2013年国际热喷涂会议论文

ITSC 2013: Innovative Coating
Solutions for the Global Economy

May 1315, 2013
Busan Exhibition and Convention Center
Busan, Republic of Korea
Proceedings of the
International Thermal Spray Conference
Copyright 2013
by
ASM International
All rights reserved
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ISBN-13: 978-1-62708-021-7
ISBN-10: 1-62708-021-X
SAN: 204-7586
ASM International
Materials Park, OH 44073-0002
www.asminternational.org
ORGANIZING COMMITTEE
Mr. John Hayden, Chair

Hayden Corporation
Mr. Albert Kay

Asb Industries
Mr. Charles Kay, Past Chair

ASB Industries
Mr. Komal Laul

Chromalloy
Mr. Luc Pouliot

Tecnar Automation Limited
Dr. Rogerio Lima

National Research Council of Canada
Dr. Aaron Hall, Board Liaison

Sandia National Laboratories
Mrs. Simone Mahlstedt

DVS German Welding Society
Mr. Robert Miller, Board Liaison

Kennametal Stellite
Dr. Basil Marple

Natl Research Council Canada
Prof. Kirsten Bobzin

Surface Engineering Institute
Dr. Christian Moreau

National Research Council Canada
Prof. Thomas Coyle

University of Toronto
Dr. Kazuhiro Ogawa

Tohoku University
Mr. Mitchell Dorfman

Sulzer Metco
Dr. Robert Tucker

The Tucker Group
Prof. Masahiro Fukumoto

Toyohashi University of Technology
Dr. Julio Villafuerte

Centerline Windsor Limited
Dr. Robert Gansert

Advanced Materials and Technology
Services Incorporated
Prof. Petri Vuoristo

Tampere University of Technology
Dr. Wilson Wong
Sulzer Metco
Mr. Peter Heinrich

Gemeinschaft Thermisches Spritzen E.v.
Mr. Greg Wuest

Sulzer Metco
Mr. Jens Jerzembeck

DVS German Welding Society
Dr. Dongming Zhu

NASA
Dr. Jeganathan Karthikeyan

Asb Industries
iii
Contents
Organizing Committee ...........................................................................................................iii
Advanced Thermal Spray Coatings

Vapor Deposition of Metallic Coatings by Very Low Pressure Plasma Spraying ...............1
B. Vautherin1, M.-P. Planche1, R. Bolot1, G. Montavon1, A. Quet2, and L. Bianchi2
(1) IRTES-LERMPS, UTBM, Belfort, France
(2) CEA Le Ripault, Mons, France
Comparative Investigation of Standard WC-Co and a

New WC-FeCrAl Feedstock Powder .......................................................................................8
B. Hussong, J. Pfeiffer, B. Lehmert, L. Wojarski, and W. Tillmann
Institute of Materials Engineering, Dortmund, Germany
Deposition and Oxidation of Oxide-Dispersed CoNiCrAlY Bondcoats ............................ 16

M. Okada1, R. Vaen2, M. Karger2, D. Sebold2, D.E. Mack2, M.O. Jarligo2, and F. Bozza3
(1) Central Research Institute of Electric Power Industry, Yokosuka, Japan
(2) Forschungszentrum Jlich GmbH, Jlich, Germany
(3) University of Modena and Reggio Emilia, Modena, Italy
Effects of Dry-Ice Blasting On Plasma-Sprayed Thermal Barrier Coatings .................... 22

S.-J. Dong1, B. Song1, H.-L. Liao1, C. Coddet1, and B. Hansz2
(1) IRTES-LERMPS, UTBM, France
(2) HMRexpert, France
Mechanical Properties of Plasma Sprayed YSZ Coatings

Measured Using TAT and TCT Test ..................................................................................... 29
Andrew Siao Ming Ang and Christopher C. Berndt,
Swinburne University of Technology, Melbourne, Australia
Y2O3 and Yb2O3 Co-Doped Strontium Hafnate as a

New Thermal Barrier Coating Material ................................................................................. 35
W. Ma, P. Li, H.-Y. Dong, Y. Bai, J.-L. Zhao, and X.-Z. Fan,
Inner Mongolia University of Technology, Hohhot, Inner Mongolia, P.R. China
A Novel Modification for Twin Wire Arc Spraying to

Improve the Variety of Application ...................................................................................... 41
W. Tillmann, M. Abdulgader, and L. Hagen,
Technische Universitt Dortmund, Dortmund, Germany
High-Temperature Oxidation-Resistant Thermal Spray Coatings Based on

MoSi2 for Furnace Applications ............................................................................................ 47
S. Schuberth, T. Uhlig, H. Pokhmurska, C. Rupprecht, and T. Lampke,
Chemnitz University of Technology, Chemnitz, Germany
Friction and Wear Properties of (Ti,Mo)(C,N) Hardmetal Coatings Prepared by

Gas and Liquid Fuel HVOF Processes ................................................................................. 51
L.-M. Berger1, J. Kitamura2, F. Kasahara2, J. Yamada2, K. Sato2, P. Vuoristo3,
A. Milanti3, K. Niemi3, . Houdkov4, and J. Savkov5
(1) Fraunhofer Institute Material and Beam Technology, Dresden, Germany
(2) Fujimi Incorporated, Gifu, Japan
(3) Tampere University of Technology, Department of Materials Science, Tampere, Finland
(4) Vzkumn a zkuebni stav Plze s.r.o, Plzen, Czech Republic
(5) University of West Bohemia, Plzen, Czech Republic
Dense MoB/CoCr Coatings to Apply to Pot-Roll of

Galvanizing Lines in Steel Industries .................................................................................. 57
J. Kitamura, T. Tosaki, and H. Mizuno,
Fujimi Incorporated, Gifu, Japan
Effect of WC-Co-Cr Powder Properties on

Coating Characteristics by Recent HVAF Spraying ........................................................... 63
Kazuto Sato1, Hidenori Miyajima2, Masami Kato2, Junya Kitamura1, and Kazuhiko Sakaki2,
(2) Shinshu University, Nagano, Japan
Investigation of HVOF-Sprayed Hardmetal Coatings for

Static Friction Applications .................................................................................................. 68
L.-M. Berger1, J. Spatzier1, M. Grfensteiner2, J. Vidner2, E. Leidich2, S. Schiefer2,
S. Grger2, and M. Gerlach2
(1 ) Fraunhofer Institute, Dresden, Germany
(2) Chemnitz University of Technology, Chemnitz, Germany
Thermally Sprayed Ti3SiC2 and Ti2AlC MAX-Phase Coatings ........................................... 74

R. Trache1, R. Puschmann1, C. Leyens1, L.-M. Berger2, B. Matthey3, and M. Herrmann3
(1) Dresden Technical University, Dresden, Germany
(2) Fraunhofer IWS, Dresden, Germany
(3) Fraunhofer IKTS, Dresden, Germany
Development of Thermal Spray Coating Solution for Ceramic Substrates ..................... 79

F.-L. Toma1, L.-M. Berger1, T. Hoffmann1, U. Klotzbach1, S. Scheitz2, S. Thiele3, and M. Fries3
(1) Fraunhofer Institute for Material and Beam Technology, Dresden, Germany
(2) Dresden University of Technology, Dresden, Germany
(3) Fraunhofer Institute for Ceramic Materials and Systems, Dresden, Germany
Applications and Case Study

Corrosion Properties of Selected Coatings Produced by
Atmospheric Plasma Spraying, HVOF and Laser Remelt Methods .................................. 85
P.T. Nielsen, T. Mathiesen, and S.E. Nielsen,
Force Technology, Broendby, Denmark
Macroporous Titanium Coatings by Thermal Plasma Spray ............................................. 91

P. Robotti1, A. Sabbioni1, L. Glass2, and B. George2
(1) Eurocoating Spa, Trento, Italy
(2) Surface Dynamics, Cincinnati, OH, USA
vi
High Performance Arc Sprayed Coatings for

Active Corrosion Protection in Offshore Applications ....................................................... 97
Werner Kroemmer, Linde AG, Unterschleissheim, Germany
Fabrication of Wire Mesh Heat Exchangers for

Waste Heat Recovery Using Wire-Arc Spraying ............................................................... 103
R. Rezaey, S. Salavati, L. Pershin, T. Coyle, S. Chandra, and J. Mostaghimi,
Centre for Advanced Coating Technologies, Toronto, Ontario, Canada
The Definition of Power in Plasma Spraying:

Kilowatts or Powder Melting Capacity? ............................................................................. 109
J. Colmenares-Angulo, O. Sabouni, and C. Ibanez,
Sulzer Metco, Westbury, NY, USA
Superhydrophobicity and Water Repelling Characteristics of

Thermally Sprayed Coatings .............................................................................................. 113
N. Sharifi1, F. Ben Ettouil1, M. Mousavi1, M. Pugh1, A. Dolatabadi1, and C. Moreau2
(1) Concordia University, Montreal, Quebec, Canada
(2) National Research Council of Canada, Boucherville, Quebec, Canada
High Temperature Oxidation Behavior of a

Novel Ni-20Cr Alloy Powder Coating on T22 Steel ........................................................... 120
Manoj Kumar, Harpreet Singh, and Narinder Singh,
Indian Institute of Technology Ropar, Rupnagar, Punjab, India
Cold Spray
Corrosion Protection of 5xxx Series Aluminum-Alloy by Cold Spray Process ............. 126
K. Sridharan, B. Maier, B. Hauch, and D. Devan,
University of Wisconsin - Madison, Madison, WI, USA
Characterization of Cold-Sprayed Copper Coatings with

New Evaluation Parameter of EBSD Method ..................................................................... 132
Yusuke Watanabe, Yuji Ichikawa, Isamu Nonaka, and Hideo Miura,
Tohoku University, Sendai, Japan
Comparison of the Mechanical and Electrochemical Properties of

WC-25Co Coatings Obtained by High Velocity Oxy-Fuel and
Cold Gas Spraying onto Al7075-T6 .................................................................................... 138
M. Couto, S. Dosta, J. Fernndez, and J.M. Guilemany,
Universitat de Barcelona, Barcelona, Spain
Effects of Spark Plasma Sintering Treatment for

Cold-Sprayed Metallic Coatings ......................................................................................... 143
K. Ito and K. Ogawa,
Tohoku University, Sendai, Japan
Investigation on Microstructural & Mechanical Properties of

Cold Sprayed & P/M Processed Composites .................................................................... 149
T. Chandanayaka and F. Azarmi,
North Dakota State University, Fargo, ND, USA
vii
Mechanical Properties of Cold-Sprayed Ti-6Al-4V Coatings ........................................... 155

A. List1, C. Lyphout2, M. Villa1, F. Grtner1, and T. Klassen1
(1) Helmut Schmidt University, Hamburg, Germany
(2) University West, Trollhattan, Sweden
Study on the Restoration of Aluminum Aerospace IVD Coatings Using

Cold Gas Dynamic Spray .................................................................................................... 161
D. MacDonald1, B. Jodoin1, S. Gaydos2, M. Pollack2, and J. Falkowski2
(1) University of Ottawa, Ottawa, Ontario, Canada
(2) The Boeing Company, USA
Near-Net Shape Fins for Compact Heat Exchanger Produced by Cold Spray ............... 166
Y. Cormier1, P. Dupuis1, B. Jodoin1, and A. Corbeil2
(2) Brayton Energy Canada, Gatineau, Quebec, Canada
Comparison of Microstructures and Mechanical Properties between

Thermal and Kinetic Sprayed Thick Fe Deposits on Fe-Si Alloy Sheets ........................ 172
Jaeick Kim1, Gyuyeol Bae1, Juyeon Won1, Changhee Lee1, Teasung Jun2, and
Jongkyo Choi2
(1) Hanyang University, Seoul 133-791, South Korea
(2) POSCO Technical Research Laboratories, Pohang, South Korea
Shockwave Induced Spraying Process:

Effect of Parameters on Coating Performance ................................................................. 178
M. Karimi1, G.W. Rankin1, and B. Jodoin2
(1) University of Windsor, Windsor, Ontario, Canada
Preparation and Characterization of TiO2 Scattering Layer for

Plastic Dye-Sensitized Solar Cells by Vacuum Cold Spray ............................................. 184
X.-L. He1, G.-J. Yang1, C.-X. Li1, C.-J. Li1, and S.-Q. Fan2
(1) Xi'an Jiaotong University, Xi'an, Shaanxi, China
(2) The University of Queensland, QLD, Australia
Dust Explosion Properties of Aluminum, Titanium, Zinc and

Iron Based Alloy Powders Used for Cold Spray ............................................................... 190
K. Sakata1, K. Tagomori1, N. Sugiyama1, S. Sasaki1, Y. Shinya1, T. Nanbu2, Y. Kawashita2,
I. Narita3, and H. Miyahara3
(1) Fujikikosan Corporation, Kitakyushu, Japan
(2) Nissan Motor Co., Ltd., Yokosuka, Japan
(3) Kyushu University, Fukuoka, Japan
Design and Development of High-Pressure Warm Spray Gun ........................................ 196

H. Katanoda1, B. Sun2, N. Ohno2, H. Fukanuma2, S. Kuroda3, M. Watanabe3,
and O. Ohashi3
(1) Kagoshima University, Kagoshima, Japan
(2) Plasma Giken Co., Ltd., Toshima-ku, Tokyo, Japan
(3) National Institute for Materials Science, Tsukuba, Ibaraki, Japan
Mechanical Properties of Cold Sprayed Al Coatings Reinforced by Ceramics ............. 200

K.H. Ko, J.O. Choi, and H. Lee,
Ajou University, Suwon, Republic of Korea
viii
Influence of Carrier Gas Composition on Microstructures and

Mechanical Properties of Cold-Sprayed Titanium Coatings ............................................ 205
Y. Ichikawa1, K. Ogawa1, N. Nose2, Y. Nomura2, M. Takahashi2, and H. Amano2
(1) Tohoku University, Sendai, Japan
(2) Taiyo Nippon Sanso Corporation, Tokyo, Japan
Anisotropic Mechanical Properties of Cold Sprayed Copper Coatings .......................... 210

Y. Watanabe, K. Atsumi, M. Yamada, and M. Fukumoto
Toyohashi University of Technology, Toyohashi, Aichi, Japan
High-Pressure Cold-Sprayed Ni and Ni-Cu Coatings

- Improved Structures and Corrosion Properties ............................................................. 215
H. Koivuluoto1, A. Milanti1, P. Vuoristo1, G. Bolelli2, and L. Lusvarghi2
(1) Tampere University of Technology, Tampere, Finland
(2) University of Modena and Reggio Emilia, Modena, Italy
Fundamental Cost Analysis of Cold Spray ....................................................................... 221

O. Stier, Siemens AG, Berlin, Germany
High Temperature Oxidation Behavior of

Cold Sprayed Ni-Al2O3 Composite Coating ...................................................................... 227
C.J. Huang1, W.Y. Li1, M. Yu2, and H. Liao2
(1) Northwestern Polytechnical University, Xian, P.R. China
(2) Universit de Technologie de Belfort-Montbliard, Belfort, France
Strength and Wear Properties of Stainless Steel Coatings Produced by

Cold Spray with Various Powder Sizes ............................................................................. 235
P. Vo1, E. Irissou1, S. Kudapa2, and M. Nestler2
(1) National Research Council Canada, Boucherville, Quebec, Canada
(2) Sulzer Metco (US) Inc., Troy, MI, USA
Super Hard WC Cermet Coating by Low Pressure Cold Spray Based on

Optimization of Powder Properties .................................................................................... 241
T. Sonoda1, T. Kuwashima1, T. Saito1, K. Sato2, H. Furukawa2, J. Kitamura2, and D. Ito3
(1) Iwate Industrial Research Institute, Iwate, Japan
(3) Spec, Iwate, Japan
Multi-Response Optimization of Process Parameters for

Low-Pressure Cold Spray Coating Process Using Taguchi and Utility Concept ........... 246
Tarun Goyal1, T.S. Sidhu2, and R.S. Walia3
(1) SUS College of Engineering and Technology, Tangori, Mohali, India
(2) Shaheed Bhagat Singh College of Engineering & Technology, Ferozepur, Punjab, India
(3) Delhi Technological University, Delhi, India
Coating Performance and Durability of Zn-Based Composite Materials

Prepared by Using Low-Pressure Cold Spraying ............................................................. 252
H. Koivuluoto1, J. Ketola1, A. Milanti1, P. Vuoristo1, L.-L. Descurninges2,
N. De Dave-Fabregue2, and M. Jeandin2
(2) MINES ParisTech, Evry, France
ix
Splat Formation and Adhesion Mechanisms of

Cold Gas Sprayed Al Coatings on Al2O3 ............................................................................ 258
B. Wielage1, R. Drehmann1, T. Grund1, D. Rafaja2, T. Schucknecht2, and K. Manygoats2
(1) Chemnitz University of Technology, Chemnitz, Germany
(2) Freiberg University of Mining and Technology, Freiberg, Germany
Velocity Measurement of Sprayed Particles and Coatings Fabrication of

Titanium Alloys by High-Pressure Warm Spray ............................................................... 263
S. Kuroda1, R.M. Molak1, M. Watanabe1, H. Araki1, H. Katanoda2, B. Sun3, N. Ohno3,
and H. Fukanuma3
(1) National Institute for Materials Science, Tsukuba, Ibaraki, Japan
(2) Kagoshima University, Korimoto, Kagoshima, Japan
(3) Plasma Giken Co., Ltd., Toshima-ku, Tokyo, Japan
Analysis of Thermal History and Residual Stress in Cold Sprayed Coatings ................ 269
Z. Arabgol1, H. Assadi1, T. Schmidt2, F. Grtner2, and T. Klassen2
(1) Tarbiat Modares University, Tehran, Iran
The Optional Facilities for the Low Pressure Cold Spray ................................................ 275
A. Shkodkin, A. Kashirin, O. Klyuev, and T. Buzdygar
Obninsk Center for Powder Spraying, Obninsk, Russia
The Effect of Shock-Induced Plastic Deformation on

Alumina Deposition during Vacuum Kinetic Spraying ..................................................... 279
Hyungkwon Park, Fei Cao, Juhyuk Kwon, and Changhee Lee,
Hanyang University, Seoul, Republic of Korea
Effect of Liquid Feedstock on Downstream Cold Spray Nozzle ...................................... 292

E. Farvardin1, M. Karimi2, J. Villafuerte2, and A. Dolatabadi1
(2) CenterLine Ltd., Windsor, Ontario, Canada
Deformation and Adherence of Fe40Al- Particles in Cold Gas Spraying ....................... 297
N. Cinca1, A. List1, F. Grtner1, J. Fernndez2, J.M. Guilemany2, and T. Klassen1
(2) Universitat de Barcelona, Barcelona, Spain
Electronic and Semiconductor Applications

Microstructure Influence on Electromagnetic Properties of
Thermal Sprayed Ferromagnetic Composites .................................................................. 302
E. Brousse-Pereira, J. Neige, S. Pereira, K. Wittmann-Teneze, A.L. Adenot-Engelvin,
and L. Bianchi,
CEA DAM Le Ripault, Monts, France
Dense and High Purity Yttria Coatings by APS with a New Yttria Powder ..................... 307
A. Allimant1, D. Billires1, and H. Wallar2
(1) Saint-Gobain Coating Solutions, Avignon, France
(2) Saint-Gobain Coating Solutions, Worcester, MA, USA
x
Comparable Study of Electrical and Mechanical Properties in

Plasma Sprayed Alumina Coatings .................................................................................... 312
T. Tosaki, Y. Kobayashi, K. Ohta, and J. Kitamura,
Multi-Scale Analysis between Microstructure and Absorbing Performance of

Thermal Sprayed Fe-(-SiC/SiO2) Coatings ....................................................................... 318
Xiaojing Yuan, Bailin Zha, and Hangong Wang,
Xian Research Institute of Hi-Tech, Shaanxi, P.R. China
Manufacturing and Processes

A Coupled Model between Robot Trajectories and Thermal History of the
Workpiece during Thermal Spray Operation ..................................................................... 329
R. Bolot, S. Deng, Z. Cai, H. Liao, and G. Montavon,
IRTES-LERMPS, UTBM, Belfort, France
High Productivity PS-PVD Process .................................................................................... 335

A. Barth, M. Gindrat, and S. Usai,
Sulzer Metco AG, Switzerland
Influence of Surface Contamination on the

Adhesion Strength of HVOF Coatings ............................................................................... 339
J. Barr1, C. Estrada1, and B. White2
(1) Watson Laboratories, Houston, TX, USA
(2) Watson Grinding & MFG, Houston, TX, USA
Development of High Density Twin Wire Arc Sprayed Coatings on

Metallic Foam Substrates ................................................................................................... 345
S. Salavati, R. Rezaey, L. Pershin, T.W. Coyle, and J. Mostaghimi,
University of Toronto, Toronto, ON, Canada
Research and Development

Development and Characterization of
B4C Reinforced Detonation Sprayed Al Coatings ............................................................. 351
W. Tillmann1, P.S. Hollingsworth1, G. Fischer2, and J. Nellesen2
(1) Technische Universitt Dortmund, Dortmund, Germany
(2) RIF e.V. Institut fr Forschung und Transfer, Dortmund, Germany
Sliding Wear Behavior and Wear Effects of HVOF Sprayed Coatings

Derived from Conventional, Fine and Nanostructured WC-12Co Powders .................... 357
W. Tillmann, I. Baumann, P. Hollingsworth, and L. Hagen
Depicting the Behavior of a Mono-Cathode

Plasma Spray Torch with an Emulator .............................................................................. 365
T. Liu, S. Deng, M.-P. Planche, and G. Montavon,
IRTES-LERMPS, Belfort, France
xi
Infiltration Bonding of a Hot Isostatic Press Clad Aluminum Layer to

Plasma Sprayed Zirconium Coatings ................................................................................ 377
K. Hollis and P. Dickerson,
Los Alamos National Laboratory, Los Alamos, NM, USA
Investigation of a Pulsed Current Wire Arc Spray Process ............................................. 383

S. Kirner, J. Schein, and G. Forster,
Universitaet der Bundeswehr Muenchen, Neubiberg, Germany
Investigation and Characterization of HVAF WC-Co-Cr Coatings and

Comparison to Galvanic Hard Chrome Coatings ............................................................. 389
K. Bobzin1, N. Kopp1, T. Warda1, M. Schfer1, and A. Verstak2
(1) RWTH Aachen University, Aachen, Germany
(2) Kermetico Inc., Benicia, CA, USA
Behavior of Ceramic Thermal Spray Coatings under Plasma Exposure ........................ 395
H. Yokota and M. Inaba, TOCALO Co., Ltd., Hyogo, Japan
A Numerical Investigation: Influence of the Operating Gas on the

