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Surface&CoatingsTechnology206(2012)26822689

ContentslistsavailableatSciVerseScienceDirect
http://www.sciencedirect.com/science/journal/02578972
Surface&CoatingsTechnology
journalhomepage:www.elsevier.com/locate/surfcoat

 
PhasetransformationbehaviorofnanocrystallineNiWPalloyscontainingvarious
WandPcontents
J.N.Balaraju a,#Pages b un
ⁿ ,Kalavati,N.T.Manikandanath,V.K.WilliamGrips
[1] #Pages [1] #Pages [1]
un
#Pages [1]
un
SurfaceEngineeringDivision,CSIRNationalAerospaceLaboratories,Bangalore560017,India
b
MaterialsScienceDivision,CSIRNationalAerospaceLaboratories,Bangalore560017,India

articleinfo e x t r a c t o

Articlehistory:  
Inthepresentinvestigation,electroless(EL)ternaryNiWPcoatingswerepreparedusinghypophosphite
PalabrasclaveReceived10July2010 
basedalkalinebathbyvaryingsodiumtungstateastungstensource(580g/L).MaximumamountofWin-
Acceptedinrevisedform14November2011 corporación(8.2±1wt.%)wasobtainedwhenthebathcontainedabout20g/Loftungstensource.Atvery
Availableonline23November2011
highconcentrationsofWsourceinthebaththedepositcontainedabout4wt.%Wand2wt.%P.Alltheas-
depositedternarycoatingsexhibitednodularsurfacemorphology.X-raydiffractograms(XRD)obtainedfor
:
Electroless
as-depositedELNiWPalloysindicatedthatcrystallinityofthecoatingsincreasedwithdecreaseinphospho-
TernaryNiWP   ruscontent.Calculatedgrainsizeforthedepositsvariedfrom1.2to12.7nmwhenthetungstensourcevaried
XRDDSC from5to80g/Linthebath.HighercrystallizationtemperatureswereobtainedduetoWcodepositioninNiP
Phasetransformation matrix.PresenceofmetastablephasessuchasNiPandNiPapartfromstableNiandNiPwasidentiedfor
5 2 3 fi
theheattreateddeposits(400°C/1h)containingloweramountofWandhigheramountofP.Whereasother
ternarydepositsaftertheheattreatmentpredominantlyrevealedfacecenteredcubic(f.c.c).Ni(111)pico.
ActivationenergyforthecrystallizationofallthealloyshasbeencarriedoutbymodiedKissingermethod.
fi
Microhardnessmeasurementswerecarriedoutonallthedepositsisothermallyheattreatedat600°Cfor1h.
©2011ElsevierB.V.Allrightsreserved.

1.Introducción
Electroless(EL)depositionofmetalsisconsideredasoneofthe
mostwidelyusedmethodstoengineerthesurfacesspecicallyto fi
combatwer,sind
ion.AmgthevarusypfEL
depositcang,hbklum- fi Thermalstabilityofthesedepositsdependsonthecodepositedphos-
gineeringindustriesduetotheirexcellenthardness,wearandcorro-
sionresistance[1] .Byvirtueofitsmechanism,ELdepositednickel
coatingsareusuallybinarymetal-metalloidtypecoating (eitherEL
NiPorNiB;exceptthoseformulationsthatuseshydrazineasare-
 
ducingagent).Thepossibilityofalloyingoneormoreelementsin
thebinaryELnickelsystemenablesthedevelopmentofternaryand
quaternaryalloydeposits.AlthoughW,Cu,Co,Sn,Zn,etc.,canbe
alloyedwiththebinaryELNiPandNiBsystem,alloyingofWtopre
 -
pareternaryELNiWPcoatinghasreceivedconsiderableattentionbe-
causetungstenexhibitsuniquepropertiessuchashighhardness,
highermeltingpoint,lowercoefcientoflinearexpansion,highten
fi -
silestrengthetc.IthasbeenreportedthatevensmallamountofW
codepositionaffectsthechemicalcomposition,morphologyand
roughnessofelectrolessNiPdeposits[2].
AlkalinebasedbathsareusedcommonlytocodepositWinNiP
matrix.IncorporationofWinENmatrixaffectstheternaryNiWP
ⁿ Correspondingauthor.Tel.:+918025086239;fax:+918025210113.
electrónico-mailaddress:
jnbalraj@nal.res.in(J.N.Balaraju).
depositcompositionwhichspecicallyreducesthephosphoruscon
fi -
tiendadecampaña[3].Theas-depositedternaryalloycoatingexhibitshigherhard-
nessandincreasedcrystallinityduetotheWcodepositioncompared
toplainNiPdeposit[4,5].Ingeneral,alteringthedepositcomposition
#Pages [7]
isaneffectivemethodtoobtainvariousnanocrystallineNiPdeposits.
phoruscontent.Differentialscanningcalorimetry(DSC)isauseful
techniquetondoutthethermalstabilityofnanocrystallineNiP
fi
alloycoatings.Crystallizationprocess/phasetransformationbehavior
ofelectrolessbinaryNiPalloyscontainingvariousamountsofphos-
phorushasbeenverywellstudied[610].Ithasbeenreportedthat

