ASelfHealingCarbonFibreReinforcedPolymerforAerospace Applications

G.Williams,DrR.Trask,andDrI.Bond
DepartmentofAerospaceEngineering,UniversityofBristol QueensBuilding,UniversityWalk,BristolBS81TR.UK. G.J.Williams@bristol.ac.uk

ABSTRACT
Selfhealingisreceivinganincreasingamountofresearchworldwideasatechnologytoaddressdamage tocompositematerialsautonomously.Thispaperdescribestheresultsoffourpointbendflexuraltesting (ASTMD627202) of T300/914 epoxy Carbon fibre reinforced plastic (CFRP) with embedded hollow glass fibres (HGF) which provide a selfhealing functionality. The testinginvestigatedthe effect of the embedded HGF on the host CFRP and also the healing potential of the laminates after they were subjectedtoquasistaticimpactdamage.Specimensweretestedundamaged,damagedandhealedusinga commercialtwopartepoxyhealingagent.MicroscopiccharacterisationoftheHGFembedmentwasalso usedtounderstandtheeffectonthehostlaminatefibrearchitecture.

1 Introduction One area of focus in the development of advanced composite materials has been to address their vulnerability to impact damage. The orthotropic nature of composite materialsresults inrelatively lowthroughthickness strengthwhich isoftenaccounted forbycreatingdamagetolerantdesignsforstructuralcomponents.Forexample,CFRP is typically designed to an allowable strain level of < 0.4% [1],[2] where as T300 Carbonfibreshaveastraintofailureofaround1.5%(TorayIndustries).Thisresultsin conservativedesignandthushigherweightstructures. Selfhealing is a novel concept for advanced composite materials as an alternative to damage tolerant design and temporary repairs to damaged structures. It derives inspiration from biological responses to damage, such as the human process of hemostasis, in order to impart an autonomous healing functionality into a composite material.Thistechnologyhasthepotentialtomitigatedamageresultingfromanimpact event,therebyprovidinganopportunitytoimprovethedesignallowablesforCFRPor offerotherbenefitssuchasreducedmaintenanceandinspectionschedules. To date,research into selfhealing of polymeric materials has considered a number of approaches[37].Therehasalsobeensignificantresearchintotheuseofsuchsystems in fibre reinforced polymers (FRP) [813]. Research at the University of Bristol is seeking to impart selfhealing functionality to a composite by using embedded resin filled hollow glass fibres (HGF) [1113]. A bespoke fibre making facility[1417] has been used to produce HGF between 30100m diameter and a hollowness of around 50%. These were then embedded within glass fibre reinforced plastic (GFRP) and infusedwithuncuredresintoprovideahealingfunctionalitytothelaminate.Thispaper focuses on the progression of this work by considering its application to carbon fibre reinforcedplastic(CFRP),amaterialmorewidelyusedforaerospaceapplications.

2 SpecimenManufactureandMechanicalTesting The HGF selfhealing work to date has incorporated HGF within GFRP laminates as discrete plies. It was decided that this approach would not be suitable for CFRP laminatesasitwouldeffectivelyproduceahybridglasscarbonlaminateandresultina significantreductioninmechanicalproperties.Alessdetrimentalmethodistodirectly embed asmall numberofdiscreteHGFswithin aCFRPplywherethey actsolely as distributedstoragevesselsforthehealingagent. Usingthis approach, it isessentialthattheembeddedHGFwithinthe CFRPdoes not detrimentally affect the mechanical performance of the laminate but provides a sufficientvolumeofhealingresintoaddressanydamage.Therefore,thedistributionof HGFwithinthe laminate mustbeoptimised.Fourpointbend flexuraltesting(ASTM D627202)wasselectedtoassesstheselfhealingefficiencyoftheresultingCFRPasit hasalreadybeensuccessfullyusedtodemonstrateselfhealinginGFRP. 2.1 SpecimenManufacture Carbonfibre/epoxy(T300/914Hexcel)prepregwasselectedasthehostlaminateasit is typically used for aerospace applications. Quasiisotropic (QI) plates were manufactured [16 ply (45/90/45/0)2S] using a hand layup technique (230mm x 160mmx2.5mm).Curewasundertakenaccordingtomanufacturersrecommendations. TwodifferentHGFdistributions(fibrepitchspacingof70mand200mrespectively) were wound directly onto CFRP plies prior to lamination. This was to determine the effectofHGFonthehostlaminatepropertiesandthehealingeffectivenessofdifferent HGFvolumes.HGFwaslocatedattwo0/45interfaceswithinthelayupasfollows: (45/90/45/0/HGF/45/90/45/0/0/45/90/45/HGF/0/45/90/45) 2.2 MechanicalTesting Asupportspantodepthratioof32:1andasupportspantoloadspanratioof3:1were selected according to ASTM D627202. This resulted in specimen dimensions of 100mmx20mmx2.5mm.Tensampleswerecutfromaplatewiththeuseofawater cooleddiamondgritsaw.The sampleedgesweresmoothed(SiCP2500)toavoidany unwantededgeeffects.Sampleswerethendried,sealedinsamplebagsandstoredina temperatureandhumiditycontrolledenvironmentpriortotesting. Immediatelypriortotesting,theHGFwithineachspecimenwereinfiltrated withpre mixedCycom823(Cytec)twopartepoxyresin,mixratio4:1/wt.usingavacuumassist technique. Quasistatic impact damage was imparted to each specimen using a 5mm spherical tup mounted on a Hounsfield H20KW electromechanical test machine running in load control with the sample supported by a steel ring of 27mm outer diameter and 14mm inner diameter. The indentations were stopped at a peak load of either1700Nor2000N.Atypicalloaddisplacementcurve(Figure1)showsthattwo yield points exist, one at around 1400N, and another at 1700N with a maximum load achievedat2000Natwhichthe loadcan no longerbesustainedandthetupbeginsto penetrate the laminate causing significant back face damage. Up to this point the damage is contained within the laminate and can be likened to BVID, as the impact