Flow Characteristics of a Three-Cathode Air Plasma Spraying System ......................... 400
K. Bobzin, N. Kopp, T. Warda, M. Schfer, and M. te,
RWTH Aachen University, Aachen, Germany
Microscopic Characteristics and Mechanical Properties of

Plasma Sprayed Al2O3 Coatings ......................................................................................... 406
T. Sakoda, M. Inaba, and K. Taguchi,
TOCALO Co., Ltd., Hyogo, Japan
TEM Characterization of the Coating/Substrate Interface in

Vacuum Cold-Sprayed Nano-TiO2 Coating ........................................................................ 412
Hai-Long Yao, Guan-Jun Yang, Xue-Long He, Cheng-Xin Li, and Chang-Jiu Li,
Xian Jiaotong University, Xian, Shaanxi, China
Analysis of Liquid Feedstock Behavior in

High Velocity Suspension Flame Spraying for the
Development of Nanostructured Coatings ........................................................................ 418
Ebrahim Gozali, Spyros Kamnis, and Sai Gu,
Xi'an Jiaotong-Liverpool University
Wear Performance of Thermally Sprayed and Welded Coatings Using

Conventional and Nanostructured Materials .................................................................... 424
C.R.C. Lima1, B.V. Bette1, F. Camargo2, H.C. Fals3, and V.A. Ferraresi4
(1) Methodist University of Piracicaba, So Paulo, Brazil
(2) OGRAMAC Surface Engineering, So Paulo, Brazil
(3) Oriente University, Santiago de Cuba, Cuba
(4) Federal University of Uberlndia, Minas Gerais, Brazil
Fabrication of Dense Ceramic Coatings by Using HVOF Spraying ................................. 429

Jin-Hong Kim, Byeong-Geun Seong, and Hyung-Jun Kim,
Research Institute of Industrial Science & Technology, Pohang, South Korea
xii
Development of Low Power Plasma Spray Process Using

Atmospheric Pressure Microwave Plasma ........................................................................ 433
T. Yasui, A. Redza, and M. Fukumoto,
Toyohashi University of Technology, Toyohashi, Japan
Characterization of the Flow Regimes in the Jet Spray for

Different Twin-Wire Arc Spraying Nozzles by Adapting the
Background Oriented Schlieren Technique ...................................................................... 437
W. Tillmann, A. Mohamed, A. Nassir, L. Hagen, and H.G. Rademacher,
Current Activities for Standardization on Indentation Method to

Evaluate Adhesion Strength of Thermal Spray Coatings in Japan ................................. 451
Y. Yamazaki1, M. Suzuki2, M. Arai3, Y. Miyashita4, and H. Waki5
(1) Niigata Institute of Technology, Kashiwazaki, Japan
(2) The National Institute of Advanced Industrial Science and Technology, Tsukuba, Japan
(3) Central Research Institute of Electric Power Industry, Yokosuka, Japan
(4) Nagaoka University of Technology, Nagaoka, Japan
(5) Iwate University, Morioka, Japan
Friction Evolution of WC-CoCR Thermally Sprayed Coatings during

Dry Sliding in Different Environment ................................................................................. 457
J.A. Wesmann1, R. Johnsen1, N. Espallargas1, J. Herland2, and D. Twist2
(1) NTNU Tribology Laboratory, Trondheim, Norway
(2) Aker Solutions AS, Tranby, Norway
Nucleation and Growth Transformations in

Vacuum Plasma Sprayed Ti-6Al-4V Alloy .......................................................................... 460
H.R. Salimijazi1, Z.A. Mousavi1, M.A. Golozar1, J. Mostaghimi2, and T. Coyle2
(1) Isfahan University of Technology, Isfahan, Iran
(2) University of Toronto, Toronto, Canada
Structure and Properties of HVOF and Plasma Sprayed Ceramic AluminaChromia Coatings Deposited from Fused and Crushed Powders .................................. 465
P. Vuoristo1, K. Niemi1, V. Matikainen1, L. Hyvrinen1, H. Koivuluoto1, L.-M. Berger2,
S. Scheitz3, and I. Shakhverdova3
(2) Fraunhofer Institute for Material and Beam Technology, Dresden, Germany
(3) Dresden University of Technology, Dresden, Germany
Suspension and Solution Plasma Spray

Structural Modifications on Material Surfaces by
Thermal Nanoparticle Spraying and Microlines Patterning ............................................. 471
S. Kirihara, Osaka University, Ibaraki, Osaka, Japan
Electro-Catalytically Active Porous Nickel-Based Electrode Coatings Formed by

Atmospheric and by Suspension Plasma Spraying ......................................................... 475
M. Aghasibeig1, M. Mousavi1, F. Ben Ettouill1, R. Wuthrich1, A. Dolatabadi1, and C. Moreau2
(2) National Research Council, Boucherville, Quebec, Canada
xiii
A Numerical Study of Suspension Injection in Plasma Spraying Process ..................... 481

F. Jabbari, M. Jadidi, R. Wuthrich, and A. Dolatabadi
Concordia University, Montreal, Quebec, Canada
Surface Engineering
3D Wear Analysis of Thermal Spray Coatings .................................................................. 487
W. Tillmann, W. Luo, and U. Selvadurai,
TU Dortmund University
Plasma Spray-Physical Vapor Deposition of La1-xSrxCoyFe1-yO3- Thin Film

Oxygen Transport Membrane on Porous Metallic Supports ........................................... 493
M.O. Jarligo, G. Mauer, M. Bram, S. Baumann, and R. Vaen,
Forschungszentrum Jlich GmbH, Jlich, Germany
Influence of Surface Pre-Treatment on Aluminum Alloy Mechanical Behavior ............. 499

A. Lamraoui, S. Costil, and C. Langlade,
Universit de Technologie de Belfort Montbliard, Belfort, France
Tungsten Carbide Deposition Processes for Hard Chrome Alternative:

Preliminary Study of HVAF vs. HVOF Thermal Spray Processes ................................... 506
C. Lyphout1, J. Kitamura2, K. Sato2, J. Yamada2, and S. Dizdar3
(1) University West, Production Technology West, Trollhttan, Sweden
(2) Fujimi Incorporated, Japan
(3) Hgans Sweden AB, Sweden
Microstructure and Mechanical Properties of

Plasma Sprayed Nanostructured and Conventional Al2O3-13TiO2 Coatings .................. 512
Wojciech rawski1, Anna Gral2, Otakar Bokuvka3, and Katarzyna Berent2
(1) Kielce University of Technology, Poland,
(2) Institute of Metallurgy and Materials Science PAS, Cracow, Poland
(3) University of Zilina, Slovakia
Adhesion/Cohesion Strength of Plasma Sprayed Ceramic Coatings by

Scratch Testing On Cross-Section .................................................................................... 516
Eungsun Byon1, Soo-Wohn Lee2, Junya Kitamura3, and Kenneth Holmberg4
(1) Korea Institute of Materials Science, Changwon, Korea
(2) Sunmoon University, Asan, Korea
(3) Fujimi Incorporated, Kakamigahara, Japan
(4) VTT Technical Research Centre of Finland, VTT, Finland
Biofilm Formation and Evaluation for

Spray Coated Metal Films on Laboratory Scale ................................................................ 520
H. Kanematsu1, T. Kogo1, D. Kuroda1, H. Itoh1, and S. Kirihara2
(1) Suzuka National College of Technology, Suzuka, Mie, Japan
(2) Osaka University, Ibaraki, Osaka, Japan
The Effect of CFRP Surface Treatment on the Splat Morphology and

Coating Adhesion Strength ................................................................................................ 526
Amirthan Ganesan, Mohammed Shahien, Motohiro Yamada, and Masahiro Fukumoto,
Toyohashi University of Technology, Toyohashi, Aichi, Japan
xiv
External Powder Injection in Twin Wire Arc Spraying to

Control the Coating Composition ...................................................................................... 532
W. Tillmann, M. Abdulgader, and L. Hagen,
Surface Hardening of HVOF Sprayed Stainless Steel Coatings by

Plasma Nitriding and Nitrocarburizing .............................................................................. 538
Gayoung Park, Gyuyeol Bae, and Changhee Lee,
Hanyang University, Seoul, South Korea
Abrasive Wear Resistance of Thermal Surfacing Materials for

Soil Tillage Applications ..................................................................................................... 543
Senad Dizdar and Barbara Maroli,
Hgans AB, Hgans, Sweden
Abrasion Wear and Corrosion Resistance in

Chlorine Containing Conditions of Iron Based Thermal Spray Coatings ....................... 550
J. Laurila, A. Milanti, K. Niemi, and P. Vuoristo,
Tampere University of Technology, Tampere, Finland
Turbine Coatings
Impact of Impurity Content on the Sintering Resistance of Dysprosia and
Yttria Stabilised Zirconia Thermal Barrier Coatings ......................................................... 557
N. Curry1, Wyszomir Janikowski2, and N. Markocsan1
(1) University West, Trollhttan, Sweden
(2) University of Manchester, Manchester, UK
Increasing Durability of a Multilayer Oxidation Protection System for

Gamma-TiAl ......................................................................................................................... 564
K. Bobzin, N. Kopp, T. Warda, and T.F. Linke,
RWTH Aachen University, Aachen, Germany
MCrAlY Bondcoats by High Velocity Atmospheric Plasma Spraying ............................. 570

G. Mauer, D. Sebold, and R. Vaen,
Forschungszentrum Jlich, Jlich, Germany
Effect of Plasma Spray Parameters on Thermal Barrier Coating Formation and

Microstructural Properties .................................................................................................. 577
M.L. Sesso, C.C. Berndt, and Y.C. Wong,
Swinburne University of Technology, Australia
Improved Thermal Cycling Durability of Thermal Barrier Coatings

Manufactured by PS-PVD..................................................................................................... 583
S. Rezanka, G. Mauer, and R. Vaen,
Forschungszentrum Jlich, Jlich, Germany
Comparison Study of Three or Two Dimensional Analytical Model for

Simulation of Thermal Conductivity in Thermally Sprayed Ceramic Coatings .............. 590
G.-J. Yang, Y.-C. Xie, H. Xie, C.-X. Li, and C.-J. Li,
Xi'an Jiaotong University, Xi'an, Shaanxi, China
xv
Influence of Topcoat-Bondcoat Interface Roughness on Stresses and

Lifetime in Thermal Barrier Coatings ................................................................................. 596
M. Gupta, K. Skogsberg, and P. Nyln,
University West, Trollhttan, Sweden
Tribological Characterization of Plasma Sprayed

CoNiCrAlY-BN Abradable Coatings ................................................................................... 602
E. Irissou1, A. Dadouche2, and R.S. Lima1
(1) National Research Council Canada, Boucherville, Quebec, Canada
(2) National Research Council Canada, Ottawa, Ontario, Canada
Controlling YSZ Abradable Erosion Performance by

Optimizing Spray Parameters ............................................................................................. 608
A. Hawkins1, R. Wellman1, M. Craig1, J.R. Nicholls1, K. Laul2, and R. Shankar2
(1) Cranfield University, Cranfield, Bedfordshire, UK
(2) Chromalloy, Orangeburg, NY, USA
Poster
New Method for Carbon Nanofibers-Metal Powder Formation and
Their Use in Thermal Spray Coatings ................................................................................ 620
D.R. Vidal, I.G. Cano, J. Fernndez, and J.M. Guilemany,
Universitat de Barcelona, Barcelona, Spain
A Study on the Metal EDTA Complexes Thermal Spray ................................................... 626

Yu Li1, Masahiro Noguchi1, Hiroki Akasaka2, Atsushi Nakamura3, and Hidetoshi Saitoh4
(1) Nippon Steel & Sumikin Hardfacing Co., Ltd., Fukuoka, Japan
(2) Tokyo Institute of Technology, Tokyo, Japan
(3) Chubu Chelest Co. Ltd., Mie, Japan
(4) Nagaoka University of Technology, Niigata, Japan
Friction Coefficient Improvement of Cold Sprayed Al-Al2O3 Coatings ............................ 631

K.H. Ko, J.O. Choi, and H. Lee,
Ajou University, Suwon, Republic of Korea
Formation Mechanism of Fe-Al2O3-FeAl2O4 and FeAl Coatings by

Reactive Plasma Spraying under Atmosphere and Low Pressure Conditions .............. 636
L. Zhu1, R. Bolot2, H. Liao2, C. Coddet2, N. Zhang3, and Q. Zhao4
(1) Mariee-CFHI, Tianjin, China
(2) LERMPS-UTBM, Belfort, France
(3) Shenyang University of Technology, Shenyang, China
(4) Tianjin University of Science & Technology, Tianjin, China
Numerical Simulation of Heat Transfer in

Thermal Spray-Formed Metal Foam Heat Exchangers ..................................................... 642
M. Taheri, S. Chandra, and J. Mostaghimi,
University of Toronto, Toronto, Ontario, Canada
xvi
Modeling the Influence of Solution Properties on Precipitations of

Vaporizing Droplets in Plasma Gases ................................................................................ 648
L.S. Xu and Y.G. Shan,
University of Shanghai for Science and Technology, China
Numerical Simulation of Gas Dynamics and Particles Behavior in

Low-Temperature Oxygen-Fuel Spray Process ................................................................ 654
C.H. Shen1, Y.G. Shan1, and L.B. Jia2
(1) University of Shanghai for Science and Technology, Shanghai, China
(2) Siemens (Shanghai) Gas Turbine Parts Ltd., Shanghai, China
Effect of Substrate Hardness and Spray Angle on the

Deposition Behavior of Cold Sprayed Ti Particles ........................................................... 660
S. Yin1, X.K. Suo1, H.L. Liao1, X.F. Wang2, and W.Y. Li3
(1) Universit de Technologie Belfort-Montbliard, Belfort, France
(2) Dalian University of Technology, Dalian, Liaoning, China
(3) Northwestern Polytechnical University, Xi'an, Shaanxi, China
Microstructure and Magnetic Properties of

Atmospheric Plasma-Sprayed Fe-40Al Coating Obtained from
Nanostructured Powders .................................................................................................... 666
B. Song1, S.-J. Dong1, N.-E. Fenineche1, H.-L. Liao1, C. Coddet1, and T. Grosdidier2
(1) IRTES-LERMPS, Belfort, France
(2) LETAM, Metz, France
Parameter Optimization of Dry-Ice Blasting during

Plasma Spraying Process by Characterizing CoNiCrAlY Coatings ................................ 672
S.-J. Dong1, B. Song1, H.-L. Liao1, C. Coddet1, and B. Hansz2
(1) IRTES-LERMPS, UTBM, France
(2) HMRexpert, France
Characterization of WC Particle-Reinforced In-Situ FeAl Intermetallic

Matrix Composite Coating by Cold Spraying .................................................................... 677
H.-T. Wang1, G.-C. Ji1, and R.-Y. Wang2
(1) School of Mechanical and Materials Engineering, Jiujiang, Jiangxi, P.R. China
(2) Jiujiang University Library, Jiujiang, Jiangxi, P.R. China
Effect of Ceramic Content on the Microstructure and Wear Behaviour of

Al/SiCp Composite Coatings by Cold Spraying ................................................................. 684
H.-T. Wang1, G.-C. Ji1, and R.-Y. Wang2
(1) School of Mechanical and Materials Engineering, Jiujiang, Jiangxi, P.R. China
(2) Jiujiang University Library, Jiujiang, Jiangxi, P.R. China
Deposition Behaviors of Fe-Based Amorphous Materials in

Vacuum Kinetic Spraying Process .................................................................................... 690
Juhyuk Kwon, Hyungkwon Park, and Changhee Lee,
Hanyang University, Seoul, Republic of Korea
xvii
Effect of SiC Particle Size and Fraction on Microstructure and Properties of

Cold Sprayed AZ91D/SiCp Composite Coatings ............................................................... 695
X.-K. Suo1, M. Yu1, M.-P. Planche1, H.-L. Liao1, and Q.-L. Suo2
(1) Universit de Technologie de Belfort-Montbliard, France
(2) Beijing University of Aeronautics and Astronautics, Beijing, China
Prediction of Critical Velocity during Cold Spraying Based on a

Coupled Thermomechanical Eulerian Model .................................................................... 701
F.F. Wang1, W.Y. Li1, C.J. Huang1, M. Yu2, and H.L. Liao2
(1) Northwestern Polytechnical University, Xian, Shaanxi, P.R. China
(2) Universit de Technologie de Belfort-Montbliard, Belfort, France
Influence of the Substrates Shape Complexity on the Coating Properties

Produced by HVOF Spraying of Fine WC-12Co (2-10 m) Powders ............................... 707
W. Tillmann1, P. Hollingsworth1, I. Baumann1, S. Flossbach1, H. Mller2, and T. Wiederkehr2
(1) Institute of Materials Engineering, TU Dortmund, Germany
(2) Computer Science VII - Computer Graphics, TU Dortmund, Germany
Wear Resistant Coatings on Ball Valves for Coal-Slurry Pipelines ................................. 712
L. Pershin1, J. Mostaghimi1, Afshin Maknoni2, Y.S. Ma3, Q. Gao3, Z.D. Chang3,
H.B. Liu3, and Q.M. Wu3
(1) University of Toronto, Toronto, Canada
(2) Metal Morphosis Specialty Metals Inc., Cambridge, ON, Canada
(3) Wuzhong Instruments, Wuzhong, China
Computational Simulation for Gas Heater of Cold Spray System ................................... 717
Huang Guosheng1, Gu Daming1, Li Xiangbo2, and Xing Lukuo2
(1) Harbin Institute of Technology, Harbin, China
(2) Science and Technology on Marine Corrosion and Protection Laboratory, Qingdao, China
Author Index ........................................................................................................................ 723
xviii
Thermal Spray 2013Innovative Coating Solutions for the Global Economy

Proceedings of the International Thermal Spray Conference
May 1315, 2013, Busan, Republic of Korea
R.S. Lima, A. Agarwal, M.M. Hyland, Y.-C. Lau, G. Mauer, A. McDonald, F.-L. Toma, editors
Copyright 2013 ASM International

All rights reserved
Vapor Deposition of Metallic Coatings by Very Low Pressure Plasma Spraying

*B. Vautherin, M.-P. Planche, R. Bolot, G. Montavon
IRTES-LERMPS, UTBM, 90010 Belfort cedex, France
*E-mail: beatrice.vautherin@utbm.fr
A. Quet, L. Bianchi
CEA Le Ripault, Mons, France
processes (such as APS for example) and the compact and

dense structure of coatings manufactured by thin film
processes such as physical vapor deposition.
Abstract
In recent years, the very low pressure plasma spraying
(VLPPS) process has been developed and implemented to
manufacture thin, dense and finely-structured ceramic coatings
for various applications, such as Y2O3 for diffusion barriers.
This paper aims at presenting developments carried out on
metallic coatings. Aluminum was chosen as a demonstrative
material due to its "moderate" vaporization enthalpy (i.e.,
38.23 KJ.cm-3) compared to copper (i.e., 55.33 KJ.cm-3),
cobalt (i.e., 75.03 KJ.cm-3) or even tantalum (i.e., 87.18
KJ.cm-3). The objective of this work is primarily to better
understand the behavior of a solid precursor injected into the
plasma jet leading to the formation of vapors and to better
control the factors affecting the coating structure. Nearly
dense aluminum coatings were successfully deposited by
VLPPS at 100 Pa with an intermediate power plasma torch
(i.e., Sulzer Metco F4 type gun with maximum power of 45
kW). Optical emission spectroscopy (OES) was implemented
to study and analyze the powder behavior into the plasma jet.
Simplified CFD modeling allowed better understanding of
thermo-physical mechanisms. The effect of powder size
distribution, substrate temperature and spray distance were
studied. Coatings were characterized by SEM observations
and Vickers microhardness measurements.
Nowadays, various centers in the world carry on research

activities on this process to better apprehend its potential:
Swiss Federal Institute of Technology/Plasma Physics
Research Center (Lausanne) and Sulzer Metco in Switzerland
(Ref 1-2, 4-8), Institute of Energy Research (IEF-1) of Jlich
in Germany (Ref 3), Department of Metallurgical and
Materials Engineering/ACSEL Research Center/Colorado
School of Mines (Ref 9) and Sandia National Laboratories
(Ref 10) in USA, Thermal Spraying Center of Dalian
Maritime University in China (Ref 11-12), Department of
Materials Engineering/ School of Engineering/University of
Tokyo in Japan (Ref 13), University of Technology of BelfortMontbliard in France (Ref 14-15), etc.
In order to illustrate the effect of the surrounding pressure on
the process, radial profiles of 8% yttria stabilized zirconia
particles (8% YSZ, -22+5 m size distribution) velocity and
temperature are presented in Fig. 1 for two surrounding
pressures (i.e., 150 and 104 Pa). The pressure decrease induces
lower radial variations in the particles properties. There is still
the need for a clear and complete understanding of all
thermophysical and chemical, in some cases, mechanisms
involved in the coating formation mechanisms and their
related structural characteristics and properties. This work is a
contribution to the effort of the scientific community to better
understand those mechanisms. Optical emissions spectroscopy
(OES), simplified computational fluid dynamic (CFD) and
coating structural attributes analyses were combined together.
Introduction
The very low pressure plasma spray (VLPPS) process is an
emerging process allowing manufacturing ceramic and
metallic coatings. It is operated in an inert atmosphere (i.e.,
Ar) at unusually low pressures of typically between 100 and
1000 Pa. As a consequence, the deposition mechanisms are
different compared to the ones encountered with the
atmospheric plasma spray (APS) process since they result
mostly from the condensation of vapors instead of the stacking
of flattened particles. Depending upon spray operating
parameters, coating structures vary from nearly dense to
highly porous. As shown by K. Von Niessen et al. (Ref 1), M.
Gindrat et al. (Ref 2), A. Hospach (Ref 3), and J.-L. Dorier et
al. (Ref 4), the VLPPS process has an important potential.
Those authors proved that this process can be seen as
combining the high deposition rate of conventional spray
Experimental Methods
Feedstock and Substrates
Atomized aluminum 1050 powder particles manufactured at
IRTES-LERMPS, with a size distribution ranging from 25 m
(d10) and 65 m (d90) and an average size diameter (d50) of 45
m, were used as starting feedstock material (see Fig. 2). In
order to highlight the effect of the particles size on the coating
Figure 1: Particles characteristics (a) velocity (m.s-1) and (b)

temperature (C) at 150 Pa and 104 Pa [5].
Figure 3: VLPPS system at IRTES-LERMPS.
Table 1: Operating spray parameters.
Parameters
Plasma torch
Anode internal diameter at torch exit (mm)
Arc current intensity (A)
Arc voltage (V)
Ar plasma forming gas flow rate (L/min)
He plasma forming gas flow (L/min)
H2 plasma forming gas flow (L/min)
Plasma mass enthalpy (J.kg-1)
Chamber pressure (Pa)
Injector internal diameter at exit (mm)
Feedstock carrier gas flow rate (L.min-1)
Spray distance (mm)
Spray velocity (mm.s-1)
Scanning step in between two passes (mm)
Substrate average temperature during
deposition (without cooling) (K)
Figure 2: SEM view of the aluminum powder used as

feedstock.
microstructures, the starting feedstock was sieved to get three
distinct size distributions: 25-65 m, 18-63 m, 9-28 m.
Stainless steel plates of 80302 mm3 were used as substrates.
In order to improve the adhesion of the coatings, the substrates
were previously degreased in alcohol vapors and grit-blasted
(with -Al2O3 grits of 250 m, average dimension). They
exhibited prior spraying an average surface roughness of 10
m and an average maximum peak-to-valley ratio of 126 m.
During spraying, the substrate temperature was monitored
using type K thermocouples brazed on the front of the
substrate in order to avoid the conductive losses and the
thermal resistances in between the samples and the sampleholder. Indeed, the rather long spray distance and the rarefied
atmosphere do not damage the thermocouples during tests.
Set 1
Set 2
F4
6
650
73
45
0
10
15.0
100
650
64
17
33
5
31.4
100
1.5
3
650 to 800
200
200
950
1300
aluminum optical emissions. 396.2 nm and 394.6 nm are

specific wavelengths recorded for Al I. The exposition time
used for the measurements was 1 s because of the very low
intensity of aluminum species optical emissions.
Computational Fluid Dynamic (CFD) Modeling
CFD modeling was carried to underline the plasma jet
structure heterogeneities and to estimate the thermodynamic
property values. The axisymmetric computational domain was
restricted to the free expansion zone of the flow and
predetermined velocity and temperature profiles at the torch
exit were considered. The implemented stationary twodimensional model considers the local thermodynamic
equilibrium (LTE) and a voluminous heat source (Ref 16-17) :
such an assumption does not correspond to the physics of
thermal plasmas under such low pressures but allows
understanding the global plasma flow structures. The plasma
flow / hot gas mixture thermodynamic properties and transport
coefficients are determined from the calculation of chemical
equilibriums by minimizing of the Gibbs free energy (Ref 1820). For the individual species, thermodynamic properties of
individual substances from Gurvich (Ref 21) were used.
ANSYS FLUENT package (released version 13.0) was used.
VLPPS System and Spray Operating Parameters

