Yujia RISE 2017 Poster
Graduate Category: Engineering and Technology Degree Seeking: PhD Abstract ID# 1667
Pulse Current Electrodeposition of Ni-W-TiO2 Composites Yujia Zhang and Elizabeth Podlaha Approach
Background Tungsten alloys with nickel are well known for their superior properties in the following areas: corrosion resistance, hardness, wear resistance, and catalytic activity towards hydrogen evolution, as comprehensively reviewed by Tsyntsaru et al.1 Composite electrodeposition of Ni-W alloys with solid particles allows for further tailoring of these properties. Reported studies on Ni-W-TiO2 composites focus on properties of the material. For example, Kumar et al.2 showed that the hardness was further increased with the addition of titania in the deposit, and when pulse deposited there was an enhancement in corrosion resistance. Similarly, Goldasteh and Rastegari3 reported an increase in hardness due to refining of the crystallite size in the deposit with titania. Corrosion resistance was found to be better in pulse deposited Ni-W-TiO2 composites, compared to their DC counterparts. However, there are no studies that address the impact of the particle on the metal ion reaction rate, which is critical in determining the deposit composition and hence the resulting property. Ni-W-TiO2 codeposition takes place through an adsorption mechanism. Adsorbed intermediates of Ni, W and H form on the cathode surface. The metal intermediates then reduce to form the alloy, and the adsorbed particles are included into the metal matrix. Hads Hads Niads
Wads Hads Hads Hads Niads
TiO2
Hads Hads Hads Niads
π$
π΅π
Wads Hads Hads Hads Hads HadsHads Hads
+π
π ' π
β π΅π$ ππ π
π΅π$ ππ π
Table 1. Electrolyte (ammonium-free!!!) and Condition
π ' π
+ π β π΅π
Objectives The goal of this study is to electrodeposit Ni-W-TiO2 composites and for the first time study the influence of titania particle electrolyte concentration on the metal ion reduction rate and side reaction that determines the deposit composition and thickness. In parallel, an ammonia-free electrolyte is used and further characterized as a path towards a more health conscious working environment for those in the plating industry.
Nickel Sulfate
0.1 M
Sodium Tungstate
0.15 M
Sodium Citrate
0.285 M
Boric Acid
1M
Titanium Dioxide
0, 2.5, 7.5, 12.5 (PC), 25, 50 g/L
pH
8
Temperature
25 Β°C
Rotation Rate
500 rpm
Magnetic Stirring
300 rpm
Pulse Frequency
0.2, 2, 20, 200 Hz
(a)
Results
working electrode: Cu
DC Deposition Ratio of W Partial Current Density to Ni Partial Current Density
65 0 g/L
1.6
55
2.5 g/L
1.4
50
7.5 g/L 12.5 g/L
45 40 50
100 -i (mA/cm2 )
150
Particle loading 0 g/L 2.5 g/L
1.2
7.5 g/L
1
25 g/L
0.8
50 g/L
0.6
12.5 g/L 25 g/L 1.1
Ni Partial Current Density
1.2
1.3 -E (V) vs SCE
1.4
1.5
2.5 g/L
0.9
7.5 g/L 12.5 g/L
0.6
1.2
0 g/L 2.5 g/L
0.9
7.5 g/L 12.5 g/L
0.6
25 g/L 0.3 1.4
1.5
1.1
1.2
1.3 -E (V) vs SCE
1.4
0.15
25 g/L
0.05
50
100 -i (mA/cm2 )
SEM analysis
0
150
0
10
Langmuir-like!!!
20 30 C (g/L)
40
50
20,000 X 5,000 X
80 40
1.5
0
50 g/L
2.5 g/L
5%
0% 1.1
1.2
1.3 1.4 -E vs SCE (V)
1.5
insulator
12.5 g/L 25 g/L 1.1
1.2
1.3 1.4 -E vs SCE (V)
1.5
50 g/L
0 g/L
PC Deposition Ni Partial Current Density
10
0.2 Hz
45
2 Hz
1.8 Frequency
8
DC
6
0.2 Hz
4
2 Hz
40
20 Hz
2
20 Hz
35
200 Hz
0
200 Hz
1
0
0.2 0.4 0.6 0.8 Dimensionless length, L = x/h
1
iNi (mA/cm2 )
DC
50
TiO2 (wt %)
Frequency
55
W Partial Current Density
1.5
Frequency
1.2
DC
0.9
0.2 Hz
0.6
2 Hz
0.3
20 Hz
0 0
0.2 0.4 0.6 0.8 Dimensionless length, L = x/h
1
200 Hz
1.8 -iW (mA/cm2 )
Deposit TiO2 Content
60 W (wt %)
2.5
working electrode: Cu
counter electrode: Pt
0.5 0 0.2 0.4 0.6 0.8 1 Dimensionless length, L = x/h
SEM analysis
1.5
Frequency
1.2
DC
0.9
0.2 Hz
0.6
2 Hz
0.3
20 Hz
0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Dimensionless length, L = x/h
20,000 X 5,000 X
200 Hz
DC
200 Hz
20,000 X
q Deposit W content is affected under PC condition; the W content slightly decreases. Inspection of partial current densities shows there is a larger enhancement of Ni partial current density than W partial current density, resulting in less W in the final deposit. q Deposit TiO2 content is affected under PC condition; the TiO2 content slightly increases regardless of pulse frequency. q The Ni(II) and W(VI) ion partial current densities are both enhanced under PC condition, leading to a larger current efficiency. q Deposit morphology is not significantly affected by PC deposition.
