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www.mejournal.

orgJournalofMetallurgicalEngineering(ME)Volume4,2015
doi:10.14355/me.2015.04.006

LaserSurfaceTreatmentofMetalImplants:
AReviewArticle
IbrahimM.Ghayad,NabilN.Girgis,WafaaA.Ghanem
CentralMetallurgicalResearch&DevelopmentInstitute(CMRDI),P.O.Box:87Helwan,Cairo,Egypt
ighayad@yahoo.com

Abstract
Metal implants are mainly fabricated from stainless steels, cobalt base or titanium base alloys. In addition to mechanical
properties, metal implants must have excellent corrosion resistance as well as good bioconductivity and biocompatibity.
Biocompatibity is achieved on a metal implant by the application of proper surface treatment. This paper reviews the
techniques used for surface treatment of metal implants with a special focusing on laser surface treatment as a new and
promisingtechnologyforsurfacetreatments.Publishedpapersindicatedthatsurfacetreatmentsperformedonmetalimplants
aremainlyoftwo types; the first concernedwith the deposition of hydroxyapatite (HA),bonelike material while the second
focusedonthedepositionofdiamondlikecarbon(DLC).PresentreviewcoversindetailthelasersystemsusedforeitherHA
orDLCcoating.
Keywords
Laser;MetalImplants;DiamondLikeCarbon;Hydroxyapatite

Introduction
Metallic materials are widely used as internal fixation implants in bone fracture surgery to provide temporary
support during the bone healing period [1] Stainless steels, titanium alloys, cobaltchromium based alloys and
magnesiumalloysarecommonlyusedforthispurpose.Alimitationofthesealloysisthepossiblereleaseoftoxic
metallicionsand/orparticlesthroughcorrosionorwearprocesses[26]thatleadtoinflammatorycascadeswhich
reducebiocompatibility,causingtissuelossoradverselyaffecttheirmechanicalintegritybeforehealing[713].
Several techniques have existed to improve the corrosion resistance and biocompatibility of above mentioned
alloys;themosteffectiveissurfacetreatment.Inthistexttwotypesofsurfacetreatment,usedformetalimplants,
will be discussed. The first concerns with the deposition of phosphates, mainly hydroxy apatite (HA), while the
seconddealswiththedepositionofdiamondlikecarbon(DLC).
Hydroxylapatite (HA), is currently used as a biomedical material due to its excellent biocompatibility and
bioactivitywhichattributedtoitschemicalandstructuralsimilaritiestoboneandtoothmineral[14].Onaccountof
itslowstrengthandhighbrittleness,HAisusedasabioactivecoatingonmetallicsubstrates.
Whennaturalhumanheartvalvesundergodegenerativeprocesssuchascalcificationofleaflets,duetoinfections,
ageing, or dietary problems, artificial heart valves replacement is a solution and low temperature isotropic
pyrolytic carbon (LTIC) is the most common and widely used material. Unfortunately, its blood compatibility is
still not adequate and as a result, patients must continue to take blood anticoagulation medicine. However,
amorphous carbon (ac) or diamondlike carbon (DLC) films are potential biomedical materials due to their
chemicalinertness,impermeabilityandexcellentmechanicalproperties.
ManymethodshavebeendevelopedtoprepareHAcoatingsandtodepositDLCthinfilms.Thesemethodsare:
solgelprocess,electrophorticdeposition,thesputteringprocess,biomimeticmethodsplazmaspraying,physical
vapordepositionaswellaslasertechniques[1521].
Thisreviewfocusesonlasersurfacetreatmentasanewandpromisingtechnologyforsurfacetreatmentsofmetal
implants. Hydroxyapatite coatings and diamondlike carbon films deposited on metallic substrates using laser
technologyaredescribedanddiscussed.