#Pages [7]
theinclusionofthirdcomponentsuchasW,Cu,SnorSbinelectroless
amorphousNiPincreasesthecrystallizationtemperature[1113]. 
RoleofWinstabilizingtheamorphousstateinNiWPlmswithdif-fi
#Pages [8]
ferentPcontentwasstudiedbyAntonellietal.[12].Ithasbeencon-
cludedthatWinhibitsnucleationoftheNiPphaseinNiWP
3   fi lms,
buthaslimitedabilitytosuppressFCCNiduetothehighersolubility
(17at.%)inNi.TheincorporationofWelementinNiPmatrixnot 
onlyimprovesthethermalstabilitybutalsoenhancesthemicrohard-
nessduetothebenecialcontributionfromtheformationoftheNi
fi 
Wsolidsolution[14,15].ithasbeenreportedthatinclusionoftung-
#Pages [8] http://dx.doi.org/10.1016/j.surfcoat.2
stenelementinNiPmatrixrevealednodularmorphologyandbecame
smootherduetothelasersurfaceheattreatment[16].Studieshave
beencarriedouttodepositELternaryNiWPcoatingsusinganalka-
linenickelsulfamatebath(pH:9.0)[17].SinceSnelementimproves
theamorphousformingability,attemptshavebeenmadetoobtain

$ de  0257-8972/seefrontmatter©2011ElsevierB.V.Allrightsreserved.
doi:10.1016/j.surfcoat.2011.11.024

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J.N.Balarajuetal./Surface&CoatingsTechnology206(2012)26822689 2683