A VLPPS system developed in house was used to carry on the
experiments. The configuration of this system is depicted in
Figure 3. It is made of an operating chamber of 12 m3. The
pumping system allows varying the chamber pressure during
operation from 20 Pa to 5 kPa. The system is equipped with a
45 kW F4-type plasma torch. Two sets of parameters were
considered to process the three considered aluminum
feedstock powders as shown in Table 1.
Optical Emission Spectroscopy (OES) Analyses
Optical emissions spectroscopy (OES) was performed using a
JOBINYVON OES spectrometer (TRIAX190, UK) equipped
with a CCD detector (1024128 pixels). A 300-1000 nm
wavelength range was selected. An axial scanning along the
plasma jet was performed to record the evolution of the
Analyses of Coating Structural Attributes and Mechanical

Properties
Coating cross-sections and coating fractured surfaces were
observed using a JEOL JSM-5800LV scanning electron
microscope (SEM). A LEITZ MINILOAD-2 Vickers tester was
used to measure the microhardness of the coatings. A load of
25 g and a dwell time of 30 s were selected. 12 indentations
were impressed randomly; the average value allowed
estimating the coatings hardness. Hydrostatic pressure
porosimetry (METTLER TOLEDO, Viroflay, FR) was
implemented to estimate the coatings close void content. 12
tests were performed for each coating; the average value
allowed estimating the coatings closed void content.
surrounding pressure. Indeed, with an increase in pressure,

collisions frequencies are promoted, rarefaction phenomenon
(Knudsen effect) is reduced and power vaporization is very
likely more important due to a better heat transfer to particles.
Table 2: Modeling conditions.

Anode internal diameter at torch exit (mm)
Ar plasma forming gas flow rate (L/min)
Arc current intensity (A)
Voltage (V)
Plasma mass enthalpy (J.kg-1)
Chamber pressure (Pa)
Results and Discussion
6
30
500
33.3
9.01
150
CFD Modeling
Figure 4 represents an example of computed fields (i.e.,
pressure, temperature, thermal conductivity, density, velocity
and effective viscosity) for the conditions depicted in effect) is
reduced and power vaporization is very likely more important
due to a better heat transfer to particles.
a)
Table 2.
The plasma jet structure is highly affected by the low
surrounding pressure and presents a succession of
compression and expansion areas. Expansion areas correspond
to thermodynamic properties decreasing except for velocity
field which suddenly increases and vice-versa. According to
Figure 4, axial gradients strongly decreased after 40 cm from
the nozzle exit indicating the full expansion of the flow.
Indeed, a spray distance equal to or longer from 40 cm can be
considered to deposit coatings.
b)
c)
Optical Emission Spectroscopy (OES)

In Figure 5 and Figure 6, OES results for Ar-He-H2 and Ar-H2
plasmas are considered. Firstly, optical emissions are mostly
intense in the compression areas. Then, they decrease
suddenly in the expansion areas. They change as the plasma
thermodynamic property structure. These compression areas
exhibit high pressure, temperature and thermal conductivity
fields. This can explain intensity increasing. Secondly, optical
emissions intensities are more important in the Ar-H2 plasma
case despite the Ar-He-H2 plasma mass enthalpy is higher
(31.4 J.kg-1 vs. 15.0 J.kg-1 for Ar-H2 plasma). This could be
very likely due to the formation of an insulating vapor layer
around the particle under highly energetic load that prevents a
homogeneous thermal conduction on the whole particle
volume (Ref 22). Besides, the pressure increase affects the
plasma structure, as shown in Figure 6, 7 and 8. The
surrounding pressure, which was varied from 100 to 500 Pa
and 5000 Pa, decreases the pressure gradient between the
plasma flow and the surrounding atmosphere. Consequently,
compression and expansion areas are less emphasized. Also,
the maximum intensity is increased in the same way as the
d)
e)
Figure 4: Computed fields of: (a) pressure (Pa), (b)

temperature (K), (c) thermal conductivity (W.m-1.K-1), (d)
density (kg.m-3), (e) velocity (m.s-1).
Effect of the Powder Size
30000
Three size distributions were tested. Substrates were cooled

and the surface temperature was controlled to about 400 K at a
spray distance of 800 mm. As shown in Figure 99, the
particles size decrease leads to a decrease in the coating
surface roughness: 12 m, 11 m and 7 m for particle size
ranges of 25-65 m, 18-63 m and 9-25 m, respectively.
Intensity (u.a)
3000
20000
15000
10000
5000
0
0
2500
Intensity (u.a)
394.6 nm (Al I)
396.2 nm (Al I)
25000
100
200
300
400
Distance from the torch nozzel (mm)
2000
1500
Figure 8: Optical emissions of aluminum along the Ar-H2

plasma jet for a chamber pressure of 5000 Pa.
1000
500
0
0
100
200
300
400
500
600
700
800
Intensity (u.a)
16000
14000
12000
10000
8000
6000
4000
2000
0
100 m
100 m
396.2 nm (Al I)
394.6 nm (Al I)
c)
100 m
0
100
200
300
400
500
600
700
Figure 9: SEM surface coatings morphologies for (a) 25-65

m, (b) 18-63 m and (c) 9-28 m feedstock size distributions.
800

The average maximum peak-to-valley ratio also tends to

decrease accordingly (120 m, 115m and 70 m,
respectively). Surface morphology is indeed finer for smaller
size distributions. This suggests clearly that the vaporization
of aluminum particles is higher when the initial powder is
finer and consequently the resulting coating microstructure is
more based on condensed vapors rather than lamellae. These
microstructural evolutions lead to an increase in the average
coating microhardness (see Fig. 10).
12000
Intensity (u.a)
b)
a)
Figure 5 : Optical emissions of aluminum along the Ar-He-H2

394.6 nm (Al I)
396.2 nm (Al I)
10000
8000
6000
4000
2000
Effect of the Substrate Temperature and Work Distance

In order to highlight the effect of the deposition temperature
on the coating microstructure, experiments were made without
and with cooling, and substrate temperatures were measured
by a type K thermocouple. Without substrate cooling,
deposition average temperature reached 950 K leading to the
partial remelting of the coating as seen in Fig. 11c. This is
evidenced in Figs. 11a and b which depict a diffusion interface
zone, near the coating and substrate interface (identified by the
red dotted line), which is made of Cr, Fe, Mn, Ni, and Cu (see
the energy disperse spectra (EDS) in Fig. 12). With substrate
cooling (substrate temperature ~400 K), the coating structure
is much more homogeneous and finer than that without
substrate cooling, suggesting a more homogeneous
condensation of metallic vapors (see Fig. 12). Due to the
0
0
100 200 300 400 500 600 700 800 900

decrease in deposition temperature (from 950 K to 400 K),

residual stress in the coatings is more important leading to
modified coating hardnesses varying from 50 HV0.025g.f to 75
HV0.025g.f when the temperature changes from 950 K to 400 K.
Figure 133c) and d) show the effect of the spray distance on
surface morphology while surface substrate temperature was
regulated to 400 K. Coating characteristics are summarized in
Table 3. The coatings manufactured at a 650 mm spray
distance exhibit a surface roughness of 11 m and an average
maximum peak-to-valley ratio of 119 m. This can be
explained by the presence of unmelted particles at the surface,
which is reduced for an 800 mm spray distance.
110
100
90
80
70
60
50
40
30
20
10
0
18m
40m
45m
d50 (m)
Figure 12: EDS analysis of the interfacial zone shown in

Figure 11a.
Microhardness(HV0.025)
Moreover, the lower microhardness is also a consequence of

the coating void content which was found to be higher than
10%. Figure 144a shows that the coating sprayed at a 650 mm
from the nozzle exit exhibits typical structural features of APS
coatings such as unmelted particles, voids and delamination.
At higher spray distance, such typical features are not
identified anymore and the coating is denser and harder (all
together, a clear indication that the deposition mechanisms are
different).
a)
b)
c)
d)
Figure 10: Coating average microhardness evolution as a

function of the feedstock size distribution at d50.
a)
b)
100 m
50 m
c)
Figure 13: Surface morphology SEM observations for (a) no
cooled coating (950 K), (b) cooled sample (400 K), (c) spray
distance of 650 mm, and (d) spray distance of 800 mm.
Table 3: Coatings characteristics.
50 m
Figure 11: SEM observations of (a) non-cooled sample, (b)

chemically etched coating (c) surface morphology of the
coating.
Characteristics
Surface roughness (m)
Average maximum peak-to-valley ratio
(m)
Microhardness (HV0.025g.f)
Void content estimation (%)
Spray distance
(mm)
650
800
11
8
119
78
78
> 10
90
<1
a)
3.
b)
4.
Figure 14: SEM coating observations for (a) spray distance of

650 mm and (b) spray distance of 800 mm.
Conclusion
5.
Very low pressure plasma spray was applied to prepare

aluminum coatings. CFD modeling and OES measurements
were performed to highlight the heterogeneous plasma jet
structure and to study aluminum optical emission evolution
along the jet axis. It has been shown that because of the very
low surrounding pressure, the plasma jet exhibits succession
of compression and expansion areas. Aluminum optical
emissions are more intensive in compression areas, where
temperature, pressure, thermal conductivity and density fields
are the higher. The effect of powder size distribution on the
coating microstructure was investigated. It brings out that the
coating surface roughness is reduced as the particles are finer,
suggesting a better powder vaporization. Moreover,
microhardness is increased as size distribution is reduced.
Substrate temperature and spray distance have been studied
also. For non-cooled samples, EDS analysis underlines a
diffusion interfacial area. Cooling and longer spray distance
allow getting dense coating with lower surface roughness and
microhardness closed to the theoretical value. Fine size
distribution, sample cooling and long spray distance were
shown as factors affecting significantly the coating
microstructure and microhardness.
6.
7.
8.
9.
Acknowledgements
The authors gratefully thank S. Lamy, A. Lamraoui and O.
Ribet (IRTES-LERMPS) for their contributions to the coating
characterizations, L. Dembinski (IRTES-LERMPS) for the
manufacturing of the aluminum feedstock.
10.
The authors also gratefully thank the IRTES-LERMPS / CEA

joint research laboratory on advanced surface engineering for
its financial support.
11.
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All rights reserved
Comparative Investigation of Standard WC-Co and a

New WC-FeCrAl Feedstock Powder
B. Hussong, J. Pfeiffer, B. Lehmert, L. Wojarski, W. Tillmann*
Institute of Materials Engineering, Dortmund, Germany
*E-mail: wolfgang.tillmann@udo.edu
Conference 2012 in Houston, Texas (Ref. 1). Additional XRD

measurements have been conducted as well to study phase
transformations, which have been presumed to take place
during the spraying process.
Abstract
The presented work compares a new WC-FeCrAl-matrix
feedstock powder with a standard WC-Co powder. The
investigation covers the powder analysis, spray jet properties,
splat flattening and coating properties, as well as, XRD
analyses of the feedstock powders and as sprayed coatings. As
the formation of single splats sets up the foundation for any
thermal spray coating, this step was chosen as the major
subject of investigation in this paper. A new method to create
a footprint of splats from a spray jet with an extremely short
exposure time was used to perform these splat examinations
(Ref. 1). It was found, that the interdependencies between
spray parameters and coating properties are generally the same
for both materials. Differences occurred in the phase stability
of the materials during the spraying process. In XRD
measurements the standard WC-Co material did not exhibit
any recognizable phase transformations of the WC, while a
significant formation of W2C and oxidation of the matrix was
observed for the WC-FeCrAl powder.
Experimental Procedure
Feedstock Powder
Two agglomerated and sintered cermet powders were used for
the experiments. The first one was a new WC-FeCrAl material
from H.C. Starck (Ref. 6). The second feedstock material was
a standard WC-Co powder of the type WOKA 3102 from
Sulzer Metco. The chemical compositions of the powders are
given in Tab. 1. The particle size distribution was determined
by laser scattering and sieve analysis with a Microtrack S3500
for both materials (Fig. 1). The carbide size was measured to
be between 0.5 and 4 m for the standard WC-Co and
between 0.2 and 2 m for the WC-FeCrAl by means of digital
picture analysis on SEM pictures at backscatter electron (BE)
mode. The inner porosity was measured using digital picture
analysis on SEM pictures at secondary electron (SE) mode
(Fig. 2). The average inner porosity of the powder particles
was approx. 26 vol.-% for both powders.
Introduction
WC-Co powders were introduced as a wear protection
material for thermal spray applications in the 1980s (Ref. 2).
Since Co proved to be hazardous, applications in the food
industry were inaccessible for this coating system. Thus, WCbased cermets with alternative matrix compositions have been
developed to avoid the toxic effect of Co. Fe-based matrix
materials are one promising group of materials, which is under
recent development (Ref. 3-5). The two powders compared
here are a standard WC-Co 88/12 and a new WC-FeCrAl
85/10/4/1 material. The aim of this investigation is to discover
differences in the processability of the new alternative powder
material compared to standard WC-Co feedstock powder.
Therefore, extensive investigations on the processing
parameters and the resulting properties of the microstructures
and mechanical properties were necessary and are presented
here. These cover the powder analysis, spray jet properties,
coating properties and splat flattening. One focal point is the
formation of single splats. They form the foundation of any
thermal spray coating. The results are used to help
understanding the correlation between the particle in-flight
properties and the coating morphology. The splat capturing
device is a new development of the TU-Dortmund and has
been first presented at the International Thermal Spraying
Figure 1: Particle size distribution of powder materials
recognized by the VisiSize software. To ensure a full

formation of the flame, a stabilization time of 1 min was
induced before starting each sequence. A detailed description
of the beam shutter and the calculation of the exposure time
can be drawn from Ref. 1.
Table 1: Powder chemical compositions [wt.-%]

Powder
WC-Co
WC-FeCrAl
W
82.3
79.2
C
5.5
5,3
Co
12.1
Fe
0.1
Cr
0
Al
0
9.8
4,2
1,5
Table 2: Encoding of parameters for the design of experiments
Figure 2: SEM pictures of powder cross sections on WC-Co

powder at BE mode (left) and WC-FeCrAl powder at SE mode
(right)
WC-Co
Oxygen/fuel ratio ()
Kerosene [l/h]
Stand-off distance [mm]
Powder feed rate [g/min]
-2
1.0
15
200
8.5
-1
1.075
17,5
225
32
0
1.15
20
250
55.5
1
1.225
22,5
275
79
2
1.3
25
300
102.5
WC-FeCrAl
Oxygen/fuel ratio ()
Kerosene [l/h]
Stand-off distance [mm]
Powder feed rate [g/min]
-2
0.9
15
250
8.5
-1
1,0
16.75
300
32
0
1,1
18.5
350
55.5
1
1,2
20.25
400
79
2
1,3
22
450
102.5
Particle in-Flight Measurement

A Tecnar Accuraspray g3 analyzing system was employed for
particle velocity and temperature measurements. The particle
sizes and shapes were recorded in-flight by a particle shape
imaging system (VisiSizer N60) from Oxford Lasers. The
measuring time in each run was marked by the VisiSizer
system so that at least 300 particles were counted.
Thermal Spray Process

All experiments were conducted using a Wokajet 400 HVOF
system from Sulzer Metco with a TWIN 120AH powder
supply. The spray parameters kerosene flow, fuel/oxygen
ratio, stand-off distance and powder feed-rate were varied
according to a statistic experimental plan (Central Composite
Design). The corresponding encoding list of parameter
settings for both materials is given in Tab. 2. The powder
feeder gas level was kept constant at 4.5 bar. During
preliminary experiments this level was found ideal for circular
footprints. These preliminary experiments also showed that
the parameter field, which was first chosen for the WC-Co
standard powder, could not be adapted to the WC-FeCrAl
powder. The minimum stand-off distance of 200 mm had to be
increased to at least 250 mm to avoid a melting of the beam
shutter masks and an overheating of the sample tubes. The
range of the oxygen/fuel ratio was expanded to a minimum
value of 0.9 in order to slightly cool the flame down, while the
maximum kerosene value was lowered to 22 l/h. The
experimental setup included the HVOF spraying system, two
particle in-flight measurement systems, a turning lathe, and
the beam shutter device. The coating and measuring sequence
of each run started with the coating of 50 mm diameter steel
tubes of 100mm length on the turning lathe. After completing
the coating, the running spray gun was moved in front of the
beam shutter (Ref. 1) and a footprint of splats was taken.
These footprints were sprayed on polished flat samples of
90mm x 60mm. Each footprint-specimen was exposed to the
spray jet for 9 ms, using the beam shutter device. The
exposure time was calculated assuming a free fall of the slitmask with a 3 mm wide slit. All steel tubes and samples for
splat collection were preheated at 100C. In a final step the
spray gun was moved into the measuring position in front of
an Accuraspray g3 and VisiSizer N60 until 300 particles were
Coating and Splat Sample Analysis

