1. PlasmaChem
Tribological investigation of
silver and gold electroplated in
presence of nano-diamonds
and nano-alumina
Dr. Alexei Antipov
PlasmaChem GmbH
www.plasmachem.com
antipov@plasmachem.com
Tel.: +49 30 6392-6313
Fax: +49 30 6392-6314

2. PlasmaChem Use of Silver and Gold for Plating
Circuit breakers and switches
MusikInstruments
Jewellery
Electronics
2%
13%
7%
24%
54%
Industrial
Jewelry
Coins
Photo
Investment
Cutlery

3. PlasmaChem
Year 2001 2003 2005 2007 2009 2011
Ag consumption
for electronic and
electric industries
worldwide (tons)
4.258 4.711 5.640 6.207 6.350 6.470
Price (in Mio. EUR) 809 895 1.072 1.179 1.185 1.224
Silver consumption for electric and
electronics industries worldwide

4. PlasmaChem
Silver and gold are noble,
silver has the highest conductivity
but ...
they have very poor mechanical properties

5. PlasmaChem Nanoparticles for co-Plating with Ag and Au
Composite coating
Alloy coating (e.g. Ag-Sb)
(not stable in time)
?
Ground metal
Integrated coating

6. PlasmaChem
THE BEST PERFORMANCE
What to choose?

7. PlasmaChem
Not all nanoparticles are the same.
Here is one example:
Gold plated with NanoDiamonds of two types
0 2 4 6 8 10 12 14
4
5
6
7
8
9
10
11
12
Wear,mm
3
Nanodiamonds concentration, g/L
Standard ND (HNO3
purified)
DiamoGold (PlasmaChem GmbH)

8. PlasmaChem Method of synthesis is important
Production of raw material
Isolation and purification
of nanoparticles
impurities

9. PlasmaChem
Industrial
Plating
Decorative
Plating
Hull-Cell Tests (estimation of
current density conditions)
Hull-cell experiments deliver
perfect coatings with both ND and
Al2O3 with both industrial and
decorative platings.
Hull-Cell Tests

10. PlasmaChem
Tribological Investigation and
Wear Calculation
Tribometer (Wazau GmbH, Germany)
Indenter – ball of 100Cr6 d=10mm
Normal Force: 8 N
Frequency: 8 Hz Amplitude: 4 mm
Wear track
X-ray Fluorimeter (Fisher AG, Germany)
Wear calculation by 360-points
calculation of layer thickness
168
169
170
171
172
173
174
-0,008
-0,007
-0,006
-0,005
-0,004
-0,003
-0,002
-0,001
0,000
111,0
111,2
111,4
111,6
111,8
112,0
112,2
112,4
112,6
112,8
Y
Axis
X Axis
Conventional wear calculation
from the width of a track
(semi-quantative)
Precise wear calculation from the
real 3-D profile of a track

11. PlasmaChem
Industrial
Plating
Decorative
Plating
Hull-Cell Tests (estimation of
current density conditions)
0,65 1,08 1,65 A/dm2
Z = 22,9 µm 34,8 µm 54,4 µm
V = 0,00338 mm3
0,0049 mm3
0,0145 mm3
Z = 26,5 µm 38,5 µm -
V = 0,0011 mm3
0,0106 mm3
-
Pure Ag:
ca. 0,015 mm3

12. PlasmaChem
168
169
170
171
172
173
174
-0,004
-0,003
-0,002
-0,001
0,000
111,0
111,2
111,4
111,6
111,8
112,0
112,2
112,4
112,6
112,8
Y
Axis
X Axis
168
169
170
171
172
173
174
-0,004
-0,003
-0,002
-0,001
0,000
111,0
111,2
111,4
111,6
111,8
112,0
112,2
112,4
112,6
112,8
Y
Axis
X Axis
Improvement of tribological properties in comparison with normal Ag:
Friction coefficient decrease up to 50%
Wear decrease up to 70%
Microhardness increase ca. 20%
Al2O3
Results on Ag/Al2O3

