Teer Coatings Ltd Hydrogen Energy Universities of Birmingham & Warwick, Hydrogen Energy, 22 nd January, 2010 © Teer Coatings, 2010 Kevin Cooke Teer Coatings

Teer Coatings Ltd Hydrogen Energy

Universities of Birmingham & Warwick, Hydrogen Energy, 22nd January, 2010 © Teer Coatings, 2010Kevin Cooke

Teer Coatings LimitedCoatings for Fuel Cells & Hydrogen Applications

Teer Coatings Ltd, West Stone House,Berry Hill Industrial Estate, Droitwich, Worcestershire, WR9 9AS, UKwww.teercoatings.co.uk

Kevin Cooke



• Introduction to Teer Coatings Ltd: TCL’s proprietary technology: Closed Field Unbalanced

Magnetron Sputter Ion Plating (CFUBMSIP)

• Applications in Fuel Cells and Hydrogen Example: coatings for PEM cell electrodes TCL’s Low Carbon related Collaborative Research

• Summary & Conclusions• Acknowledgements

Outline of Presentation



Founded1982 Coating Services

(Hartlebury)1985

Closed Field System

1987

1st Prod EquipSale 1989

LargerPremises

1992

UK PatCFUBMSIP

1994US Pat

CFUBMSIP 1996

MoST Patent 1999 +2nd

Building1999

+3rd Building

2001 ISO:90022001

Key Facts:• Turnover Approaching £4-5M/yr• Equipment Sales Approaching £2-3M/yr• High Proportion of Export Sales• Now ~57 Employees

Company History

ISO:90012003

NewFactory

2004

US PatentDymon-iC

2008

25 yrs!2007

ISO:90012008



Company Structure

PRODUCTION COATINGS

EQUIPMENT BUILDING

RESEARCH & DEVELOPMENT

• 15 Coating Systems• Automated cleaning, etc.• Single items to 10,000’s/wk

• ~17 Coating Systems• plus, range of Testing

& Analysis Equipment

• Design & Manufacture• Coating & Test Equipment• Inc. “bespoke” designs

3 PRIMARY DIVISIONS:



• July 2009: Miba AG took a minority share (24.9%) of TCL full ownership is expected by the

end of 2010. until then TCL remains a SME!

• The Miba Group is a leading international company, of ~2600 employees, headquartered in Austria.

• Miba is a leading strategic partner of the international engine and automotive industry. Miba’s product portfolio includes sintered components,

engine bearings, friction and coated materials. • TCL & HTC (Miba’s Coatings Competence Centre,

with ~40 employees) will collaborate closely.



Routine Production Coatings:

• Hard coatings, e.g. for cutting tools, etc.– e.g. single nitrides TiN, CrN… & alloy nitrides TiAlN,

CrAlN, CrTiAlN…, oxides, multilayers, etc.• Self lubricating, low friction coatings for wear resistance

– e.g. carbon based: TCL Graphit-iC™& Dymon-iC; and MoS2 based: TCL MoST™

• Plus, coatings for corrosion resistance, electrical conductivity, optical properties, etc.

• Coatings typically 1-3µm thick, but…– nm to mm thickness possible for special applications



1

H 1.0079

2

He 4.0026

3

Li 6.941

4

Be 9.012

5

B 10.811

6

C 12.011

7

N 14.007

8

O 16.00

9

F 19.00

10

Ne 20.179

11

Na 22.99

12

Mg 24.30

13

Al 26.98

14

Si 28.09

15

P 30.974

16

S 32.06

17

Cl 35.453

18

Ar 39.948

19

K 39.10

20

Ca 40.08

21

Sc 44.96

22

Ti 47.90

23

V 50.94

24

Cr 52.00

25

Mn 54.938

26

Fe 55.85

27

Co 58.93

28

Ni 58.69

29

Cu 63.55

30

Zn 65.39

31

Ga 69.72

32

Ge 72.59

33

As 74.92

34

Se 78.96

35

Br 79.90

36

Kr 83.80

37

Rb 85.47

38

Sr 87.62

39

Y 88.91

40

Zr 91.22

41

Nb 92.91

42

Mo 95.94

43

Tc (98)

44

Ru 101.1

45

Rh 102.91

46

Pd 106.42

47

Ag 107.87

48

Cd 112.41

49

In 114.82

50

Sn 118.71

51

Sb 121.75

52

Te 127.60

53

I 126.91

54

Xe 131.29

55

Cs 132.91

56

Ba 137.33

57 *La

138.91

72

Hf 178.49

73

Ta 180.95

74

W 183.85

75

Re 186.21

76

Os 190.2

77

Ir 192.2

78

Pt 195.08

79

Au 196.97

80

Hg 200.59

81

Tl 204.38

82

Pb 207.2

83

Bi 208.98

84

Po (209)

85

At (210)

86

Rn (222)

As a major constituent

As a minor component

Coatings: a continually expanding range….



….for many different applications….

Cutting ToolsGears, Bearings and other Wear Components

Body Jewellery….!



….including Coating of Powders & Grits!

Barrel Coater(Load Locked)

Coating sources project into barrel

Powder exposed to coating flux



• Unbalanced field.• Field lines “closed” with another

magnetron.• Plasma confined around

substrates.• Electrons loss to chamber walls

minimised.• Increased ionisation.• Dense, adherent coatings• Typical energies 20-30eV,

ideal for high quality film growth.

Closed Field Magnetron Sputtering



• FC&H2 Example - coatings for bipolar plates:

– TCL’s magnetron sputtering technology is• industrially qualified• ideal for the deposition of thin, dense, well adhered,

high quality coatings on a wide range of substrates (including metals and vacuum-stable polymers).

