ResearchArticle In uenceo ur actantsontheCharacteristicso...

Hindawi Publishing CorporationISRN ElectrochemistryVolume 2013 Article ID 486050 8 pageshttpdxdoiorg1011552013486050

Research ArticleInuence o uractants on the Characteristics oNickel Matrix Nanocomposite Coatings

Abbas Fahami Bahman Nasiri-Tabrizi Mohsen Rostami and Reza Ebrahimi-Kahrizsangi

Materials Engineering Department Islamic Azad University Najafabad Branch Najafabad Isfahan Iran

Correspondence should be addressed to Abbas Fahami abfahamigmailcom

Received 4 December 2012 Accepted 23 December 2012

Academic Editors I Casella F Deorian -R Li X R Nvoa and E Valls

Copyright copy 2013 Abbas Fahami et al is is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Nickel-based nanocomposite coatings were prepared from a Watts-type electrolyte containing reinforcementrsquos particles (siliconcarbide and graphite) to deposit onto the steel St-37 substrate e electrochemical plating of the coatings in absence and presenceof surfactants and reinforcements particles was carried out to optimize high quality coatings with appropriate mechanical andmorphological features e surfactants such as cetyltrimethylammonium bromide (CTAB) sodyumdodecyl sulfate (SDS) andsaccharine affected electrodeposition plating and subsequently changed mechanical characteristics Based on XRD results thedominant phases in the absence of surfactants were nickel oxide (NiO) nickel and silicon carbide (SiC) while the main phasesin presence of surfactants were nickel (Ni) and SiC e hardness of the resultant coatings was found to be from 332 to 593 (Hv)depending on the bath parameter and the reinforcements weight percentage (wt) in the Ni matrix Microscopic observationsillustrated a cluster-like structure which consisted of some ne sphere particulates with average particle size of 65ndash150 nmAccording to elementalmapping spectra a homogenous distribution of nickel silicon and carbon particles appeared into the nickelmatrix coating Finally the experimental outcomes demonstrated that the surfactants have signicant inuence on the compositionof coatings surface morphology and mechanical properties

1 Introduction

e recent researches in surface engineering were signi-cantly focused on the development of low carbon steels (St-37) surfaces which can meet the industrial request [1ndash4]e mechanical properties of many parts of surfaces werepromoted by coating of numerous pure metals ceramicsand alloys which can be deposited with ne grain sizesfor example Ni Pd Cu NindashP NindashW and NindashFendashCr [5 6]Furthermore various methods such as electrodepositionion implantation chemical vapor deposition (CVD) laserbeam deposition physical vapor deposition (PVD) plasmaand high-velocity oxygen fuel (HVOF) spraying have beendeveloped [7 8] Among these procedures electrochemicalplating is a proper method with remarkable features suchas easy maintainability easy low working temperatures lowcost and high production rate [9] In chemical techniquessurfactants have beenused to absorbmuchmore ne particlesinto the matrix so that the repulsion force between particles

with the same charges can be increased is in turnreduces the agglomeration and provides a solution withmorestable particles It should be mentioned that nanocompositecoatings are valuable for promoting of the surface propertiesso that they have been revolutionized surface sciences andapplicationse use of particles in coatings could decline theproblem of created imperfection such as voids between theparticles and matrix interfaces In addition the depositionof enough amounts of reinforced particles could lead togeneration of stronger and more resistant covers [10]

Electrodeposition of nickel coating has receivedwidespread acceptance as it provides a uniform depositon irregular surfaces direct deposition on surface activatedhigh hardness and excellent resistance to wear abrasion andcorrosion Additionally nickel as an engineering materialwas broadly used among the electrodeposited materials[11] Many studies illustrated that deposition of coatings inthe presence of ne particles such as hard materials (egSiC [12 13] Al2O3 [12] WC [14] and diamond [15]) or

2 ISRN Electrochemistry

lubricating particles (eg MoS2 PTFE and graphite (Gr)[16 17]) into the nickel matrix might effectively improvethe mechanical and tribological properties of the surfaces[9] Also numerous researchers have studied synthesis ofNi-based nanocomposites by electrodeposition for instanceNi-SiC [18ndash20] Ni-P-SiC [21] Ni-Al2O3 [22] and Ni-ZrO2[22]e deposition of nanocomposites was affected bymanyfactors including processing parameters (eg surfactantpH value current density magnetic eld and waveform)bath composition and particle content Meanwhile bymanipulating the processing parameters some noticeableresults were acquired [18 23ndash25] It should be noted thatthe determination of optimum conditions for productionof nickel coatings from the reported results is difficultbecause they are in some cases different or paradoxical Forinstance the different results have been reported about effectof reinforcement grain size into the nickel-based coatings[26]

Although different nickel matrix nanocomposite coatingswith suitable mechanical and tribological properties wereknown but to the authors knowledge the inuence ofsurfactants (CTAB SDS and saccharine) and reinforcements(SiC andGr) on the characteristics of nickelmatrix nanocom-posite coating was not investigated In order to obtain the Ni-based coating with acceptable microhardness it is necessaryto use surfactants to absorb SiC and graphite (Gr) particlesinto the matrix during plating In this paper the maintarget was the electrodeposition ofNi-SiC-Gr nanocompositecoating onto the St-37 substrate with suitable mechanicaland morphological properties Moreover the inuence ofsurfactants on the morphological features and distributionof SiC and Gr particles into the Ni matrix was evaluated byXRD SEMFE-SEM EDS and elemental mapping analysistechniques Finally the mechanical properties of all speci-mens were compared under different circumstances whichexhibited valuable results