The coating characterization was carried out by
metallographic means, using cross sections. The investigative
focus was set on the coating hardness and porosity. The
analyses of phase contents and phase transformations were
conducted at the particle accelerator DELTA at the TUDortmund, using synchrotron radiation. Splat samples were
analyzed using a scanning electron microscope (SEM) with a
secondary and backscatter electron detector.
From Spray Parameters to Particle in-Flight Properties
Starting with the correlations between the spray parameters
and particle in-flight properties, it can be expected that the
general interdependencies will be similar for both powders.
However, it has already been proven in preliminary
experiments that the parameter fields for the stand-off
distance, kerosene flow, and oxygen/fuel-ratio had to be
altered for the WC-FeCrAl material to avoid sample and mask
overheating and even melting, which did not occur during
spraying of WC-Co powder. Thus, a difference in the particle
temperature can be expected.
Fig. 3a and b show the standardized pareto significance
(Ref. 7) of the spray parameters linear and quadratic effects
on the particle temperature as well as the 2-way interactions
between spray parameters.
For the WC-Co standard powder the influence of the kerosene

level is the most striking and the stand-off distance the second
most important factor. All other effects do not exceed the level
of significance. For the WC-FeCrAl powder, the importance
of the stand-off distance is even a little higher than the
kerosene level. Further, the oxygen/fuel-ratio () turns out to
be another significant factor.
One reason for this difference could be the shift of the range
chosen for the stand-off distance to significantly higher values
and the narrowing of the kerosene range. Although the results
are difficult to compare due to the differences in the fields of
parameter settings, these results represent the effects one will
find when using reasonable parameter settings for each
material. Thus, the particle temperature of the WC-FeCrAl
powder can be controlled almost equally by altering the
kerosene level and stand-off distance, which might be of
practical use for coatings on temperature sensitive substrates.
Looking at the response surface plots of Fig. 4, it can be seen
that the assumption, drawn from the preliminary experiments
with the WC-FeCrAl powder, are confirmed.
The overall temperatures, which were reached during the
spraying of the WC-FeCrAl material, are significantly higher
than those for the WC-Co material, although the minimum
stand-off distance for the WC-FeCrAl was set 50 mm higher
and the maximum kerosene level was set at 22 l/h instead of
25 l/h.
As the thermal conductivity and heat capacity of Fe-alloys
with analog compositions, like the FeCrAl matrix material, are
similar to Co (Ref. 8), the explanation for this difference in
particle temperatures cannot be related to a difference in the
physical properties of the matrix. Instead, it can be assumed
that phase reactions inside the powder particles release a
specific amount of thermal energy, which causes a
temperature increase.
Figure 3: Pareto chart of standardized effects of the spray

parameters on WC-Co particle temperatures (a) and WCFeCrAl particle temperatures (b)
Figure 4: Response surface plots for particle temperature of WC-Co (a) and WC-FeCrAl material (b) as a function of kerosene level
and stand-off distance
10
This assumption is supported by XRD measurements,

showing, that W2C and delta Fe2O3 are generated during the
spraying process with WC-FeCrAl, but not with the WC-Co
standard powder. Calculations of the free Gibbs energy of the
potentially generated phase reactions prove that these phases
are likely to form at temperatures expected during HVOF
thermal spraying process (Fig. 5). The reactions which have
been calculated here are all exothermal (Ref. 9, 10).
apply here because the particle sizes in his experiment ranged

from 15 to 45 m for both powders.
For the particle velocities, no significant difference can be
observed (Fig. 6). The pareto charts reveal kerosene, the
oxygen/fuel ratio and the stand-off distance as significant
influential factors. The steeper slope on the axis of the standoff distance for the WC-FeCrAl material in Fig. 6 is a result of
the widened range of distances during the experiments with
the WC-FeCrAl powder. The directions of the influences and
the range of velocities are as expected for both materials,
taking into consideration the slight differences in the
parameter settings for the WC-FeCrAl material.
Particle in-Flight Properties and Splat Morphology
For the correlation between particle in-flight properties and
splat morphologies it is difficult to plot response surfaces, as
the input data (particle temperature and velocity) are not
distributed according to a central composite design. In this
case we analyze the influence of particle temperatures and
velocities using 2D plots in Fig. 7. It displays a general
difference between the importance of the particle temperature
on the splat formation for WC-Co standard powder and WCFeCrAl powder. The wide range of splat morphologies in the
temperature-graph for WC-Co indicates that the temperature
influence is less significant than the influence of the particle
velocity. For the WC-FeCrAl powder, the curve progression
for the splat morphologies is almost the same in both graphs.
It can be concluded that the splat morphology in the case of
the WC-FeCrAl powder is more dependent on the particle
temperature than in the case of the WC-Co standard powder.
In fact, the curves also appear to have a turning point at a
critical velocity/temperature of about 780m/s / 1650C, where
the number of mountain-like splats drops extremely, while the
number of pancake-like splats increases significantly. This
tendency cannot be seen in the WC-Co graphs.
3Fe+2O2 Fe3O4
4Fe3O4+O2 6Fe2O3
2WC+2O2 W2C+2CO2
2W2C+O2 2W+2CO
Figure 5: Calculations on the free Gibbs energy for possible

oxidation and decarburization reactions.
As conditions inside the spray jet do not represent equilibrium
conditions, which have to be assumed for the calculation, this
is still not a reliable proof that these phase reactions are
responsible for the temperature increase.
However, Baumann (Ref. 11) also recorded significantly
higher particle temperatures for WC-Co powders with WC
grains of 0.1m compared to WC grains of 2.4 m. He
explains this difference by a more intensive heat transfer from
the combustion gas to the powder particles, which does not
Figure 6: Particle velocities for WC-Co (a) and WC-FeCrAl powder in dependency of Stand-off distance and kerosene level.
11
Figure 7: Plot of the relative numbers of mountain-like and pancake-like splats plotted against corresponding particle velocities
(upper graphs) and particle temperatures (lower graphs) for the WC-Co standard powder (left) and WC-FeCrAl (right).
Splat Formation and Coating Properties
The selected properties of interest are primarily the coating
hardness and the coating porosity. Fig. 8 shows the
corresponding curves in dependency to the relative number of
pancake-like splats. The tendency for both materials shows
that an increasing percentage of pancake-like splats correlates
with an increasing coating hardness and decreasing coating
porosity, although the porosity appears to be generally much
lower for the WC-FeCrAl powder. It can be seen that the
maximum of 1420 HV 0.3 for the coating hardness of the WCFeCrAl material is a little higher than that of the WC-Co
standard powder. Still, the difference is negligible with regard
to the average standard deviations of hardness measurements,
which are about the same dimension.
Looking at the coating porosities, it is obvious that within the

range of parameters chosen for the experiments, the minimum
porosities of the WC-FeCrAl powder are by far lower than
those of the WC-Co standard powder. While the most
unfavorable parameter settings for the WC-Co powder
generate porous coatings with a pore volume of 11%, the
maximum pore volume for the WC-FeCrAl is only 4.3%.
Even though the tendency of the curve in the case of the WCFeCrAl coating is generally the same as for the WC-Co, the
scattering range in Fig. 8d reveals a less rigid correlation
between the porosity and relative number of pancake-like
splats.
12
Figure 8: Correlation graphs of coating hardness and porosity versus relative number of pancake-like splats on the substrate
Spray Parameters and Phase Reactions
In the previous graphs the most significant correlations have
been shown in each step, from the spray parameters to the
particle properties, to the splat morphologies and coating
morphologies. Yet, critical phase transformations inside the
powder material and the coating can be further relevant factors
for the evaluation of the coating quality. The generation of
brittle intermetallic phases is just one possible undesired
reaction that could take place during the thermal spray process
with an HVOF spray gun. As already mentioned during the
interpretation of the particle temperatures in the spray jet,
XRD investigations were conducted, using the high-intensity
synchrotron radiation of the electron accelerator DELTA at
the TU-Dortmund.
Although Guilemany et al. propose that spraying powders with

fine carbide grain sizes create less porous coatings than those
with coarser grain size (Ref. 12), other scientists do not report
such an improvement of porosity (Ref. 11, 13, 14). Still, Fig. 8
clearly displays a porosity decreasing effect during the present
experiments.
One possible explanation for this effect is the decrease of the
viscosity of particle containing fluids with a decrease of the
particle size (Ref. 15, 16). This is a well-known effect in fluid
dynamics. Transferring this effect to the powder particles with
a molten matrix and solid carbides, the smaller tungsten
carbides in the WC-FeCrAl particles might lead to the effect
that the material can float into open pores or fill irregularities
on the surface more easily than in the case of the WC-Co
powder.
13
For the WC-Co standard powder, no significant changes

between the diffractograms of the feedstock powder and assprayed coatings were found. In contrast to this, relevant
changes were visible in the diffractograms of the WC-FeCrAl
material in the range of 35 to 50 2. Fig. 9 shows the XRDgraph of the WC-FeCrAl feedstock-powder (grey line) and a
graph taken from an as sprayed coating (black line). It can be
seen that a clear W2C-Peak and significant amounts of DeltaFe2O3 were detected. Instead of a quantitative phase
measurement, which is quite complex, a qualitative
comparison of the phase generation was performed. The
highest WC-peak in every graph was set as 100% intensity
and the whole graph stretched to fit into the resulting scale.
The heights of the peaks for W2C and Delta-Fe2O3 were
measured and compared according to the initial central
composite design. The result is a response surface for each
phase, showing the importance of the two most influencing
spray parameters on the phase generation (Fig. 10)
The response surfaces were fitted as quadratic functions. It can
be seen that the surfaces correlate very well with all
corresponding data points. The graphs indicate that increasing
kerosene levels are related to higher W2C and Delta-Fe2O3peaks in the XRD analyses.
Fig. 10a shows that the W2C peak is also dependent on the
stand-off distance. A shorter distance is related to lower W2C
peaks. This indicates that the formation of W2C might take
place during the particle flight time. The particles cool down
rapidly at the surface, so that the W2C production stops. The
Delta-Fe2O3 peaks show an opposite behavior to the stand-off
distance. Shorter stand-off distances are related to higher
peaks. Thus, it can be assumed that the Delta-Fe2O3 formation
might take place after the deposition of the particles on the
substrate surface. Fig. 5 displays the free Gibbs energy
(Ref. 9-10) calculated for Fe2O3, Fe3O4 and W2C. The slope of
the Fe2O3 curve reveals that most of the energy could be
released due to the formation of Fe2O3. Still, the Fe3O4 phase
is needed as a preliminary oxidation phase before Fe2O3 can
exist. Interestingly, the curves of Fe3O4 and W2C have a point
of intersection, indicating that above 1750 K the WC W2C
reaction is preferred. The lower the temperature, the more
likely is the generation of Fe3O4, which is needed for Fe2O3
formation. This supports the assumption that the WC W2C
reaction is more likely to happen at high temperatures, while
Figure 9: XRD-graphs of the WC-FeCrAl feedstock powder

(grey) and as-sprayed coating (black)
Figure 10: Response surfaces for W2C and Delta Fe2O3-peaks as quadratic fits versus stand-off distance and kerosene level
14
the Fe Fe3O4 reaction is likely to take place at lower

temperatures. However, these conclusions need further
investigations and confirmation by experiments and phase
calculations.
4.
5.
Summary
In this study a new WC-FeCrAl and a common WC-Co
standard HVOF feedstock powders were compared. It was
found that the range of spray parameters for the new WCFeCrAl material had to be altered to slightly higher stand-off
distances and slightly lower kerosene levels to obtain
reasonable coating results. A significantly higher particle
temperature for the WC-FeCrAl powder was recorded during
spraying, which is supposed to be an effect of phase reactions
during the particle dwell-time in the spray jet. XRD graphs
revealed W2C and Delta-Fe2O3 formations. Calculations of the
free Gibbs energy propose that energy is being released during
the formation of these phases. Comparable correlations
between particle in-flight measurements and splat
morphologies were found for both feedstock powders.
Resulting coating hardness values ranged between 1100 to
1400 HV 0.3 for both powders, whereas, the porosity of the
coating reached significantly lower values for the WC-FeCrAl
powder than for the WC-Co standard powder within the
chosen field of parameters. This effect was attributed to the
smaller carbide grain size of the new powder, which might
promote a lower viscosity of the molten particles at impact. A
response surface analysis of the XRD measurements indicates
that the W2C formation occurs during the particle flight time
in the spray jet, while the Delta-Fe2O3 formation is supposed
to take place on the surface of the substrate after the particle
deposition.
6.
7.
8.
9.
10.
11.
12.
Acknowledgement
The authors gratefully acknowledge the financial support of
the DFG (German Science Foundation) within the
collaborative research center SFB 823 B1
13.
14.
References
1.
2.
3.
W. Tillmann, B. Hussong, T. Priggemeier, et al.,

Influence of Parameter Variations on WC-Co Splat
Formation in an HVOF Process Using a New Beam
Cutter Device, Conference Proceedings of ITSC 2012,
ASM International, 2012, p 12-21
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Powders for HVOF Spraying with Improved Corrosion
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(Physical Properties of Metals and Alloys), B. G.
Livschitz, 1988, VEB-Verlag, Leipzig, Germany (in
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All rights reserved
Deposition and Oxidation of Oxide-Dispersed CoNiCrAlY Bondcoats

M. Okada*
Central Research Institute of Electric Power Industry, Yokosuka, Japan
*E-mail: mitutosi@criepi.denken.or.jp
R. Vaen, M. Karger, D. Sebold, D. E. Mack, M.O. Jarligo
Forschungszentrum Jlich GmbH, Jlich, Germany
F. Bozza
University of Modena and Reggio Emilia, Modena,Italy
power plant, TBCs play increasingly important role. However,

topcoat can undergo delamination owing to thermal cycling
caused by the startup and shutdown of the power plant and
because of the microstructural change such as the formation of
thermally grown oxide (TGO). The development of more
durable TBCs should help prevent these issues.
Abstract
Deposition of two types of oxide-dispersed bond coats and
their oxidation behavior were examined. CoNiCrAlY powder
and nano-size -alumina powder were milled by a highenergy-attrition ball-mill, resulting in an oxide-dispersed
powder with a mixed structure of metal and alumina in each
particle. The oxide-dispersed bondcoat powder was deposited
under the deposition condition of a fine CoNiCrAlY powder
by HVOF. Pores, however, were observed in the coating since
the dispersed alumina was deposited without a high degree of
melting. Isothermal oxidation tests were carried out for the
bondcoat specimens at a temperature of 1373 K up to 1000
hours in air. As a result, oxidation proceeded not only at the
surface but also inside the coating, since oxygen penetrated
through pores created by the dispersed alumina. Another
deposition was performed using higher power levels. This
produced a bond coat without pores. A commercially available
oxide-dispersed CoNiCrAlY powder was also deposited by
HVOF and VPS, and isothermal oxidation tests were
performed in air. The HVOF bond coat exhibited the thinnest
thermally grown oxide than those of the VPS bond coat and
conventional metallic bond coat. The internal oxidation,
however, proceeded in the HVOF-sprayed coating since the
powder particles due to particle cohesion issues. Furnace
cycling tests were conducted using the specimens with an
additional ceramic thermal barrier coating. The specimen with
the bond coat sprayed by VPS using commercial oxidedispersed powder exhibited almost same number of cycles to
delamination compared with the specimen with the
conventional metal bond coat.
There have been several attempts to improve the durability of

bondcoats by dispersing oxides in its inside. The properties of
oxide-dispersed (OD) bondcoats, including their thermal
cycling (Ref 1, 2), oxidation and corrosion (Ref 3, 4), and
wear resistances (Ref 5-7) have been examined. Since these
properties are significantly affected by the processes used to
manufacture the OD powders and by the spraying conditions,
there is some room for improvement. In this study, bondcoats
are deposited using two kinds of OD powders. One is prepared
using high-energy-attrition ball milling, and the other is a
powder available commercially. The properties of these OD
bondcoats, such as their oxidation and thermal cycling, are
examined.
Preparation of Oxide-Dispersed Powders and Bondcoats
The specimen material was IN-738, and specimen shape was
30 mm of diameter and 3 mm of thickness. To deposit the OD
bondcoats, two OD powders were used. The first powder,
which was prepared using CoNiCrAlY powder and alumina
powder by means of a high-energy-attrition ball-mill
(Simoloyer CM01, Zoz GmbH, Wenden, Germany), was
denoted as Powder HB. The other one, which was available
commercially, was denoted as Powder CA.
Introduction
The chemical composition of the CoNiCrAlY powder (Sulzer
Metco, Wohlen, Switzerland) used to prepare Powder HB was
Co-32Ni-21Cr-8Al-0.5Y (wt.%). Figure 1a shows the
morphologies of the particles of this powder. The oxide
powder was -alumina (io-li-tec, Heilbronn, Germany), and
its nominal particle size is 80 nm, as shown in Fig. 1b. The
CoNiCrAlY and alumina powders were placed in the highenergy-attrition ball mill in an 80/20 ratio and the mixture was
milled at the maximum rotational speed of 1600 rpm for 1 h.
Powder HB was deposited by high-velocity oxy-fuel (HVOF)
Thermal barrier coating (TBC) is applied as well as internal

cooling to protect hot-gas-path parts such as blades, vanes, and
combustors of gas turbines subjected to high temperatures. A
TBC typically consists of a metallic bondcoat deposited on a
nickel- or cobalt-based superalloy and a ceramic topcoat
having low thermal conductivity deposited on top. MCrAlY
(M is nickel, cobalt, or a combination of the two) is often used
as the bondcoat. Since the turbine inlet temperature is
increasing for higher thermal efficiency of a combined-cycle
16
20m
50m
50m
(b) -alumina powder
(a) CoNiCrAlY powder
Figure 2: Morphology of the particles of Powder CA.
Figure 1: Morphologies of starting powders for oxidedispersed powder manufactured by high-energy-attrition ball
milling.
deposited by HVOF or by vacuum plasma spraying (VPS)

using F4 gun (Sulzer Metco) and the deposited bondcoats are
denoted as Bondcoat CA-V and Bondcoat CA-H, respectively.
The spraying conditions for VPS and HVOF are indicated in
Tables 1 and 2, respectively. For comparison, a reference
specimen was coated using a conventional CoNiCrAlY
powder (Sulzer Metco), which was deposited by VPS (the
deposited bondcoat was denoted as Standard Bondcoat).
spraying using DJ gun (Sulzer Metco) under the conditions

listed in Table 1. The spraying conditions 1 and 2 are
optimized for a metallic CoNiCrAlY powder and an alumina
powder, respectively. It is considered that the temperature of
the spraying flame under the spraying condition 2 was higher
than under the spraying condition 1. The bondcoats obtained
under the conditions 1 and 2 are denoted as Bondcoat HB-1
and Bondcoat HB-2, respectively.
Table 2: VPS condition.
Table 1: HVOF spraying condition.

Condition 1
HB-1
Condition 2
HB-2
CA-H
Nitrogen (nlpm)
450
300
460
Oxygen (nlpm)
155
395
230
-
Methane (nlpm)
245
Hydrogen (nlpm)
630
690
200
250
200
500
500
300
Spraying distance
(mm)
Robot velocity
(mm/s)
Specimen
CA-V
Current
750
Process pressure
(mbar)
60
Argon (nlpm)
50
Hydrogen (nlpm)
Spraying distance
(mm)
Robot velocity
(mm/s)
275
440
After the deposition of the bondcoats, the coated specimens

were heat treated in vacuum (<10-2 Pa) at 1120C for 2 h and
then at 845C for 24 h.
Figure 2 shows the morphologies of the particles of Powder

CA (Perpetual Technologies, Inc, Canmore, Canada). As
shown in the figure, no oxide was observed within the
particles even when high-resolution scanning electron
microscopy (SEM) (Ultra55, Carl Zeiss NTS GmbH,
Oberkochen, Germany) was used to image the particles.
However, the results of infrared (IR) spectroscopy revealed
that this powder contained about 0.131% oxygen, which is
about 3 to 4 times higher than that present in conventional
CoNiCrAlY powders. The bondcoats of Powder CA were
To perform furnace cycle tests, 8wt%Y2O3-ZrO2 powder

(Sulzer Metco) was deposited on the surfaces of Bondcoat
HB-1, Bondcoat CA-V, and Standard Bondcoat by air plasma
spraying (APS) using TriplexPro gun (Sulzer Metco), with the
thickness of the topcoat being about 400 m. These specimens
were, labeled as TBC HB-1, TBC CA-V and Standard TBC,
respectively.
17
20m
50m
Figure 4: Morphology of cross section of Bondcoat HB-1.
Figure 3: Morphology of the particles of Powder HB.
The test specimens were cut at the center before or after the
tests, and their cross sections were polished for microstructural
observations, which were made using optical microscopy and
scanning electron microscopy (SEM).
Isothermal Oxidation Test and Furnace Cycle Test
Isothermal oxidation tests were performed using the
Bondcoats HB-1, CA-V, CA-H and Standard Bondcoat in an
electric furnace. The tests were performed in air at the
temperature of 1373 K with the test time of 100 h, 500 h and
1000 h.
20m
Figure 5: Morphology of cross section of Bondcoat HB-2.
In the furnace cycle tests, TBC specimens were subjected to

thermal cycling by moving the specimen holder in and out of
the furnace repeatedly and automatically. First, the specimens
were heated to 1373 K for 2 h inside the furnace. Then, the
specimens were moved out of the furnace for 20 min to cool
them in room temperature. The cooled specimens were moved
back into the furnace again and the process repeated. The
specimens were inspected visually after every 10 cycles, and
the number of cycles to delamination was decided when the
topcoat delamination was observed. Two specimens for each
kind of the bondcoats were tested.
the bondcoat as indicated by the arrows in the figure. This is

because the OD powder was deposited without the alumina
being properly melted. Bondcoat HB-2 also exhibits a layered
microstructure, but no pores are found within the coating as
shown in Fig. 5. This bondcoat is dense because the higher
flame temperature could melt the alumina during the spraying
process. However, a gray-colored oxide is observed in
Bondcoat HB-2 as indicated by arrows in the figure and is
assumed a spinel. The oxide was formed because the metal
part of the bondcoat was oxidized during the spraying process.
In order to optimize the spraying conditions further, it is
necessary to melt the alumina adequately while ensuring that
the metal part does not undergo oxidation.