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Types of Laser Surface Treatment Techniques


Krishnanetal.[21]reviewednovellasertechniquesusedforsynthesisofnanostructuredcoatingsandthinfilms.
Thesetechniquesare:Laserpyrolysis,laserassistedatmosphericchemicalvapordeposition(LAACVD)andpulsed
laser deposition (PLD). In the laser pyrolysis technique the aerosols generated using an ultrasonic particle
generator or compressed air nebulizer, (metal nitrate solution droplets), are passed through a quartz tube. The
laserwascoupledintothequartztubeinacoaxialmannerandthelaserbeamalongwiththeaerosolwasdirected
towards the substrate kept very close to the focal point of the focusing lens. The laser interacts with the aerosol
duringitstransitthroughthetubeaswellasatthesubstrate,leadingtoreactionwithatmosphericoxygenatthe
substrate forming an oxide coating. By adjusting the process parameters, localized novel nanostructures are
obtained.TheselocalizedstructuresareproducedbecauseoftheGaussiandistributionoflaserpowercoupledwith
nonequilibriumnatureofsurfacereaction.
Inlaserassistedatmosphericchemicalvapordeposition(CVD)techniquethecoatingprecursorusedisasuitable
metalorganiccompounddissolvedinethanol.Theprecursorisatomizedusinganultrasonicparticlegeneratorto
produce aerosols of 1 to 5 micron size. Upon laserprecursor aerosol interaction, the metal organic compound
undergoesvaporizationwithoutdecompositionandthevaporsreactwiththeoxygenpresentintheatmosphereat
the laser focused spot on the substrate surface to give oxide coating. Uniform large surface area coatings are
obtainedbyrastering.Acomputerizedrasterstageisusedforthispurpose.
Pulsedlaserdeposition(PLD)isathinfilmdepositiontechniquewhereahighpowerpulsedlaserbeamisfocused
insideavacuumchambertostrikeatargetofthedesiredcomposition.Materialisthenvaporizedfromthetarget
and deposited asa thin film on a substrate. This process can occur in ultra high vacuum or in the presence of a
backgroundgas,suchasnitrogenwhichisusedwhendepositingnitrides.Whenthelaserpulseisabsorbedbythe
target, energy is first converted to electronic excitation and then into thermal, chemical and mechanical energy
resulting in evaporation, ablation, plasma formation and even exfoliation. The ejected species expand into the
surrounding vacuum in the form of a plume containing many energetic species including atoms, molecules,
electrons,ions,clusters,particulatesandmoltenglobules,beforedepositingonthetypicallyhotsubstrate.
Laser surface melting technique modifies the metal implant surface by refining the structure after melting and
rapid crystallization. It is wellknown that grain refinement improves mechanical properties and corrosion
resistance.
Hydroxiapatite Coatings
Nelea et al. [22] investigated hydroxiapatite thin films grown by pulsed laser deposition (PLD) (Figure 1). The
targets were prepared from highpurity (99.98%) polycrystalline HA powder (grains 100 mm) by cold pressing
followed by annealing in air at 600oC. A Ca/P atomic ratio of 1.6 was inferred by energy dispersive Xray
spectrometry. The TiN buffer interlayer was deposited by reactive pulsed laser deposition (RPLD) by ablating a
stoichiometric TiN target in nitrogen, whereas the metallic substrate was heated at 650oC. A Series of 104
subsequentlaserpulseswereappliedforthegrowthof<1mmthickHAfilm.Theaverageablationratewas0.5
A.U.perpulse.
In the work of Grigorescui et al [23], a hydroxyapatite target was ablated in an oxygen controlled atmosphere
chamber bymeans ofa KrF excimer laser beam of248 nm wavelength,generating pulses of10 nsduration. The
laser source was operated at a frequency repetition rate of 2 Hz. The spot area was between 4.55 mm2, and the
incidentlaser fluence on the target was 2.6 J/cm2. Inorder to avoid target piercing during multipulse ablation, a
rotationmovementwasapplied.Thecoatingsweredepositedon15mmdiameterdisksmadeofhighpurityc.p.Ti,
heatedat400C.Priortoeveryfilmdeposition,thechamberwasevacuateddowntoaresidualpressureof104Pa.
Thenadynamicalfluxof10PaO2wasintroducedandcarefullymonitoredduringdeposition.Forobtainingone
film,15000subsequentlaserpulseswereapplied.Afterdeposition,thefilmsweretreatedinwatervapourenriched
atmosphereat400Cfor6hours,inordertoimprovetheircrystallinestate.Othersampleshavebeenpreparedby
the insertion of a buffer layer interlayers of TiN deposited by PLD before the application of HA coatings. The
thicknessofTiNlayerwasestimatedto~200nm,whilethethicknessofHAlayerswasestimatedtobeintherange
11.5m.