2 Experimental Procedures

21 Nanocomposite Coating Preparation Nickel coatingswere deposited fromWatts bath by direct current (DC) elec-troplating Electrochemical bath components were consistedof nickel sulfate (Merck 99) boric acid (Merck 998)and nickel chloride (Merck 98) e basic compositionsof the bath and the experimental operating parameters areprovided in Table 1 SiC nanopowders in the range of40minus100 nm (Hefeikaier Nanometer Energy amp Technology99) and Graphite (Gr) particles in the range of 5ndash150 120583120583m(Merck 998) were utilized as reinforcements Meanwhilethe electrostatic adsorption of suspended particles on thecathode surface increased by enhancing of their positivecharge [27] and the surfactants such as cetyltrimethylammo-niumbromide (CTABMerck 98) sodiumdodecyl sulphate(SDS Acros Organics 98) and Saccharine (Merck 99)were used To obtain suitable nanocomposites coatings allthe bath ingredients were agitated (stirring rate = 500 rpm)for 20min by magnetic stirring Subsequently the sonicationprocess was served for 15min to provide homogeneous

dispersion and to prevent agglomeration of the particlesLow carbon steel (St-37) plates 10mm times 10mm times 1mm assubstrate and nickel cylindrical were utilized for electroplat-ing process Before the electrodeposition the substrates havebeen prepared by the following procedures (a) degreasingusing a surfactants solution at 50∘C for 5min (b) acidpickling in a diluted sulfuric acid solution (10H2SO4) for1min and (c) polishing with silicon carbide metallographicpapers Aer each preparation step the substrates have beenrinsed by distilled water in order to completely remove theresiduals of each stage

22 Characterization Techniques Phase analyses and struc-tural changes of nanocomposite powders were determinedby X-ray diffraction (Philips X-ray diffractometer (XRD)Cundash119870119870120572120572 radiation 40 kV 30mA and 002∘Sminus1 step scan)For qualitative analysis XRD graphs were recorded in theinterval 20∘ le 2 120579120579 le 70∘ at scan speed of 1∘min PANalyticalXrsquoPert HighScore soware was also utilized for the analysisof different peaks e obtained experimental patterns werecompared to standards compiled by the Joint Committee onPowder Diffraction and Standards (JCPDS) which involvedcard number 04ndash0850 for Ni number 029ndash1128 for SiCnumber 01ndash0646 for Gr and number 047ndash1049 for NiOesurface morphologies of coatings were observed by scanningelectron microscopy (SEM VEGA Tescan easyprobe) X-ray energy dispersion spectroscopy (EDS) and elementalmapping analysis system attached to the SEM were utilizedto determine the weight percentage of nanoparticles anddistribution of materials e particle size and thickness ofthe coated layer were measured by a eld emission scanningelectron microscope (FE-SEM Hitachi S1831) that operatedat the acceleration voltage of 15 kV Microhardness analysiswas performed on polished samples at room temperatureusing aVickersmicrohardness tester (MICROMET3 BuehlerLtd USA) with Vickers pyramidal diamond indenter Aload of 50 g was applied for 20 s and the nal value quotedfor the hardness of the deposit was the average of atleast three measurements It should be mentioned that thereported values of the microhardness are representative ofthe deposited coatings without signicant inuence fromunderlying substrate

3 Results and Discussions

31 XRD Analysis Figure 1 shows the XRD prole of theSiC nanoparticles As can be seen the single phase of SiCwith high crystalline structure is close to the standard cardof SiC (no 29-1128) Figure 2 illustrates the XRD patternof Ni matrix coating deposited in absence of reinforcementmaterials (SiC and Gr) in electrolyte According to the XRDpattern it can be observed that aer 20min of plating thedominant phase was nickel e XRD prole of the Ni-based coatings in the absence and presence of surfactants arepresented in Figures 3(a) and 3(b) respectively As can beseen in Figure 3(a) the strong peakwas related to nickel oxideand it proposes that the surface of the Ni matrix was oxidizedduring contacting with the plating bath [28] In addition

ISRN Electrochemistry 3

T 1 Electrochemical plating process at different bath compositions (I) without any reinforcements powders (II) in absence of surfactantssolution and (III) in presence of surfactants solution

Bath composition (gL) Operating conditionsSample NiSO4sdot6H2O NiCl2sdot6H2O H3BO3 SiC Graphite CTAB SDS C7H5NO3S 119879119879 (∘C) pH DC (Adm2)I 200 20 40 mdash mdash 5 5 1 45 48 4II 200 20 40 12 1 0 0 0 45 48 4III 200 20 40 12 1 5 5 1 45 48 4

20 30 40 50 60 70

lowast

lowast

lowastlowastlowast lowast

lowast

lowast

(00-029-1128 SiC)

SiC lowast

Inte

nsi

ty (

au

)

F 1 XRD pattern of the SiC nanoparticles

20 30 40 50 60 70

(00-004-0850 Ni)

(200)

(111)

Inte

nsi

ty (

au

)

Ni

F 2 XRD pattern of Ni matrix coating without any reinforce-ment materials (sample I)

the weak signal of nickel was found on the diffraction patternFine peaks of SiC were also identied which can be inferredthat the low amount of SiC was absorbed into the nickelmatrix Figure 3(b) shows the XRD pattern of Ni-SiC-Grnanocomposite coating deposited in presence of surfactants

20 30 40 50 60 70

NiO SiC

Ni

(102)