surfacesuffersa minimal indentandtheback faceexperiences minimaldistortiondue tobackfacedelamination.

0 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 200 400 600 800 1000 1200 1400 1600 1800 2000 Displacement(mm) 0

After indentation, the specimens were left at 70C for 45 mins to facilitate resin infiltrationatminimumviscosity (25cps)followedby125Cfor75minswhichinitiates cure. The use of a premixed healing resin and elevated temperature after the damage event was an attempt to mitigate some of the shortcomings of the Cycom 823 when employed as a healing agent and to achieve the optimum healing possible with this system.Cycom823isnotdesignedforuseasahealingagent.Infact,noresinsystems currently exist which are specifically designed for this type of application (i.e. low viscosity, 1:1 mix ratio, room temperature cure and long shelf life). The advantage of usingthissystemisthatthetemperatureactivationprovidesexcellentcontrolofthecure initiation,eliminatingtimeconstraintsonthetesting/manufacturingprocess. After healing, test specimens were mounted on a Roell Amsler HCT25 electromechanical test machine with roller spacing determined by the specimen dimensions, as depicted by the test standard [ASTM D627202]. An Instron 8800 controller/datalogger was used to drive the test machine and record data. Specimens were loaded to catastrophic failure at which point the crosshead displacement was stoppedandtheloadremoved.Specimensweremonitoredtoensureaconsistentfailure mode and optical microscopy used to record detailed observations. Results were obtainedfrom10undamaged,5damagedand5healedspecimens. Specimensections fromtwodifferenttestpanels werepotted in epoxyresin,polished and the microstructure examined under optical microscopy. This provided a visual assessment of the disruption caused by the different HGF configurations on the host CFRPpliesandidentifiedanyinconsistenciespresent.Furthermore,itprovidedimages toaccuratelydeterminetheouterdiameterandhollownessoftheHGF,andthemodeof damagepropagationthroughthematerial.

Load(N)

Figure1:TypicalLoadDisplacementcurveforQuasiStaticindentationofCFRP

3 ResultsandDiscussion 3.1 MechanicalTesting

Laminate Strength(MPa) Plain CFRP %ofundamaged Strength(MPa) %ofundamaged Strength(MPa) %ofundamaged Undamaged (S.D%) 583.26(2) 100% 534.85(2) 92% 568.84(3) 98% Damaged(S.D%) @1700N @2000N 538.64(10) 92% 527.31(2) 90% 490.12(7) 84% 404.95(16) 69% 443.74(11) 76% 401.03(13) 69% Healed(S.D%) @1700N @2000N 529.05(3) 91% 523.43(4) 90% 519.62(6) 89% 466.59(5) 80%

HGF spaced @70m HGF spaced @200m

Table1:ResultsofFlexuralFourPointBendTestingofCFRPwithEmbeddedHGF
Undamaged 900 800 700 600 Load(N) 500 400 300 200 100 0 0 2 4 6 8 10 Displacement(mm) Damaged Healed

Figure2:ComparativeLoadDisplacementCurvesunder4PointBendforUndamaged, DamagedandHealedfor70mSpacedHGF Theresultsofthefourpointbendflexuraltestingareshownin Table1above,also Figure2showstypicalloaddisplacementcurvesarisingfromthefourpointbend flexuraltesting.

