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OCAS: a joint venture between ArcelorMittal and the Flemish Region
Philippe Verpoort, Eva Diaz Gonzalez Ionic Liquids at Interfaces workshop
04/10/2015 Belek
Towards understanding the anodic reactions
in plating from Deep Eutectic Solvents
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OCAS: R&D center for the application of steel
• A joint venture between ArcelorMittal and the Flemish region. • Market oriented R&D center. • Steel industry and applications of metal
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OCAS Hard Chrome Plating Technology
OCAS is developing an alternative chrome plating process based on proprietary ionic liquid technology
OCAS matures the technology to an industrial deployable level, creates OCAS IP, and generates revenues by licensing the technology to third parties.
By setting up a Partnership Program, OCAS plans an early industry involvement & support of our R&D endeavours
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Workshop Santiago (nov. 2014): Lab-scale setups
4
SET-UP Electrolyte volume (l)
Sample size Temp. control Flow
CELLS 1 – 4 • Flat: 5 x 5 cm • Cylinder: Ø 2 – 4 cm, l = 6 cm
• Double wall jacket
•Magnetic stirrer •Pumping •Vertically rotation
HORIZONTAL SETUP
13 • Cylinder: Ø 4 cm, l = 15 cm
• Cooling coil • Buffer tank
•Rotating cylinder •Flex. immersion level •Pumping
BATH 10 • Flat: 10 x 10 cm • Cylinder: Ø 2 – 4 cm, l = 6 cm
• Cooling coil •Anode/cathode relative horizontal movement
•Pumping •Vertically rotated cylinder
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Semi-industrial pilot installation
5
SET-UP Electrolyte volume (l)
Sample size Temp. control Flow
SEMI-INDUSTRIAL PILOT UNIT
1300 •Flat: < A4 •Cylinder:
Ø = 5 – 25 cm l = 50 – 100 cm M = 7 – 385 kg
• Buffer tank • Possibility
for cooling coil
•Rotating cylinder •Pumping, eventual direct refreshment to part through directable nozzles
•Sheets: specific cell with laminar flow installed in bath
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6
IBC and hanging device Buffer tank
Degreasing Plating bath Rinse
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DES Chromline: basic reactions
7
Choline chloride Chromium chloride
hexahydrate
Cathode
Cr3+ + 3e- Cr0
2H2O + 2e- 2OH- + H2
Anode (Dimensional Stable Anode)
2Cl- Cl2 + 2e-
2H2O O2 + 4H+ + 4e-
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Upscaling observations
• Conductivity – viscosity Low conductivity (20 mS/cm): distance anode-cathode of
higher importance than in aqueous systems High viscosity (ν = 85 mm²/s): transport mechanism
different than aqueous systems
• Modelling Fluid-dynamics in pilot line Almost no data available on
• Complexation mechanism • (Side)reactions in IL/DES
8
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Cl2 gas measurements
• Inert DSA anodes: 3000 – 4000 ppm measured during deposition With flow at OCAS: still under emission limit
• Using Chromium nuggets: 99.8% pure Cr Basket = PP mesh No Cl2 gas could be measured But …
9
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Dissolution of Cr in DES
• Chemical dissolution
10
0%
20%
40%
60%
80%
100%
0 20 40 60 80 100 120 140 160 180
Δ[C
r3+ ]
Time (h)
RT 40 °C 60 °C
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Influence on IL + mechanism
• Electrochemical (anodic) dissolution of Cr in IL
11
0%
5%
10%
15%
20%
0
5
10
15
20
25
0 2 4 6 8 10
Δ[C
r3+ ]
Co
nd
uct
ivit
y (m
S/cm
)
Deposition time (h)
Conductivity Cr increase (%)
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Influence on liquid properties
• Chemical ratio changing • Conductivity and viscosity: Walden’s rule?
40
50
60
70
80
90
100
10
12
14
16
18
20
22
0 2 4 6 8 10
Vis
cosi
ty (
mm
²/s)
Co
nd
uct
ivit
y (m
S/cm
)
Deposition time (h)
Conductivity Viscosity 0.0
0.1
0.2
0.3
0.4
0 5 10
Conductivity/viscosity
Viscosity increase
Conductivity decrease
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Increase viscosity
• Mainly due to Cr change
13
0%
5%
10%
15%
20%
60
65
70
75
80
85
90
95
100
0 2 4 6 8 10
Δ[C
r3+ ]
Vis
cosi
ty (
mm
²/s)
Deposition time (h)
Viscosity Cr increase (%)
Increase of Cr
concentration
Stability
Increase
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Cathodic efficiency
14
0%
5%
10%
15%
20%
25%
0
5
10
15
20
25
0 2 4 6 8 10
Δ[C
r3+ ]
Cat
ho
dic
eff
icie
ncy
(%
)
Deposition time (h)
Cathode eff. [%] Cr increase (%)
• Cathodic efficiency increasing with Cr concentration
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Conclusions
DSA anode Effect Action
Soluble anode Effect Action
Dimensional changes over lifetime
No changes
-
Influence on critical parameter (anode-cathode distance)
Constant finetuning of
distance anode-cathode needed
Side reactions Cl2 formation Gas scrubber could be
needed on industrial site
No Cl2
[Cr3+] ↗
-
Take out anode when not plating
15
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Future work
• Complexation mechanism Almost no data available on (side-)reactions in IL, DES Modelling of reaction mechanism and complexation
useful
• Degradation mechanism of organic part Methodology done on inorganic parts No data yet on concentrated organic part
16
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All questions and inputs are welcome!
17
Acknowledgement