(a)

(b)

(111)

(200)

(110)

(00-029-1128 SiC)

(00-004-0850 Ni)

Inte

nsi

ty (

au

)

lowast lowast

lowast lowast

∆

∆

∆∆

lowast∆

F 3 XRD pattern of Ni-SiC-Gr nanocomposite coatingsdeposited (a) in absence of surfactants (sample II) and (b) inpresence of surfactants (sample III)

solution e prole of the sample conrms the presenceof Ni SiC graphite (Gr) and NiO phases e strong peakof nickel shows that the electrochemical deposition wasdone almost perfectly so that this event shows key roleof surfactants in plating of nickel-based coating e XRDpattern demonstrates typical peaks corresponding to (111)and (200) crystallographic planes of nickel as well as the(102) and (110) planes of SiC It has been reported that[11] the embedding of SiC particulates in the nickel matrixcould modify the Ni texture from the so [1 0 0] modeto the mixed preferred [2 1 1] orientation Note that thepeaks corresponding to Gr particles could not be completelydetected in XRD patterns from nanocomposite coatings dueto very low content (1 gL) e specimen is prepared bysurfactants solution and the intensity of (111) peak is higherthan the other planes is result indicated that the preferredorientation of Ni is (111) plane It should be noted that (111)peak at 2120579120579 = 44508∘ is the strongest peak (relative intensity =100) in the standard XRD pattern from randomly orientedpolycrystalline nickel (no 04-0850)e crystallinity (Crl) of


9131

8288 8438

0

50

100

I II III

Cry

stal

lin

ity

()

Ni matrix coatings

(a)

1789

21932035

0

10

20

30

I II III

Ni matrix coatings

Cry

stal

lite

siz

e (D

) (n

m)

(b)

3523 3543 3526

2

3

4

I II III

Ni matrix coatings

Lat

tice

par

amet

er c

on

stan

t (A

)

(c)

F 4 Crystallite size (119863119863119863 crystallinity () and lattice parameter constant (120572120572) of nickel in nanocomposite coatings deposited (a) inabsence of reinforcements powders in electrolyte (SiC and Gr) (sample I) (b) in absence of surfactants (sample II) and (c) in presence ofsurfactants (sample III)

Ni particulates of the sample was determined by using theXRD data according to the following equation [29]

Crl =119868119868111 minus 119868119868120572120572m

119868119868111times 100 (1)

where 119868119868111 is the diffraction intensity of (111) plane and 119868119868120572120572mis the intensity of the measured amorphous peak (200)

e crystallite size (119863119863119863 for nickel was calculated usingScherrer equation [22] as follows

FWHM =119870119870119870119870

119863119863 119863119863119863 119863119863180∘

120587120587 (2)

where FWHM is full width half maxima in 2119863119863 degrees 119863119863 isthe crystallite size in nm 119870119870 is constant (usually evaluated as094) and119870119870 is thewavelength ofCundash119870119870120572120572 radiation (0154 nm)

Also as part of the structural characteristics the effect ofsurfactants on Ni lattice (cubic) constant (119886119886119888119888119863 was evaluatedby the following relation [30]

119889119889ℎ119896119896119896119896 =119886119886119888119888

1003526100352610076501007650ℎ2 + 1198961198962 + 119896119896210076661007666 (3)

where the Miller indices (ℎ119896119896119896119896119863 obtained from the diffractionspectra were identied using CDS cards (no 04050)and 119889119889ℎ119896119896119896119896 is the distance between adjacent Bragg planesFigure 4 shows the structural features of Ni phase forall the nanocomposite coatings deposited at different bathconditions (see Table 1) From the results of crystallinity(Figure 4(a)) it could be observed that the crystallinity of Nideposited in absence of any reinforcements is higher than theother coatings (sample I) e crystallinity degree of Ni into


(a) (b)

(c) (d)

F 5 SEM micrographs of Ni-SiC-Gr nanocomposite coatings deposited (a b) in absence of surfactants (sample II) and (c d) in thepresence of surfactants (sample III)

500 nm

(a)

500 nm

(b)

F 6 FE-SEM image of Ni-SiC-Gr nanocomposite coatings deposited (a) in absence of surfactants (sample II) and (b) in the presenceof surfactants (sample III)


SiNi

C

0 5 9

NiNi

NiSiO

C

Ni

Ni

Si

NiO

C

Ni

C

Si

Energy (keV)

Inte

nsi

ty (

au

)

0 5 9

Energy (keV)

Si (wt ) = 089C (wt ) = 013

Si (wt ) = 176

C (wt ) = 021

Inte

nsi

ty (

au

)

(a)

(b)

F 7 EDS and Elemental mapping spectra of Ni-SiC-Gr nanocomposite coatings deposited (a) in absence of surfactants (sample II)and (b) in the presence of surfactants (sample III)

the coating prepared in absence of surfactants is decreased(sample II) Also it seems that incorporating of SiC and Grin electrolyte led to increase of crystallinity degree of Nitherefore this indicates that SiC and Gr affected the crys-tallinity (samples III) e high crystallinity degree of Ni atdifferent circumstances proposes that all of the coatings haveappropriate thermal stability at high temperatures [26] Ascan be seen in Figure 4(b) crystallite size of the nickel for allthe coatingswas less than 25 nm It is revealed that the averagecrystallite size of Ni is affected in different specimens Figure4(c) displays the variation of lattice parameter constant (119886119886119888119888)as a function of different bath conditions (samples I IIand III) e lattice parameter values for all the samples areclose to the standard value (3524 Aring) which indicates thatdiverse electrochemical parameters have very little effect onthe lattice constant ofNi during plating processus it couldbe concluded that the surfactants have very little effect on thelattice constant of Ni during plating process