quaternaryELNiWSnPalloysusinganalkalinebath[18].Yong-junHu continuouspurgingoftheheatingchamberwithanitrogen  ow
etal.havealsoobtainedELternaryNiWPdepositsusinganalkaline of30mL/min.toavoidsampleoxidation.Thecrimpedsamplespec-
bathcontainingaproprietarycomplexingagent[15].whereaspala- imenandreferencewereplacedinaplatinumfurnace.
niappaandSeshadrihavedepositedELNiWP  lmsusinganacidic
bathatapH:5.5[19].MostoftheresearchershaveobtainedEL
NiWPdepositseitherusing fi xedconcentrationofsodiumtungstate 2.4.Microdureza
orproprietarycomplexingagentsinthealkalineelectrolessnickel
bath.Recentlythepresentauthorshavereportedthemorphology, Isothermalheattreatmentwascarriedoutforallthedepositsat
structureandmicrohardnessofternaryNiWPalloyscontainingvari- 600°Cfor1h.Metallographiccross-sectionswerepreparedand
microhardnessmeasurementsweremadebyapplyingaloadof50
ousWandPcontents[20].Inthepresentwork,wehavesystemati- gf
callystudiedthephasetransformationbehaviorofvariousEL usingVickersmicrohardnesstester(Buehler).Fivereadingswere
ternaryNiWPalloysobtainedbyvaryingthetungstensourcefrom5 takenoneachdepositandthevalueswerethenaveraged.
to80g/Lintheelectrolessnickelplatingbath.Theobtaineddeposits
werecharacterizedfortheircomposition,morphologyandphase
transformationbehavior.Depositswerealsoheattreatedatcrystalli- 3.Resultsanddiscussion
zationtemperaturesandX-raydiffraction(XRD)studieswerecarried
fioutto ndoutthephasesformedatthosetemperatures.Usingthe 3.1. Composición EDX
modiedKissingerequationtheactivationenergyvaluesforthecrys
fi -
tallizationoftheternarydepositswerealsodetermined.Thethermal Compositionalanalysisofas-depositedelectrolessternaryalloy
stabilityofthesedepositshadalsobeenanalyzedbycarryingoutthe depositsbyEDXanalysis(Higo1)revealsthepresenceofNi,
microhardnessmeasurementsonheattreateddepositsat600°Cfor
PandW. #Pages [2]
Itiswellknownthattungsten,beingarefractorymetal,cannotbede-
1h. positedfromanyaqueoussolution.However,tungstenalloyswith
theirongrouptransitionmetalscanbereadilydepositedfromaque-
2. oussolutionscontainingtungstateion[21].AnincreaseinWcontent
(8.2±1wt.%)ofthedepositisobservedwhentheconcentration
ofsodiumtungstateis20g/L.However,whentheconcentrationof
2.1experimental.Samplepreparation sodiumtungstateisincreasedto40g/L,adecreaseinWcontent(4.8wt.
%)isresulted.Withfurtherincreaseinitsconcentrationto
VariousternaryNiWPdepositswerepreparedusingthefollowing 60and80g/L,saturationinWcontentisnoticed.Increaseinsodium
ingredients:Nickelsulfate(20g/L)andsodiumtungstateasNiandW tungstateconcentrationfrom20to80g/Lleadstoacontinuousde-
fuentes,sodiumhypophosphite(20g/L)asreducingagent, creaseinthePcontentofthedeposit,followingtheincreasein
citratodesodio(35g/L)andammoniumsulfate(30g/L) metaliontohypophosphiteionratiointheplatingbath[22].Osakaetal.
ascomplexingand [3]havealsoreportedadecreaseinPcontentfrom8.9to
2.3wt.%andaconsequentincreaseincrystallinityuponcodeposition
bufferingagents.ElectrolessnickelalloybathswereoperatedatpH8.89.0andtemperature88±2°C.Sodiumtungstateconcentration
ofWinternaryNiWPalloydeposits.AdecreaseinPcontentwasalso
 observedwiththecodepositionofCoinELNiCoPternaryalloydepos-
wasvariedfrom5to80g/Lbykeepingotheringredientsconstant esto[23].IntheformationofNiPlm,thecodepositionofPplaysanes-
toobtainelectrolessternaryNiWPdepositswithvariousWandP
contenidos.Mildsteelspecimens(2.5cm×2.5cm×0.08cm)eran
usedassubstratesforthedepositionofelectrolessnickel(EN)alean
lms.Specimensweredegreasedinacetone,cathodicallycleanedin fi
fi sentialro.ThPmd
formaphustcewiN
2 i whent lmcontaisreh10%P.Adfug
10%sodiumhydroxidesolutionfor5minat15A/dm,rinsedinrun - fi
ningwateranddeionizedwater.Thenthesamplesweredeoxidized notlyprmeshdi
nofWbutalsprehc
-thodicreanfHPO,bysgu -
in50vol.%sulfuricacidsolutionfor30s,rinsedinrunninganddeio- 2 2
nizedwaterandplacedinthebathforplating.Electrolessnickelbath ingthecompetitionbetweenthesereactionsduringthedepositionof
wastakenina250mlglassbeakerwhichwaskeptinaconstanttem- NiWPternaryalloy.Formationofacomplexcompoundcanalsobe
peraturewaterbath(SiskinJulaboVPCmodel)at88±2°C.Plating anotherpossibilitythatleadstoadecreaseinPcontentandsatura-
wascarriedoutfor2hwithadepositionrateof1012m/h.After  … tionofWcontentwithincreaseintungstateionconcentration.
theplatingduration,sampleswererinsedinrunninganddeionized
water,driedandpreservedforcharacterization.
16
W/P incorporación (% del Peso)

2.2.XRDandSEMstudies 14 P % del peso

W % del peso
X-raydiffraction(XRD)measurementsofthedepositswere 12
madeinasplatedconditionwithaRigakuD/max2200powderdif-radiación
–
fractometerusingCuK. Scanningelectronmicroscope 10
(SEM,modelLeo440I)withEDAX(energydispersiveX-rayanalysis,
8
Oxford)attachmentwasusedtodeterminetheelementalcomposi-
tionofthedeposits. 6

2.3.Differentialscanningcalorimetryanalysis 4

Forperformingdifferentialscanningcalorimetry(DSC)análisis, 2
samplesintheformoffoilwerecutintosmallpieces.About50mg
0
samplewasputinanaluminumpanandcrimpedusingacover. 0 2 0 4 0 6
Emptyaluminumpanwithcovercrimpedwasusedasareference.
Sodio tungstate (g/L)
Continuousheatingprocessesunderdifferentconstantheatingrates
of10,20,30and40°C/min.wereperformedinaDiamondDSC Higo1. Effectofsodiumtungstateconcentrationintheelectrolessnickelternaryalloy
(PerkinElmerModel).Theexperimentswereperformedunder bathonthedepositcomposition.