stir bar
insulator Figure 2. Schematic of rotating cylinder electrode for polarization measurement, the cathode has a diameter of 0.6 cm and a length of 1 cm.
Figure 1. (a) Schematic of Rotating Hull cell for electrodeposition, the cathode has a diameter of 0.6 cm and a length of 8 cm; (b) Primary current distribution along the working electrode (bottom to top).
Impact The present study developed guidelines for electrodepositing Ni-W-TiO2 composites for surface finishing applications
5,000 X
Deposit W Content
0.2 0.4 0.6 0.8 Dimensionless length, L = x/h
3
20,000 X
12.5 g/L
q Deposit W content is affected by the particle electrolyte concentration; the effect is most significant at high current density region where increasing particle electrolyte concentration decreases the amount of W. Inspection of partial current densities shows in this region the reduction of Ni is enhanced, while the reduction of W is inhibited, compared to a particle-free electrolyte. Thus, both effects lead to less W in the final deposit. q Deposit TiO2 content is affected by the particle electrolyte concentration; the TiO2 content increases as the amount of particle increases in the electrolyte up to a certain point. The particle behavior can be described by a limit of the classic Guglielmi4 model: following a Langmuir-like behavior with the amount of particle in the electrolyte. q Deposit morphology is affected by the addition of the particle; the deposit becomes rougher as the particles are included in the deposit, and thus the growth of the deposit is dramatically changed.
0
reference electrode: SCE insulator
0
0 g/L 7.5 g/L
q The partial current densities at each potential then can be calculated using XRF data and Faradayβs Law: ππ πΉ π π ππ π ππ = with ππ = πΊπ π΄π π β ππ βππ
1
stir bar
Particle loading 10%
q The polarization curves allow for a correlation between the estimated current density and the working electrode potential.
1.5
15%
120
(b)
q X-ray fluorescence (XRF) was used for measuring deposit composition and thickness at each dimensionless length L.
2
counter electrode: Pt
Simulated Curve Experimental Data
0.1
50 g/L
25 g/L 0.3
50 g/L
7.5 g/L
160 -iside (mA/cm2 )
0 g/L
1.3 -E (V) vs SCE
2
0
Particle loading -iW (mA/cm2 )
1.2
0.2
Side Reaction and Current Efficiency
Particle loading -iNi (mA/cm2 )
50 g/L
2.5 g/L 12.5 g/L
0
1.5
1.2
4
W Partial Current Density
1.5
1.1
6
plastic
2,000 X
0.25
Particle loading
Current Efficiency
0
iW : iNi
W (wt %)
60
1.8
Deposit TiO2 Volume Fraction (Ξ±) Ratio
8 TiO2 (wt %)
Particle loading
Deposit TiO2 Content
Ξ±/(1-Ξ±)
Deposit W Content
insulator
Procedure
ix/iavg
Opportunity
q Deposit W content β adding TiO2 and PC control both decrease the deposit W content, perhaps due to the change of adsorption. q Deposit TiO2 content β deposit TiO2 content exhibits a Langmuir-like behavior, and PC control facilitates particle adsorption. q Deposit morphology β TiO2 incorporation creates a rougher deposit, and PC control doesnβt significantly change it.
Reference: 1. N. Tsyntsaru, H. Cesiulis, M. Donten, J. Sorte, E. Pellicer, and E. J. Podlaha-Murphy, Surface Engineering and Applied Electrochemistry, 48 491 (2012). 2. K.A. Kumar G. P. Kalaignan, and V.S. Muralidharan, Ceramics International, 39 2827 (2013). 3. H. Goldasteh and S. Rastegari, Surface and Coatings Technology, 259 393 (2014). 4. N. Guglielmi, Journal of the Electrochemical Society, 119 1009 (1972).
