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 What to choose?

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

PlasmaChem

Big thanks to Siemens AG and Heyday‘s OHG for fruitful cooperation

Thank you for your attention!