Microstructure of OD Powder and Bondcoat
Figure 3 shows the morphology of the particles of Powder HB,
obtained by SEM, after being subjected to high-energy ball
milling. The particles are inhomogeneous in shape, and the
images of the microstructures show bright and dark parts,
which correspond to the metallic and alumina parts,
respectively.
Figures 6a, b, and c indicate the microstructural morphologies

of Bondcoat CA-V, Bondcoat CA-H and Standard Bondcoat,
respectively. The microstructures of all the bondcoats consists
of - and phases. The oxide observed in Bondcoat CA-H is
considered to be formed during the HVOF deposition,
compared with conventional CoNiCrAlY coating deposited by
HVOF. The dispersed oxide, however, cannot be found in
Bondcoat CA-V or Bondcoat CA-H, even when SEM was
used to image them.
Bondcoat HB-1 has layered microstructure comprising layers

of metal and alumina as shown in Fig. 4. In addition, the
bondcoat is not dense, and pores exist in the alumina part of
18
30m
(a) Bondcoat CA-V
30m
30m
(b) Bondcoat CA-H
(c) Standard Bondcoat
Figure 6: Morphologies of cross section of Bondcoats CA-V and CA-H and Standard Bondcoat before test.
30m
(a) Before test
30m
(b) 100h
30m
(c) 500h
Figure 7: Morphologies of cross section of Bondcoat HB-1 after isothermal oxidation test at the temperature of 1373K in air.
Isothermal Oxidation Test
Figure 7 indicates the microstructure of Bondcoat HB-1 before
and after the isothermal oxidation test. A gray-colored oxide is
formed after 100 h, and it grows within the coating. X-ray
diffraction analysis of the surface of the bondcoat after the test
shows the presence of spinel oxides, such as the mixed oxide
of Co, Ni, and Cr, and of alumina. The mixed oxide is formed
by the oxidation of the metal part of the bondcoat since
oxygen can penetrate into the coating through the pores
described in the previous section. Thus, in order to prevent the
internal oxidation of the metal part, it is necessary to spray a
dense coating of the TBC using higher-temperature flames.
conditions involving higher-temperature flames should help

prevent internal oxidation in the case of Bondcoat CA-H.
Magnified images of the microstructures of the specimens
near their surfaces are shown in Fig. 9. White-colored oxides
are observed in the surface oxide of Bondcoat CA-V and
Standard Bondcoat as indicated by arrows in the Figs. 9a and c.
It is known that these oxides, which are yttrium rich, are
formed in the surface oxide of MCrAlY coatings (Ref 8).
Previous reports (Ref 9-11) have suggested that these Y-rich
oxides might promote the formation of the thermally grown
oxide (TGO) since the diffusion rate of oxygen in the Y-rich
oxide or at its boundary with alumina could be comparatively
higher than that in alumina. On the other hand, the whitecolored oxides are not observed in Bondcoat CA-H. It has
been reported that a fine oxide containing Al and Y is formed
in CoNiCrAlY coatings due to oxidation during HVOF
spraying (Ref 12). In addition, the presence of excessive
oxygen in Powder CA may also lead to the formation of the
finely dispersed Y-rich oxide in the coating. Therefore,
smaller amount of yttrium is available to form the Y-rich
Figures 8a, b and c show the microstructures of Bondcoat CAV, Bondcoat CA-H and Standard Bondcoat, respectively, after
500 h of the isothermal oxidation test. Internal oxidation
occurs only in Bondcoat CA-H since the sprayed particles do
not adhere due to the insufficient melting, resulting in oxygen
penetrating into the coating. Deposition under spraying
19
(a) Bondcoat CA-V
100m
100m
100m
(b) Bondcoat CA-H
Figure 8: Morphologies of cross section of bondcoats after 500h at the temperature of 1373K in air.
30m
(a) Bondcoat CA-V
30m
30m
(b) Bondcoat CA-H
Figure 9: Magnified views of cross section of bondcoats after 500h at the temperature of 1373K in air.
oxide in TGO in Bondcoat CA-H. Figure 10 shows the
relationship between TGO thickness and the test time. The
thickness increases with the test time in all the bondcoats. No
significant difference in the thickness between Bondcoat CAV and Standard Bondcoat is found. On the other hand, the
thickness in the case of the Bondcoat CA-H specimen was half
that of the other specimens. The fine oxides dispersed within
the coating can hinder elemental diffusion. In addition, the
smaller amount of the Y-rich oxide in TGO also can reduce
the growth.
significant difference is found in the number of cycles to

delamination between TBC CA-V and Standard TBC. The
deposition of Powder CA under optimized HVOF spraying
conditions may lead to an improvement in the resistance to
thermal cycling owing to the retardation of the TGO growth.
Summary and Conclusion
Two types of OD powders were prepared and used to deposit
bond coats. The first was manufactured using high-energyattrition ball milling, and the other was procured commercially.
The coated specimens were analyzed, and the results of the
analyses are as follows.
Furnace Cycle Test

Figure 11 shows the number of cycles to delamination in
furnace cycle test. The number of cycles in the case of TBC
HB-1 is significantly smaller than those in the case of TBC
CA-V and Standard TBC. In all the specimens, the
delamination of the topcoat occurred at the boundary of the
topcoat with the bondcoat. However, some of the bondcoat
were also spalled at the boundary with the substrate in TBC
HB-1. The internal oxidation of Bondcoat HB-1, which is
described in the previous section, can increase the stress at the
interface and may promote the bondcoat delamination. No
1) OD powder was fabricated by the high-energy-attrition

ball milling of a mixture of CoNiCrAlY and an alumina
powder with nanosized particles. A dense bondcoat can be
deposited by HVOF, provided the flame temperature
during the spraying process is high enough to melt the
alumina. However, this might cause the metal part of the
bond coat to undergo oxidation. Thus, the optimized
20
Number of cycles to delamination

(cycles)
15
TGO thickness (m)
CA-H bondcoat
CA-V bondcoat
Standard CoNiCrAlY
10
200
400
600
Test time (h)
800
1000
Standard
Technol., 2009, 204, p 291-299

K. Ma, and J. M. Schleonung, Isothermal Oxidation
Behavior of Cryomilled NiCrAlY Bond Coat:
Homogeneity and Growth Rate of TGO, Surf. Coat.
Technol., 2011, 205, p 5178-5185
5. L. Zhao, J. Zwick, and E. Lugscheider, The Influence of
Milling Parameters on the Properties of the Milled
Powders and the Resultant Coatings, Surf. Coat. Technol.,
2003, 168, p 179-185
6. L. Zhao, J. Zwick, and E. Lugscheider, HVOF Spraying
of Al2O3-Dispersion-Strengthened NiCr Powder, Surf.
Coat. Technol., 2004, 182, p. 72-77
7. K. Bobzin, T. Schlfer, K. Richardt, and M. Brhl,
Development of Oxide Dispersion Strengthened
MCrAlY Coatings, J. Therm. Spray Technol., 2008,
17(5-6), p 853-857
8. A. Rabiei, and G. Evans, Failure Mechanism Associated
with the Thermally Grown Oxide in Plasma-Sprayed
Thermal Barrier Coatings, Acta Mater., 2000, 48, p
3963-3976.
9. L.Lelait, S.Alprine, and R.Mvre, Alumina Scale
Growth
at
Zirconia-MCrAlY
Interface:
A
Microstructural Study, J. Mater. Sci., 1992, 27(1), p. 512
10. J. Klwer, Factors Affecting the Oxidation Behaviour of
Thin Fe-Cr-Al Foils Part The Effect of Alloying
Elements: Overdoping, Mater. Corros., 2000, 51 (5), p
373-385
11. H. Arikawa, Y. Kojima, M. Okada, T. Yoshioka, and T.
Hisamatsu, Oxidation Behavior and Main Causes for
Accelerated Oxidation in Plasma Sprayed Thermal
Barrier Coatings, Ceram. Eng. Sci. Proc., 2006, 27(3), p
69-80
12. W. Brandl, D. Toma, J. Kger, H. J. Grabke, and G.
Matthus, The Oxidation Behaviour of HVOF ThermalSprayed MCrAlY Coatings, Surf. Coat. Technol., 1997,
94-95, p 21-26
spraying conditions would be such that the alumina is

melted sufficiently while the oxidation of the metal part is
minimized.
4.
2) The commercially available OD powders were deposited

by HVOF and VPS. Isothermal oxidation tests were
performed on the bond coated specimens. OD bond coat
deposited by HVOF exhibited smaller TGO thickness than
OD bond coat deposited by VPS and standard TBC.
However, internal oxidation occurred due to insufficient
cohesion of the spraying particles. The optimization of
HVOF spraying condition may improve the resistance to
thermal cycling due to smaller TGO growth.
Acknowledgements
The authors would like to acknowledge gratefully Mr. KarlHeinz Rauwald, Mr. Ralf Laufs and Mr. Frank Vondahlen for
the manufacture of the sprayed specimens, Mr. Mark Kappertz
for his support in metallographic preparations and Mrs.
Miriam Peterlick for X-ray diffraction analysis (all
Forschungszentrum Jlich GmbH, IEK-1).
References
2.
3.
HB-1
Figure 11: Number of cycles to delamination.
Figure 10: Relationship between TGO thickness and test time.
1.
CA-V
T. A. Taylor, and D. F. Bettridge, Development of

Alloyed and Dispersion-Strengthened MCrAlY Coatings,
Surf. Coat. Technol., 1996, 86-87, p 9-14
F. Tang, L. Ajdelsztajn, G. E. Kim, V. Provenzano, and J.
Schoerung, Effects of Variations in Coating Materials
and Process Conditions on the Thermal Cycle Properties
of NiCrAlY/YSZ Thermal Barrier Coatings, Mater. Sci.
Eng., 2006, A425, p 94-106
G. Sreedhar, MD. M. Alam, and V.S. Raja, Hot corrosion
Behavior of Plasma Sprayed YSZ/Al2O3 Dispersed
NiCrAlY Coatings on Inconel-718 Superalloy, Surf. Coat.
21


All rights reserved
Effects of Dry-Ice Blasting On Plasma-Sprayed Thermal Barrier Coatings

S.-J. Dong,* B. Song, H.-L. Liao, C. Coddet
IRTES-LERMPS, UTBM, France
*E-mail: shujuan.dong@utbm.fr
B. Hansz
HMRexpert, France
coat and the thermally insulating performance of ceramic top

coat are two important properties of TBCs.
Abstract
The quality of bond coat and the top coat of thermal barrier
coatings (TBCs) have strong influences on their lifetime at
high temperature. Especially, the oxygen content level and the
surface roughness of the bond coat have been demonstrated to
play an important role in the thermal behavior of TBCs. In this
study, dry-ice blasting was used during the preparation of
TBCs which were composed of air plasma sprayed
CoNiCrAlY bond coat and air plasma sprayed YSZ top coat.
Three sets of TBCs deposited with different treatments of dryice blasting were compared with respect to the coating
microstructure evolution, the growth behavior of thermally
grown oxide (TGO), crack propagation and thermal shock
behavior during thermal exposure. It was interesting to find
that different microstructures of bond coat and top coat were
obtained under different conditions. Moreover, the results
showed that CoNiCrAlY bond coats continue to be oxidized
during the deposition process of YSZ top coats which were
plasma-sprayed without dry-ice blasting. These three sets of
TBCs have different thermal shock lifetime. TBC with APS
dry-ice blasted bond coat and APS dry-ice blasted top coat
was the most durable and exhibited much improvement in
lifetime.
The typical failure mode of plasma-sprayed TBCs under

service conditions is fracture and delamination of YSZ top
coat near to and parallel to the irregular bond coat interface
(Ref 8-11). It is generally agreed that this tendency of the
ceramic top coat is induced by residual stresses arising from
metal-ceramic thermal expansion mismatch and growth of
thermally grown oxide layer (TGO) formed at the interface
between the bond coat and ceramic coating during high
temperature operation (Ref 3, 12-16). Apart from this factor,
bond coat plays a critical role in the reliability and lifetime of
TBCs. On one hand, the degree of oxidation and porosity of
bond coat during the preparation process of thermal spraying
directly affect the growth of TGO. This is because the
oxidation may reduce the Al content of the interior of particles,
while the oxide film of the particle surface as a diffusion
barrier can prevent Al diffusion from splats to the surface of
bond coat (Ref 17), finally leading to the oxidation on the
coating surface and circulating the depletion of Al during
thermally cyclic tests. Thus, it is not easy to generate a
continuous dense Al2O3 oxide, which is desired in TBC
systems instead of composite oxides rich in Ni, Cr (Ref 18). In
addition, the pores in the bond coat could cause internal
oxidation in the bond coat at the high temperature, and thus
also lead to the depletion of Al. On the other hand, from the
point of view of the roughness, a review of the literature
indicates that the surface topography of the bond coat
seriously affects generate the uniformity of TGOs and the
lifetime of TBCs. The lower surface roughness is conducive to
the generation of a uniform oxide film, but also reduces the
bonding strength between the ceramic top coat and the bond
coat, and ultimately would affect the lifetime of thermal
barrier coatings. Although many efforts have been done to
solve the above problems, the deposition of bond coat by cold
spraying (CS) (Ref 16, 19) or vacuum plasma-spray (VPS)
(Ref 20) for example, there is still an inadequate cost-effective
method to significantly improve TBC lifetimes.
Introduction
Thermal barrier coatings (TBCs) are highly advanced material
systems, which were usually thermally insulating materials
with a relatively low thermal conductivity coated on hightemperature-exposed components, such as gas turbine and
aeronautical engine components (Ref 1-4). These coatings can
allow for extending part life by reducing oxidation and
thermal fatigue. Therefore, thermal barrier coating technology
is one of most important technologies for perfectly
manufacturing the entire gas turbine system. At present,
plasma-sprayed TBCs, composed of yttria-stabilized zirconia
(YSZ) ceramic top coat (TC), an oxidation-resistant MCrAlY
bond coat (BC), where M = Fe, Ni, Co, CoNi, or NiCo, are
commonly used (Ref 5-7). The oxidation-resistance of bond
T
22
Taking into account that dry ice blasting has a better cooling
effect during the coating deposition process, and its peening
effect as reported in our previous studies (Ref 21, 22), dry ice
blasting in this study was used to prepare thermal barrier
coatings. The primary objective of this study was to
systematically investigate the influence of dry-ice blasting on
the microstructure of as-sprayed bond coat and top coat. Then,
the thermal cycle lifetimes of the various types of TBCs were
compared by furnace cycling at an elevated temperature
(1150C) to accelerate the coating degradation process.
condensation arising from the treatment of dry-ice blasting

with long duration. Afterwards, the sending powder system
was turned on to deposit coatings. In other words, during the
deposition process, dry-ice blasting was also employed to cool
the sprayed sample.
Table 1: Plasma spraying parameters used for depositions of
coatings.
Parameters/Unit
Arc current /A
Arc voltage /V
Primary plasma gas /Ar / SLPM
Secondary plasma gas /H2 /SLPM
Powder carrier gas /Ar / SLPM
Material and Experimental Procedures

Sample Preparation
A gas-atomized CoNiCrAlY (AMDRY 9951, Sulzer Metco)
and a commercial ZrO2-8 wt.%Y2O3 (Plasmatex 1086, Sulzer
Metco) powder were used as feedstock to be deposited for
TBC systems, which were characterized by spherical and
angular particles. Their size distributions determined by laser
light scattering are D(0.5) of 21.80 m and 31.08 m for
CoNiCrAlY and YSZ powders, respectively Disk-shaped
nickel base Ni625 superalloy substrates (diameter 25 mm, 10
mm thickness) were used in this study for thermal cycling
experiments. Besides the manufacture of the thermal cycling
specimens, 316L steel substrates were also coated in order to
characterize the as-sprayed coating microstructure, coatings
thickness, and coatings porosity. All the substrates were grit
blasted with alumina before the spraying.
CoNiCrAlY
600
66.9
60
11
2.0
YSZ
630
65.0
30
11
3.0
Table 2: Description of the prepared samples.

Reference
AA
CA
CC
CoNiCrAlY
APS without dry-ice
blasting
APS with dry-ice
blasting
APS with dry-ice
blasting
YSZ
APS without dry-ice
blasting
APS without dry-ice
blasting
APS with dry-ice
blasting
Thermal Cycling Test

In order to evaluate and compare the durability of the various
TBC systems, the thermal cycling test was conducted in a
programmable, automated bottom-drop furnace (PYROX,
France). The disc specimens were placed on a porous Al2O3
circular tube which was installed on a vertical elevator during
cycling tests. When the elevator was lowered, TBC specimens
were naturally cooled. Each thermal cycle consisted of 3 hours
ramping to 1150C (6C), an isothermal hold at 1150C for
0.5 hours, and cooling down for 0.2 hours at room temperature
environment. The TBC specimens were taken out of the
furnace after completion of a predetermined 50 cycles. Failure
was defined as visible cracking of the APS YSZ (away from a
specimen edge) or spallation of more than 50% of the YSZ.
The thermal barrier coating systems have been produced by

atmospheric plasma spraying using a Sulzer-Metco F4 plasma
gun. Argon was used as both primary plasma operating and
powder carrier gas and hydrogen was used as secondary gas to
adjust the arc voltage. The detailed spraying parameters for
bond coat and ceramic coating (top coat) were listed in Table
1. The plasma spray distances were fixed at 115 mm for all
coatings. Dry-ice blasting has been employed during some
coating preparation processes, which was carried out using a
mobile blasting device (ic4000 system, HMRexpert, France).
This machine comprises a similar-Laval nozzle with a
rectangular outlet dimension of 9 40 mm, a mass flow
controller with a pneumatic motor, a storage tank, and a
compressed air supplier. In the present work, dry-ice pellets
with a diameter of 3 mm and a length of 3 to 10 mm were used
for dry-ice blasting medium. The mass flow rate of dry-ice
pellets was 42 kg.h-1 under a gas pressure of 0.6~0.8 MPa. The
distance between the axis-exit of the dry-ice blasting nozzle
and substrates is about 25 mm. Under the condition above, the
velocity of dry-ice pellets could achieve 100 m/s, as simulated
in our previous study (Ref 23). Three different sets of TBCs
were prepared according to the conditions in Table 2 and
referred to as Sample AA, Sample CA, and Sample CC,
respectively. For the cases with the treatment of dry-ice
blasting, the grit-blasted substrates or the bond-coated samples
were pre-treated for 4 double-passes up- and downwards by
dry-ice blasting; meanwhile plasma flame was turned on but
not providing the powder, which aims to avoid the
Characterization
The morphologies of the as-sprayed coatings were examined
using an optical microscope (OM). The porosities and oxide
contents of the as-sprayed coatings were then estimated using
an image analysis of the OM micrographs. More than 5 photos
randomly observed in the polished cross-section were
averaged to evaluate the porosity and oxide contents.
Surface roughness profiles of the three types of bare
CoNiCrA1Y bond coats on 316L steel substrates were
measured for their average surface roughness (Ra) using a
AltiSurf 500 roughness tester produced by Altimet. Three
measurements of 17.5 mm length were made at random
23
locations on each bond coat surface to evaluate the surface

roughness.
and pores in the bond coat can be considerably reduced by

employing dry-ice blasting. Similar results have been reported
in our previous work (Ref 21).
TBC specimens after thermally cycling tests were vacuum

imbedded in epoxy before cutting to reduce the possibility of
damage, cut with a slow speed of 0.001 mm.s-1, and again
mounted in epoxy. They were sequentially polished by SiC
sandpaper. Metallographic cross sections were characterized
by scanning electron microscope (SEM) equipped with energy
dispersive X-ray spectroscopy (JEOL, JSM-5800LV, Japan).
(a)
(b)
(c)
(d)

Microstructure Characterization of As-Sprayed Coatings
Typical microstructures of as-deposited TBCs with APS bond
coat and APS top coat are shown in the photographic images
in Fig. 1a and b and the backscattered electron (BSE) images
Fig. 1c and d, respectively. From the cross section of the TBC
system (Fig. 1a), it can be found that the bond coat (BC)
thickness was about 200 m and the top coat (TC) thickness
was about 600 m. The as-deposited APS CoNiCrAlY bond
coat (Fig. 1b and c) contained high levels of porosity and
entrained oxides, due to oxidation of Al and Y during plasma
processing at atmospheric environment. As for top coat,
different pores could also be observed in Fig. 1d, i.e., the
spherical or nearly spherical three-dimensional pores, twodimensional planar space between particle unconjugated
regions, and the interior crack perpendicular to the splats.
Some cracks in TBC system, for example, cracks
perpendicular to the splats on one hand is helpful to improve
the propagation resistance of cracks along the BC/TC interface
direction; On the other hand, they contribute to improve the
ability of the strain relaxation of the coating and consequently
lead to longer lifetime.
Figure 1: Optical micrographs of cross section of asdeposited TBCs (sample AA) with APS bond coat and APS top
coat (a) over view, (b) CoNiCrAlY bond coat with porosity
and oxide inclusions and BSE images showing (c) CoNiCrAlY
bond coat, (d) YSZ.
Figure 2 shows typical microstructures of as-deposited TBCs

with APS and dry-ice blasted bond coat and APS top coat. The
bond coat (BC) thickness was also about 200 m and the top
coat (TC) thickness was about 600 m. Although dry-ice
blasting was employed during the bond coating deposition, the
oxides in the TBC system were not reduced a lot. This is due
to the occurrence of oxidation arising from the heat flux
during the top ceramic layer deposition without the application
of dry-ice blasting. In other words, the bond coat continues to
be oxidized during the top coat deposition process, if the work
piece temperature is enough high during the process of
spraying.
(a)
(b)
(c)
(d)
Figure 2: Optical micrographs of cross section of asdeposited TBCs (sample CA) with APS-dry-ice blasted bond
coat and APS top coat (a) over view, (b) CoNiCrAlY bond
coat with porosity and oxide inclusions and BSE images
showing (c) CoNiCrAlY bond coat, (d) YSZ.
For the case of TBC system in Fig. 3, dry-ice blasting was

used both in the bond coat deposition and in the top coat
deposition. The bond coat (BC) has a thickness of about 200
m and the top coat (TC) of about 600 m. Evidently, the
bond coat displayed typical lamellar structure with relatively
high density and no evident oxide inclusions. The dense
microstructure was attributed to the successive impacting of
dry-ice blasting. Thus, the amount of internal oxide stringers,
On a quantitative level, these three TBCs have different top

coat porosity level measured by image analysis: Sample AA
(TC with 18.980.4% of porosity), Sample CA (TC with
15.010.2% of porosity) and Sample CC (TC with 20.111%
of porosity), and different bond coat porosity and oxide
24
Thermal Cycling Behavior

Furnace thermal cycling testing of TBC specimens at 1150oC
revealed significant differences in TBC lifetimes after the
application of dry-ice blasting. By comparing the average
lifetimes of the TBCs in this study, it can be considered that
sample CC (TBC with APS dry-ice blasted bond coat and APS
dry-ice blasted top coat) was the most durable and exhibited
much improvement in lifetime as compared to sample AA
(TBC with APS bond coat and APS top coat) and sample CA
(TBC with APS dry-ice blasted bond coat and APS top coat).
The lifetime of TBCs with APS dry-ice blasted bond coat and
APS dry-ice blasted top coat was increased to at least 10 times.
content: Sample AA (BC with 17.21% of oxide and 5.5% of

porosity),(a)
Sample CA (BC with 15.61% of oxide and 2.6%
of porosity) and Sample CC (BC with 8.31% of oxide and
0.6% of porosity).
(a)
(b)
(c)
(d)
Figure 4 shows the macro morphology of the thermally cycled

TBCs at thermal shock temperature of 1150oC (after 50
cycles). During the thermal cycling tests, there is a common
trend that the first cracking was observed at the extreme edges
of all the samples and then gradually propagated around the
sample with increment of thermal shock cycles. After 50cycles,
sample AA and sample CA nearly completely delaminated,
while the decohesion of sample CC was not evident except for
the spallation area in the edge, which was significantly
affected by stresses originating at the specimen free edges.
Figure 3: Optical micrographs of cross section of asdeposited TBCs (sample CC) with APS-dry-ice blasted bond
coat and APS-dry-ice blasted top coat (a) over view, (b)
CoNiCrAlY bond coat with porosity and oxide inclusions and
BSE images showing (c) CoNiCrAlY bond coat, (d) YSZ.
Characterization of top surface of the thermally cycled TBCs

in Fig. 5 indicated similar failure modes for sample AA and
sample CA in this study. The fracture microstructure presented
a typical brittle structure with some smooth flat particle debris
and unmelted micro-scale particles. In fact, the smooth flat
particle debris corresponds to the nonbonded interface region
in the YSZ coating. The crack extension in this area easily
occurred, i.e., they are the rapid channel for the crack
propagation. Their presence reduces the fracture toughness of
the YSZ coating, thus resulting in the rapid growth of the
cracks in the YSZ coating. This implies that the microstructure
and the porosity of YSZ top coat are associated to the crack
propagation during the thermal cyclic test. As for sample CC,
the crack with larger dimension is localized after 50 cycles on
the surface of the sample, even in the not delaminated areas.
Surface Roughness of Bare Bond Coat