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2684 J.N.Balarajuetal./Surface&CoatingsTechnology206(2012)26822689

3.2. Estructura XRD Table1

Peakposition(2 ‚ ),fullwidthathalfmaximumandgrainsize(fromDebyeScherrer
fórmula)foras-platedelectrolessternaryNiWPalloycoatings.
Thediffractionpatternsofas-depositedELNiPandELNiWPter
 -
naryalloydepositsareshowninFig.2.Inspiteofcodepositionof Typeofcoating Peakposition(2) ‚ FWHM
#Pages [3]
varyingcontentsofW,allELternaryNiWPalloydepositsexhibitNi(111)
NiP
 44.523 5.204 1.25deGrainsize(nm)
asmajordiffractionpeak.Osakaetal.[3]havereportedthat
NiWP-5 45.035 6.117 1.41
ELternaryNiWPdepositsobtainedintheabsenceofammoniumsul- NiWP-10 44.682 5.997 1.43
NiWP-20 44.856 6.255 1.38
fatedisplaypeakspertainingtoNi(111)andNi(200)planeswhereas
NiWP-30 44.955 4.897 1.78
depositspreparedinpresenceofammoniumsulfateexhibitonlyNi NiWP-40 44.291 2.482 3.46
(111)plane.Accordingtothem,adsorptionofammoniumsulfateor NiWP-60 44.396 0.701 12.25
theinteractionbetweenammoniumsulfateandnickelionscould NiWP-80 44.412 0.705 12.74
havealteredthecrystallatticeofthenickelgrainsothatitcanbeori-
entedpreferentiallytotheNi(111)avión.Inthepresentinvestiga-
tion,asimilarmechanismmighthaveoccurredforalltheternary hasbeenreportedthatcrystallinestateoftheternaryNiWPdeposits
NiWPdepositssothatallofthemdisplayNi(111)planeasonlydif- mainlydependsontheamountofphosphoruspresentinthem.How-
fractionpeak. ever,thecrystallinityofternaryNiWPdepositsislessthanbinaryNiP
Thegrainsizeofthesedeposits,calculatedusingDebyeScherrer  depositswhenbothofthemcontainanequalamountofP[25].
formula,isgiveninTable1.AsdepositedplainELNiPdepositex  -
#Pages [3] singlepeakat44°2
hibitsabroad, ‚ whichcanbeascribedtoNi 3.3. Morfología SEM
(111)avión.TheintensityoftheNi(111)diffractionpeaksobtained
foras-depositedternaryNiWPdepositsisincreasedwithincreasein Themorphologicalfeaturesofas-platedELbinaryNiPandELter
 -
sodiumtungstatecontentfrom5to80g/Lintheelectrolessplating naryNiWPdepositsareshowninFig.3(a&b).ELbinaryNiPdeposit 
bath.Thisisduetothecompositionvariationoftheternaryalloyde- exhibitsasmoothmorphologywithfewscatterednodules(Talla:
#Pages [4]
postula,substantiatedbytheEDXanalysis(Higo1).Thegrainsizeof 4m).NiWP-10deposit … (about3wt.%W)exhibitedmorenumber

#Pages [2]
plainbinaryELNiPdepositis1.2nm.Amarginalincreaseingrain ofindividualandagglomeratednodules.ForNiWP-30,scatteredbig-
sizeisobservedforELNiWP-5toNiWP-30deposits(530g/Lofsodi-  gernodules(Size:10m)areobserved. … Incontrast,ELNiWP-80de-
umtungstate).ThegrainsizeisalmostdoubledforNiWP-40deposit positexhibitsasmoothsurfacewithveryfi neandsmallernodules.
whileitisabout10timeshigherforNiWP-60andNiWP-80deposits Theobservedchangesinmorphologicalfeaturesarelargelydueto
whencomparedtoELNiPdeposit.Itiswellknownthattheamount
 thechangeinchemicalcompositionofthesedeposits,substantiated(higo1)
ofPpresentintheELNiPdepositsplaysanimportantroleindecid
 - byEDXanalysis.Ingeneral,formationofnodulesisacommon
ingtheirstructureandproperties.Thesedepositsexhibitanamor- characteristicofelectrolessplatedcoatings.Therapidformationof
#Pages [2]
phousstructurewhenthePcontentishigherthan8wt.%.Mixture nucleiandsubsequentgrowthoftheELnickeldepositspromotethe
ofamorphousandnanocrystallinestructurecouldbeobserved nodularity.
whenthePcontentisbetween4and7wt.%.WhenthePcontentis
below3wt.%,theyexhibitamicrocrystallinestructure.WhentheP 3.4.Phasetransformationbehavior
contentishigherthan8wt.%,thelatticestrainofNi(111)orientó
grainsincreases,whichresultsinX-rayamorphousdeposits [24].In Metastablealloys,whicharethermodynamicallyunstable,under
thepresentinvestigation,ELternaryNiWPdepositshavingmore -gophasetransformationtobecomecompletelystablecrystalline
fase.Differentialscanningcalorimetry(DSC)isaveryusefultool
than8wt.%Pexhibitanamorphous/nanocrystallinestructure.
tostudythephasetransformationbehaviorofsuchmetastablealloys.
NiWP-30andNiWP-40alloydeposits,thoughcontainsabout4to TheDSCthermogramsofNiWPternaryalloydeposits,recordedover
6wt.%P,exhibitabroadpeak.Thiscouldprobablybeduetothecode- atemperaturerangeof50to575°Catascanrateof40°C/min.,are
positionofW,whichcouldhaveincreasedthelatticedisorderthat showninFig.4.Thepresenceofexothermicpeakssuggeststheoccur-
renceofphasetransformation.Thepeaktemperaturesandtheen-
leadstoapeakbroadening[3,14].niwp-60andniwp-80alloyde-
#Pages [7]
positsrevealednanocrystallinity(grainsizesabout12nm)dueto
thalpy(H)valuesarecompiledinTable2.ELbinaryNiPdeposit #Pages [4]
theirlowerPcontent(approximately2.5wt.%)inthesedeposits.Esto ”
displaythrexomcknugbw36142°C.ELNWP-5(0%f)
#Pages [4] intensidad
Ni (111) higo 2  
typemajorexothermicpeakat370°Candashallowpeakat421°C.
Amarginalincreaseinpeaktemperaturehasbeenobservedfor
NiWP-10deposit.NiWP-20(8wt.%Wand8.7wt.%P)depositshows
evidenceoftwoexothermicpeaksat362and400°Crespectively.In
thecaseofNiWP-30deposit,threeexothermicpeaks,alowtempera-
NiWP-80 turepeakat319°C,awtypeofmediumtemperaturepeakat442°C
 