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IntheworkofSyedetal.[24],apowder,blendofdifferentpowdersorpowdersfromtwoormorepowderfeeders
weredeliveredtoalasergeneratedmeltpoolonasubstratesurface(Figure1).Therelativemovementofthelaser
and the substrate causes the enlarged melt pool to solidify and a wellbonded clad/tack with the substrate is
formed.Thismethodcanalsoproducefunctionallygradedmaterials(FGMs).Dependingupontherequirementfor
the final part, varying proportions of different materials can be added on top of each other to obtain a graded
structure.Themainpurposeofusingagradedlayercoatingistoovercomethestressrelatedfailureofcomposite
coatingsthatmightresultfromasharpcontrastofproperties,suchasthermalexpansionbehavior.

FIGURE1SCHEMATICDIAGRAMOFTHEEXPERIMENTALAPPARATUSFORPOWDERPOWDERDEPOSITION(SCHEMATIC)

Vasanthan, Drukteinis and Lacefield (2008) [25] deposited commercially pure hydroxiapatite on cpTi substrate
using pulsed laser technique. They used KrF excimer laser (248 nm), with an energy density of 410 J/cm2 and a
repetitionrateof30Hzwhilethesubstratetemperaturewaskeptbetween625oCand715oC.Adeflectingmirror
was used to guide the laser into a controlled atmosphere chamber where it ablated the HA target to generate a
plume ofatoms, ions, and particles (Figure 2). These particles then coalescedand deposited themselves onto the
surfaceoftheheated,rotatingalloyinanargon/wateratmosphere,therebyformingthecoating.

FIGURE2SCHEMATICDIAGRAMOFTHEPULSEDLASERCOATINGSYSTEM

Rau et al [26] deposited fluorinated hydroxyapatite (FHA) films on Ti using pulsed laser technique. The use of
FHA in biomedical applications is expected to be advantageous, since it can promote mineralization and
crystallizationofcalciumphosphateduringthedentalandboneformationprocessesandensuretheformationofa
mechanicallyandfunctionallystrongerbonebyprovidingthefluorinereleaseatacontrolledrate.Thesynthesisof
fluorinatedhydroxyapatitewascarriedoutbymixingCaO,(NH4)2HPO4andNH4F.FHAfilmsweredepositedon
heated Ti substrates inahigh vacuum PLD chamber. Depositions were performed byablating thesintered FHA
rotatingtargetwithalaserbeamgeneratedbyapulsedKrFexcimerlaser(l=248nm);thelaserpulsedurationwas
17nm,andtherepetitionratewas5Hz.Thelaserbeamwasorientedwithaninclinationangleof45owithrespect
tothetarget,whereasthesubstrateandtargetwereassembledinafrontalgeometryat4cmofreciprocaldistance.
The PLD chamber was evacuated down to a base pressure of 1x106 mbar prior to the film deposition; then,