There was some difference in the average surface roughness
(Ra) of the as-sprayed bond coats (Table 3). Moreover, there
were slight differences in the standard deviations. This
suggests that there may be differences in the morphology of
the surface roughness. Qualitatively, the surfaces of BC-CC
appeared to be somewhat more regular than the other surfaces.
On one hand, the decrease in the roughness can be attributed
to the peening effect of dry-ice blasting on the CoNiCrAlY
splats which were accumulated to form a coating during the
thermal spraying process. On the other hand, the splashing of
splats during droplet impact during plasma spraying process
can be constrained and even some debris which could lead to a
highly irregular morphology could be removed by dry-ice
blasting, which can be clearly observed in the results reported
in our previous work (Ref 24).
Examination of cross section of thermally cycled TBCs after

the thermal cycling test revealed that the growth of TGOs was
profiling copy, the sine groove and periodic were keep
unchanged almost for all the three samples, as shown in Fig. 6.
Moreover, it can be seen that two types of cracks (Fig. 6a and
b) were present in the YSZ coating and the YSZ/TGO
interface for the thermally cycled samples AA and CA. They
again confirmed the failure mode of fracture and delamination
of the YSZ layer near to, but typically above, the bond coat
interface. These cracks originated from the protruding TGO
and propagated along the lamellar interface in the YSZ coating.
As reported by Li et al. (Ref 17, 19), the growth of the TGO at
the interface between the YSZ and bond coat causes the
localized expansion and consequently resulted in additional
tension to the YSZ top coat. When the intensity of the tension
exceeds the cohesive strength of the YSZ lamellae, the crack
will propagate into the bonded interface area along the
Accordingly, thermal cyclic behavior of TBCs with bond coat

plasma-sprayed with dry-ice blasting, in particular, also with
top coat plasma-sprayed with dry-ice blasting, may be largely
different from others due to the different morphologies.
Table 3: Bond coat surface roughness corresponding to
different conditions
Bond coat type
BC-AA
BC-CA
BC-CC
6.54
5.30
5.21
Ra (m)
Standard Deviation
0.24
0.21
0.20
25
nonbonded interface area between the lamellae and possibly

into the nonmolten YSZ porous particles, which would cause
the spalling of the top coat as observed in Fig. 5a and b.
(a)
In addition, for those three sets of TBCs, different

morphologies and constituents of TGOs were observed in the
thermally cycled TBCs. There are mainly two contrasts in the
BSE images. Combined with the EDS results in Fig. 7, the
lighter grey line or amorphous phases present in the coatings
corresponds to spinel-based oxides. The darker grey
corresponds to Al2O3-based oxides, whose growth rate is only
half of that of spinel-based oxides. In the failed sample AA
and CA, spinel-based oxides dominant along the APS bond
coat/YSZ top coat interface, as shown in Fig. 6a and b, while a
uniform continuous Al2O3-based TGO was formed and a small
proportion of local protruding spinel-based oxides were found
in the thermally cycled sample CC. Thus, it can be speculated
that such spinel-based oxide plays an important role in the
lifetime of TBCs. This agrees with the result that TGO
compositions and their coverage ratios contribute to different
thermal cyclic lifetimes as reported by Li et al. (Ref 16). As
well known, the spinel with a high growth rate is detrimental
to the lifetime of TBCs. With increasing the surface coverage
of spinels, the thermal cycling lifetime decreased rapidly. A
better thermal cycling lifetime was associated to the reduced
spinel coverage ratio. The differences in the TGO composition
and their coverage ratios in this study could be explained by
the different morphologies of bond coats for sample AA, CA
and CC. The severe oxidation of bond coats for sample AA
and CA would lead to the depletion of Al in bond coat.
Moreover, the pores in the bond coat caused internal oxidation
at the high temperature, and thus also led to the depletion of
Al. The spinels preferably formed in such bond coat, as
reported in many literatures (Ref 19, 25). The uniform oxide
layer for sample CC can be attributed to the relatively smooth
surface of bond coat resulting from the peening effect of dryice blasting.
(a)
(b)
(b)
(c)
Figure 5: SEM-BSE observation of top surface of thermally

cycled TBCs (50 cycles): (a) AA, (b) CA and (c) CC.
(a)
(b)
(c)
Figure 6: SEM-BSE observation of cross-sectional

microstructure of thermally cycled TBCs (50 cycles): (a) AA,
(b) CA and (c) CC, showing the TGO type and crack
propagation style.
(c)
(a)
Figure 4: Photos of the samples after thermal cycling tests

(50 cycles): (a) AA, (b) CA and (c) CC.
26
fracture and delamination of the YSZ layer near to, but

typically above, the bond coat interface. The lifetime of TBCs
is correlated to the microstructure of bond coat and top coat.
(b)
References
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History and Directions, J. Thermal. Spray. Technol., 1997,
6(1), p 35-42
2. C.T. Sims, Non-Metallic Materials for Gas Turbine
EnginesAre They Real?, Adv. Mater. Process., 1991,
139, p 32-39
3. R. Vaen, S. Giesen, D. Stover, Lifetime of PlasmaSprayed Thermal Barrier Coatings: Comparison of
Numerical and Experimental Results, J. Thermal. Spray.
Technol., 2009, 18(5-6), p 835-845
4. B.H. Kear, E.R. Thompson, Aircraft Gas Turbine Materials
and Processes, Science, 1980, 208, p 847-856
5. N.P. Paduture, M. Gell, E.H. Jordan, Thermal Barrier
Coatings for Gas-Turbine Engine Applications, Science,
2002, 296, p 280-284
6. A. Scrivani, G. Rizzi, U. Bardi, C. Giolli, M. Muniz
Miranda, S. Ciattini, A. Fossati, and F. Borgioli, Thermal
Fatigue Behavior of Thick and Porous Thermal Barrier
Coatings Systems, J. Thermal. Spray. Technol., 2007,
16(5-6), p 816-821
7. J.A. Haynes, M.K. Ferber, W.D. Porter, Thermal Cycling
Behavior of Plasma-Sprayed Thermal Barrier Coatings with
Various MCrAIX Bond Coats, J. Thermal. Spray. Technol.,
2000, 9(1), p 38-48
8. L.D. Xie, D.Y. Chen, E.H. Jordan, Formation of Vertical
Cracks in Solution-Precursor Plasma-Sprayed Thermal
Barrier Coatings, Surf Coat Technol, 2006, 201, p 10581064
9. R. Va en, G. Kerkhoff, D. St over, Development of a
Microme-Chanical Life Prediction Model for Plasma
Sprayed Thermal Barrier Coatings, Mater. Sci. Eng. A, 2001,
303(1-2), p 100-109
10. K.W. Schlichting, N.P. Padture, E.H. Jordan, M. Gell,
Failure Modes in Plasma-Sprayed Thermal Barrier
Coatings, Mater. Sci. Eng., A, 2003, 342, p 120-130
11. R.V. Hillery, B.H. Pilsner, R.L. McKnight, T.S. Cook,
M.S. Hartle, Thermal Barrier Coating Life Prediction
Model Development, Final Report, NASA CR 180807,
1988, National Aeronautics and Space Adminis-tration,
Washington, DC
12. A.G. Evans, D.R. Mumm, J.W. Hutchinson, Mechanisms
Controlling the Durability of Thermal Barrier Coatings,
Prog Mater Sci, 2001, 46(5), p 505-553
13. S. Kuroda, T.W. Clyne, The Quenching Stress in
Thermally Sprayed Coatings, Thin Solid Films, 1991,
200(1), p 49-66
14. T.S. Hille, T.J. Nijdam, A.S.J. Suiker, S. Turteltaub, W.
Sloof, Damage Growth Triggered by Interface
Irregularities in Thermal Barrier Coatings, Acta Mater,
2009, 57, 2624-2630
(c)
Figure 7: (a) Typical BSE microstructure of TGOs in the

thermally cycled sample CA at high magnification and the
corresponding EDS analysis on the position marked as (b) A
and (c) B.
Conclusions
Three sets of thermal barrier coatings (TBCs), composed of a
bond coat with a thickness of 200 m and a top coat with a
thickness of 600 m, were made by APS with different
treatments of dry-ice blasting. The results showed that
different microstructures of bond coat with different porosity
levels and oxide contents and top coat were obtained under
different conditions. CoNiCrAlY bond coats continue to be
oxidized during the deposition process of YSZ top coats which
were plasma-sprayed without dry-ice blasting. When dry-ice
blasting was employed both in the bond coat and the top coat
deposition processes, the surface roughness of bare bond coat
is most regular. Moreover, the lifetime of TBCs can be
significantly influenced by dry-ice blasting. The lifetime of
TBCs with APS dry-ice blasted bond coat and APS dry-ice
blasted top coat was increased to at least 10 times. The
thermally failed TBCs exhibit a similar failure mode of
27
21. S.J. Dong, B. Song, B. Hansz, H.L. Liao, C. Coddet,

Improvement in the Microstructure and Property of
Plasma Sprayed Metallic, Alloy and Ceramic Coatings by
Pre-/during-Treatment of Dry-Ice Blasting, Surf Coat
Technol, 2012, DOI:10.1016/j.surfcoat.2012.03.071
Study on the Mechanism of Adhesion Improvement
Using Dry-Ice Blasting for Plasma-Sprayed Al2O3
Coatings, J. Thermal. Spray. Technol.,2012,
accepted
Modelling of Dry Ice Blasting and Its Application in
Thermal Spray, Mater. Res. Innovations, 2012, 16(1), P
61-66
Combination Effect of Dry-Ice Blasting and Substrate
Preheating on Plasma-Sprayed CoNiCrAlY Splats, J.
Thermal. Spray. Technol., 2012, DOI: 10.1007/s11666012-9845-z
25. C. Giolli, A. Scrivani, G. Rizzi, F. Borgioli, G. Bolelli, L.
Lusvarghi, Failure Mechanism for Thermal Fatigue of
Thermal Barrier Coating Systems, J. Thermal. Spray.
Technol.,
2009,
18(2),
p
223-23
15. T. Wakui, J. Malzbender, R.W. Steinbrech, Strain

Analysis of Plasma Sprayed Thermal Barrier Coatings
under Mechanical Stress, J. Thermal. Spray. Technol.,
2004, 13(3), p 390-395
16. W.R. Chen, X. Wu, D. Dudzinski, Influence of Thermal
Cycle Frequency on the TGO Growth and Cracking
Behaviors of an APS-TBC, J. Thermal. Spray. Technol.,
2012, 21, p 1294-1299
17. Y. Li, C.J. Li, Q. Zhang, G.J. Yang, C.X. Li, Influence of
TGO Composition on the Thermal Shock Lifetime of
Thermal Barrier Coatings with Cold-Sprayed MCrAlY
Bond Coat, J. Thermal. Spray. Technol., 2010, 19(1-2), p
168-177
18. S. Taniguchi, A. Andoh, Improvement in the Oxidation
Resistance of an Al-Deposited Fe-Cr-Al Foil by
Preoxidation, Oxid Met, 2002, 58(5-6), p 545-562
19. Y. Li, C.J. Li, Q. Zhang, L.K. Xing, G.J. Yang, Effect of
Chemical Compositions and Surface Morphologies of
MCrAlY Coating on Its Isothermal Oxidation Behavior, J.
Thermal. Spray. Technol., 2010, 20, p 121-131
20. C. Verdy, C. Zhang, D. Sokolov, H. Liao, D. Klein, C.
Coddet, Gas-Tight Coatings Produced by Very Low
Pressure Plasma Spraying, Thermal Spray 2008:
Proceedings of the International Thermal Spray
Conference, E. Lugscheider et al. (Ed.), p 386-390
28


All rights reserved
Mechanical Properties of Plasma Sprayed YSZ Coatings Measured Using

TAT and TCT Test
1
Andrew Siao Ming Ang1,2* and Christopher C. Berndt1,2,3

Industrial Research Institute Swinburne, Swinburne University of Technology, Melbourne, Australia
2
Defence Materials Technology Centre (DMTC), Swinburne University of Technology, Australia
3
Department of Materials Science and Engineering, Stony Brook University, Stony Brook, USA
*E-mail: AANG@swin.edu.au
Abstract
microstructural texture that followed the spray direction, and

(ii) a transverse orientation, perpendicular to the spray
direction (See Fig. 1), that reflected the cross sections of
splats.
The adhesion and cohesion bond strength of plasma sprayed

YSZ coatings were measured by performing tensile adhesion
test (TAT) and tubular coating tensile (TCT) test. The TAT
allowed measurements of adhesion/ cohesive bond strength of
YSZ-bond coat microstructure perpendicular to the spray
direction. The TCT test was used to measure the strength of a
thermal spray coating parallel to the spray direction without
the use of any adhesive. The failure strength of the coatings
from the respective tests can be approximated to a Weibull
distribution and also indicated the anisotropic behaviour of
YSZ plasma sprayed coatings. The average coating strength
parallel to the spray direction is approximately 1.5 times
greater than the bond strength perpendicular to spray direction.
The anisotropic behaviour of YSZ coatings have also been
verified by Knoop hardness measurements.
The standard tensile adhesion test method for thermal sprayed

coatings, ASTM C633-08(Ref 3), provides measurements for
the coating strength perpendicular to the spray direction. As
the initial test load is applied normally to the plane of the
coating, the tensile fracture mechanism can be attributed
mainly to cumulative splat delamination occurring due to poor
intersplat cohesion or splat-substrate adhesion. However, the
anisotropic nature of thermal sprayed coatings implies that the
coating strength parallel to the spray direction should differ
from the coating strength measured via the ASTM C633 test
method.
There are several references that illustrate methods to measure
the strength of a thermal spray coating parallel to the spray
direction. Different designs have been discussed (Ref 4) for
the application of load parallel to the coating lamellae. The
test design of W.E. Stanton employed a specimen
configuration during coating operation to create a coating
layer that bridged two substrates. Stantons design would
result in the test piece being subjected to eccentric loading due
to the coating-substrate sprayed geometry. However, the
novelty was that adhesive glue was not required and the
applied load would have a force component parallel to the
coating surface. An adaptation of this test method is the
tubular coating tensile test (TCT) (Ref 5). The test was
proposed to be suitable to measure the ultimate tensile strength
of cold sprayed coatings. The TCT orientation indicates that
the forces exerted on the test specimen were mostly parallel to
the coating surface. The two substrates were firmly connected
by the as-sprayed coating. Thus, upon tensile loading across
the horizontal plane, the interconnected splats would fracture.
Thus, the TCT is a measurement of the coatings intersplat
cohesive strength in the direction parallel to the coating.
Introduction
The fundamental feature of any thermal spray coating is its
lamellar microstructure formed by the rapid solidification of
impinging molten droplets and cohesion among splats.
Formation of this lamellar microstructure is a stochastic
process and is associated with interdependent processing
variables such as the feedstock size, feedstock material, flame
jet temperature, and particle velocity (Ref 1, 2). An illustration
of a typical ceramic thermal spray microstructure was depicted
in Fig. 1. Due to the cumulative interactions of variables
within the spray stream, discriminating features such as splat
dimensions, pore sizes, crack density, inter-splat coalescence,
and associated artefacts can be ascertained.
The lamellar splat structure also gave rise to highly anisotropic
mechanical properties of thermal spray coatings. Thus, the
coating material properties depended on the direction
measured as opposed to an isotopic bulk material. The
anisotropic nature of a thermal sprayed microstructure has
been specifically defined as transversely isotropic because the
architecture has two orthogonal planes of symmetry: i.e., (i) a
29
was used as the primary plasma operating gas and hydrogen

was used as the auxiliary gas. The primary gas flow was fixed
at 42.1 L/min at 0.7 MPa and the flow of the auxiliary gas was
6.1 L/min at 0.34 MPa. Argon was used as the powder feeding
gas and the powder feed-rate was 30 g/min. Plasma arc current
and voltage were set at 35 kW (500 A and 70 V). The plasma
torch was mounted on a robotic arm (YR-SK16-J00 Motoman,
Yaskawa Electric Corp, Japan) to transverse across the
individual substrate holders. Specialized substrate holders
were individually designed to allow batch thermal spraying of
TAT and TCT coupons. The merit of batch spraying is that
multiple samples can be produced in a single spray run and,
thereby, eliminate variability associated with samples
produced over multiple runs, which could held the substrates.
Prior to coating application, the substrate surfaces were
prepared in accordance to the typical preparations of
degreasing, pre-heating and surface roughening via grit
blasting.
In this work, the standard TAT was used while a TCT setup
was adapted as shown in Fig. 2. These tests allowed the
evaluation of plasma sprayed yttria stabilised zirconia (YSZ)
coatings mechanical strength for in plane as well as the
perpendicular orientations. The in plane orientation is
parallel to the substrate surface whereas the perpendicular
orientation refers to the coating thickness cross section. In
addition, the anisotropic behaviour of YSZ coatings was also
tested using orientated Knoop hardness measurements
Experimental Methods
The use of YSZ ceramics in the context of this work are for
thermal barrier coating (TBC) applications. TBCs can be
found in advanced gas turbine engine components operating
above 1,000C (Ref 6).
YSZ powder (Metco 204NS, Sulzer Metco Inc., USA) with a
composition of ZrO2-8wt% Y2O3 was used for this work. The
powders were manufactured by the HOSP method and were
spherical with good flowability and chemical homogeneity.
The particle cut was from +16 -125 m and the mean particle
size was 71.5 m. For TAT specimen, a metallic bond coat of
Amdry 365 (Sulzer Metco Inc., USA) was used. Amdry 365 is
a proprietary NiCrAlY alloy powder with a particle size cut
between +5 -45 m. It is manufactured by a gas atomization
route and a spheroidal powder is produced.
Once the thermal spraying of specimens was completed, they

were individually checked with an electronic thickness gauge
(Minitest 650, ElektroPhysik) to ensure that the thickness did
not vary across the surface by more than 25 m. For TAT
assembly, a film epoxy (FM1000. Cytec Industries Inc, NJ,
USA) was placed in between both mating surfaces. A Vee
block had slots milled out to hold the cylindrical specimens in
parallel position and maintain alignment during tightening.
The assembly was tightened to approximately 150 kPa using a
torque wrench and the specimens were cured under gravity at
a 70 - 75 angle with the pull-off bar placed in the bottom
position of the assembly. Required conditions for epoxy
curing were 190C for 2.5 hours under a light vacuum
environment of 70 kPa.
Coatings were produced on TAT and TCT specimens using an

industrial air plasma spray system (Metco 7MB, Sulzer Metco
Inc., Westbury, NY-USA). In these experiments, operating
conditions were selected to correspond to typical
manufacturers coating parameter recommendation. Argon
Figure 1: Illustration of the ceramic thermal spray coating microstructure.
30
Figure 3 Photo scan image of failure interface of plasma

sprayed YSZ coating. Failure is identified at the bond coatceramic interface.
The effects of the indenter orientation with respect to the

coating cross sectional lamellar microstructure was
investigated by orientating the Knoop indenter in two
directions: (i) along the lamellar layers, and (ii) against the
lamellar layers. This was accomplished for direction 1 by
careful alignment of the coating-substrate axis to the major
diagonal of the Knoop indenter. For direction 2 the entire
sample stage was re-orientated at 90, without moving the test
specimen. The Knoop microhardness test uses a calibrated
machine (Micromet 2103 Microhardness Tester, Buehler,
USA) to force a pointed, rhombic base pyramidal diamond
indenter having specified angles, under a predetermined load,
into the surface of the cross sectioned YSZ coating sample.
The rate of indenter motion prior to contact with the specimen
was set to 0.060 mm/s. The time of application of the full test
load selected to be 15 s unless otherwise specified. After the
indenter contacted the specimen for the required dwell time, it
was raised from the sample and diagonal readings recorded
using the inbuilt microscope. Image analysis software (Image
J) was used to process the FESEM images to evaluate the
porosity in the coatings.
Figure 2: Typical tensile test configuration for TCT specimen.
A universal joint design was used for the tensile testing rig as
recommended by the ASTM C633 Standard. An
electromechanical-type universal testing machine: (Uniaxial
MTS Criteron Model 43, MTS Systems Corporation, MN,
USA) with measuring capabilities rated at 50 kN was used to
apply the tensile load for TAT. After a TAT sample had been
assembled in the loading devices via the threaded couplings,
the machine program was activated. A pre tensile load of 30 N
was applied to remove any slack in the load train. No data was
recorded when the preload was applied. Subsequently, the
tensile load was applied, at constant crosshead rate of
0.015 mm/s, to each TAT specimen until rupture occurred.
The time to failure, crosshead displacement and maximum
failure load were recorded at 50 Hz for analysis. A total of
thirty five YSZ coupons were plasma sprayed and evaluated
using TAT.

