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PlasmaChem
Tribology investigation of silver and goldelectroplated in presence of nano-diamondsand nano-alumina
Alexei AntipovPlasmaChem GmbHwww.plasmachem.cominfo@plasmachem.com
NANOTECH EUROPE 2009, 30th September
PlasmaChem Use of Silver and Gold for Plating
Circuit breakers and switches
Mus
ik In
stru
men
ts
Jewellery
Electronics
2%
13%
7%
24%
54%
Industrial Jewelry Coins Photo Investment
Cutlery
PlasmaChem
Year 2001 2002 2003 2004 2005 2006 2007
Ag consumption for electronic and electric industries worldwide (tons)
4.258 4.479 4.711 4.956 5.640 5.901 6.207
Price (in Mio. EUR) 809 851 895 942 1.072 1.121 1.179
Silver consumption for electric electronics industries worldwide
PlasmaChem
Silver and gold are noble,
silver has the highest conductivity
but ...
they have very poor mechanical properties
PlasmaChem PlasmaChem GmbH: Innovative Products
PlasmaChem GmbH
Stents Analytical Tools
DLC StentsBioDiamond
Drug-Eluting Stents„Trio“ and „Quadro“
BiodegradableStents
(New!!!)
Nano-Particlesfor R&D
Nano-Particlesfor Industry
Nano-Luminograph
GenomeSequencing
Nano-Business
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
PlasmaChem
Not all nanoparticles are the same.Here is one example:
Gold plated with NanoDiamonds of two types
0 2 4 6 8 10 12 144
5
6
7
8
9
10
11
12
Wea
r, m
m3
Nanodiamonds concentration, g/L
Standard ND (HNO3 purified) DiamoGold (PlasmaChem GmbH)
PlasmaChem Method of synthesis is important
Production of raw material
Isolation and purificationof nanoparticles
impurities
PlasmaChem
IndustrialPlating
DecorativePlating
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
PlasmaChemTribological Investigation and
Wear CalculationTribometer (Wazau GmbH, Germany)
Indenter – ball of 100Cr6 d=10mmNormal Force: 8 N
Frequency: 8 Hz Amplitude: 4 mm
Wear track
X-ray Fluorimeter (Fisher AG, Germany)
Wear calculation by 360-pointscalculation of layer thickness
168 169170
171172
173174
-0,008-0,007-0,006-0,005-0,004-0,003
-0,002
-0,001
0,000
111,0111,2
111,4111,6
111,8112,0
112,2112,4
112,6112,8
Y Axis
X Axis
Conventional wear calculationfrom the width of a track
(semi-quantative)
Precise wear calculation from thereal 3-D profile of a track
PlasmaChem
IndustrialPlating
DecorativePlating
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
PlasmaChem
168 169170
171172
173174
-0,004
-0,003
-0,002
-0,001
0,000
111,0111,2
111,4111,6
111,8112,0
112,2112,4
112,6112,8
Y Axis
X Axis
168169
170171
172173
174
-0,004
-0,003
-0,002
-0,001
0,000
111,0111,2
111,4111,6
111,8112,0
112,2112,4112,6112,8
Y AxisX 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
PlasmaChem
168 169170
171172
173174
-0,008-0,007-0,006-0,005-0,004-0,003
-0,002
-0,001
0,000
111,0111,2
111,4111,6
111,8112,0
112,2112,4
112,6112,8
Y Axis
X Axis
168 169170
171172
173174
-0,008-0,007-0,006-0,005-0,004-0,003
-0,002
-0,001
0,000
111,0111,2
111,4111,6
111,8112,0
112,2112,4
112,6112,8
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
PlasmaChem
1000 1500 2000 2500 3000 35000,3
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, m
m3
Fict
ion
coef
ficie
nt
Total charge, Ampere-hours
0,21 % ND
Tribo-Properties vs. Concentration
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 15,0100
1000
10000
100000
1000000
1E7
Coun
ts p
er s
econ
d
Depth, micron
Al Ag
Nanoparticles Distribution in Layer
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 / A
g In
tens
ität
C Konzentration, Gew.%
0,0 0,2 0,4 0,6 0,8 1,00,00
0,05
0,10
0,15
0,20Ag-(N)Al2O3
Eichprobe, 1%
Eichprobe, 0,01%Al /
Ag In
tens
ität
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
PlasmaChem Not the Composite Materials
Composite material contains a large ammount of reinforcing materials, which having 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.
PlasmaChem
Silver / NanoDiamond Silver/Al2O3
• Optimization of nanoparticles synthesis
• Optimization of nanodiamonds purification
• Development of additives package
• Development of technological parametersincluding electrolyte on-line control
• Final quality control of plated parts
Flute parts coated with Silver-DiamoSilb
PlasmaChem Conclusions
• Optimization of Nanoparticles synthesis and purification was performed
• Reduction of wear and friction by over 50%
• Increase of hardness by ca. 30%
• Successful transfer into industrial-scale plating baths
• 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