NiWP-60 andaveryshallowandfaintpeakat543°Careobserved.NiWP-40
NiWP-40
depositshowedtwoexothermicpeaksat224and453°Cwhereas
(a.u)

NiWP-60andNiWP-80depositsrevealonlyoneexothermicpeakat
NiWP-30
484and493°Crespectively.ThemajorexothermicpeakintheDSC
NiWP-20
thermogramsobtainedforELbinaryNiPandallternaryNiWPde-
NiWP-10 positscorrespondstothelong-rangeatomicmovements,causingpre-
NiWP-5
cipitationofstablephasessuchasfccnickelandnickelphosphide
(PELLIZCO)
3 .Alowtemperaturepeakpresentinnanocrystallinecoatings
NiP
couldbeattributedtothestructuralrelaxationsuchasannihilation
20 25 (grado)
30 35 40 45 50 55 60 65 ofpointdefectsanddislocationswithinthegrainsandgrainbound-
2q aryzones[7].Splittingofthesecondmajorcrystallizationpeak
couldbeduetothedifferenceinactivationenergiesforcrystallization
. XRDpatternsofas-depositedelectrolessnickelpolyalloys. frompartiallycrystallizedmatrixandamorphousmatrixorthe fi rst

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 J.N.Balarajuetal./Surface&CoatingsTechnology206(2012)26822689 – 2685

400

Heat Flow EnDo Up (mW)

300
Ni-P
200 NiWP-5

100
NiWP-10

0
NiWP-20
-100

150 200 250 300 350 400 450 500 550

Temperature (oC)

300

250

Heat Flow EnDo Up (mW)

200
NiWP-30
150

100 NiWP-40

50 NiWP-60

NiWP-80
0

-50

100
200 300 400 500
Temperature (oC)

Fig.4. DSCthermogramsobtainedforelectrolessnickelpolyalloycoatingsat40°C/min.
scanrate.