The majority of YSZ coatings failed at the bond coat-ceramic
coat interface and the failure mode can be termed as internal
adhesive failure mode. Fig. 3 shows the scanned image of a
typical YSZ test sample exhibiting failure along the bond coatceramic coat interface. Most of the YSZ material was
transferred onto the pull off bar while bond coat material was
exposed along with some retained YSZ coating on the coated
substrate. The average adhesive strength of plasma sprayed
YSZ coatings was 8.46 2.01 MPa with a coefficient of
variance (COV) of 23.8%.
Due to the relatively small cross sectional area tested for the
TCT specimen, a table-top electromechanical-type universal
machine Z010/ TN2S (Zwick GmbH & Co, Ulm, Germany)
was used. The Z010/ TN2S crosshead was screw driven with a
500 W DC actuator and was equipped with an interchangeable
load cell capable of measuring up to 1 kN. The constant
crosshead speed of 0.008 mm/s was selected as the testing
condition for all samples. This test speed was almost twice
less than that used for the conventional ASTM C633 standard
since the intention was to maintain the strain rate range within
the quasi-static or pseudostatic mode of tensile testing; i.e.,
between 10-5 to 10-1 s-1. A total of thirty five YSZ coupons
was also used for TCT.
31
Tensile adhesion
strength (MPa)
Tensile intersplat
strength (MPa)
Transverse rupture
strength of bulk
dense ceramic (MPa)
(Ref 7)
APS / YSZ
Porosity (%)
Table 1: Comparison of tensile strength of YSZ coating from

different orientation.
23.45
(4)
8.46
(2)
20.43
(11)
600-700
A random fractured TCT sample was also chosen for SEM

analysis as shown in Fig 4. The top SEM image revealed the
existence of intralamellar cracks and interlamellar pores. The
bottom SEM image provided evidence concerning incomplete
splat stacking and the vertical columnar grain growth
associated with rapid quenching and solidification of
impacting splats. Cracks and pores would be arbitrarily
scattered within the test plane that joins the two substrates
together. These crack and pore networks had the damaging
effect of acting as nucleation sites for coating failure during
tensile loading.
The TAT and TCT measure coating strength under tensile
loading but the principal stress orientations were different. The
TAT assessed the tensile strength in the weakest plane parallel
to the spray direction while the TCT was carried out to
evaluate intersplat strength perpendicular to the spray
direction. A comparison of the mean values from the
respective tensile tests is presented in Table 1. It can be
determined that the plasma spray coating intersplat cohesive
strength was greater than the tensile adhesion strength. The
difference in strength arose due to the anisotropic
microstructure in the cross section plane of the coating. Since
the testing orientations were normal to each other, the higher
TCT results suggested that the strength in the axis
perpendicular to spray direction was greater. The mechanical
property values for coatings were compared to dense sintered
ceramics that were isotropic (Ref 7), Table 1. It was
determined that the strengths of thermal spray coatings were
significantly less than the equivalent dense bulk ceramics. The
reduction in coating strength was due to the lamellar
microstructure that was defective in nature, and the disparity
in material phases that existed within the as-sprayed coating.
Figure 4: Fracture morphologies of plasma sprayed YSZ

(Metco 204NS) coating recovered from TCT component. Top
SEM image shows cracks and pore network. Bottom image
gives evidence of incomplete splat stacking and columnar
grain growth.
For TCT test, high resolution photo-scanned images of the

cross sectional failure areas were used to calculate the coating
inter-splat cohesive strength. The average failure stress for the
plasma sprayed YSZ coatings was 12.8 MPa with a large
standard deviation of 6.83 MPa.
Finite element stress modeling of the TCT method indicated
that the geometrical design of mating two substrates via a
thermal spray coated structure can lead to a local stress
concentration along the plane of the two substrates (Ref 5).
The local stress concentration was similar to a notch effect and
there was an increase in the Mises stress as the two substrates
were pulled apart. Thus, the measured stress required a
correction factor of 1.5 to 1.7 to obtain a proper representation
of the ultimate tensile strength. A correction factor of 1.6 was
used to account for the increase in Mises stress due to the
notch effect from the two mating substrate surfaces.
Therefore, the average intersplat cohesive strength, or
effective ultimate tensile inter-splat strength, of YSZ coatings
was 20.43 MPa.
The failure distributions of TAT and TCT data were examined

for the APS YSZ coatings to further assess whether thermal
spray ceramic coatings followed the Weibull theory. Similar
methodology of treating microhardness data was used
previously (Ref 8). The Weibull distributions are shown as a
red line in Fig. 5 and Fig. 6. The R2 values from the regression
analysis were all above 0.9. Recollecting that the Weibull
material, Table 2 compiles the Weibull modulus (m) for the
32
Table 2: Compilation of YSZ coating Weibull modulus values

from TAT and TCT.
Weibull modulus, m
Porosity
TAT
TCT
(%)
APS / YSZ
23.45
4.78
2.30
modulus is a measure of variability in the strength of a test

data. The m value is estimated to be between 5 to 10 (Ref 9)
dense engineered ceramics. Therefore, since thermal spray
coatings intrinsically contained flaws such pores and cracks, a
lower value of m was expected.
The horizontal and vertical Knoop orientations were
specifically chosen to measure the mechanical response of the
lamellar thermal spray microstructure. With respect to the
coating cross section plane, it was found that the
microhardness values were higher when indents were
orientated perpendicular to the flattened splats or Direction
2. Lower microhardness values were consistently recorded
when the measurements were orientated to measure
deformation parallel to the lamellar splats or Direction 2
Knoop indentation test results are presented in Table 3. A
paired one way Students t-testing conducted at 0.05 level
significance had a P value of 0.000294 and indicated that the
data sets were statistically from different populations.
Figure 5: Weibull regression analysis of tensile adhesion test

data for plasma sprayed YSZ coatings (n = 35).
Therefore, this is further evidence that coating microhardness

property exhibited anisotropic behaviour and the value
obtainable was sensitive to indenter orientation. These results
are consistent with those gathered from the TAT and TCT
measurements in which the mechanical strength in the axis
perpendicular to spray direction was greater.
Figure 6: Weibull regression analysis of corrected intersplat

strength data for plasma sprayed YSZ coatings (n = 35).
Table 3: Knoop microhardness test results of plasma sprayed

YSZ (Metco 204NS) coating.
Knoop microhardness of APS YSZ (Metco 204NS)
Orientation
300 g
Can
compare
d1 (m) HK(GPa)
dataset?
n = 34
112.61
3.64
Direction 1 Average
Standard
23.27
1.19
Deviation
Yes
COV
20.66%
P
value=
n = 33
2.92E-04
97.27
4.65
Direction 2 Average
Standard
13.16
1.19
deviation
COV
13.53%
Conclusion
The mechanical strength of plasma sprayed YSZ coatings
were measured by performing TAT, TCT and Knoop
microhardness indentation test.
The adhesion strength of YSZ-bond coat system measured by
TAT was 8.46 MPa while the TCT tests, measuring the
coatings intersplat strength parallel to the spray direction
without the use of any adhesive, yielded strength of up to
20.43 MPa. In both datasets, the failure strength of the
coatings from the respective tests can be approximated to a
Weibull distribution and also indicated the anisotropic
behaviour of YSZ plasma sprayed coatings. The average
coating strength parallel to the spray direction is
approximately 1.5 times greater than the bond strength
perpendicular to spray direction. The anisotropic behaviour of
YSZ coatings have also been verified by the Knoop
microhardness measurements. It was found that the
33
4. C. C. Berndt and C. K. Lin, Measurement of Adhesion for

Thermally Sprayed Materials. Journal of Adhesion Science
and Technology, 1993, 7(12 pt 2), p.1235-1264.
5. T. Schmidt, F. Grtner and H. Kreye, New Developments
in Cold Spray Based on Higher Gas and Particle
Temperatures. Journal of Thermal Spray Technology, 2006,
15(4), p.488-494.
6. S. Stecura, Two- Layer Thermal Barrier Coating for
Turbine Airfoils- Furnace and Burner Rig Test Results,
Cleveland, Ohio 44135, Lewis Research Center, National
Aeronautics and Space Administration, 1976.
7. R. L. Lehman, Overview of Ceramic Design and Process
Engineering, Engineered Materials Handbook, 4, Ceramics
and Glasses, Materials Park, OH, USA, ASM International,
1991, p.30.
8. C. K. Lin and C. C. Berndt, Statistical Analysis of
Microhardness Variations in Thermal Spray Coatings. Journal
of Materials Science, 1995, 30(1), p.111-117.
9. Donald R. Askeland, Pradeep P. Fulay and D. K.
Bhattacharya, Weibull Statistics for Failure Strength Analysis,
Essentials of Materials Science and Engineering: Si Edition,
Stamford, CT, USA, Cengage Learning, 2009, p.201.
microhardness values were higher when indents were

orientated perpendicular to the flattened splats; i.e., normal to
the spray direction. The ratio of Knoop microhardness in the
respective orientation was about 1.28.
Acknowledgement
The authors sincerely thank Mr Andrew Moore for expert
assistance in the preparation and plasma spray procurement of
samples. This work is supported under a Swinburne University
Postgraduate Research Award. We also acknowledge support
from the Defence Materials Technology Centre (DMTC).
References
1. R. McPherson, The Relationship between the Mechanism
of Formation, Microstructure and Properties of PlasmaSprayed Coatings. Thin Solid Films, 1981, 83(3), p.297-310.
2. S. Fantassi, M. Vardelle, A. Vardelle and P. Fauchais,
Influence of the Velocity of Plasma-Sprayed Particles on Splat
Formation. Journal of Thermal Spray Technology, 1993, 2(4),
p.379-384.
3. "Astm C633-01(2008) Standard Test Method for
Adhesion or Cohesion Strength of Thermal Spray Coatings",
ASTM International, West Conshohocken, PA, 2008.
34


All rights reserved
Y2O3 and Yb2O3 Co-doped Strontium Hafnate as a New Thermal Barrier Coating
Material
W. Ma*, P. Li, H.-Y. Dong, Y. Bai, J.-L. Zhao, X.-Z. Fan
Inner Mongolia University of Technology, Hohhot, Inner Mongolia, P.R. China
*E-mail: wma66@163.com
low thermal conductivity and high CTE. Perovskites

additionally offer the possibility of extensive substitution of
ions at the A or/and B site, which enables the properties of the
materials to be selectively influenced by mixed-crystal
formation (Ref 7).
Abstract
Y2O3 and Yb2O3 co-doped strontium hafnate powder with
chemistry of Sr(Hf0.9Y0.05Yb0.05)O2.95 (SHYY) was synthesized
by a solid-state reaction at 1450oC. The SHYY showed good
phase stability not only from 200oC to 1400oC but also at a
high temperature of 1450oC for a long period, analyzed by
differential scanning calorimetry (DSC) and X-ray diffraction
(XRD), respectively. The coefficient of thermal expansion
(CTE) of the sintered bulk SHYY was recorded by a hightemperature dilatometer and revealed a positive influence on
phase transitions of SrHfO3 by co-doping with Y2O3 and
Yb2O3. The thermal conductivity of the bulk SHYY was
approximately 16% lower in contrast to that of SrHfO3 at
1000oC. Good chemical compatibility was observed for
SHYY with 8YSZ or Al2O3 powders after a 24 h heat
treatment at 1250oC. The phase stability and the
microstructure evolution of the as-sprayed SHYY coating
during annealing at 1400oC were also investigated.
Among the perovskites, SrHfO3 has been proven as one of the

most refractory oxides with melting point as high as 2927oC
(Ref 8). Kennedy et al. (Ref 9) examined the phase transition
of SrHfO3 by a high-resolution neutron powder diffraction
method, and reported the phase transitions are as follows:
600 C
750 C
1130 C
orthorhombic orthorhombic tetragonal cubic

Pbnm
Cmcm
I 4/ mcm
Pm 3m
The phase transitions of SrHfO3 normally give a negative

influence for TBC applications. Fortunately, three phase
transitions occur with very small volume change (Ref 9). In
addition, the values of the thermal conductivity of SrHfO3 are
~5.20 W/mK at room temperature and ~2.90 W/mK at 1000oC
(Ref 10), these values are too high to utilize it for TBC
application. The value of better TBC materials should have
much lower thermal conductivity (< 2 W/mK). Normally, the
improved phase stability and lowered thermal conductivity for
TBC materials could be realized by co-doping with some
selected oxides such as SrZrO3 (Ref 11-13).
Introduction
In recent years, much effort has been devoted to the
development of new ceramics as thermal barrier coating (TBC)
materials, in order to increase the efficiency of gas turbines
(Ref 1, 2). The current state-of-the-art TBCs are usually based
on 7-8 wt.% Y2O3-stabilized ZrO2 (8YSZ) due to its low
thermal conductivity, phase stability at temperatures below
1200oC and chemical inertness in combustion atmospheres
(Ref 3). However, YSZ cannot be operated long-term at
~1200oC because of phase transition and accelerated sintering
(Ref 4-6).
In the present study, the phase stability and the thermophysical

properties of Y2O3 and Yb2O3 co-doped SrHfO3 (SHYY)
powder and bulk material, as well as the phase stability and
the microstructure evolution of the as-sprayed SHYY coating
during annealing are presented.
In order to remedy such phenomenon, a wide search has been

conducted for new TBC materials which allow operation
temperatures higher than 1200oC without phase transition,
aside from thermochemical and thermophysical compatibility
with the substrate layer to be coated. Recently, perovskites
(ABO3) have been considered for this purpose. Such
perovskites are usually characterized by high melting point,
Solid-state synthesis of SHYY was carried out through ball
milling using the starting powders of Y2O3 (99.99%, Grirem
Advanced Materials Co. Ltd., China), Yb2O3 (99.99%, Grirem
Advanced Materials Co. Ltd., China), SrCO3 (>98%, Shanghai
35
Reagent Co. Ltd., China) and HfO2 (99.99%, Aldrich, USA).

The powder mixture was milled for 24 h using zirconia balls
as milling media in deionized water with a solid loading of 50
wt.%. The weight percentage of both the powder mixture and
the zirconia balls was 50%. The milled suspension was then
dried and sintered at 1450C for 24 h. The powder after
sintering was crushed with a milling machine for 15 min using
zirconia balls as milling media to avoid introducing
contaminants. The synthesis procedure was repeated three
times to obtain a purer phase material. The bulk SHYY was
cold pressed under 30 MPa and sintered at 1700oC for 6 h in
air. The sample dimensions for CTE and thermal diffusivity
measurements were 3 4 25 mm and 10 1~2 mm,
respectively. The CTE, thermal diffusivity and specific heat
capacity of the bulk SHYY were recorded by a high
temperature dilatometer (Model DIL 402PC, Netzsch,
Germany), laser flash method (Model LFA 427, Netzsch,
Germany), and a simultaneous thermal analysis apparatus
(Model STA 449PC, Netzsch, Germany) equipped with a
sample holder for thermogravimetry-differential scanning
calorimetry (TG-DSC), respectively. The TG-DSC
measurement was conducted in air atmosphere. The density ()
of the sintered sample was measured according to Archimedes
principle. The porosity of the bulk SHYY used for thermal
diffusivity measurement was ~5%. The thermal conductivities
of the sintered samples were calculated with Eq. (1) and then
calibrated with Eq. (2):
Dth (T )C p (T ) (T )
(Eq 1)
/ 0 1 4 / 3
(Eq 2)
scanning electron microscope (SEM) (Model JXA 840, JEOL,

Japan).
The chemical compatibility of SHYY with 8YSZ or Al2O3
was analyzed by XRD after heat treatment at 1250oC for 24 h.
The weight fraction of the two component powders in the
mixture was 50%.
Synthesis of the SHYY Powder and Its Phase Stability
The XRD patterns of the SHYY powder sintered at 1450oC for
different times are presented in Fig. 1. The powder has an
orthorhombic structure after sintering at 1450oC for 24 h
without any second phase (Fig. 1a), indicating SHYY was
successfully synthesized. The synthesized SHYY powder was
heat treated at 1450oC up to 360 h (Fig. 1b-g), and no new
phase developed during the long period heat treatment,
implying very high long-term phase stability.
where , Dth (T ) , C p (T ) , (T ) , 0 and are the thermal

conductivity, the thermal diffusivity, the specific heat capacity,
the measured density, the calibrated value of the thermal
conductivity and the porosity, respectively.
Figure 1: XRD patterns of the SHYY powder sintered at
1450oC for different times: (a) 24 h, (b) 48 h, (c) 72 h, (d) 144
h, (e) 216 h, (f) 288 h and (g) 360 h.
The phase analysis of the synthesized powder and the coating

was characterized by XRD (Model D/MAX 2200, Rigaku Co.
Ltd, Japan) at a wavelength of 1.5406 .
In addition to the long-term phase stability for TBC candidate

materials at high temperatures, the phase stability of those
materials in the temperature range between room temperature
and high temperature is also important. Figure 2 shows the
DSC curve of the SHYY powder, the DSC curve of the
SrHfO3 is also presented for comparison. There is no obvious
peak appeared in the DSC curve of the SHYY in the tested
temperature range compared to SrHfO3, revealing that the
phase transition from tetragonal to cubic for SrHfO3 indicated
by an arrow at ~1130oC is suppressed by co-doping with Y2O3
and Yb2O3.
The synthesized SHYY powders were milled with ethanol and

1.5 wt% dispersing agent, then subsequently spray-dried.
Sieved particles with sizes between 48 and 100 m were used
for plasma spraying.
The SHYY coating was air plasma sprayed (F4 gun, Sulzer
Metco, Switzerland) on steel substrates to a total coating
thickness of ~1 mm. The spray parameters were as follows:
current = 600 A, voltage = 60 V, plasma gas Ar/H2 = 40/10
L/min, spray distance = 120 mm. The freestanding coating,
which was produced by removing the steel substrate from the
sprayed coating with hydrochloric acid, was used to
investigate the phase stability and microstructure evolution.
The microstructure of the coating was investigated by a
36
increasing temperature, it is ~10% lower than that of SrHfO3

in the whole tested temperature range. The Cp curves of the
bulk SHYY and SrHfO3 are shown in Fig. 5. The Cp values of
SHYY are slightly lower compared to that of SrHfO3 and, in
addition, the obvious three peaks representing three-phase
transitions in SrHfO3 do not appear in the Cp curve of SHYY
(Ref 9). This confirms that the phase stability of SrHfO3 can
be improved by co-doping with Y2O3 and Yb2O3. It is worth to
note that the three phase transition temperatures are ~650oC,
~760oC and ~1030oC respectively, which are different from
that of reported by Kennedy et al. (Ref 9). This might be due
to the different measurement methods. The Cp curve of
SrHfO3 is much different from that of Yamanaka results, in
which no peak in the tested temperature range can be observed,
even both results were measured by a differential scanning
calorimeter (Ref 10). Normally, the heat capacity
measurement is very sensitive to phase transition of a material,
it is also observed in SrZrO3 (Ref 15).
Figure 2: DSC curve of the synthesized SHYY powder.

Thermophysical Properties of the Bulk SHYY
Figure 3 shows the CTEs of the bulk SHYY, as well as
SrHfO3 for comparison. The CTE of SrHfO3 is 8.09-10.24106
K-1 (200-1300oC), whereas it is ~10.510-6 K-1 (200-1100oC)
for YSZ (Ref 14). The slope of the CTE curve of SrHfO3 has
two abnormal changes at ~650oC and ~1050oC, which are in
accordance with the phase transitions between two
orthorhomibic structures (PbnmCmcm), as well as between
tetragonal structure and cubic structure ( I 4 / mcm Pm 3m ),
respectively. The CTE of SHYY is 8.41-10.3010-6 K-1 (2001300oC), which is higher than that of SrHfO3 in the whole
tested temperature range. Furthermore, the CTE of SHYY has
no obvious abnormal change during measurement, indicating
that co-doping with Y2O3 and Yb2O3 can improve the phase
stability of SrHfO3.
Figure 4: Thermal diffusivities of the SHYY and SrHfO3.
Figure 3: CTEs of the bulk SHYY and SrHfO3.

The thermophysical properties such as thermal diffusivity and
heat capacity for the bulk SHYY and SrHfO3 were measured.
Figure 4 shows the thermal diffusivities of the bulk SHYY and
SrHfO3. The thermal diffusivity of SHYY decreases with
Figure 5: Heat capacities of the SHYY and SrHfO3.
37
The calibrated values of the thermal conductivity for both bulk

SHYY and SrHfO3 as a function of temperature are shown in
Fig. 6. The decrease in the density due to thermal expansion
was not taken into account in the calculation, so that the real
thermal conductivity values should be slightly lower.
lifetime than that of the SHYY coating under the thermal

cycling condition as described in Ref 15.
Figure 7: XRD patterns of (a) SHYY+8YSZ and (b)

SHYY+Al2O3 mixtures after heat treatment at 1250oC for 24 h.
Phase Stability and Microstructure Evolution of the SHYY
Coating
The XRD patterns of the SHYY coating in the as-sprayed case
and after heat treatment at 1400oC for different times are
shown in Fig. 8. The Yb2O3 phase developed after plasma
spraying in the as-sprayed coating. No new phase developed
during heat treatment at 1400oC from 72 h to 288 h, indicating
that the SHYY coating has good phase stability at 1400oC.
The phase stability of the as-sprayed SHYY coating was also
evaluated by TG-DSC analysis. Figure 9 shows the TG-DSC
curves of the as-sprayed SHYY coating; both of the curves are
very smooth and horizontal in the tested temperature range.
This indicates that the coating has good phase stability from
room temperature to 1400oC, even with a minor amount of
Yb2O3.
Figure 6: Thermal conductivities of the bulk SHYY and SrHfO3.

The thermal conductivity of bulk SHYY is ~1.92 W/mK at
1000oC, which is not only ~16% lower than that of SrHfO3,
but also ~10% lower than that of 8YSZ (bulk, 2.1-2.2 W/mK
at 1000oC) (Ref 16). The reasons for the reduction in thermal
conductivity of SHYY are the introduction of vacancies and
strain fields by Y3+ and Yb3+ cation addition. Y2O3 and Yb2O3
dissolve into the SrHfO3 matrix and create oxygen vacancies
to maintain the electroneutrality of the lattice. Y3+ and Yb3+
cations also introduce strain fields as well as vacancies into
the lattice, both of which will lower thermal conductivity by
reducing the phonon mean free path. Another reason might be
'
'
the formation of the YZrVO YbZr defect cluster at nanoscale,

which is believed to be responsible for the significant
reduction of thermal conductivity. The defect clusters in
SHYY have not been verified independently, however, the
defect clusters in Nd2O3-Yb2O3 (and/or Sc2O3) co-doped YSZ
have been identified by transmission electron microscopy
(TEM) analyses (Ref 17).
Chemical Compatibility of the SHYY with 8YSZ or Al2O3
The XRD patterns of SHYY with 8YSZ or Al2O3 mixtures
after heat treatment at 1250oC for 24 h are shown in Fig. 7.
There is no new reaction product between SHYY and 8YSZ
(or Al2O3) appearing either in Fig. 7a or in Fig. 7b with the
exception of a minor Yb2O3 phase. The addition of 8YSZ or
Al2O3 into SHYY might lead to the precipitation of Yb2O3
from SHYY. The XRD results indicate that SHYY has a good
chemical compatibility with 8YSZ or Al2O3, giving the
possibility to apply a one-ceramic-layer (SHYY) coating
system or a double-ceramic-layer (SHYY/8YSZ) coating
system. The primary thermal cycling results showed that the
SHYY/8YSZ coating had much longer thermal cycling
Figure 8: XRD patterns of the SHYY coating in (a) as-sprayed

case, after heat treatment at 1400oC for (b) 72 h, (c) 144 h, (d)
216 h and (e) 288 h.
38
Figure 9: TG-DSC curves of the as-sprayed SHYY coating.