32 Morphological Features e surfaces morphology of Nimatrix nanocomposite coatings deposited in absence andpresence of surfactants were shown in Figure 5 As can beseen all the nanocomposite coatings have no regular surfacebut it could be observed that some the reinforced particulateswith cluster-like structure were dispersed into the matrixFigures 5(a) and 5(b) display the micrographs of specimenprepared in absence of the surfactants solution which showsthe compact reinforcement materials with heterogeneousstructure into the nickel matrix According to Figures 5(c)and 5(d) the surface prepared by the solution containing ofsurfactants is a relatively homogenous structure which con-sists of some ne particles Furthermore some agglomerateswere seen on the surface of the sample In fact the used

surfactants during plating led to modication of the surfacecharge of the particles by the absorbed molecules or ionswhich are a key factor for preventing of the agglomeration[31 32] e cross-sectional images of Ni-SiC-Gr nanocom-posite coatings deposited at various bath parameters areshown in Figure 6 As can be seen in Figures 6(a) and 6(b)both coatings deposited at various bath conditions were uni-form and homogenous with a good bonding to the substratee depositions were controlled to obtain a specic thicknessbetween 50 and 200120583120583m thus the thickness of coatings inspecimens II and III was acquired about 120 and 111120583120583mrespectively It seems that the reinforce SiC and graphiteparticles in the composite coatings act as physical barriersto grain growth and slow down the growth rate (hencethinner composite coatings) While hydrogen evolution atthe cathode can also result in coating thickness reductionsuch effects are not of electrodeposition from Watts bathFurthermore boric acid in the electrolyte is known forsuppressing the hydrogen evolution during electrodepositionof nickel from Watts bath e result is in agreement withother researches [22 26] From higher magnication of FE-SEM observations of the coatings surface it is observed thatNi-SiC-Gr nanocomposite coatings were formed as sphericalglobules with the average crystallite size of 65ndash150 nm Itseems that the globules have tendency to adhere onto theclean upper surface of the substrate (St-37)

33 EDSAnalysis Figure 7 shows the EDS (energy dispersiveX-ray spectroscopy) spectra of Ni-SiC-Gr nanocompositecoating deposited at different circumstances (samples IIand III) which conrms the presence of Ni Si C and elementals in the coatings ere is no specic separationin this analysis between carbon of graphite and carbide


332405

593

100

200

300

400

500

600

700

I II III

Mic

roh

ard

nes

s (H

v)

Ni matrix coatings

F 8 Variation of microhardness of Ni-SiC-Gr nanocompositecoatings deposited (I) in absence of reinforcements powders inelectrolyte (SiC and Gr) (II) in absence of surfactants and (III) inthe presence of surfactants

structures the displayed carbon signals derived from siliconcarbide and graphite sources Furthermore it is noteworthyto mention that chemically stable contaminants were notdetected and also it was demonstrated that the Ni-SiC-Gr nanocomposite coating onto the St-37 has acceptablepurity As can be seen the wt of SiC and C119892119892 in coatingsample III is higher than sample II which indicates thatpresence of surfactants led to enhancement reinforcementspowders contents (SiC and Gr) into the matrix Also thedistribution of reinforced materials such as SiC and Gr aswell as Ni particles was depicted According to elementalmapping analysis (see Figures 7(a) and 7(b)) the dispersionof particles is uniformly homogenous in the sample so thatthe presence of the particles in sample III is more obviousthan sample II It seems that the attendance of reinforcementrsquosparticulates resulted in the changing of surface charge onthe substrate and affected the deposition rate [33] ere-fore using of surfactants during electrochemical plating candevelop the efficiency of electrodeposition process of nickel-based nanocomposite coatings

34 Microhardness Analysis e microhardness of nano-composite coatings as a function of varied bath parametersis presented in Figure 8 Based on this gure the maximumhardness (593Hv) is corresponding to the coating depositedin presence of surfactants and reinforcements (sample III)As discussed earlier this condition also resulted in increasingcontent of reinforce nanoparticles in the coatings usthe improvement in the hardness of nanocomposite coatingat this situation seems to be due to increased content ofreinforced particles in the coatings e minimum hardnessof coatings was relevant to the specimen in absence ofany reinforcement materials (332Hv) It reveals that thesilicon carbide and graphite particulates have an effectiverole in mechanical properties and as a result promotesthe microhardness In fact the utilized surfactants cause toabsorb more the SiC and Gr particles into the nickel matrix

and this phenomenon led to an increase of microhardness Itshould be mentioned that the SiC particles deposited into Nimatrix played the role of obstacles versus the growth of theNi grains and the plastic deformation of the matrix [34]isresult is in good agreement with the microscopic observationand XRD analysis

