T.C.

SAKARYA UNIVERSITY
INSTITUTE OF SCIENCES
NANOSCIENCE AND NANOENGINEERING DEPARTMENT

COMPOSITE WITH NANOCOATING

FOR
ELECTRODEPOSITION TECHNIQUES

Nanocomposite Materials Course

Presenter
Ali ERARSLAN
D175010014

Lecturer
Associate Prof. Tuğrul ÇETİNKAYA

10.05.2019

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CONTENTS

Sayfa
1. NANO COATİNGS AND NANO COMPOSITES IN THIS STUDY..................iii
1.1 Our Materials Specifications..................................................................................iii
2. ELECTRODEPOSITION PROCESS......................................................................4
2.1 Step by Step Electrodeposition Process...................................................................5
2.2 Schematic Diagram of Electrodeposition Processfor Ni-W/BN Nanocomposite
Coating.....................................................................................................................5
2.3 An Example of Electrodeposition Coating Process: Ni–W/ZrO2............................6
2.4 Properties of Nano Coated Composites...................................................................6
3. NANO COATED COMPOSITES CHARACTERIZATION..................................7
3.1 Change of Element Contents in Composites due to Particle Concentration in Bath
..................................................................................................................................7
3.1.1 Ni-W/BN..................................................................................................................7
3.1.2 Ni-W/Si3N4: Si3N4 contents(%wt) depends on Duty Cycle......................................9
3.1.3 Ni-W/SiC: SiC and W contents depends on; Current density A.dm−2(R) and SiC
concentration in electrolyte (g/L)...........................................................................10
3.1.4 Ni-W/MWCNT: This table demosntrate the content composition of Ni-
W/MWCNT composite for different stirring values..............................................11
3.2 Hardness Change due to Variable Factors.............................................................12
3.2.1 Ni-W/ZrO2..............................................................................................................12
3.2.2 Ni-W/BN................................................................................................................12
3.3 Change of MicroHardness Depending on Variable Factors...................................13
3.3.1 Ni-W/Si3N4.............................................................................................................13
3.4 Change of MicroHardness depending on Stirring function...................................15
3.5 Change of Friction Coefficient and Wear Rate Depending on Stirring Function..17
4. SEM IMAGES.......................................................................................................19
4.1 SEM Images for Variable Duty Cycle...................................................................22
5. RESULTS & CONCLUSİON................................................................................24
REFERENCES..........................................................................................................................24

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1. NANO COATİNGS AND NANO COMPOSITES IN THIS STUDY

• I will inform you about some nano coated composites which coated by
electrodeposition techniques. Some of these composites are; Ni-W, Ni, Ni-Cu alloy,

• Some coating materials are; Al2O3, Boron nitride(BN), TiN, ZrO2,

On this study, I investigate these composites improvements with these nano coating elements.

1.1 Our Materials Specifications

For the development of Ni coatings; Mo, Co, W, Si and Cu can be added as alloying
elements.

Ni-W alloy coating is widely used as a functional coating, which have excellent
microhardness, high corrosion resistance, wear resistance, good tribological and magnetic
properties. It is more environment-friendly alloy than hard chromium but it is also increases
undesired residual tensile stress.

Continuation of the study we will see some different results with the change of coating
materials.

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2. ELECTRODEPOSITION PROCESS

These schematics shows us electrodeposition instruments.

Figure 2.1. The schematic representation of the electrodeposition setup

Figure 2.2. A representation of the electrodeposition assembly

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2.1 Step by Step Electrodeposition Process

Firstly, the sample is cleaned in an ultrasonic cleaner, polished and degreased in acetone.
Secondly, prepare the deposition bath, electrolyte pH was adjusted between 7-9 pH for Ni-W,
4 pH for Ni-Cu.

Deposition bath contents; NiSO4·6H 2O, NiCl4·6H 2O, CuSO4·5H2O, Na2WO4.2H2O, NH4Cl,
SDS, CTAB, Na3C6H5O7·2H2O and NaC12H25 SO4.

Deposition parameters; Avg. Current Density(1-10 A.dm−2), Deposition Time(10 min-2 h),
Frequency, Magnetic Stirring, Duty Cycle (%20-80%).

After deposition, the products were rinsed with purified water and ultrasonically treated for 5
min to remove loosely adsorbed coating nanoparticles.

