm)

M1b(nocapsule_56daysold)

M1c(nocapsule_56daysold)
16

14

M1b1

12

M1b2

10
8
6
4
2

12
10
8
6
4
2

0
0

2
Deflection(mm)

51

M1c1
M1c2
M1c3
M1c4

14
Bendingstress(MPa)

Bendingstress(MPa)

16

2
Deflection(mm)

M2a1
M2a2
M2a3

12
10
8
6
4

12
10
8
6
4

0
0

2
Deflection(mm)

M2c(preloadedto1.3mm_28daysold)

16

M2b1
M2b2
M2b3
M2b4

14
Bendingstress(MPa)

Bendingstress(MPa)

14

M2b(preloadedto1.0mm_28daysold)

16

Bendingstress(MPa)

M2a(Capsulesizeof8mm_28daysold)

16

14

M2c1

12

M2c2

10
8
6
4
2
0

2
Deflection(mm)

2
Deflection(mm)

M2b(Capsulesizeof8mm_56daysold)

16

12
10

Bendingstress(MPa)

Bendingstress(MPa)

14

8
6
4

M2c1

12

M2c2

10
8
6
4
2

0
1

2
Deflection(mm)

52

14

2
0

M2c(Capsulesizeof8mm_56daysold)

16
M2b1
M2b2
M2b3
M2b4

2
Deflection(mm)

Bendingstress(MPa)

12
10

Bendingstress(MPa)

M3a1
M3a2
M3a3
M3a4

14

8
6
4

M3b1

12

M3b2

10

M3b3

6
4
2
0

2
Deflection(mm)

M3c1

14

M3c(preloadedto1.3mm_28daysold)

16

14

2
0

M3b(preloadedto1.0mm_28daysold)

16

Bendingstress(MPa)

M3a(Capsulesizeof5mm_28daysold)

16

M3c2

12

M3c3

10
8
6
4
2
0

2
Deflection(mm)

2
Deflection(mm)

M3b(Capsulesizeof5mm_56daysold)

14

M3b1

12

M3b2

10

M3b3

8
6
4
2

14

M3c1

12

M3c2

10

M3c3

8
6
4
2

0
0

2
Deflection(mm)

53

M3c(Capsulesizeof5mm_56daysold)

16
Bendingstress(MPa)

Bendingstress(MPa)

16

2
Deflection(mm)

APPENDIXFResultsofopenedratioofcapsulesundernanoCTobservation

Sample
M2b1
M2b2
M2b3
M2c1
M2c2
M2c3
M3b1
M3b2
M3b3
M3c1
M3c2
M3c3

Numberofopenedcapsules
Front
Right
Average
6
6
6
8
7
8
4
4
4
5
5
5
4
4
4
5
5
5
5
5
5
6
6
6
8
7
8
12
11
12
9
7
8
9
9
9

Numberofclosedcapsules
Front
Right
Average
3
4
4
4
4
4
6
6
6
3
3
3
4
4
4
4
3
4
6
6
6
5
5
5
7
6
7
7
6
7
5
7
6
8
9
9