4 Conclusion

e inuence of surfactant and reinforcement powders onthe mechanical properties and morphological characteristicsof the electrodeposited Ni Matrix nanocomposite coatingswas investigated According to the XRD data the dominantphases aer electrodepositing were nickel nickel oxide andSiC e presence of nickel oxide in the sample deposited inabsence of any surfactants conrms that the plating processwas performed incompletely It can be found out that the bathsolution without any surfactants is not efficient in depositionof Ni-SiC-Gr nanocomposite coating while the solution byusing the surfactants successfully deposited SiC andGr parti-cles into the Nimatrix with high crystallinity degree Accord-ing to the SEM observations the nanocomposite coatingsdisplayed a typical cluster-like structure which consisted ofsome ne sphere particles Also from FE-SEM micrographthe coated thickness was decreased by incorporating of SiCand Gr Based on EDS spectra the presence and distributionof Ni Si and C particles were uniformly homogenous in thesamples Also from the mapping analysis system it can beseen that the presence of the particles in sample III is moreobvious than sample II Eventually the coating preparedby surfactants solutions illustrated maximummicrohardnessabout 593HV which is in accordance with the SEM and EDSresults

Acknowledgment

e authors are grateful to research affairs of Islamic AzadUniversity Najafabad Branch for supporting this paper

References

[1] D Chaliampalias G Vourlias E Pavlidou S Skolianos KChrissas and G Stergioudis ldquoComparative examination ofthe microstructure and high temperature oxidation perfor-mance of NiCrBSi ame sprayed and pack cementation coat-ingsrdquo Applied Surface Science vol 255 no 6 pp 3605ndash36122009

[2] V Vitry A-F Kanta and F Delaunois ldquoApplication of nitrid-ing to electroless nickel-boron coatings chemical and struc-tural effects mechanical characterization corrosion resistancerdquoMaterials amp Design vol 39 pp 269ndash278 2012

[3] V Vitry A F Kanta and F Delaunois ldquoInitiation and forma-tion of electroless nickel-boron coatings on mild steel effect ofsubstrate roughnessrdquo Materials Science and Engineering B vol175 no 3 pp 266ndash273 2010

[4] B Ramezanzadeh and M M Attar ldquoStudying the corrosionresistance and hydrolytic degradation of an epoxy coating con-taining ZnO nanoparticlesrdquo Materials Chemistry and Physicsvol 130 no 3 pp 1208ndash1219 2011


[5] J X Kang W Z Zhao and G F Zhang ldquoInuence ofelectrodeposition parameters on the deposition rate andmicro-hardness of nanocrystalline Ni coatingsrdquo Surface and CoatingsTechnology vol 203 no 13 pp 1815ndash1818 2009

[6] P Sahoo and S K Das ldquoTribology of electroless nickelcoatingsmdasha reviewrdquo Materials and Design vol 32 no 4 pp1760ndash1775 2011

[7] S C Tjong and H Chen ldquoNanocrystalline materials andcoatingsrdquoMaterials ScienceampEngineering R-Reports vol 45 no1 pp 1ndash88 2004

[8] C Suryanarayana and C C Koch ldquoNanocrystalline materi-alsmdashcurrent research and future directionsrdquo yperne Interac-tions vol 130 no 1-4 pp 5ndash44 2000

[9] P Gyou M Stroumbouli E A Pavlatou P Asimidis and NSpyrellis ldquoTribological study of Ni matrix composite coatingscontaining nano and micro SiC particlesrdquo Electrochimica Actavol 50 no 23 pp 4544ndash4550 2005

[10] C ZanellaM Lekka and P L Bonora ldquoInuence of the particlesize on themechanical and electrochemical behaviour ofmicro-and nano-nickel matrix composite coatingsrdquo Journal of AppliedElectrochemistry vol 39 no 1 pp 31ndash38 2009

[11] M R Vaezi S K Sadrnezhaad and L Nikzad ldquoElectrodeposi-tion of Ni-SiC nano-composite coatings and evaluation of wearand corrosion resistance and electroplating characteristicsrdquoColloids and Surfaces A vol 315 no 1ndash3 pp 176ndash182 2008

[12] E Broszeit ldquoMechanical thermal and tribological properties ofelectro- and chemodeposited composite coatingsrdquo in SolidFilms vol 95 no 2 pp 133ndash142 1982

[13] I Garcia J Fransaer and J P Celis ldquoElectrodeposition andsliding wear resistance of nickel composite coatings containingmicron and submicron SiC particlesrdquo Surface and CoatingsTechnology vol 148 no 2-3 pp 171ndash178 2001

[14] M Surender B Basu and R Balasubramaniam ldquoWear char-acterization of electrodeposited Ni-WC composite coatingsrdquoTribology International vol 37 no 9 pp 743ndash749 2004

[15] V V N Reddy B Ramamoorthy and P K Nair ldquoA studyon the wear resistance of electroless Ni-Pdiamond compositecoatingsrdquoWear vol 239 no 1 pp 111ndash116 2000

[16] F B Bahaaideen Z M Ripin and Z A Ahmad ldquoElectrolessNi-P-Cg(graphite)-SiC composite coating and its applicationonto piston rings of a small two stroke utility enginerdquo Journal ofScientic and Industrial Research vol 69 no 11 pp 830ndash8342010

[17] Y Wu B Shen L Liu and W Hu ldquoe tribological behaviourof electroless Ni-P-Gr-SiC compositerdquoWear vol 261 no 2 pp201ndash207 2006

[18] S K Kim andH J Yoo ldquoFormation of bilayer Ni-SiC compositecoatings by electrodepositionrdquo Surface and Coatings Technol-ogy vol 108-109 pp 564ndash569 1998

[19] Z X Niu F H Cao W Wang Z Zhang J Q Zhang andC N Cao ldquoElectrodeposition of Ni-SiC nanocomposite lmrdquoTransactions of Nonferrous Metals Society of China vol 17 no1 pp 9ndash15 2007