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depositions were performed at 5x 104 mbar in a controlled dynamic pressure produced by the N2 gas flow,
introduceddirectlyintothechamberthroughaneedlevalve.Thedepositiontimeforeachsamplewas25min,fora
total of 7500pulses.A setof FHAfilms were deposited at fixed temperature (400oC)and different energy of the
laserbeam(2,3,5,7J/cm2).
Bai et al [27] reported processing and characterization of functionally graded hydroxyapatite (FGHA) coatings
incorporated with Ag as an antibacterial component. FGHAcoated implants incorporated with antimicrobial
agents are able to prevent or cure infections by releasing directly the antimicrobial agents to local regions. The
amorphoustoplayerofthecoatingallowsahigherreleaserateofsilverduetoitshigherdissolutionimmediately
after implantation; the crystalline layer will maintain the silver as a reservoir, resulting in long term infection
protection.
Man, Chiu and Guo [28] studied the effects of laser drilled microholes at the surface of the metals in order to
achieve a strong adhesion for a structural joint or a bone tissue fixation for medical implants. The effect of the
numberofholesperunitareaontheadhesionstrengthoftheadhesionjointwasevaluated.Resultsshowedthat
the number of holes per unit area on the adherent surface logarithmically correlated with the bonding strength.
Otherholesgeometriesaresuggestedforenhancedadhesionandbonetissuefixation.
In the workofHu etal. [29], the Insitusynthesis and fabrication of tricalcium phosphate bioceramic coatingon
commercially pure Ti by laser rapid forming (LRF) was investigated (Figure 3). The powders of CaCO3 and
CaHPO42H2Owereusedasrawmaterials.ThepowdersweremixedwelltoyieldapowderwithaCa/Pratioof
1.5 and then loaded into the powder feeder. The cpTi substrate plate was cleaned with absolute alcohol and
acetone to remove surface contamination and then fixed to the NC working table. A computer controlled
continuouswaveCO2laserwasusedtoscanthesurfaceofthesubstratewiththeenergydensityof60J/mm2(laser
powerof400W;scanningvelocityof100mm/min;laserspotdiameterof4.0mm)andapowderfeedrateof3.0
g/min.Thecoatingwasfabricatedinaclosedchamberfilledwithargon(Ar)gastoavoidoxidation,andArgas
wasalsochosenasthepowdercarriergas.IntheLRFsystem,theNCworkingheadcontrolledthemovementof
thelaserfocusingmirrorandthelateralpowderfeednozzlesothatthelaserspotandpowderdeliverysitemoved
synchronously.Thenthemixedpowderwasmeltedandsolidifiedrapidlywiththelaserspotmovingaway,soa
single track of coating was fabricated. Since the working head moved in cycles with an overlap ratio of 35%
between adjacent tracks, multiple tracks of coating eventually converged to form a complete coating. The phase
composition of the coating contained 95 wt.% of TCP and 5 wt.% of TCP. Three layers were found in the
coating:a ceramic layer,a transitional layer,and the substratelayer. In the transitional layer, interpenetrationof
phaseswasobserved.ThebondingstrengthbetweenthecoatingandthecpTisubstratewasinexcessof40.17MPa.
Furthermore,thestaticimmersiontesthasconfirmedthatthecoatingnotonlypreventedthecorrosionofcpTi,but
alsoinducedtheredepositionofTCPinsyntheticsaliva.

FIGURE3SCHEMATICPRESENTATIONOFTHELASERRAPIDFORMINGPROCESS

Diamond-like Carbon Coatings


Diamondlikecarbon(DLC)coatingswereperformedonlyundervacuumusingpulsedlasertechnique.Authors
usedArF,KrForNdYAGlasers.

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Wangetal.[30]succeededtodepositdiamondlikecarbonfilmscontainingmetalelementsonbiomedicalTialloys.
Intheirwork,aseriesofamorphoushydrogenatedcarbonfilms(withandwithoutmetalnitrideinterlayer)were
depositedonbiomedicalTialloy(Ti6A14V)substratesusingacathodearcevaporation(CAE)system.
The experimental apparatus of the pulsed laser ablation system for film deposition used by Xiong et al [31] is
schematicallyshowninFigure4.Itconsistsofastainlesssteelhighvacuumchamberpumpedbyaturbomolecular
pumpwithabasepressureoflxl07Torr.AnArFpulsedlaserbeamwiththewavelengthof193nmandthepulse
durationof21ns(FWHM)isintroducedintothechamberthroughanantireflectioncoatedconvexfocuslensanda
supersil quartz window. The stabilized output energy of 300 mJ/pulse and a repetition rate of 5 or 10 Hz are
normallyused.Thelaserbeamimpactsthetargetatanangleof45otothesurfacenormalandhasaspotsizeof12
mm2atthetargetsurface.Theinstantaneouspowerdensityatthetargetisestimatedtobeabout5x108W/cm2.A1
inch diameter pyrolytic graphite (PG) disk is used as an ablation target. It is kept rotating at 10 rpm during the
process.Thelaserplumeisemittedalongthesurfacenormalofthetarget,intensifiedwithinafewmillimetersnear
the surface in a bluishwhite color, then expanding forward in a reddish cone. The unheated substrate is placed
about one inch away and parallel to the target. A typical deposition rate of 0.1 nm/pulse is obtained, slightly
varying with the deposition conditions, such as the vacuum condition and laser pulse energy. Ntype Si(100)
wafers (resistivity 0.1 ncm), fused quartz slides, and cover glass slides are routinely used as substrates. The
resultingfilmspossessremarkablephysical,opticalandmechanicalpropertieswhichareclosetothoseofdiamond
anddistinctfromthegraphitetargetused.Thefilmshaveamechanicalhardnessupto38GPa,anopticalenergy
band gap of 2.6 eV and excellent thermal stability. Analysis of electron energy loss spectroscopy reveals the
domination of diamondtype tetrahedral bonding structure in the films with the spl bond fraction over 95 %.
Compared to other reported results of pulsed laser deposited diamondlike carbon films, experimental results
confirmthatthelaserwavelengthorphotonenergyplaysacrucialroleincontrollingthepropertiesofpulsedlaser
depositeddiamondlikecarbonfilms.

