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Timetoheal:Thematerialsthatrepairthemselves
ByPaulRincon
Scienceeditor,BBCNewswebsite
30October2012 Science&Environment

GETTYIMAGES

Atsomepointinthenearfutureyou'llwearoutthoserunningshoes,breakthatsquash
racket,dropyoursmartphoneandcrackthescreen.
Theywillneedtobereplacedatacost.
Butwhatifwemadethingsfrommaterialsthatcanhealthemselveslikeaplantoranimalheals
awound?
Accordingtoexperts,thefirstproductswithtrulyselfhealingpropertiesmaybejustaroundthe
corner.
Seriousproposalsforthistechnologygobackatleastasfarasthe1960s,whenSoviet
researcherspublishedtheorypapersonthetopic.
Butitwasa2001studyledbyScottWhitefromtheUniversityofIllinoisatUrbanaChampaign,
thatreallyhelpedtokickstartthefield.
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Thegroupinfusedaplasticlikepolymerwithmicroscopiccapsulescontainingaliquidhealing
agent.Crackingopenthematerialcausedthecapsulestorupture,releasingthehealingagent.
Whentheagentmadecontactwithacatalystembeddedinthematerial,achemicalreaction
bondedthetwofacesofthecracktogether.Thepolymerrecoveredsome75%ofitsoriginal
toughness.
Inthelastdecade,theteamhasdevelopedandrefineditscapsulebasedsystems,recently
demonstratinganelectricalcircuitthathealeditselfwhendamaged.Microcapsulesinthegold
circuitreleasedliquidmetalinresponsetodamage,swiftlyrestoringelectricalconductivity,and
bringingselfrepairingelectronicchipsastepcloser.
CoauthorDrBenjaminBlaiszik,nowatArgonneNationalLaboratory,explainedthattheself
healingcircuitrycouldfindusesinamilitarysettingwhereitwouldbeexposedtoextreme
stressesorinlongtermspaceapplications.
Headds:"ImagineifthereisamechanicalfailureofamicrochipontheCuriosityrover,dueto
thermomechanicalstresses,oriftherehadbeenaninterconnectfailureduringthelanding
phase.Thereisobviouslynowaytomanuallyrepairnorreplacetheprobe."
TheIllinoisgroupisalreadycommercialisingtheirworkviaaspinoutcompany,Autonomic
Materials,whichhasraisedabout$4m(2.4m)ofinvestment.Itschiefexecutive,JoeGiuliani,
toldmethefirstapplicationsofmicrocapsulesystemsarelikelytobeincoatings,paintsand
adhesivesforenvironmentswherecorrosionposesachallenge."Worldwide,corrosioncosts
over$500bn(312bn)ayear,soit'sahugeproblem,"hetoldBBCNews.
Oilandgasisakeyarea.Rehealableproductsarelikelytofindusesonplatformswherethe
abilitytohealdrillingpartswouldbehighlydesirableinpipelinesandinrefineries.Theywould
potentiallylastseveralyearslongerthantheirconventionalcounterparts,lengtheningtheperiods
betweenmaintenance.
"Overthelifeofthatasset,therewouldbehugesavings,"saysGiuliani."Itisoutofcommission
foralotlesstimetoo,whichintheoilandgasbusinessishuge.Itcancostthem$500,000
(312,000)or$1m(624,000)adayifanassetisoutofservice."
Militaryvehicles,carsandshipsareothertargetsforselfhealingcoatings.Thefirmhasabout
30productsintestinganddevelopmentandexpectstofulfilitsfirstcommercialordersinthe
nextsixmonths.
Somemanufacturersmightnotwelcometheideaofproductsthatlastyearslongerthanusual.
Butpaintandcoatingsproducers"knowtheycangetmorepergallonofpaintthey'reselling,"
saysMrGiuliani,"thecustomershaveshownusthey'rewillingtopaytheupcharge."
ScottWhite,fromIllinoisUniversity'sBeckmanInstitute,saysthathealingstructuraldamagein
sportsequipmentoraircraftcomponents,forexample,representsa"midtermtarget"for
scientists.
HetoldBBCNewsthatthewholeareaofselfhealinghasseenanexplosionofinterestinthe
lastdecade,withsome200academicpaperspublishedonthetopiclastyearalone.And
scientistsareworkingoneverythingfromrehealablepolymersandcomposites(materialsmade
fromtwoormoredifferentones)toselfrepairingmetalsandceramics.