[20] M D Ger ldquoElectrochemical deposition of nickelSiC compos-ites in the presence of surfactantsrdquo Materials Chemistry andPhysics vol 87 no 1 pp 67ndash74 2004

[21] M C Choua M D Ger S T Ke Y R Huangc and ST Wu ldquoe Ni-P-SiC nanocomposite produced by electro-codepositionrdquo Materials Chemistry and Physics vol 92 pp146ndash151 2005

[22] T Borkar and S P Harimkar ldquoEffect of electrodepositionconditions and reinforcement content on microstructure andtribological properties of nickel composite coatingsrdquo Surfaceand Coatings Technology vol 205 no 17-18 pp 4124ndash41342011

[23] A Hovestad and L J J Janssen ldquoElectrochemical codepositionof inert particles in a metallic matrixrdquo Journal of AppliedElectrochemistry vol 25 no 6 pp 519ndash527 1995

[24] S C Wang and W C J Wei ldquoKinetics of electroplatingprocess of nano-sized ceramic particleNi compositerdquoMaterialsChemistry and Physics vol 78 no 3 pp 574ndash580 2003

[25] F Hu and K C Chan ldquoElectrocodeposition behavior of Ni-SiCcomposite under different shaped waveformsrdquo Applied SurfaceScience vol 233 no 1ndash4 pp 163ndash171 2004

[26] A M Rashidi and A Amadeh ldquoEffect of electroplating param-eters on microstructure of nanocrystalline nickel coatingsrdquoJournal of Materials Science and Technology vol 26 no 1 pp82ndash86 2010

[27] R Elansezhian B Ramamoorthy and P Kesavan Nair ldquoEffectof surfactants on themechanical properties of electroless (Ni-P)coatingrdquo Surface and Coatings Technology vol 203 no 5-7 pp709ndash712 2008

[28] L Burzyńska E Rudnik J Koza L Błaz and Wojciech Szy-mański ldquoElectrodeposition and heat treatment of nickelsiliconcarbide compositesrdquo Surface and Coatings Technology vol 202no 12 pp 2545ndash2556 2008

[29] Z Liao Z Huang H Hu Y Zhang and Y Tan ldquoMicroscopicstructure and properties changes of cassava stillage residuepretreated by mechanical activationrdquo Bioresource Technologyvol 102 no 17 pp 7953ndash7958 2011

[30] M A Siddig S Radiman S V Muniandy and L SJan ldquoStructure of cubic phases in ternary systems Gluco-ponewaterhydrocarbonrdquo Colloids and Surfaces A vol 236 no1ndash3 pp 57ndash67 2004

[31] H Guumll F Kiliccedil S Aslan A Alp and H Akbulut ldquoCharacteris-tics of electro-co-deposited Ni-Al2O3 nano-particle reinforcedmetal matrix composite (MMC) coatingsrdquo Wear vol 267 no5-8 pp 976ndash990 2009

[32] H Guumll F Kiliccedil M Uysal S Aslan A Alp and H AkbulutldquoEffect of particle concentration on the structure and tri-bological properties of submicron particle SiC reinforced Nimetal matrix nanocomposite (MMC) coatings produced byelectrodepositionrdquo Applied Surface Science vol 258 no 10 pp4260ndash4267 2012

[33] Y N GouW J Huang R C Zeng and Y Zhu ldquoInuence of pHvalues on electroless Ni-P-SiC plating on AZ91D magnesiumalloyrdquo Transactions of Nonferrous Metals Society of China vol20 no 2 pp s674ndashs678 2010

[34] M Srivastava V K W Grips and K S Rajam ldquoElectrochemi-cal deposition and tribological behaviour ofNi andNi-Cometalmatrix composites with SiC nano-particlesrdquo Applied SurfaceScience vol 253 no 8 pp 3814ndash3824 2007

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CatalystsJournal of


lubricating particles (eg MoS2 PTFE and graphite (Gr)[16 17]) into the nickel matrix might effectively improvethe mechanical and tribological properties of the surfaces[9] Also numerous researchers have studied synthesis ofNi-based nanocomposites by electrodeposition for instanceNi-SiC [18ndash20] Ni-P-SiC [21] Ni-Al2O3 [22] and Ni-ZrO2[22]e deposition of nanocomposites was affected bymanyfactors including processing parameters (eg surfactantpH value current density magnetic eld and waveform)bath composition and particle content Meanwhile bymanipulating the processing parameters some noticeableresults were acquired [18 23ndash25] It should be noted thatthe determination of optimum conditions for productionof nickel coatings from the reported results is difficultbecause they are in some cases different or paradoxical Forinstance the different results have been reported about effectof reinforcement grain size into the nickel-based coatings[26]

Although different nickel matrix nanocomposite coatingswith suitable mechanical and tribological properties wereknown but to the authors knowledge the inuence ofsurfactants (CTAB SDS and saccharine) and reinforcements(SiC andGr) on the characteristics of nickelmatrix nanocom-posite coating was not investigated In order to obtain the Ni-based coating with acceptable microhardness it is necessaryto use surfactants to absorb SiC and graphite (Gr) particlesinto the matrix during plating In this paper the maintarget was the electrodeposition ofNi-SiC-Gr nanocompositecoating onto the St-37 substrate with suitable mechanicaland morphological properties Moreover the inuence ofsurfactants on the morphological features and distributionof SiC and Gr particles into the Ni matrix was evaluated byXRD SEMFE-SEM EDS and elemental mapping analysistechniques Finally the mechanical properties of all speci-mens were compared under different circumstances whichexhibited valuable results