2.2 Schematic Diagram of Electrodeposition Processfor Ni-W/BN Nanocomposite

Coating

In figure 2.3, DC electrodeposition process shown step by step. And nano composite
materials deposition was performed on the cathode.

Figure 2.3. Schematic diagram of the electrodeposition process of Ni-W/BN nanocomposite coating.

2.3 An Example of Electrodeposition Coating Process: Ni–W/ZrO2

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Nickel anode and copper cathode were used to pulse deposition Ni–W/ZrO 2 nanocomposite
coating. The diameter of ZrO2 nanoparticles: 15–45 nm. At temperature of 65±2 °C.

Electrolyte contents: 0.12M “nickel sulfate”, 0.2M “sodium tungstate”, 0.5M “ammonia
chloride”, 0.4M sodium citrate, 0.001g L−1 sodium lauryl sulfate and 30g L−1 ZrO2. Stirring
speed: 400 ± 50 rpm and pH: 8.3 ± 0.2.

Firstly, the cathode was polished and ultrasonic cleaned in ethanol solution and rinsed by
distilled water. Secondly, it soaked in %10 wt hydrochloric acid solution for 20 s. Except the
duty cycle changes, the Ni–W/ZrO2 coating was deposited under the following conditions:
−2
Frequency; 500 Hz, Average current density (Iav) 2 A.dm and deposition time is 30 min.
The effects of duty cycle variable at the value of; 20%, 40%, 60%, 80% were investigated.
The total thickness of the coating was about 5–8 μm. During the deposition, continuous
magnetic stirring at 400 ± 50 rpm. Optimal duty cycle was %60 for excellent hardness and
corrosion resistance.

2.4 Properties of Nano Coated Composites

Ni-W/BN: Partical size: 50 nm, Roughness value: 78-100 nm (Ni-W: 45nm), Crystal size: 11-
13 nm. Nanoparticle contents during the experiment: %2-4 wt BN & %22-29 wt W.

Ni–W/ZrO2: Avg. Roughness: 50 nm, Corrosion Resistance: 5.09×104Ω cm2(%60 Duty Cycle)

Ni–W/S3N4: Avg. Current density: 5A/dm−2, Coating Thickness: 27 μm (Pulse), 35 μm (DC),

Microhardness: 1031 Hv, Crystallite Size: 27nm(Pulse).

Ni–W/SiC: Microhardness: 823 Hv, Wear weight loss: 0,52 mg cm−2.

Ni–W/MWCNT: Crystallite size: 14 nm, coating thickness : 28 μm, Composition contents

(wt) : %55.73 Ni, %27.57 W, %13.84 C(MWCNT), Microhardness : 753 Hv, Corrosion rate:
0.02123 mm/a , Wear Rate : 1,72x10-5mm3 (N m)-1 (for 70 W Ultrasound stirring).

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3. NANO COATED COMPOSITES CHARACTERIZATION

We will evaluate the characterization results obtained by changing different parameters.

Ni-W/BN: In this study, changing parameter is; “BN particle concentration in the bath”.
Deposition bath contents and electropolating parameters for coating is given by this table.

Table 1. Electrolyte and electroplating parameters of Ni-W/BN coating.

3.1 Change of Element Contents in Composites due to Particle Concentration in Bath

3.1.1 Ni-W/BN

Figure 3.1. Content of Ni and W in the Ni-W/BN nanocomposite coating

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 Figure 3.2. Content of BN nanoparticle in Ni-W/BN nanocomposite coating

Fig. 3.1, illustrated that the Ni content in the coating is 67e75 wt%. The W content is 22e29
wt%. It indicates that increasing the BN in bath, the Ni content first decreases and then
increases with the lowest value of 67.4 w.t% at 6 g L-1 BN particles. At the same time, the W
content increases to 28.4 wt% at 6 g L-1 BN, beyond which it decreases. Fig. 3.2, shows the
content of BN particles in coating is between 2.1 wt% and 4.2 wt%. It indicates that BN
content increases as the BN increases from 2 to 6 g L -1. When the BN concentration surpasses
6 g L-1, the BN particle content in the coating slightly decreases. In general, with the increase
of nanoparticles, the nanoparticles content in coating increases till to a certain value. The
decline of the BN particle content in coating beyond 6 g L -1 is associated with the
agglomeration of the particles. In this case, carbamide plays the role of a multifunctional
additive. First of all, it can adsorb on the surface of the BN particle as a surfactant. Then it
charged the particles, which is beneficial to the particle electrophoresis. Finally, it can
optimize the electro-crystallization process and make the coating smooth and compact.