Acknowledgement: the author acknowledge NASF/AESF Foundation for supporting this project.
Pulse Current Electrodeposition of Ni-W-TiO2 Composites Yujia Zhang and Elizabeth Podlaha Approach
Background Tungsten alloys with nickel are well known for their superior properties in the following areas: corrosion resistance, hardness, wear resistance, and catalytic activity towards hydrogen evolution, as comprehensively reviewed by Tsyntsaru et al.1 Composite electrodeposition of Ni-W alloys with solid particles allows for further tailoring of these properties. Reported studies on Ni-W-TiO2 composites focus on properties of the material. For example, Kumar et al.2 showed that the hardness was further increased with the addition of titania in the deposit, and when pulse deposited there was an enhancement in corrosion resistance. Similarly, Goldasteh and Rastegari3 reported an increase in hardness due to refining of the crystallite size in the deposit with titania. Corrosion resistance was found to be better in pulse deposited Ni-W-TiO2 composites, compared to their DC counterparts. However, there are no studies that address the impact of the particle on the metal ion reaction rate, which is critical in determining the deposit composition and hence the resulting property. Ni-W-TiO2 codeposition takes place through an adsorption mechanism. Adsorbed intermediates of Ni, W and H form on the cathode surface. The metal intermediates then reduce to form the alloy, and the adsorbed particles are included into the metal matrix. Hads Hads Niads
Wads Hads Hads Hads Niads
TiO2
Hads Hads Hads Niads
π$
π΅π
Wads Hads Hads Hads Hads HadsHads Hads
+π
π ' π
β π΅π$ ππ π
π΅π$ ππ π
Table 1. Electrolyte (ammonium-free!!!) and Condition
π ' π
+ π β π΅π
Objectives The goal of this study is to electrodeposit Ni-W-TiO2 composites and for the first time study the influence of titania particle electrolyte concentration on the metal ion reduction rate and side reaction that determines the deposit composition and thickness. In parallel, an ammonia-free electrolyte is used and further characterized as a path towards a more health conscious working environment for those in the plating industry.
Nickel Sulfate
0.1 M
Sodium Tungstate
0.15 M
Sodium Citrate
0.285 M
Boric Acid
1M
Titanium Dioxide
0, 2.5, 7.5, 12.5 (PC), 25, 50 g/L
pH
8
Temperature
25 Β°C
Rotation Rate
500 rpm
Magnetic Stirring
300 rpm
Pulse Frequency
0.2, 2, 20, 200 Hz
(a)
Results
working electrode: Cu
DC Deposition Ratio of W Partial Current Density to Ni Partial Current Density
65 0 g/L
1.6
55
2.5 g/L
1.4
50
7.5 g/L 12.5 g/L
45 40 50
100 -i (mA/cm2 )
150
Particle loading 0 g/L 2.5 g/L
1.2
7.5 g/L
1
25 g/L
0.8
50 g/L
0.6
12.5 g/L 25 g/L 1.1
Ni Partial Current Density
1.2
1.3 -E (V) vs SCE
1.4
1.5
2.5 g/L
0.9
7.5 g/L 12.5 g/L
0.6
1.2
0 g/L 2.5 g/L
0.9
7.5 g/L 12.5 g/L
0.6
25 g/L 0.3 1.4
1.5
1.1
1.2
1.3 -E (V) vs SCE
1.4
0.15
25 g/L
0.05
50
100 -i (mA/cm2 )
SEM analysis
0
150
0
10
Langmuir-like!!!
20 30 C (g/L)
40
50
20,000 X 5,000 X
80 40
1.5
0
50 g/L
2.5 g/L
5%
0% 1.1
1.2
1.3 1.4 -E vs SCE (V)
1.5
insulator
12.5 g/L 25 g/L 1.1
1.2
1.3 1.4 -E vs SCE (V)
1.5
50 g/L
0 g/L
PC Deposition Ni Partial Current Density
10
0.2 Hz
45
2 Hz
1.8 Frequency
8
DC
6
0.2 Hz
4
2 Hz
40
20 Hz
2
20 Hz
35
200 Hz
0
200 Hz
1
0
0.2 0.4 0.6 0.8 Dimensionless length, L = x/h
1
iNi (mA/cm2 )
DC
50
TiO2 (wt %)
Frequency
55
W Partial Current Density
1.5
Frequency
1.2
DC
0.9
0.2 Hz
0.6
2 Hz
0.3
20 Hz
0 0
0.2 0.4 0.6 0.8 Dimensionless length, L = x/h
1
200 Hz
1.8 -iW (mA/cm2 )
Deposit TiO2 Content
60 W (wt %)
2.5
working electrode: Cu
counter electrode: Pt
0.5 0 0.2 0.4 0.6 0.8 1 Dimensionless length, L = x/h
SEM analysis
1.5
Frequency
1.2
DC
0.9
0.2 Hz
0.6
2 Hz
0.3
20 Hz
0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Dimensionless length, L = x/h
20,000 X 5,000 X
200 Hz
DC
200 Hz
20,000 X
q Deposit W content is affected under PC condition; the W content slightly decreases. Inspection of partial current densities shows there is a larger enhancement of Ni partial current density than W partial current density, resulting in less W in the final deposit. q Deposit TiO2 content is affected under PC condition; the TiO2 content slightly increases regardless of pulse frequency. q The Ni(II) and W(VI) ion partial current densities are both enhanced under PC condition, leading to a larger current efficiency. q Deposit morphology is not significantly affected by PC deposition.