54

Totalcapsules Openedratio
10
12
10
8
8
9
11
11
14
18
14
18

63%
65%
40%
63%
50%
59%
45%
55%
54%
64%
57%
51%

APPENDIXGResultsofEDXofthepreloadedECCspecimens
CracksurfaceLocation1

CracksurfaceLocation3

Element
C

Wt%
5.14

At%
9.53

KRatio
0.0156

Z
1.0500

A
0.2884

F
1.0010

Element
C

Wt%
4.85

At%
9.51

KRatio
0.0153

Z
1.0546

A
0.2989

F
1.0011

42.74

59.53

0.0625

1.0323

0.1417

1.0001

37.07

54.56

0.0488

1.0368

0.1268

1.0001

Mg

1.25

1.15

0.0056

0.9902

0.4497

1.0028

Mg

1.13

1.10

0.0050

0.9944

0.4456

1.0029

Al

1.64

1.35

0.0093

0.9610

0.5870

1.0050

Al

1.47

1.29

0.0083

0.9651

0.5836

1.0052

Si

4.82

3.82

0.0337

0.9890

0.7031

1.0064

Si

4.17

3.50

0.0293

0.9932

0.7015

1.0074

0.63

0.44

0.0053

0.9767

0.8478

1.0206

0.50

0.37

0.0043

0.9820

0.8513

1.0241

0.66

0.37

0.0066

0.9394

0.9724

1.0991

0.87

0.53

0.0090

0.9440

0.9743

1.1156

Ca

42.05

23.38

0.3994

0.9615

0.9873

1.0005

Ca

48.87

28.71

0.4665

0.9660

0.9877

1.0004

Fe

1.07

0.43

0.0090

0.8742

0.9643

1.0000

Fe

1.06

0.45

0.0089

0.8787

0.9564

1.0000

Total

100.00

100.00

Total

100.00

100.00

CracksurfaceLocation2

CracksurfaceLocation4

Element
C

Wt%
6.24

At%
11.58

KRatio
0.0186

Z
1.0501

A
0.2831

F
1.0010

Element
C

Wt%
7.12

At%
12.80

KRatio
0.0209

Z
1.0476

A
0.2794

F
1.0009

40.61

56.61

0.0581

1.0324

0.1385

1.0001

42.87

57.88

0.0649

1.0300

0.1470

1.0001

Mg

1.34

1.23

0.0061

0.9903

0.4554

1.0030

Mg

1.60

1.42

0.0073

0.9880

0.4600

1.0030

Al

1.82

1.50

0.0104

0.9612

0.5920

1.0052

Al

2.01

1.61

0.0115

0.9589

0.5944

1.0050

Si

5.35

4.25

0.0376

0.9891

0.7058

1.0065

Si

5.75

4.42

0.0403

0.9868

0.7061

1.0059

0.67

0.47

0.0057

0.9768

0.8454

1.0206

0.54

0.37

0.0045

0.9739

0.8427

1.0187

0.70

0.40

0.0070

0.9396

0.9710

1.0988

0.67

0.37

0.0066

0.9371

0.9704

1.0898

Ca

42.51

23.65

0.4032

0.9616

0.9860

1.0003

Ca

38.66

20.83

0.3656

0.9591

0.9858

1.0003

Fe

0.77

0.31

0.0064

0.8744

0.9636

1.0000

Fe

0.77

0.30

0.0065

0.8719

0.9681

1.0000

Total

100.00

100.00

Total

100.00

100.00

55

NoncracksurfaceLocation5

NoncracksurfaceLocation6

Element
C

Wt%
9.01

At%
15.36

KRatio
0.0264

Z
1.0431

A
0.2808

F
1.0008

Element
C

Wt%
6.65

At%
11.70

KRatio
0.0193

Z
1.0457

A
0.2778

F
1.0009

46.64

59.67

0.0766

1.0256

0.1600

1.0001

45.88

60.62

0.0807

1.0281

0.1711

1.0002

Mg

1.60

1.34

0.0073

0.9839

0.4632

1.0028

Mg

1.71

1.48

0.0085

0.9863

0.5037

1.0032

Al

2.11

1.60

0.0121

0.9549

0.5978

1.0047

Al

2.24

1.75

0.0137

0.9572

0.6352

1.0053

Si

5.85

4.26

0.0409

0.9828

0.7084

1.0051

Si

6.82

5.13

0.0499

0.9851

0.7384

1.0056

0.48

0.31

0.0040

0.9688

0.8435

1.0162

0.54

0.35

0.0045

0.9717

0.8558

1.0174

0.72

0.38

0.0070

0.9326

0.9717

1.0775

0.64

0.35

0.0063

0.9352

0.9716

1.0823

Ca

33.06

16.88

0.3115

0.9546

0.9867

1.0003

Ca

34.68

18.29

0.3273

0.9572

0.9857

1.0004

Fe

0.54

0.20

0.0045

0.8675

0.9746

1.0000

Fe

0.85

0.32

0.0072

0.8700

0.9763

1.0000

Total

100.00

100.00

Total

100.00

100.00

56