2 Experimental Procedures

21 Nanocomposite Coating Preparation Nickel coatingswere deposited fromWatts bath by direct current (DC) elec-troplating Electrochemical bath components were consistedof nickel sulfate (Merck 99) boric acid (Merck 998)and nickel chloride (Merck 98) e basic compositionsof the bath and the experimental operating parameters areprovided in Table 1 SiC nanopowders in the range of40minus100 nm (Hefeikaier Nanometer Energy amp Technology99) and Graphite (Gr) particles in the range of 5ndash150 120583120583m(Merck 998) were utilized as reinforcements Meanwhilethe electrostatic adsorption of suspended particles on thecathode surface increased by enhancing of their positivecharge [27] and the surfactants such as cetyltrimethylammo-niumbromide (CTABMerck 98) sodiumdodecyl sulphate(SDS Acros Organics 98) and Saccharine (Merck 99)were used To obtain suitable nanocomposites coatings allthe bath ingredients were agitated (stirring rate = 500 rpm)for 20min by magnetic stirring Subsequently the sonicationprocess was served for 15min to provide homogeneous

dispersion and to prevent agglomeration of the particlesLow carbon steel (St-37) plates 10mm times 10mm times 1mm assubstrate and nickel cylindrical were utilized for electroplat-ing process Before the electrodeposition the substrates havebeen prepared by the following procedures (a) degreasingusing a surfactants solution at 50∘C for 5min (b) acidpickling in a diluted sulfuric acid solution (10H2SO4) for1min and (c) polishing with silicon carbide metallographicpapers Aer each preparation step the substrates have beenrinsed by distilled water in order to completely remove theresiduals of each stage

22 Characterization Techniques Phase analyses and struc-tural changes of nanocomposite powders were determinedby X-ray diffraction (Philips X-ray diffractometer (XRD)Cundash119870119870120572120572 radiation 40 kV 30mA and 002∘Sminus1 step scan)For qualitative analysis XRD graphs were recorded in theinterval 20∘ le 2 120579120579 le 70∘ at scan speed of 1∘min PANalyticalXrsquoPert HighScore soware was also utilized for the analysisof different peaks e obtained experimental patterns werecompared to standards compiled by the Joint Committee onPowder Diffraction and Standards (JCPDS) which involvedcard number 04ndash0850 for Ni number 029ndash1128 for SiCnumber 01ndash0646 for Gr and number 047ndash1049 for NiOesurface morphologies of coatings were observed by scanningelectron microscopy (SEM VEGA Tescan easyprobe) X-ray energy dispersion spectroscopy (EDS) and elementalmapping analysis system attached to the SEM were utilizedto determine the weight percentage of nanoparticles anddistribution of materials e particle size and thickness ofthe coated layer were measured by a eld emission scanningelectron microscope (FE-SEM Hitachi S1831) that operatedat the acceleration voltage of 15 kV Microhardness analysiswas performed on polished samples at room temperatureusing aVickersmicrohardness tester (MICROMET3 BuehlerLtd USA) with Vickers pyramidal diamond indenter Aload of 50 g was applied for 20 s and the nal value quotedfor the hardness of the deposit was the average of atleast three measurements It should be mentioned that thereported values of the microhardness are representative ofthe deposited coatings without signicant inuence fromunderlying substrate

3 Results and Discussions

31 XRD Analysis Figure 1 shows the XRD prole of theSiC nanoparticles As can be seen the single phase of SiCwith high crystalline structure is close to the standard cardof SiC (no 29-1128) Figure 2 illustrates the XRD patternof Ni matrix coating deposited in absence of reinforcementmaterials (SiC and Gr) in electrolyte According to the XRDpattern it can be observed that aer 20min of plating thedominant phase was nickel e XRD prole of the Ni-based coatings in the absence and presence of surfactants arepresented in Figures 3(a) and 3(b) respectively As can beseen in Figure 3(a) the strong peakwas related to nickel oxideand it proposes that the surface of the Ni matrix was oxidizedduring contacting with the plating bath [28] In addition




20 30 40 50 60 70

lowast

lowast


lowast

lowast

(00-029-1128 SiC)

SiC lowast

Inte

nsi

ty (

au

)


20 30 40 50 60 70

(00-004-0850 Ni)

(200)

(111)

Inte

nsi

ty (

au

)

Ni



20 30 40 50 60 70

NiO SiC

Ni

(102)

(a)

(b)

(111)

(200)

(110)

(00-029-1128 SiC)

(00-004-0850 Ni)

Inte

nsi

ty (

au

)

lowast lowast

lowast lowast

∆

∆

∆∆

lowast∆




9131

8288 8438

0

50

100

I II III

Cry

stal

lin

ity

()

Ni matrix coatings

(a)

1789

21932035

0

10

20

30

I II III

Ni matrix coatings

Cry

stal

lite

siz

e (D

) (n

m)

(b)

3523 3543 3526

2

3

4

I II III

Ni matrix coatings

Lat

tice

par

amet

er c

on

stan

t (A

)

(c)



Crl =119868119868111 minus 119868119868120572120572m

119868119868111times 100 (1)



FWHM =119870119870119870119870

119863119863 119863119863119863 119863119863180∘

120587120587 (2)



119889119889ℎ119896119896119896119896 =119886119886119888119888

1003526100352610076501007650ℎ2 + 1198961198962 + 119896119896210076661007666 (3)



(a) (b)

(c) (d)


500 nm

(a)

500 nm

(b)