stir bar
insulator Figure 2. Schematic of rotating cylinder electrode for polarization measurement, the cathode has a diameter of 0.6 cm and a length of 1 cm.
Figure 1. (a) Schematic of Rotating Hull cell for electrodeposition, the cathode has a diameter of 0.6 cm and a length of 8 cm; (b) Primary current distribution along the working electrode (bottom to top).
Impact The present study developed guidelines for electrodepositing Ni-W-TiO2 composites for surface finishing applications
5,000 X
Deposit W Content
0.2 0.4 0.6 0.8 Dimensionless length, L = x/h
3
20,000 X
12.5 g/L
q Deposit W content is affected by the particle electrolyte concentration; the effect is most significant at high current density region where increasing particle electrolyte concentration decreases the amount of W. Inspection of partial current densities shows in this region the reduction of Ni is enhanced, while the reduction of W is inhibited, compared to a particle-free electrolyte. Thus, both effects lead to less W in the final deposit. q Deposit TiO2 content is affected by the particle electrolyte concentration; the TiO2 content increases as the amount of particle increases in the electrolyte up to a certain point. The particle behavior can be described by a limit of the classic Guglielmi4 model: following a Langmuir-like behavior with the amount of particle in the electrolyte. q Deposit morphology is affected by the addition of the particle; the deposit becomes rougher as the particles are included in the deposit, and thus the growth of the deposit is dramatically changed.
0
reference electrode: SCE insulator
0
0 g/L 7.5 g/L
q The partial current densities at each potential then can be calculated using XRF data and Faradayβs Law: ππ πΉ π π ππ π ππ = with ππ = πΊπ π΄π π β ππ βππ
1
stir bar
Particle loading 10%
q The polarization curves allow for a correlation between the estimated current density and the working electrode potential.
1.5
15%
120
(b)
q X-ray fluorescence (XRF) was used for measuring deposit composition and thickness at each dimensionless length L.
2
counter electrode: Pt
Simulated Curve Experimental Data
0.1
50 g/L
25 g/L 0.3
50 g/L
7.5 g/L
160 -iside (mA/cm2 )
0 g/L
1.3 -E (V) vs SCE
2
0
Particle loading -iW (mA/cm2 )
1.2
0.2
Side Reaction and Current Efficiency
Particle loading -iNi (mA/cm2 )
50 g/L
2.5 g/L 12.5 g/L
0
1.5
1.2
4
W Partial Current Density
1.5
1.1
6
plastic
2,000 X
0.25
Particle loading
Current Efficiency
0
iW : iNi
W (wt %)
60
1.8
Deposit TiO2 Volume Fraction (Ξ±) Ratio
8 TiO2 (wt %)
Particle loading
Deposit TiO2 Content
Ξ±/(1-Ξ±)
Deposit W Content
insulator
Procedure
ix/iavg
Opportunity
q Deposit W content β adding TiO2 and PC control both decrease the deposit W content, perhaps due to the change of adsorption. q Deposit TiO2 content β deposit TiO2 content exhibits a Langmuir-like behavior, and PC control facilitates particle adsorption. q Deposit morphology β TiO2 incorporation creates a rougher deposit, and PC control doesnβt significantly change it.
Reference: 1. N. Tsyntsaru, H. Cesiulis, M. Donten, J. Sorte, E. Pellicer, and E. J. Podlaha-Murphy, Surface Engineering and Applied Electrochemistry, 48 491 (2012). 2. K.A. Kumar G. P. Kalaignan, and V.S. Muralidharan, Ceramics International, 39 2827 (2013). 3. H. Goldasteh and S. Rastegari, Surface and Coatings Technology, 259 393 (2014). 4. N. Guglielmi, Journal of the Electrochemical Society, 119 1009 (1972).
Acknowledgement: the author acknowledge NASF/AESF Foundation for supporting this project.