Presenceofmetastablephases,viz.,NiPandNiPisseenapartfrom
5 2
NiPandNiwhenthistypeofdepositisheat-treatedat370°C.Com-
3
pletetransformationofthesemetastablephasestostablecrystalline
phasessuchasNiandNiPcouldbeobservedwhenthedepositsare
3
heat-treatedathighertemperatures.ForNiWP-10deposit,bothsta-
bleandmetastablephasescouldbeobservedevenafterheat-
treatmentat400°Cfor1handtransformationtostablephaseoccurs
onlyuponheat-treatmentat600°C(Fig.6).InNiWP-20deposit
(Fig.7)metastablephasesarepresent(withverylowintensitypeak
Fig.3. Surfacemorphologyofas-depositedelectrolessnickelpolyalloycoatings. proles)forheat-treateddepositsattemperaturesexceptthosetrea-
fi
tedat600°C.However,heat-treatmentat600°C,leadstotheforma-
peakwasduetotheprecipitationofnickelcrystalliteandthesecond tionofonlystableNi(111)andNiPpeaks.LowintensityNiPpeak
3 3
peakwasduetothenickelphosphideprecipitation[10,26].Thehigh alongwithveryhighintensityNi(111)peakisseenforNiWP-30
temperaturepeakobtainedforsometernaryalloydepositscouldbe andNiWP-40depositsheat-treatedatandabove415°C.Incontrast,
duetofurthergraingrowthandthepresenceoftungsten[27].From NiWP-60andNiWP-80deposits(havingsimilaramountsofW:
theaboveitisevidentthatdepositcompositionplaysanimportant 4wt.%andP:2.2wt.%)revealonlyasingleNi(111)peakatall
roleonthephasetransformationbehaviorofternarydeposits. heat-treatmenttemperatures.ThediffractionpatternsofELternary
AmountofWandPelementspresentinthenanocrystallineternary
alloydepositsissignicantinobtainingthenumberofexothermic
fi Table2
peakspresentintheDSCthermograms.Itisalsorelevanttoconrm, fi Peaktemperaturesand ΔHvaluesobtainedatascanrateof40°C/min.
forallthedeposits,whetherornotanystablephaseshaveformedat Typeof Peaktemperature(°C)and ΔH(J/g)
respectivepeaktemperatures.Hence,allthedepositsweresubjected coating
P1 ΔH2 P Δ H 3 P H 4P Δ H Δ
forisothermalheattreatmentfor1hatrespectiveexothermicpeak
temperaturesandwereanalyzedusingX-raydiffractiontechnique NiP
– 361 − 62.5 401 − 4.6 442 − 10 – –
NiWP-5 369.7 − 56.4 420.9 − 6.6 – – – –
(XRD)to fi ndoutthephasesformed.X-raydiffractionpatterns NiWP-10 399 − 70.5 – – – – – –
obtainedforallthedepositsatvariousheattreatmenttemperatures NiWP-20 362 − 2.9 400 − 38 – – – –
andphasesformedatpeaktemperaturesaregiveninFigs.511. – NiWP-30 319 − 7.4 414 − 26 442 − 9.5 543 − 1.7
Fig.5showsthediffractogramsofNiWP-5depositheatedatvari- NiWP-40 224 − 23.9 453 − 33.4 – – – –
oustemperatures.Thediffractionpatternsofas-depositedNiWP-5 NiWP-60 484 − 15.0 – – – – – –
(Fig.2)andthoseheat-treatedat200°Cfor1h,arequitesimilar. NiWP-80 493 − 11.7 – – – – – –
2686 J.N.Balarajuetal./Surface&CoatingsTechnology206(2012)26822689 –

Ni NiWP-5 NiWP-30
Ni
Ni3P
Ni3P
NiP
Ni5P 2
Intensity (a.u)

Intensity (a.u)
600°C

415°C

600°C
370°C
545°C
200°C 415°C
320°C
20 30 40 50 60 70 200°C
2q(deg)
20 30 40 50 60 70
Fig.5. XRDpatternsofNiWP-5depositatvariousheattreatmenttemperatures.
2q(deg)

NiWP-10 Fig.8. XRDpatternsofNiWP-30depositatvariousheattreatmenttemperatures.

Ni3P
NiP
Ni
Intensity (a.u)

Ni5P 2 NiWP-40
Ni3P
600°C
Ni(111)

Intensity (a.u)
400°C

200°C
600°C

20 30 40 50 60 70 450°C
2q(deg)
200°C
Fig.6. XRDpatternsofNiWP-10depositatvariousheattreatmenttemperatures.
20 30 40 50 60 70
2q(deg)
NiWPalloydeposits,bothintheiras-platedandheat-treatedcondi-
tionsexhibitnocharacteristicpeakofWinsteadashiftinNi(111)
‘ ’ Fig.9. XRDpatternsofNiWP-40depositatvariousheattreatmenttemperatures.
peakisobservedduetothecodepositionofWinthesedeposits.
ThepeakshiftisduetothedissolutionofWinthenickelmatrix,
whichresultsinthelatticeexpansionofnickel[28]. requiredbythereactantstoundergoareaction.UsingmodiedKis-fi
Ingeneral,crystallizationprocesscanhavetwomajorstages;ther- singermethod,activationenergiesforallthecoatingswerecalculated
malactivationleadingtolocalatomicmovementsandincipientcrys- (Fig.11).Inthismethod,alinearregressionlinehasbeenobtained
tallizationintometastablecrystallinestructures,followedbylong 2
fromtheploton(Tm/ø)versus1000/RTm,whereT
fl m(in°K)stands
rangethermalmigrationofatomsanddecompositiontotheequilib-
riumphases.Theactivationenergyistheminimumamountofenergy forpeaktemperatureofcrystallizationprocessbythemajorexother-
micpeakofDSCcurve,øfordifferentheatingrate(°K/min.)andRfor
gasconstant(8.3145Jmol − 1 K − 1 )respectively.Theslopeofthisline

Ni3P NiWP-20 Ni (111) NiWP-60

Ni
Intensity(a.u)

Intensity (a.u)

600°C

400°C

370°C 600°C
495°C
200°C
200°C

20 30 40 50 60 70 20 30 40 50 60 70
2q(deg) 2q(deg)

Fig.7. XRDpatternsofNiWP-20depositatvariousheattreatmenttemperatures. Fig.10. XRDpatternsofNiWP-60depositatvariousheattreatmenttemperatures.