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3.1.2 Ni-W/Si3N4: Si3N4 contents(%wt) depends on Duty Cycle.

Figure 3.3. Content of Si3N4 as a function of duty cycle, avg. current density of 5A/dm2, frequency of 1000 Hz
and Si3N4 nanoparticle concentration of 30g/L.

Si3N4 contents(%wt) depends on function of frequency (for %60 Duty Cycle)

Figure 3.4. Content of Si3N4 as a function of frequency, avg.current density of 5A/dm2, duty cycle of %60 and
Si3N4 nanoparticle concentration of 30g/L.

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3.1.3 Ni-W/SiC: SiC and W contents depends on; Current density A.dm −2(R) and SiC
concentration in electrolyte (g/L)

Figure 3.5. Effects of SiC nanoparticle concentration in the electrolyte on the composition of Ni-W/SiC
composite coatings, deposition time 10 min, current density 1 A dm-2 , pH 8.5.

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 Figure 3.6. Effect of current density on the composition of Ni-W/SiC composite coatings, deposition time 10
min, pH 8.5, SiC 3 g L-1.

3.1.4 Ni-W/MWCNT: This table demosntrate the content composition of Ni-W/MWCNT

composite for different stirring values.
Coating I: Ni-W, Coating II: Ni-W/MWCNT (500rpm-Mech) ,

Coating III: Ni-W/MWCNT (40W-Ultrasound Stirring), Coating IV: 70W (Ultrasound

Stirring), Coating V: 100W (Ultrasound Stirring).

Table 2. Mass fraction of elements in Ni-W and Ni-W/MWCNTs coatings deposited under various conditions.

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3.2 Hardness Change due to Variable Factors

3.2.1 Ni-W/ZrO2
Hardness, depends on duty cycle for Ni-W/ZrO2 composite in this study.

Figure 3.7. Hardness of Ni–W/ZrO2 nanocrystalline composite coating fabricated under different duty cycle.

3.2.2 Ni-W/BN
The graphic of hardness and wear weight loss due to BN nanoparticle concentration in
"deposition bath".

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 Figure 3.8. Microhardness and wear weight loss of the deposited Ni-W/BN coating

3.3 Change of MicroHardness Depending on Variable Factors

3.3.1 Ni-W/Si3N4
Current density of 5A/dm−2, Si3N4 nanoparticle concentration of 30g/L. The microhardness of
the coating thickness of 35 mm was measured by Vickers indenter. The experiment time is
10s with a load of 100g. In Graph a; log f =1 means 10 Hz, log f =3 means 1000 Hz.

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Figure 3.9. Microhardness values for different frequency with current density of 5A/dm2 and Si3N4 nanoparticle
concentration of 30g/L

Fig. 3.10. Microhardness values for different duty cycles at same conditions

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Fig. 3.11 Microhardness values of different current type, Ni-W and Ni-W- Si3N4 coatings with current density of
5A/dm2 and Si3N4 nanoparticle concentration of 30g/L.

3.4 Change of MicroHardness depending on Stirring function

Ni-W/MWCNT composites; were tested with 2 different stirring types and 4 different values.

Coating 1= Ni-W (500rpm), C2=Ni-W/MWCNTs (500rpm-Mech. Stirr.),

C3=Ni-W/MWCNTs (40W-Ultrasound Stirr.), C4 for (70W) and C5 for (100W).

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 Fig. 3.12. Comparisons of the microhardness of Ni-W alloy coating and Ni-W/MWCNTs composite coatings
deposited under different conditions.

Ni-W/SiC: Microhardness and Wear Weight Loss change graph for Ni, Ni-W and Ni-W/SiC.

Ni-W composite is better than Ni, and Ni-W/SiC nano coated composite is more than others.

Fig. 3.13. Microhardness and wear weight loss of deposited Ni, Ni-W and Ni-W/SiC.

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3.5 Change of Friction Coefficient and Wear Rate Depending on Stirring Function

Ni-W/MWCNT: In this graphic, both Friction Coefficient and Wear Rate are given by
different Stirring techniques and values.

Fig. 3.14. Comparisons of the friction coefficients and wear rates of Ni-W and Ni-W/MWCNTs composite
coatings deposited under different conditions.