FIGURE4SCHEMATICDIAGRAMOFTHEPULSEDEXCIMERLASERABLATIONSYSTEMFORFILMDEPOSITION

HanabusaandTsujihara[32]depositedDiamondlikecarbon(DLC)filmsbylaserablationwiththetargetmadeof
frozenacetylene,insteadofconventionalgraphite(Figure5).Theyusedastainlesssteelvacuumchamber,20cmin
diameterand25cmhigh,containedaquartzsubstrateonaheatedholder.Thetargetwaspreparedonacopper
plate and placed in contact with a liquid nitrogen reservoir. Acetylene was blown through a quarter of an inch
stainlesssteelpipetowardthecopperplate.Arotarypumpevacuatedthechamberduringthetargetpreparation.
After a frozen acetylene layer grew into roughly 12mm thick layers, the gas supply stopped and a turbo
molecularpumpwasturnedontoimprovethepressureofthechamberto106Torr.Itincreasedto105Torrduring
deposition. The light source used was a 193nm ArF laser with a pulse width of roughly 14 ns. The repetition
frequencywassetat10Hz.Thespotsizeoflaserbeamsonthetargetwasadjustedbyaquartzlenswithafocal
length of 35 cm. Laser beam was moved constantly across the target to avoid ablation of the copper surface
exposedafterlosingthefrozengas.Thequartzplatewasplacedinthevacuumchamberatadistanceof40 mm
fromthetargetaftersurfacecleaning.TheCHbondwasmoreabundantinthefilmsdepositedbytheKrFlayer.
Itwaspossibletodepositparticlesfreefilmsincontrasttolaserablationofgraphitetargets.Experimentalresults
suggesttheimportanceofenergeticandchargedspeciesejectedfromfrozenacetylene.

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FIGURE5SCHEMATICDIAGRAMOFTHEARRANGEMENTLASERABLATIONFORDEPOSITIONOFDLCFILMS