 J.N.Balarajuetal./Surface&CoatingsTechnology206(2012)26822689 – 2687

10.8
10.6 NiWP-5
10.8 10.4
10.6 NiP
10.4 10.2

In(Tm2/f)
In(Tm2/f) 10.2 10
10 9.8
9.8 9.6
y = 200.4x - 28.734 y = 271.91x - 41.02
9.6
9.4 R2 = 0.9963 9.4 R2 = 0.9446
9.2 9.2
9 9
0.188 0.19 0.192 0.194 0.196 0.198 0.184 0.186 0.188 0.19 0.192
1000/RTm 1000/RTm
10.8 10.8
10.6 NiWP-10 10.6 NiWP-20
10.4 10.4
In(Tm2/f)

In(Tm2/f)
10.2 10.2
10 10
9.8 y = 295.47x - 44.59 9.8 y = 221.96x - 30.352
9.6 9.6
R2 = 0.9165 R2 = 0.9737
9.4 9.4
9.2 9.2
0.182 0.183 0.184 0.185 0.186 0.187 0.188 0.178 0.18 0.182 0.184 0.186
1000/RTm 1000/RTm
11
10.8 10.8 NiWP-40
10.6 NiWP-30 10.6
10.4
In(Tm2/f)

10.4
In(Tm2/f)

10.2
10.2
10
10 y = 355.57x - 49.273
9.8 y = 289.85x - 41.407
9.8 R2 = 0.9484
9.6 R2 = 0.9955
9.4 9.6
9.2 9.4
0.174 0.176 0.178 0.18 0.182 0.165 0.166 0.167 0.168 0.169 0.17
1000/RTm 1000/RTm

11 11.2
NiWP-60
10.8 11 NiWP-80
10.6 10.8
In(Tm2/f)

10.6
In(Tm2/f)

10.4
10.2 10.4
10.2
10
10 y = 356.15x - 46.369
9.8 y = 326.84x - 42.324
9.8 R2 = 0.9869
9.6 R2 = 0.9945
9.6
9.4 9.4
0.158 0.159 0.16 0.161 0.162 0.163 0.164 0.156 0.157 0.158 0.159 0.160 0.161
1000/RTm 1000/RTm

Fig.11. Relationshipbetweenheatingrateandcrystallizationtemperatureofelectrolessnickelalloys(ModiedKissingerMethod).
fi