– Product-specific results of TCL’s previous work in this field are obviously confidential to the customers concerned!

[V Fox: presented at - Manufacturing of Bipolar Plates event, Swerea IVF, Stockholm, 29th January 2008]



• “Metallic” thin film coatings for bipolar plates:– dense, homogeneous coatings of metals are deposited

at high rates– multiple elemental targets (typically 4 or 6)

• alloys and/or graded compositions easily created

– compounds (nitrides, oxides, etc.) can be synthesised by reactive deposition

• reactive gas (e.g. N2) introduced during the deposition process

• compound (e.g metal + nitrogen = MeN) formed in situ• automatic feed back control (reactive gas flow slaved to metal

content of the plasma)



• Transition metal nitrides (e.g. TiN, CrN etc.)– hard, dense and relatively inert– routine coating sources up to 1m (>2m demonstrated!) – metallic levels of electrical conductivity– excellent adhesion (Rockwell and scratch adhesion results on M42 tool steel substrate

shown below)

TiN (~3µm)

SEM cross section

TiN (~3µm)

SEM cross section

TiN

Rockwell C indentation

TiN

Rockwell C indentation

0 20 40 60 80 1000

5

10

15

20

Load (N)

Friction force (N)

TiN, Critical load ~ 90N

1st derivative

0 20 40 60 80 1000

5

10

15

20

Load (N)

Friction force (N)

TiN, Critical load ~ 90N

1st derivative



• New high rate magnetron deposition of TiN:– 2 magnetrons (12.5kW each)– 50 mins deposition: total thickness 3.36 μm– deposition rate 4 μm/hr 4x higher than from

conventional magnetrons– hardness: 33 GPa

– scratch adhesion – Lc>60N (i.e. very good)

• So, achieved 4x increase in rate with no obvious deterioration in coating quality



• Graphit-iC™ coatings – originally developed for demanding, high load

bearing, tribological applications• contains ~5 at. % chromium• hardness H = 10 to 40 GPa (selectable); • Young’s modulus E* ~ 155 GPa• low coefficient of friction (<0.1)• very low specific wear rate (~ 10-17 m3N-1m-1)• electrically conducting (like graphite) – high sp2

content

– conventional process, ~2µm takes several hrs



Graphit-iC™ Coating Process• 3-steps:

– in-situ ion cleaning– deposition of thin metallic Cr interlayer– deposition of C-Cr layer

0.2 m

1.8 m



Magnetron 1(Conventional magnetron)

Magnetron 3(Conventional magnetron)

Target size 380 x 175mm

Two high power magnetronsused in place of conventional

magnetrons for the carbon targets

Carbon target Carbon target

Chromium target

Chromium target

Towards high rate Graphit-iCdeposition



• Graphit-iC™ coatings for bipolar plates:– power input can be increased by up to 3x cf TCL’s

“conventional” Graphit-iC coating process– deposition rates improved by 2 to 2.7x, say– here, 2-axis rotation improves coating uniformity. In-line

systems with magnetrons sputtering simultaneously onto both sides of the plates could be used in a production process.

– pure carbon or Graphit-iC coatings can be deposited at thickness ranging from <100nm to a few microns

– coatings can be (have been) deposited with or without Cr adhesion layers

– rates as high as ~5 µm/hour are already achievable for a stationary substrate (equivalent to 85nm per min)



TSB Projects

CLUSTERBEAMMNT (’06-’09)

HYPNOMEMTP (’06-’09)

PROSVACTTP (’08-’11)

NECLASSTP (’08-’10)

Low Cost PVsTP (’08-’11)

HydroGENTP (’08-’11)

TCL’s Collaborative Projects related to “Low Carbon”



• Technology Programme projects include:– NECLASS: improving FC catalyst utilisation– HydroGEN: coatings for electrolysis

– HYPNOMEM: thin film membranes for H2 purification

– CLUSTERBEAM/PROSVACT: creating nano-clusters for model catalysts, etc.

– Low cost Photovoltaics: cheap, PV materials by thin film, with improved spectral response & long life

• TCL project leader – except for HydroGEN &NECLASS



Summary & Conclusions

• PVD coatings have multiple potential applications in Fuel Cells and the Hydrogen Economy

• Teer Coatings Limited offers relevant, industrially-qualified, thin film coatings– e.g. environmentally resistant, electrically conductive

thin film coatings for electrode plates• TCL can support partners’ process and

equipment needs, from R&D through to full production

• TCL’s research portfolio includes relevant collaborative projects



Acknowledgements

• The collaborative projects described above have benefited from DTI/Technology Strategy Board (MNT and Technology Programme) support.

• HYPNOMEM was a joint feasibility project by Univ B’ham’s Metallurgy & Materials Department (Rex Harris, John Speight, David Book, Vicky Mann, Sean Fletcher, Jo Grant) and TCL (Joanne Hampshire).

• Other project collaborators are too numerous to mention, but are gratefully acknowledged!



• For more information please contact:

Teer Coatings Limited,

West Stone House,

Berry Hill Industrial Estate,

Droitwich, Worcs, WR9 9AS, UK.Tel: +44(0)870 220 3910; Fax: +44(0)870 220 3911

www.teercoatings.co.uk



• Key Contacts:Paul Teer – Managing Director

Dennis Teer – Chairman/Technical Director

Dr Kevin Cooke – Collaborative Research Coord

Dr Glynn Dyson – Sales & Marketing Manager

Wayne Southall – Production Coatings Manager

Dr Joanne Hampshire – Special Coatings Manager

Documents

Teer Coatings Ltd Hydrogen Energy Universities of Birmingham & Warwick, Hydrogen Energy, 22 nd January, 2010 © Teer Coatings, 2010 Kevin Cooke Teer Coatings