Especially, the Ni-W/MWCNTs composite coatings prepared with ultrasonic agitation power
of 70W has a minimum wear weight loss and lowest friction coefficient. The friction
coefficient of the Ni-Walloy coating is decreased from 0.205 to 0.185, which was the friction
coefficient of the composite coating manufactured with mechanical stirring.

As presented in Fig. 3.14, the wear rate of the Ni-W alloy around 3.07x10-5mm3(N m) -1 is
decreased to 2.51x10-5mm3 (N m)-1 for the Ni-W/MWCNTs composite coating prepared under
mechanical stirring condition. Particularly, the composite coating prepared with ultrasound
stirring power of 70W shows the lowest wear rate, and the wear resistance of such composite
coating is improved tripled compared to the Ni-W alloy coating.

Ni-W/Si3N4:

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Friction coefficent graph due to coating deposition time for different deposition current type.

Fig. 3.15. Friction coefficient vs. time for different coatings

The coefficient of friction as a function of the wear test time for pulse electro deposited
Ni-W-Si3N4 composites coating and Ni-W alloy are illustrated in Fig. 3.15. averages of five
readings are noted under the identical test conditions. During the measurement period, the
friction coefficients of composite coatings exhibited little change and keepstable while the
friction coefficient of Ni-W alloy increases continually with prolonging the wear test time.
And it is observed that the friction coefficients of Ni-W-Si3N4 composite coatings were
significantly lower than that of the Ni-W alloy.

Table 3. Corrosion potentials and corrosion current densities of the composite coatings.

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4. SEM IMAGES

Ni-W/MWCNT: SEM images of Ni-W alloy and Ni-W/MWCNTs composite coatings for
different stirring mechanisms. (a) Ni-W (500 rpm-Mechanical), (b) Ni-W/MWCNTs (500 rpm)
(c)Ni-W/MWCNTs (40 W) and (d)Ni-W/MWCNTs (70 W).

Fig.4.1. SEM images of Ni-W alloy and Ni-W/MWCNTs composite coatings deposited under different
conditions: (a) coating-I; (b) coating-II; (c) coating-III; (d) coating-IV.

Ni-W(Coating-I) and Ni-W/MWCNTs (Coating-II)’s treatment methods of the electrolyte is

“Mechanical Stirring” under 500rpm.

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 Fig.4.2. Backscattered (BS) SEM images of the cross-sections of the various Ni-W/MWCNTs composite
coatings: (a) coating-II and (b) coating-IV.

In fig. 4.2 a. the MWCNT are agglomerated in the composite coating prepared underthe
mechanical stirring. With the help of ultrasound agitation, the well-dispersed MWCNTs are
shown in the Ni-W/MWCNTs composite coating, as presented in Fig. 4.2b. It demonstrates
that the ultrasound agitation is more favorable to distribute MWCNTs in the matrix during the
process of pulse electrodeposition, which are obviously different from the mechanical stirring.

Backscattered (BS) SEM images of the cross-sections of the various Ni-W/MWCNTs

composite coatings for showing agglomerates. To compare “Ultrasound” and “Mechanical
Stirring” techniques.

Fig.4.3. SEM morphology of worn surface of different coatings: (a) coating-I (adhesive) and (b) c-IV (abrasive).

The worn surface morphologies of Ni-W alloy coating and Ni-W/MWCNTs composite
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coating produced with ultrasound agitation power of 70W after wear measurements are shown
in Fig.4.3. As seen from Fig.4.3a, the wear scar of the Ni-W alloy coating is wide and deep,
implying the occurrence of fatigue wear and severe adhesive. In Fig.4.3b, different from the
alloy coating, the composites prepared by ultrasound agitation of 70W shows smaller scar.
The worn surface of the Ni-W alloy coating shows some larger wear debris indicating plastic
deformation, while the composite coating manufactured through ultrasound agitation of 70W
(Coating IV) only exhibits some clear abrasive grooves. As a result, compared with Ni-W
alloy coating, the wear resistance of Ni-W/MWCNTs composite coating increased, due to the
dispersion strengthening effect generated by ultrasonic agitation.

Ni-W/Si3N4:

SEM images of Ni-W/Si3N4 nanocomposite coatings for different frequency values.

Fig.4.4. Surface morphologies of Ni-W/Si3N4 composite coatings; Si3N4 nanoparticles concentration of 30g/L,
avg. Current density of 5A/dm2, frequency of 1000Hz and duty cycle of (a) %20, (b) %40, (c) %60 and (d) %80.