SiNi

C

0 5 9

NiNi

NiSiO

C

Ni

Ni

Si

NiO

C

Ni

C

Si

Energy (keV)

Inte

nsi

ty (

au

)

0 5 9

Energy (keV)

Si (wt ) = 089C (wt ) = 013

Si (wt ) = 176

C (wt ) = 021

Inte

nsi

ty (

au

)

(a)

(b)







332405

593

100

200

300

400

500

600

700

I II III

Mic

roh

ard

nes

s (H

v)

Ni matrix coatings





4 Conclusion


Acknowledgment


References













































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




20 30 40 50 60 70

lowast

lowast


lowast

lowast

(00-029-1128 SiC)

SiC lowast

Inte

nsi

ty (

au

)


20 30 40 50 60 70

(00-004-0850 Ni)

(200)

(111)

Inte

nsi

ty (

au

)

Ni



20 30 40 50 60 70

NiO SiC

Ni

(102)

(a)

(b)

(111)

(200)

(110)

(00-029-1128 SiC)

(00-004-0850 Ni)

Inte

nsi

ty (

au

)

lowast lowast

lowast lowast

∆

∆

∆∆

lowast∆




9131

8288 8438

0

50

100

I II III

Cry

stal

lin

ity

()

Ni matrix coatings

(a)

1789

21932035

0

10

20

30

I II III

Ni matrix coatings

Cry

stal

lite

siz

e (D

) (n

m)

(b)

3523 3543 3526

2

3

4

I II III

Ni matrix coatings

Lat

tice

par

amet

er c

on

stan

t (A

)

(c)



Crl =119868119868111 minus 119868119868120572120572m

119868119868111times 100 (1)



FWHM =119870119870119870119870

119863119863 119863119863119863 119863119863180∘

120587120587 (2)



119889119889ℎ119896119896119896119896 =119886119886119888119888

1003526100352610076501007650ℎ2 + 1198961198962 + 119896119896210076661007666 (3)



(a) (b)

(c) (d)


500 nm

(a)

500 nm

(b)



SiNi

C

0 5 9

NiNi

NiSiO

C

Ni

Ni

Si

NiO

C

Ni

C

Si

Energy (keV)

Inte

nsi

ty (

au

)

0 5 9

Energy (keV)

Si (wt ) = 089C (wt ) = 013

Si (wt ) = 176

C (wt ) = 021

Inte

nsi

ty (

au

)

(a)

(b)







332405

593

100

200

300

400

500

600

700

I II III

Mic

roh

ard

nes

s (H

v)

Ni matrix coatings





4 Conclusion


Acknowledgment


References













































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


9131

8288 8438

0

50

100

I II III

Cry

stal

lin

ity

()

Ni matrix coatings

(a)

1789

21932035

0

10

20

30

I II III

Ni matrix coatings

Cry

stal

lite

siz

e (D

) (n

m)

(b)

3523 3543 3526

2

3

4

I II III

Ni matrix coatings

Lat

tice

par

amet

er c

on

stan

t (A

)

(c)



Crl =119868119868111 minus 119868119868120572120572m

119868119868111times 100 (1)



FWHM =119870119870119870119870

119863119863 119863119863119863 119863119863180∘

120587120587 (2)



119889119889ℎ119896119896119896119896 =119886119886119888119888

1003526100352610076501007650ℎ2 + 1198961198962 + 119896119896210076661007666 (3)



(a) (b)

(c) (d)


500 nm

(a)

500 nm

(b)



SiNi

C

0 5 9

NiNi

NiSiO

C

Ni

Ni

Si

NiO

C

Ni

C

Si

Energy (keV)

Inte

nsi

ty (

au

)

0 5 9

Energy (keV)

Si (wt ) = 089C (wt ) = 013

Si (wt ) = 176

C (wt ) = 021

Inte

nsi

ty (

au

)

(a)

(b)







332405

593

100

200

300

400

500

600

700

I II III

Mic

roh

ard

nes

s (H

v)

Ni matrix coatings





4 Conclusion


Acknowledgment


References













































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


(a) (b)

(c) (d)


500 nm

(a)

500 nm

(b)



SiNi

C

0 5 9

NiNi

NiSiO

C

Ni

Ni

Si

NiO

C

Ni

C

Si

Energy (keV)

Inte

nsi

ty (

au

)

0 5 9

Energy (keV)

Si (wt ) = 089C (wt ) = 013

Si (wt ) = 176

C (wt ) = 021

Inte

nsi

ty (

au

)

(a)

(b)







332405

593

100

200

300

400

500

600

700

I II III

Mic

roh

ard

nes

s (H

v)

Ni matrix coatings





4 Conclusion


Acknowledgment


References













































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


SiNi

C

0 5 9

NiNi

NiSiO

C

Ni

Ni

Si

NiO

C

Ni

C

Si

Energy (keV)

Inte

nsi

ty (

au

)

0 5 9

Energy (keV)

Si (wt ) = 089C (wt ) = 013

Si (wt ) = 176

C (wt ) = 021

Inte

nsi

ty (

au

)

(a)

(b)







332405

593

100

200

300

400

500

600

700

I II III

Mic

roh

ard

nes

s (H

v)

Ni matrix coatings





4 Conclusion


Acknowledgment


References













































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


332405

593

100

200

300

400

500

600

700

I II III

Mic

roh

ard

nes

s (H

v)

Ni matrix coatings





4 Conclusion


Acknowledgment


References













































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of









































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

ResearchArticle In uenceo ur actantsontheCharacteristicso...

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