3.2 OpticalMicroscopy TwoaspectsofincorporatingHGFwereinvestigatedusingopticalmicroscopy: TheeffectontheCFRPhostlaminate Theeffectondamagepropagationthroughthelaminate The fibre spaced at 70m highlighted several issues about embedding HGF within a laminate. This small pitch spacing was selected to ensure the HGF were in close proximity (Figure 3). However, during manufacture HGF could become misplaced resulting in severe disruption to the host ply (Figure 3). This was attributed to fluctuationsinthefibrepitchcontrolatlowHGFspacingcombinedwiththelowtack ofthe914epoxyatambienttemperatureintheCFRPprepreg.Thisresultedinsections of HGF detaching from/reattaching tothe surface producing fibre clumping and resin richregionsaftercure.

Figure3:HGFspacedat70mshowinggood (a)embeddingand(b)fibreclumping withinhostlaminate

Figure4:HGFspacedat200mshowingverygoodembeddingwithinhostlaminate The fibre spaced at 200m resulted in a higher quality laminate (Figure 4). The resin rich regions surrounding the HGF are minimal and there was no evidence of HGF clumping.Thelargespacingbetweenfibresallowedthetackofthe914resinsystem to hold the HGF in place, and any that did detach were able to reattach without contactingthesurroundingHGF.ThelargespacingbetweenHGFpermittedmovement ofcarbonfibresandmatrixresinduringthecurefurtherimprovingthefibreembedment andreducingthedisruptiontothelaminate.

3.3 Discussion Both HGF spacings investigated showed similar trends. All laminates experienced an initial reduction in flexural strength in their undamaged state when compared to the baselineduetothepresenceofHGF.Thiscanbeattributedtothreeeffects: 1. Distortion of the reinforcing fibre architecture (affecting homogeneity of laminate) 2. Generationofresinrichregions(cracknucleation/propagationsites) 3. DisplacementofreinforcingfibreswithnonstructuralHGF(reductionincarbon fibrevolumefraction) Secondly,adamageeventcausesareductioninstrengthduetothegenerationofshear cracksanddelaminationswhichthenpropagateunderloadleadingtoprematurefailure. Finally, a strength recovery is experienced after fractureof HGF where healing agent hasinfiltrateddamagesitesandmitigatedsomeoftheeffectsofdamage. Analysisoftheflexuraltestdata(Table1)showsthatthefibresspacedat70mcaused the largest reduction in undamaged strength (8%). This can be attributed to the large disruption tothe fibre architectureobserved in Figure 3. However, after a quasistatic impact event of peak load 2000N, this configuration exhibited a large amount of damagetolerancewhencomparedtothe200m spacingandplain baseline laminates. This can beattributedtoenergyabsorbed bythe crushingofHGF.Itappearsthatthe initialreductioninstrengthduetothepresenceofasignificantvolumeofHGFisoffset bytheincreaseddamagetoleranceduringanimpactevent.Thelargevolumefractionof HGF in this configuration also provides a large reservoir of healing agent. This is confirmed by the 97% recovery of the undamaged strength (equivalent to 89%of the baseline laminate undamaged strength). Figure 2shows that a damaged specimen containingHGFunderloadexperiencesanumberofintermittentloaddropswhichare probablythepropagationofmatrixcracksanddelaminationstoacriticallevelatwhich they effect the load bearing performance of the laminate. Conversely, the healed specimens appear to rebond these damage sites, inhibiting the onset of crack growth andtherebydelayingthefailureofthelaminate. The 200m fibre spacing specimens exhibited very little reduction in undamaged strength(2%).Again,thiscanbeattributedtothemuchreduceddisruptiontothehost laminatearchitecture(Figure4).Thesespecimensbehavedverysimilarlytothebaseline laminate under impact, presumably due to the limited amount of HGF available for crushing. However, healed samples achieved 82% of their undamaged strength (equivalent to 80% of the baseline laminate undamaged strength), despite the significantlylowervolumeofavailablehealingresin. 4 Conclusions TheincorporationofHGFwithinaCFRPlaminatehasbeenshowntoproduceminimal degradationinflexuralstrengthandminimalplydisruption.Ithasalsobeenshownthat atfibrespacingsofoverthreefibrediameters,nearperfectembedmentoftheHGFcan beachievedevenonthemostdemanding0/45interface.TheembedmentofHGFby windingdirectlyontoCFRPprepregishelpedbythetensionproducedduringthefibre