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Electrodeposition bath composition and operation conditions of Ni-W/Si3N4 given by table.

Table 4. Bath composition and operating conditions used to prepare electrodeposited Ni-W/Si3N4 composite
coatings.

4.1 SEM Images for Variable Duty Cycle

Fig. 4.5 presents the effect of duty cycle on the structure of the Ni-W /Si3N4 coatings. The
nanocomposite coating that produced with duty cycle of %60 (Fig. 4.5c) reveals finest
structure and nearly smooth and uniform surface than the coatings fabricated with duty cycle
of %20 and %40 (Fig. 4.5a–b).

In Fig.4.6, SEM image shows Ni-W’s surface morphologhy of %60 Duty Cycle and in the
same parameters.

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 Fig.4.5. Surface morphologies of Ni-W/Si3N4 composite coatings processed with Si3N4 nanoparticles
concentration of 30g/L, avg. current density of 5A/dm2, frequency of 1000Hz and duty cycle of (a) %20, (b)%40,
(c) %60 and (d) %80.

Fig.4.6. Surface morphology of Ni-W processed with Si3N4 nanoparticles concentration of 30g/L and the avg.
current density of 5A/dm2, frequency of 1000Hz and duty cycle of %60.

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5. RESULTS & CONCLUSİON

Ni-W/Si3N4: Optimum working conditions are 1000 Hz and Duty cycle of %60 with Pulse
current deposition techniques. These values provide maximum micro hardness and minimum
crystal size: 27μm (from 37), Crystal size: 27nm (from 40), corrosion rate: 0.01911 mm/a
(from 0.249), Si3N4 content : %2.1 wt.

Ni-W/BN: Optimum values: %5 BN in electrodeposition bath and Growth rate is 0.4μm/min.

Results are; Wear weight loss: 0,29 mg.cm-2, Hardness : 990 Hv, BN content : % 3.5 wt.,
Grain size: 11,8 nm,

Ni-W/MWCNT: Optimum value: 70 W Ultrasound Stirring. Friction Coefficient: 0.158.

Hardness: 753 Hv, Corrosion Rate (mm/a): 0.02123 (0.26141) Crystal size: 14 nm (from 35),
Wear Rate: 1.96x10-5mm-3 (N m) -1,

Ni-W/SiC: Optimum value: 6 gL-1, Wear weight loss : 0,52 mg.cm-2 (from 1,4), Hardness :
823 Hv (from 729).

Ni-W/ZrO2: Optimum values at Duty Cycle of %60. Mean average roughness: 50 nm,
Crystal size: 12-14 nm, Hardness:765 Hv (859-%80), Growth rate: 0.17μm/min at 2 A.dm-2.
Corrosion Resistance (Rp): 5.09×104 Ω cm2.

REFERENCES

Han Li, Yi He, Teng He , Yi Fan, Qiangbin Yang, YingQing Zhan, (2016) “The influence of
pulse plating parameters on microstructure and properties of Ni-W-Si3N4 nanocomposite
coatings”, Ceramics International42(2016)18380–18392, Sichuan-PR China.
Baosong Li, Weiwei Zhang, Wen Zhang, Yuxing Huan, (2017), “Preparation of Ni-W/SiC
nanocomposite coatings by electrochemical deposition”, Journal of Alloys and Compounds
702 (2017) 38-50, PR China and USA.
Baosong Li, Dandan Li, Tianyong Mei, Wenzhe Xia, Weiwei Zhang, (2017), “Fabrication
and characterization of boron nitride reinforced Ni-W nanocomposite coating by
electrodeposition”, Journal of Alloys and Compounds 777 (2019) 1234-1244, PR China.
Weiwei Zhang, Cuicui Ji, Baosong Li, (2019), “Synthesis and properties of Ni–W/ZrO2
nanocomposite coating fabricated by pulse electrodeposition”, Results in Physics 13 (2019)
102242, Changzhou 213022 PR China.

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Teng He, Yi He, Han Li, Yi Fan, Qiangbin Yang, Ze He, (2017), “A comparative study of
effect of mechanical and ultrasound agitation on the properties of pulse electrodeposited Ni-
W/MWCNTs composite coatings”, Journal of Alloys and Compounds 743 (2018 63-72,
Chengdu-PR China.

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