yieldstheactivationenergy(Q)ofthedeposit.Theactivationenergy
(Q)ofELbinaryNiPdepositcalculatedusingtheexothermicpeak
temperaturesis200±3kJ/mole.Thecorrelationcoefcient(R)i fi s 2
0.9963.Thisisinagreementwiththeearlierreports[27].Theactiva-
tionenergiesforthecrystallizationofternaryNiWP-5,10,20,30,40,
60and80depositsare272,295,222,290,355,327and356kJ/mole,
respectively.Keongetal.[7]havereportedthatbinaryhighphospho-
ruselectrolessnickeldepositsexhibitarelativelylowercrystalliza-
tiontemperature.Incontrast,binarylowphosphoruselectroless
nickeldepositsdisplayrelativelyhighercrystallizationtemperatures
[29].Fromthisitisevidentthatthermalenergyrequirementtoobtain
morestablephasesislessforamorphousdeposits(P>8wt.%)and
b
moreformicrocrystallinedeposits(P4wt.%).Theactivationenergy
forthecrystallizationoflowandhighPELbinaryNiPdepositsis280
–
and222kJ/mole,respectively[6,29].Hence,itappearsthattheacti-
vationenergyforthecrystallizationofternaryNiWPdeposits(with
codepositedWandlowerPcontent)ishigh(about356kJ/mole)
comparedtootherdeposits.Inthepresentinvestigation,theamount
ofWinalltheternaryNiWPdepositsislessthan10wt.%,whichisin
theformofNiWsolidsolution,asevidencedbytheXRDmeasure-
–
ments(Figs.511).Ithasbeenreportedthatitismoredifcultto
– fi
crystallizeNiWthanNisincethequantityofcodepositedWisnot
–
sufcienttopreventfccNinucleationinternaryNiWPdeposits.
fi
Moreover,WisnotsolubleinNiP.Hence,diffusionisrequiredto
3
separatetheNiandPfromWandaccumulateenoughPinonearea
beforeNiPcannucleate [12].Inthepresentinvestigation, 3
2688 J.N.Balarajuetal./Surface&CoatingsTechnology206(2012)26822689
Fig.12. Relationshipbetweenheatingrateandcrystallizationtemperatureofelectro-
lessnickelalloys(Duswaltmethod).
suppressionofNiPformationisobservedduetothecodepositionof
3
WinmostofthedepositsandtheNiPphaseisseenwithmoresup-
3
pressionofNipeakonlyincaseofNiWP-10deposit,wherethe
amountofPpresentisabout10wt.%(eutectic).Hence,itcanbecon-
cludedthatthebathcompositionplaysasignicantroleinobtaining
fi
variousternaryNiWPdepositscontainingphosphorusandtungsten,
whichinturndecidesthestructureandphasetransformationbehav-
iorofelectrolessternaryNiWPdeposits.
Inthepresentinvestigationwehavealsomadeanattempttocal-
culatetheactivationenergyrequiredforthecrystallizationprocessof
binaryNiPandternaryNiWP30alloysbyDuswaltmethodandcom-
paredwiththeactivationenergyvaluesobtainedbymodiedKissin-
fi
germethod.
Usingtheonsettemperaturesobtainedatdifferentheatingratesit
ispossibletocalculatetheactivationenergy(Q)forthecrystalliza-
c
tionprocessofelectrolessnickelalloydepositsusingtherel
ationshipdevelopedbyDuswalt [30]:
Q c ¼ −RdlnV
ð Þ=1T
ð = Þ
whereRisthegasconstant(8.314J/K-mole),Vistheheatingrate
(K/min.)andTistheonsetofcrystallizationtemperature(inK).A
plotoflnVversus1/Tismadeusingthevariationinonsettempera-
tureswithheatingrate(Fig.12).Theactivationenergyvaluesobtained
forthecrystallizationprocessofNiPandNiWP30depositsare192and
259kJ/molerespectively.Whereasmarginallyhighactivationenergy
valuesareobtained(200and290kJ/mole)forthesamedeposits
whenmodiedKissingermethodwasused.Ithasbeenreportedthat
fi 933.
–
theexperimentalthermogramsobtainedbyDSCofmajorcrystalliza-
tionprocessarenotalwaysreproducibleattheregionbetweenthe
crystallizationonsetandendtemperatures [31].Thismaybethereason
forthevariation/higheractivationenergiesobtainedforthecrystalliza-
tionprocessofelectrolessnickelalloysinthelattermethod.
3.5.Microhardness
Allthedepositsareisothermallyheattreatedathighertemperature
(600°C,1h)andmicrohardnessmeasurementsaremadeonthecross-
sectionaldeposits.ThemicrohardnessvaluesobtainedforNiWP5to
NiWP80are893,845,919,701,636,626and633respectively.From
thisitisevidentthattheNiWP5deposithasexhibitedmaximumhard-
nesscomparedtoNiWP10deposit.Ithasbeenreportedthattheelec-
trolessnickeldepositwithhigherPcontent(>10Wt.%)exhibitsthe
peakhardnessuponheattreatment.WhentheincorporatedPcontent
islower,themicrohardnessuponannealingwillbelower.Thevaria-
tioninmicrohardnesswithrespecttoheattreatmenttemperatureof
theelectrolessnickeldepositscanbeattributedtothevariationin
grainsize.Theamountofnickelphosphidecompoundsformeddue
totheheattreatmentwillberesponsibleforthevariationinthe
grainsize.ThehardeningeffectoftheneNiPparticlesisassumed
fi 3
toberesultedfromtheirhigherstrengthandshearmodulus.From
Fig.1itisevidentthatNiWP20deposithashigherW(8.2wt.%)and
alsohighP(8.7wt.%)contents.ItappearsthathigherWwhichisin
solidsolutionformandnickelphosphideformedathigherannealing
temperaturebothhavecontributedinexhibitingmaximumhardness
ofNiWP20deposit.Fromtheaboveitcanbeconcludedthatamong
allthedepositsNiWP20hasexhibitedthebetterthermalstability
basedonthemicrohardnessmeasurements.
4.Conclusions
ELNiWPternaryalloydepositswithvariousWandPcontents
werepreparedusinganalkalinecitratebathbyvaryingsodiumtung-
state(580g/L).Compositionalanalysisrevealedthatcodepositionof
–.-fiⁿP⁽⁾
–ⁿP.-fi
25
andNiPapartfromstableNiandNiPwereidentiedint
3 fi
hecaseof
heattreateddeposits(400°C/1h)containingloweramountofW
andhigheramountofP.Activationenergyforthecrystallizationpro-
cessofELternaryNiWPdepositswashigherforlowerphosphorus
deposits.BetterthermalstabilitywasexhibitedbyELNiWP20depos-
itcomparedtoothers.
Acknowledgment
TheauthorsthanktheDirector,NAL,CouncilofScienticandIn-
fi
dustrialResearch(CSIR),NewDelhiforgivingpermissiontopublish
thiswork.HelpreceivedfromMr.K.RaghavendraforSEMworkis
greatlyacknowledged.
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