IntheworkofLackneretal.[33],GraphitetargetswereablatedwithpulsedNd:YAGlaserat1064nmwavelength
in argon and C2H2 atmospheres to deposit amorphous hydrogenfree (aC) and hydrogenated (aC:H) DLC onto
various steel substrates (AISI 1045H, B7, H13, D2, M2). The targets were rotated during the laser irradiation in
ordertoavoidtheformationofdeepcraters.Depositionratesbetween15and35nm/minhavebeenreachedfor
bothaCandaC:Hcoatings,depositedinArandC2H2atmospheres,respectively.
Honglertkongsakul, May and Paosawatyanyong [34] investigated the pulsed laser ablation of a graphite target by
ArFexcimerlaserdepositionatalaserwavelengthof193nmandfluenciesof10and20J/cm2toproducediamond
like carbon (DLC) films (Figure5). DLC films were deposited on siliconand quartz substratesunder 1106 Torr
pressureatdifferenttemperaturesfromroomtemperatureto250C.Theeffectoftemperatureontheelectricaland
optical properties of the DLC films was studied. Raman spectroscopy (LRS) showed that the DLC band slightly
increased to higher frequency with increasing film deposition temperature. Spectroscopic ellipsometry (SE) and
ultravioletvisible absorption spectroscopy showed that the optical bandgapof the DLC films was0.82 eVand
decreasedwithincreasingsubstratetemperature.Theseresultswereconsistentwiththeelectricalresistivityresults,
which gave values for the films in the range 1.01042.8105 cm and which also decreased with deposition
temperature.Weconcludethatathighersubstratedepositiontemperatures,DLCfilmsshowincreasinggraphitic
characteristicsyieldinglowerelectricalresistivityandasmalleropticalbandgap.
YapandTou[35]depositeddiamondlikecarbonfilms(DLC)onsiliconandglasssubstratesbyusinga10Hz,4.7
ns, NdYAG laser at thirdharmonic and fundamental wavelengths of 355 nm and 1064 nm, respectively. A
pyrolytic graphite target was fixed in position while the laser beam, which was focused to a 0.5 mm diameter,
ablated overanarea6.5mm x 6.5 mm at an incident angle of45 byan XY steppermotor beam scanner. Laser
fluenciesof21J/cm2and42J/cm2wereusedingraphiteablation.Theptypesiliconwafer(100)witharesistivityof
10ohmcmwasusedassubstrates.Inatypicaldeposition,substratewithdimensionof0.8cmx0.8cmwasplaced
at3cmdistancefromthetarget.Thebasepressureofthedepositionwas106Torr.
In the studyof Cho et al [36],functionally gradientdiamondlike carbon (FGDLC) filmswere fabricated usinga
novelpulsedlaserdepositiontechniquetoenhanceadhesionstrength.A355nmpicosecondslaserbeamwassplit
intotwobeams,andthepowerofeachsplitbeamwaschangedindividuallybyamotorizedbeamattenuatorasa
function of time. In this way, two laser beams with customized timevarying powers were available for ablating
twodifferenttargetmaterials.Twobeamswereirradiatedongraphiteand316Lstainlesssteeltargets,respectively,
inavacuumchamber,andtheproduceddissimilarplasmasweremixedinspacebeforetheyweredepositedona
stainlesssteel316Lsubstrate.Usingthismethod,theyhavebuiltFGDLCfilmswithathicknessof510nm,where
thecompositionchangesgraduallyfromstainlesssteeltoDLCinthedirectionofdeposition.Theyhaveconfirmed
thatFGDLCfilmsshowmuchhigheradhesionstrengththannormalDLCfilms.

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In the study of Fominski et al [37], Bilayer WSeC/diamondlike carbon (DLC) and WSex/DLC coatings were
obtained by standard and shadowmasked pulsed laser codeposition from WSe2 and graphite targets. WSeC
coatings appeared as nanocomposites containing quasiamorphous WSe2, WC, spherical W nanocrystalline
particles encapsulated in WSe2 amorphous shell, and amorphous carbon phases. In WSex/DLC coatings, the
formation of chemical bonds between W and C atoms was noticed at the interface. An increased of the C
concentrationover40at.%increaseshardnessandelasticity(upto2timesat~60at.%C),andtheSe/Wratiowas
alwayscloseto1.4.Theuseofshadowmaskedconfigurationavoidedthedepositionofmicroandnanoparticles.
However,thismethodledtoasubstantialincreaseoftheSecontent(Se/W4),andthecoatingsbecamesofter.
Conclusions

Metalimplantsaremainlyfabricatedfromstainlesssteels,cobaltbaseortitaniumbasealloys.Metalimplants
musthaveexcellentcorrosionresistanceaswellasgoodbiocompatibity.

Biocompatibity is achieved on a metal implant by the application of proper surface treatment. Laser surface
treatmentisconsideredasanewandpromisingtechnologyforsurfacetreatments.

Laser surface treatments performed on metal implants are mainly of two types; the first concerned with the
depositionofhydroxyapatite(HA),bonelikematerialwhilethesecondfocusedonthedepositionofdiamond
likecarbon(DLC).DLCcoatingsareformedonlyundervacuum.

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