drawing process and further improved during the cure process as the initial viscosity dropduringcurefacilitatesresinandfibremigrationaroundthelargerHGF. Laminates with higher volume fractions of HGF exhibit a larger degree of damage tolerance under quasistatic impact events which is attributable to energy absorbed by HGFcrushing. LaminateswithresinfilledHGFattwodifferentfibrespacingswereshowntoprovide recovery of flexural strength due to the healing process. It is noted however, that the healing process utilised a nonoptimised resin system employed in an optimised manner,i.e.premixedandallowedtoinfiltratedamageundertemperature.Thishadthe advantageofeliminatingsensitivityoftheresinsystemtostoichiometryandtheissueof resinviscosityontheinfiltrationofdamage. TheoptimalflexuralstrengthrecoverywasforHGFat70mspacing,whichachieved 97%of itsundamagedperformance,and89%of the baseline laminatesperformance. However,thisfibrespacingresultedinsignificantdisruptiontothehostlaminatefibre architectureandthustheinitialmechanicalproperties. FutureworkonselfhealingCFRPwilluseaninstrumenteddropweightimpacttesterto create a more realistic damage condition within the material and apply compression afterimpact,amorerigorousassessmentof theeffectsofHGFonthehostlaminateand thesubsequenthealingperformance. Acknowledgements

References [1] ZhouG(1998)Theuseofexperimentallydeterminedimpactforceasadamage measureinimpactdamageresistanceandtoleranceofcompositestructures CompositeStructures42375382 [2] RichardsonMOWandWisheartMJ (1996)Reviewoflowvelocityimpact propertiesCompositesPartA27:11231131 [3] Dry,C(1996)ProceduresDevelopedforselfrepairofpolymermatrixcomposites, CompositeStructures35:263269 [4] Chen,Xetal,(2002),AThermallyRemendableCrossLinkedPolymericMaterial, Science295,16981702 [5] ZakoM,andTakanoN,(1999),Intelligentmaterialssystemsusingepoxyparticles torepairmicrocracksanddelaminationinGFRP,JournalofIntelligentMaterial SystemsandStructures10,836841 [6] White, S.R. et al, (2001), Autonomic healing of polymer composites, Nature 409: 794797 [7] Brown, E.N, White, S.R. and Sottos, N.R, (2004), Microcapsule induced toughening in a selfhealing polymer composite, Journal of Materials Science 39: 17031710

[8] Motoku,M,Vaidya,U.KandJanowski,G.M.(1999),Parametricstudiesonself repairingapproachesforresininfusedcompositessubjectedtolowvelocityimpact, SmartMaterialsandStructures8:623638. [9] Bleay, S.M. et al, (2001), A smart repair system for polymer matrix composites, Composites:PartA32:17671776 [10] Brown,E.N,White,S.R.andSottos,N.R,(2005),Retardationandrepairoffatigue cracks in a microcapsule toughened epoxy compositePart 2: In situ selfhealing, Comp.Sci.Tech.SpecialAnniversaryIssue65:24742480 [11] Pang, J.W.C and Bond, I.P(2005) Bleeding compositesdamage detection and selfrepairusingabiomimeticapproachCompositesPartA36:183188 [12] Pang, J.W.C and Bond, I.P (2005) A hollow fibre reinforced polymer composite encompassingselfhealingandenhanceddamagevisibilityCompositesScienceand Technology65:17911799 [13] Trask, R.S and Bond, I.P (2006) Biomimetic SelfHealing of advanced composite structuresusinghollowglassfibresSmartMater.Struct15:704710 [14] HuckerM,BondI.P,ForemanA,HuddJ,Optimisationofhollowglassfibresand theircomposites.AdvancedCompositesLetters Vol.8No.4(1999)pp.181189. [15] HuckerM.J,BondI.P,HaqS,BleayS,ForemanA,Influenceofmanufacturing parametersonthetensilestrengthsofhollowandsolidglassfibres.J.Mat.Sci.Vol. 37No.2pp.309315. [16] HuckerM.J,BondI.P,BleayS,HaqS,Investigationintothebehaviourofhollow glassfibrebundlesundercompressiveloading.CompositesAVol.34No.11(2003) pp.10451052. [17] HuckerM.J,BondI.P,BleayS,HaqS,Experimentalevaluationofunidirectional hollowglassfibre/epoxycompositesundercompressiveloading.CompositesAVol. 34No.10(2003)pp.927932.