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Since2001,twonewapproacheshavejoinedmicrocapsulesasapproachestoselfrepair.
Takingthecirculatorysystemastheirinspiration,vascularmethodsrelyonanetworkof
channels(likecapillaries,veinsandarteries)withinthematerialtodeliverhealingagenttothe
siteofdamage.Intrinsicsystems,meanwhile,exploitthereversiblenatureofcertainchemical
bondstoincorporatehealingabilitiesdirectlyintothematerial.
Eachofthethreeapproacheshasadvantagesandlimitationsthatcomeintoplaywhen
consideringapplications.Microcapsulesarefinite:astheygetusedup,themateriallosesits
healingproperties.Andintrinsicsystemsneedastimulussuchasheatorlighttotrigger
healing,whichcanbegoodorbaddependingontheapplication.
Iftheamountofdamageismicroscopic,capsulebasedorintrinsicsystemsmaybethebest
option.But,saysProfWhite,"ifit'salargedamagedvolume,thenneitherofthoseapproaches
aregoingtoworkandyouhavetogowithavascularbasedsystem".
Thisisbecausetheyallowlargeamountsofhealingagenttobetransportedtothebreached
area.Butthesheercomplexityofvascularnetworkspresentsadauntingchallenge.

Selfhealingsystems

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ProfIanBondandhiscolleagueDrRichardTraskatBristolUniversityaredevelopingvascular
networksbasedonhollowfibresthattransmithealingagentthroughpolymercomposite
materials."Aselfhealingaeroplaneistheidea,"ProfBondtellsme.
Thecompositematerialsextensivelyusedinthestructuralelementsofaircraft"areinherently
damageprone",saysProfBond,adding:"Youoftencan'tseeiteventhoughitcanhavea
seriousknockdowneffectonperformance."
TheBristolteamistargetingknownareasofstressbuildupinsidetheskinofaplane."Self
healinginthosesortsofareasispotentiallyveryattractivebecauseyouknowyou'regoingto
getcracksthere,"heexplains.Thechallengeislikelytobeinconvincingaviationauthoritiesof
thetechnology'svalueandsafety.
SoProfBondisworkingtoovercomesomeofthehurdlesfacingvascularsystems.Thestepup
frommicrocapsulestoanetworkintwoorthreedimensions,forexample,presentsasignificant
manufacturingchallenge.Fluidflowgettingthehealingagentthroughthematerialrepresents
anotherproblem.
Thenthereistheissueofcontrollingwhenhealinghappens."Ifyouthinkofblood,itdoesn'tclot
untilit'soutsidethevessel,"hesays."Youwantsomethinglikethat,becausethedangerwith
simplechemistriesisthatthewholenetwork,oncehealinghasbeentriggered,willjustsolidify."
Despitethis,saysScottWhite,vascularnetworksofferexceptionalhealingefficiencyandvast
possibilities."Insomeofthelaboratorytestswe'vedone,we'vebeenabletoshowwecouldheal
something15,20,30timesinarow,"hesays.
ProfStuartRowanatCaseWesternReserveUniversityinCleveland,Ohio,hasdevelopeda
polymerbasedmaterialthatrepairsitselfinresponsetoanintensebeamofultravioletlight.He
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says:"Whatyoucanimagineisessentiallyapaintcoatingonyourcarthatyoucanheal
wheneversomeonehasrubbedakeydownthesideofit."

BENJAMINBLAISZIK

Unlikeconventionalpolymers,whicharecomposedoflong,chainlikemolecules,thismaterial
(anexampleofanintrinsicsystem)iscomposedofsmallermolecules.Theyareassembledinto
chainswithmetalionsactingas"glue"betweenthem.UVlightcausesthesebondstoweaken,
turningthesolidintoaliquid.Whenthelightisswitchedoff,thematerialquicklysolidifies.
ProfRowantoldBBCNews:"Havingprovedtheconcept,weareworkingonthenextgeneration
offilmsthatutilisesuchconceptsforphotohealingbutwherethematerialsexhibitbetter
propertiesbetterdesignedforaspecificapplication."
Meanwhile,HenkJonkersandErikSchlangenatDelftUniversityofTechnology(TUDelft)inthe
Netherlandswanttobringselfrepairtotheworld'smostusedbuildingmaterial:concrete.
Concretehasaseriousflaw:itispronetocracks.

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TUDELFT

Smallcracksarearoutineoutcomeofconcretehardening.Butovertimewaterandchemicals
getinsidethefracturesandcorrodetheconcrete.
ThesolutiondevelopedatTUDelftcouldimprovetheservicelifeofthestructurepromising
considerablecostsavings.Harmlesscalciteproducingbacteria,alongwithnutrients,are
embeddedintheconcretemixture.Whenwateractivatesthedormantspores,themicrobesfeed
onthenutrientstoproducelimestone,patchingupcracksandsmallholes.
Longerterm,ScottWhiteenvisagesmaterialsthatrespondinamorecomplexwaytodamageor
wear,renewingthemselvesovertheirlifetimes,inmuchthewaythatbonesdo.
Selfhealingprovidesacasestudyinthewaythatbiologicalsystemscandriveadvancesin
materials,butIanBondsays:"There'salotmorewecoulddowithwhatwehavethewaywe
currentlymakecompositesiswithflatlayersandfibresallpointinginthesamedirectionit's
thatsimple.
"We'reonlybeginningtounderstandhownaturedoeswhatitdoeswithsuchbasicmaterials."
Paul.RinconINTERNET@bbc.co.uk

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