13. PlasmaChem
168
169
170
171
172
173
174
-0,008
-0,007
-0,006
-0,005
-0,004
-0,003
-0,002
-0,001
0,000
111,0
111,2
111,4
111,6
111,8
112,0
112,2
112,4
112,6
112,8
Y
Axis
X Axis
168
169
170
171
172
173
174
-0,008
-0,007
-0,006
-0,005
-0,004
-0,003
-0,002
-0,001
0,000
111,0
111,2
111,4
111,6
111,8
112,0
112,2
112,4
112,6
112,8
Y
Axis
X Axis
ND
Improvement of tribological properties in comparison with normal Ag:
Friction coefficient up to 50%
Wear up to 50%
Improvement of tribological properties in comparison with normal Ag:
Friction coefficient decrease up to 50%
Wear decrease up to 50%
Microhardness increase ca. 35%
Results on Ag/ND

14. PlasmaChem
1000 1500 2000 2500 3000 3500
0,3
0,4
0,5
0,6
0,7
0,8
0,001
0,002
0,003
0,004
0,005
0,006
0,007
0,008
0,009
0,17 % ND
0,12 % ND
Wear,mm
3
Fictioncoefficient
Total charge, Ampere-hours
0,21 % ND
Tribo-Properties vs. Concentration

15. PlasmaChem
Secondary ion mass spectrometry (SIMS)
was employed to analyze the distribution
and content of nanoparicles in the layer.
Nanoparticles are incorporated
uniformly through the plated layer
in both lateral and normal
directions.
0,0 2,5 5,0 7,5 10,0 12,5 15,0
100
1000
10000
100000
1000000
1E7
Countspersecond
Depth, micron
Al
Ag
Nanoparticles Distribution in Layer

16. PlasmaChem
Ag-ND Ag-Al2O3
0,0 0,2 0,4 0,6 0,8 1,0
-2
0
2
4
6
8
10
12
14
Ag-(N)Diamant
Eichprobe 0,01%
Eichprobe 1%
C/AgIntensität
C Konzentration, Gew.%
0,0 0,2 0,4 0,6 0,8 1,0
0,00
0,05
0,10
0,15
0,20
Ag-(N)Al2
O3
Eichprobe, 1%
Eichprobe, 0,01%
Al/AgIntensität
Al Konzentration, Gew.%
C(C): 0,03 +- 0,01 Gew.% C(Al): 0,6 +- 0,1 Gew.%
Nanoparticles Content in Layer
The amount of nanoparticles in the plated metal is tiny

17. PlasmaChem Not the Composite Materials
Composite material contains a
large ammount of reinforcing
materials, which have different
properties from those of matrix,
alter its properties.
In our case amount of
nanoparticles is tiny. They
influence the structure of a metal
directly, reducing the crystal size of
the metal.

18. PlasmaChem
Silver / NanoDiamond Silver/Al2O3
• Optimization of nanoparticles synthesis
• Optimization of nanodiamonds purification
• Development of additives package
• Development of technological parameters
including electrolyte on-line control
• Final quality control of plated parts
Flute parts coated with
Silver-DiamoSilb
Industrial cases

19. PlasmaChem
Ni/P
+ PTFE
Ni
Watts
Ni/Fe Ni/P
Ni
Watts
+ ND
Ni Watts
+ SiC Ni/P
+ ND
Ni/P
+ SiC
Wear,
µm3/m
20´000 11´800 9´900 12´000 6´200
2´100 –
6´200
1´100 1´000
0,00
5000,00
10000,00
15000,00
20000,00
25000,00
Ni Ni + ND Ni + SiC Ni + PTFE Ni/Fe
Wear,µm³/m(taberabrasertest)
Ni-Phosphor
Ni Watts
Nanodiamonds and SiC in Nickel

20. PlasmaChem Conclusions
Successfully used for both industrial and decorative plating
Reduction of wear and friction by over 50%
Increase of hardness by ca. 35%
Nanoparticles change the metal matrix strongly, but the resulting
plated layer is not a classical composite material
Content of nanoparticles (and their consumption) is negligible
making the whole process very economical
Successfully used in electroplating facilities since 10 years

21. PlasmaChem
Thank you for your attention!