The precipitation of Yb2O3 in the SHYY coating upon
spraying can be explained as follows. It is believed to be due
to the different vapor pressures for HfO2, SrO, Y2O3 and
Yb2O3, which are 710-8 atm (2500oC), 210-5 atm (2500oC),
110-6 atm (2500oC) and 610-8 atm (2500oC), respectively
(Ref 18). During thermal spraying, SrO volatilizes more than
HfO2 due to its higher vapor pressure, resulting in the coating
composition deviating from stoichiometric SrHfO3. Hf4+ is
partially substituted in SrHfO3 by Y3+ and Yb3+, and the vapor
pressure of SrO is higher than that of both Y2O3 and Yb2O3.
Therefore, Yb2O3 might exceed its solubility in the as-sprayed
coating compared to the feedstock powder, which is also
observed in Yb2O3 doped SrZrO3 (Ref 11). Furthermore, the
amount of Yb2O3 is minor in Fig. 8, owing to the similar vapor
pressure for both HfO2 and Yb2O3. Thus, the mixture of
SHYY and a minor amount of Yb2O3 developed upon
spraying.
Figure 10 shows the fracture microstructures of the SHYY
coating after heat treatment at 1400oC for different times. The
as-sprayed SHYY coating consists of a porous structure and a
layered structure, which is comprised of the unmelted particles
and the recrystallized microstructure of the well-melted
particles. Obviously, the layered structure is composed of
columnar crystals. The columnar structure within a single splat
still remains after heat treatment for 216 h, indicating that the
SHYY coating has good sintering resistance. Considering that
a single micrograph of a fracture surface is not a good
indication of the sintering, the thermal conductivity
measurements will be used to investigate the sintering of the
coating in the future.
Figure 10: Fracture microstructures of the SHYY coating after

heat treatment at 1400oC for different times: (a) as-sprayed, (b)
72 h, (c) 144 h, (d) 216 h.
SHYY was successfully synthesized at 1450oC after 24 h
without any secondary phase. The phase transition from
tetragonal to cubic for SrHfO3, investigated by DSC
measurement, was suppressed by co-doping with Y2O3 and
Yb2O3, indicating that SHYY has a good phase stability
39
between room temperature and 1400oC. The long-term

annealing of SHYY at 1450oC for 360 h revealed very high
phase stability at high temperatures. The CTE of SHYY was
8.09-10.2410-6 K-1 (200-1300oC) and exhibited no abnormal
change during measurement, indicating that co-doping with
Y2O3 and Yb2O3 can improve the phase stability of SrHfO3.
The thermal conductivity of SHYY was ~1.92 W/mK at
1000oC, which is ~16% lower than that of SrHfO3, indicating
that co-doping with Y2O3 and Yb2O3 is an effective method
for reducing the thermal conductivity of SrHfO3. SHYY also
has a good chemical compatibility with 8YSZ or Al2O3.
and H. Seifert, Process for Production of a Ceramic

Thermal Barrier Layer for Gas Turbine Engine Component,
US patent 6602553 B2, 2003
8. S. Yamanaka, K. Kurosaki, T. Maekawa, T. Matsuda, S.
Kobayashi and M. Uno, Thermochemical and
Thermophysical Properties of Alkaline-earth Perovskites, J.
Nucl. Mater., 2005, 344, p 61-66
9. B.J. Kennedy and C.J. Howard, High-temperature Phase
Transitions in SrHfO3, Phys. Rev. B, 1999, 60(5), p 29722975
10. S. Yamanaka, T. Maekawa, H. Muta, T. Matsuda, S.
Kobayashi and K. Kurosaki, Thermal and Mechanical
Properties of SrHfO3, J. Alloy Compd., 2004, 381, p 295300
11 W. Ma, D. Mack, J. Malzbender J, R. Vaen and D. Stver,
Yb2O3 and Gd2O3 Doped Strontium Zirconate for Thermal
Barrier Coatings. J. Eur. Ceram. Soc., 2008, 28, p 30713081
12. W. Ma, F. Song, W. Lun, D. Wang, H. Dong and X.
Zheng, Sc2O3 and Gd2O3 Co-doped Strontium Zirconate as
a New Thermal Barrier Coating Material, Adv. Mater. Res.,
2011, 239-242, p 1457-1462
13. W. Ma, W. Lun, H. Dong, L. Wang and X. Zheng,
Fundamental Physical Properties of Ta2O5 and Yb2O3
Codoped Strontium Zirconate for Thermal Barrier Coating
Applications, Mater. Res. Innovations, 2011, 15(5), p 319323
14. R. Morrell, Handbook of Properties of Technical and
Engineering Ceramics, Part 1, Her Majestys Stationery
Office, London,1985, p 87
15. W. Ma, D. Mack, R. Vaen and D. Stver, PerovskiteType Strontium Zirconate as a New Material for Thermal
Barrier Coatings, J. Am. Ceram. Soc., 2008, 91(8), p 26302635
16. S. Sodeoka, M. Suzuki, T. Inoue, K. Ueno and S. Oki,
Thermal and Mechanical Properties of Plasma Sprayed
ZrO2-CeO2-Y2O3 Coatings, Proceedings of the 9th
National Thermal Spray Conference, Thermal Spray:
Practical Solutions for Engineering Problems, C.C. Berndt
Ed., ASM International, Cincinnati, OH, 1996, p 295-302
17. D. Zhu, Y. Chen and R. Miller, Defect Clustering and
Nanophase Structure Characterization of Multicomponent
Rare Earth-Oxide-Doped Zirconia-Yttria Thermal Barrier
Coatings, NASA/TM2004-212480
18. U. Schulz, B. Saruhan, K. Fritscher and C. Leyens,
Review on Advanced EB-PVD Ceramic Topcoats for TBC
Applications, Int. J. Appl. Ceram. Technol., 2004, 1(4), p
302-315
The free-standing SHYY coating was prepared by air plasma

spraying. The coating consisted of SHYY and a minor amount
of Yb2O3 secondary phase, and had good phase stability after
heat treatment at 1400oC for 288 h. The columnar structure
within a single splat still remains after heat treatment for 216 h.
Acknowledgements
The authors gratefully acknowledge the financial support by
the National Natural Science Foundation of China (51062012),
the Key Project of Chinese Ministry of Education (210035),
and the Program for New Century Excellent Talents in
University (NCET-11-1017).
References
1. X. Cao, R. Vaen and D. Stver, Ceramic Materials for
Thermal Barrier Coatings, J. Eur. Ceram. Soc., 2004, 24, p
1-10
2. H. Xu and H. Guo, Thermal Barrier Coatings, Woodhead
Publishing Limited, Cambridge, U.K., 2011, p 25-74
3. B. Saruhan, P. Francois, K. Fritscher and U. Schulz, EBPVD Processing of Pyrochlore-structured La2Zr2O7-based
TBCs, Surf. Coat. Technol., 2004, 182, p 175-183
4. R.A. Miller, Oxidation-Based Model for Thermal Barrier
Coating Life, J. Am. Ceram. Soc., 1984, 67(8), p 517-521
5. R.A. Miller, J.L. Smialek and R.G. Garlick, Phase Stability
in Plasma-Sprayed Partially Stabilized Zircoina-Yttria,
Advances in Ceramics, Vol.3: Science and Technology of
Zircoina, A.H. Heuer and L.W. Hobbs Ed., American
Ceramic Society, Columbus, OH, 1981, p 241-251
6. A.F. Renteria and B. Saruhan, Effect of Ageing on
Microstructure Changes in EB-PVD Manufactured
Standard PYSZ Top Coat of Thermal Barrier Coatings, J.
Eur. Ceram. Soc., 2006, 26(12), p 2249-2255
7. B. Heimberg, W. Beele, K. Kempter, U. Bast, T. Haubold,
M. Hoffmann, A. Endriss, P. Greil, C. Hong, F. Aldinger
40


All rights reserved
A Novel Modification for Twin Wire Arc Spraying to

Improve the Variety of Application
W. Tillmann, M. Abdulgader*, L. Hagen
Institute of Materials Technology, Technische Universitt Dortmund, Dortmund, Germany
* mohamed.abdulgader@udo.edu
Abstract
substrate surface (Ref 1-7). In thermal spraying technique, the

in-flight particle characteristics like velocity, temperature and
particle size are the controlling factors in splat formation, and
in the determination of the coating quality (Ref 2-7). The
produced layers are the result of a simultaneous overlapping of
the deformed splats from all positions in the jet to form a
continuous coating. The different degrees of particle
temperature, velocity, and size lead to a deposit containing
melted and un-melted particles, porosity, oxides, and debris.
Various approaches are presented in this paper to adapt

conventional twin wire arc spraying (TWAS) technique for the
production of smooth and finely structured coatings. Higher
particle velocities were achieved due to the applied
modification of the spraying nozzle geometry. The newly
developed
nozzle
geometries
integrate
also
the
implementation of a Laval shape, which led to the highest
improvement regarding the attained particle velocities. An
elimination of the overspray was also observed by using Laval
nozzle configuration. Furthermore the region of high velocity
in spraying plume was increased. This led to a more focused
spraying plume. The optimal spraying distance was
reconsidered regarding the obtained coating roughness and
found to be larger than 200 mm. The change in the optimal
spraying distance is due to the achieved higher velocity of the
associated gas, which affects the surface roughness of the
obtained coating. The new nozzles have showed the deposition
of the spraying particles on the nozzle wall, which causes a
restriction of the plume flow at long spray runs. The
modification of nozzle geometries is still a very promising
aspect regarding TWAS-process improvement.
In case of powder as feedstock, the size of the in-flight

particles is predefined by particle size distribution given by
powder supplier. The powder particles are finely divided by
means of the carrier gas and fed to the flame. At the
interaction with the flame the powder particles are heated and
accelerated. In TWAS process the spraying jet is formed by
the atomization of molten or semi molten droplets from the
wire tips. This is performed by the impingement of fast
moving and continuously flowing atomization gas upon
melting tips of consumable and electrical conductive wires.
The wires are connected individually one to the anode and the
other one to cathode fed together to ignite an arc at the
shortest distance between the wire tips, as shown in Fig. 1.
Introduction
Thermal spraying is a material processing technique, which is
based on the combination of thermal and kinetic energy. The
feedstock used is heated by one of the following heat sources:
chemically (by combustion), physically (by gas ionization), or
electrically (by employing arc ignition) (Ref 1). The materials
of the feedstock are accelerated, melted and then atomized by
means of atomization or process gases. These processes differ
not only in their thermal source but also in their feedstock
type. The three major categories of feedstock materials used
are powders, massive wires and cored wires. The main
properties of the thermal sprayed coatings are considered as
the sum of the parameters which directly or indirectly
influence the particle formation, particle in-flight
characteristics and the flattening behavior of droplets on the
Figure 1: Schematic of the twin wire arc spraying process.
41
Twin wire arc spraying (TWAS) is an attractive alternative for

the production of wear and corrosion protective coatings. The
main advantages of TWAS are the lower cost of acquisition
and operation, as well as extremely high energy efficiency
with the highest deposition rates compared to the other
thermal spraying processes (Ref 1-6). There are also some
major disadvantages, which limit the use of the TWAS
process. A TWAS-sprayed coating shows in general a very
inhomogeneous and coarse layer structure. The surface of the
obtained coating has a high roughness and can reach a high
porosity levels. All these drawbacks are confining the use of
such coating for high end demands.
The shroud technique consists in a protection the spraying

particles against oxidation by means of inert gas injection in
order to decrease the amount of air entrained within the jet
(Ref 15, 19). The shroud effect can be also implemented by
nozzle configuration in the way that nozzle covers a bigger
part of the spraying jet. Using of a shroud configuration in the
nozzle design in order to decrease the rate of air in the jet was
also studied in (Ref 19, 20). Shrouding by using inert gas as
secondary atomization medium may also contribute to
decrease the jet divergence (Ref 14). This type of shroud was
used by Hussary et al (Ref 20) who used the works of Wang et
al. (Ref 16) on the gun design. Their nozzle was designed in
order to obtain a properly expanded flow at the exit, whereas a
ring of twelve holes surrounding the nozzle was used for the
shroud gas injection. These holes were oriented in order to
decrease the primary jet divergence: they converged to a point
on the axis of the primary flow at a few centimeters from the
nozzle exit. An increase in the particle velocity and a
significant decrease in the droplets jet divergence were
obtained with this method (Ref 20).
At the LWT (Institute of Materials Technology) at the

Technical University of Dortmund many promising results are
gained to improve the TWAS process and to suite for the
coating of the complex surface geometries such as in the
forming tools. However, it was also observed that due to their
coarse layer structure and its high roughness, the arc sprayed
coatings show a higher need of a post-treatment. In a parallel
study at the same Institute a High Velocity Oxygen Fuel
(HVOF) sprayed coatings were investigated regarding the
relationship between the obtained coating quality and the
achieved coating performance. Decreasing the porosity and
surface roughness of the obtained coating leads to significant
improvements in its functional properties, such as a
customized tribology properties and optimized friction
coefficients. The above mentioned improvements are mainly
achieved because of the higher velocities of the spraying
particle in HVOF. In literature it was found that the nozzle
expansion ratio, accelerating gas type and pressure are among
the main factors influencing the accelerating behavior of spray
particles in a limited space (Ref 8). Furthermore, it was also
indicated that particle velocity in cold spraying could be
influenced not only by the nozzle expansion ratio (i.e., the
ratio of the area of the exit to the throat) Ref 9), but also by the
entrance convergent section length (Ref 10), the driving gas
conditions (Ref 9-12), and the particle density and size (Ref 9-
11, 13). The nozzle configuration effects directly the process
efficiency and thus the produced coating quality (Ref 14).
Increase in the particle jet spreading is mainly caused by an
under-expanded gas jet at the nozzle exit, which represents a
significant diverging component that may contribute to the
spreading effect, which is detrimental to the coating quality
(Ref 14). The converging/diverging nozzles configuration
show promising results regarding particle velocities and jet
convergence (Ref 15-18). In particular, these nozzles allow
increasing gas velocity at the intersection point of the wire tips
(Ref 14). The mean droplet size and thus the obtained coating
quality are influenced directly by the used nozzle type (Ref
15). For example, the use of a converging/diverging nozzle
causes a decrease in the mean droplet size when compared to
that obtained using a cylindrical nozzle (Ref 14, 15, 19). This
effect is directly correlated to the increase in the gas velocity,
which leads to a smaller droplet size and provides
improvements in the quality of the coatings (Ref 15, 19).
Therefore a significant increase in the particle velocity in

TWAS-process could be only established through the
modification of the spraying nozzle. This topic is a very
promising field of research and should lead to the desired
improvement in the quality of the sprayed coatings. This study
follows different modification approaches of the nozzle design
in the TWAS-gun. Laval nozzle shapes are also considered to
achieve a higher particle velocity. The determination of the
Laval shape was based on theoretical calculations, which take
in consideration the mass volume flow and pressure of
primary atomization gas and the outlet pressure. A shroud
nozzle type was also investigated.
Materials and Experiments
Materials
Smart Arc 350 PPG (Sulzer Metco, Switzerland) was used to
investigate the effect of the nozzle design on the in-flight
particle characteristics. The investigations were carried out on
solid wires (Fe ~wt.97% (Sprasteel11) and Ni wt. 99.9%
(Metco Nickel) Co.Sulzer Metco Europa GmbH). The wires
are 1.6 mm in diameter. For the comparison conventional air
caps were used to determine the impact of the nozzle design
on the plume configurations (see Fig. 2). For all design
configurations, compressed air was used as an atomizing gas.
To determine the in-flight particle velocity and temperature
Accuraspray-g3 (Tecnar, Canada) was used. The measuring
device was located at the main spraying axis at 110 mm standoff distance from the wires intersection. The in-flight particle
velocity, temperature, and flame width were recorded. At the
same stand-off distance substrates were mounted and coated.
42
Experiments
nozzle (Ref 20). The difference of these two nozzles is the

angle between the two opposite sided secondary gas outlet
holes (see Fig. 2). The number of the secondary gas outlet
holes are 10 and 12 for the nozzle at 30 and 60 secondary
gas intersection respectively. The angle of the outlet holes
effects directly the distance at which secondary and primary
gas flows intersect. The comparison with the conventional
nozzles will provide design guidelines to improve the flow
regimes at the outlet of the modified nozzle.
Three different conventional nozzles were utilized to study the

effect of the gas pressure and the intersection between the
primary and secondary atomization gases on the spraying
plums (see Fig 2).
Secondary
gas inlet
Results
Conventional Spraying Nozzles
The tests have shown that the highest particle velocities can be
produced with the nozzle 60 (168 5 m/s). The increase of
the secondary gas pressure leads to an increase in the particle
velocity. The behavior of the particle velocity in case of 4H
nozzle is different. The 4H nozzle has a detrimental effect on
particle velocity especially at higher spraying distance. The
particle velocity decreases at higher spraying distances with
increased gas pressure. Nevertheless, the measurements show
that the 4H nozzle has the narrowest spraying plume. The
focusing effect of the secondary gas is also obvious at 60
nozzle, as shown in Fig. 3 using Schlieren images. The nozzle
with 60 has a higher effect on the plume focusing than the
one with 30. In both cases the gas flow is more dominant
from the upper side of the nozzle, directly beneath the
secondary gas inlet. The images reveal no gas flow from the
wire side for both nozzle configuration 30 and 60. The
diamond shocks in the secondary gas flows are more obvious
for the outlet holes located at the nozzle upper side directly
below the gas inlet.
Wires
intersection
Secondary
gas inlet
Secondary
gas inlet
Figure 2: Concept of the conventional nozzles
Figure 3: Flow characterization in conventional nozzles using

Shlieren techniques
One of the conventional nozzles has 4 outlet holes for the

secondary atomization gas flow, two holes from the above
side of the wire intersection and two from the below (see Fig.
2 - 60 4H). The degree numbers (30 and 60) stands for the
angle between the secondary gas outlet holes. The
abbreviation 4H represents 4 holes. The secondary gas outlet
holes are arranged on a circle radius and are distributed
regularly around the nozzle exit for the other two nozzles. This
configuration is similar to those of N. Hussary developed
Comparing the plume width recorded by means of

AccuraSpray it is obvious that, the primary gas pressure has a
higher effect on the focusing of the spraying plume than
secondary gas pressure. The obtained results were the base for
the development of the Laval nozzle. The secondary gas outlet
angel of 60 is favored, because of the focusing effect at this
angle. Also the 60 angle of the secondary gas flow permits a
compact design of the nozzle, in the way that the throat of the
43
Laval nozzle is located closer to the arc zone. The location of

the Laval was determined due the findings in Schlieren images
(Fig. 4). So that the total flow of primary and secondary gas
combined directly before entering the converging part of the
Laval nozzle. The shape of the Laval nozzle is determined
theoretically for the following boundary conditions: primary
gas pressure 6 bar, secondary gas pressure 6 bar, and outlet
pressure atmospheric pressure.
Figure 5: Nozzle attachment with various types of integrated

Laval nozzles
The increase in the particle velocity can be directly related to
the increase of the obtained gas velocities caused by the
geometrical changes in the nozzle design. The diverging part
at the nozzle outlet led to an increase of the outlet gas velocity,
which reached the supersonic speed of the compressed air.
The increased gas velocity leads to finer secondary
atomization of the in-flight particles. Therefore, a significant
increase in the particle velocity was achieved with the Laval
modification. It is assumed, that a finer secondary atomization
of the spraying particles took place. Simultaneous increase of
the particle temperature (see Fig. 6) caused by the exothermal
reactions and favored by the higher oxidation of smaller
particles verifies the findings. Furthermore in contrast to the
conventional nozzle, the spray particles experience reduced
heat dissipation due to the higher residence time in the nozzle
attachment (influence of nozzle length).
Figure 4: Laval nozzle concepts for the focusing of TWAS

plume
Nozzle Modification
The approached nozzle modifications have a common goal,
which is the increasing in particle velocity and decreasing in
plume divergence.
Laval nozzle: On the basic of the obtained results of the
conventional nozzles a Laval shape and its position in the
spraying plume were suggested and manufactured (see Fig. 5).
The results show that the modified nozzle leads to an
increased particle velocity. The Laval modification 1 led to an
increase in the particle velocity of about 110 m/s compared to
conventional nozzles. The use of the modification 2 revealed
even a higher increase of 135 m/s.
Figure 6: Particle velocity and temperature

The deposition of the in-flight particles at the inside surface of
the Laval nozzle causes restrictions for the spraying process.
This problem is directly related to positioning of the Laval
throat in the spraying plume, as well as to the adjusted gas
pressures.
44
The slot form of the secondary gas outlet has a negative effect
on the achieved particle velocity as illustrated in Fig. 9. At
increased secondary gas pressure a significantly decrease in
particle velocity was obtained. The decline in particle velocity
is more obvious at a primary gas pressure of 6 bar. The
combination 6 bar - 6 bar shows a lower velocity than the
combination 4 bar - 6 bar.
For visual-evaluation of the spray plume, images of the spray

jet produced by the different nozzle attachments have been
taken. The images show clearly that a focused spray plume
can be realized by using Laval modified nozzle as shown in
Fig. 7. The plume focusing reached more than 300% of the
initial plume of the conventional nozzle. The area of the
overspray is completely eliminated. The high velocity zone in
the Spraying plume is extended. This is beneficial for
improving the process efficiency in TWAS.
Figure 7: Focusing effect by using Laval nozzle

Shrouded nozzle: The basic development concept of the
shrouded nozzle attachment is to reduce the plume divergence
and to mix the spraying particles in the plume homogenously
(Fig. 8). So that, a monomodal pattern of the spraying particles
in the plum is achieved. This is essential in the improvement
of the obtained coating quality. The design was performed in
the way that different secondary gas outlet angels were
implemented along the nozzle design. The secondary gas
outlet is realized performed through slots and not holes.
Figure 9: Particle velocity for the shrouded nozzle

The modification of the nozzle design led to a potential
improvement in the obtained particle velocity. An increase of
about 100 m/s in the particle velocity was observed by using
the Laval form on the nozzle design. The spraying plume is
focused (from 36 to 8) and the overspray is eliminated. The
shrouded design showed in some cases a negative effect. The
design of the nozzle attachments, however, requires the
consideration of numerous thermodynamic aspects and
requires further optimization loops.
Acknowledgements
The authors gratefully acknowledge the nancial support of
the DFG (German Science Foundation) within the
Transregional Collaborative Research Centre SFB708,
projects A1 and B3.
Figure 8: Shrouded nozzle design
45
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All rights reserved
High-Temperature Oxidation-Resistant Thermal Spray Coatings Based on

MoSi2 for Furnace Applications
S. Schuberth, T. Uhlig, H. Pokhmurska, C. Rupprecht and T. Lampke

Institute of Materials Science and Engineering, Chemnitz University of Technology, Chemnitz, Germany
The oxygen-diffusion is prohibited by the MoSi2-Layer due to

the so called self-protection. This effect can be explained by
the partial oxidation of Si on the layers surface resulting in a
glass like SiO2-surface that protects the component from
further oxidation (Ref 1-2). The material can be used up to
temperatures of 1650 C because the protecting SiO2-film
melts at 1723 C (Ref 3-4). Apart from the utilization as
heating conductor the material can be used for the production
of glow plugs, susceptors and gas turbines (Ref 5-6).
Abstract
In high-temperature industrial furnaces metallic components
are used for radiation shields, muffles, protective tubes and
high-temperature recuperators. In these cases, the application
of metals instead of ceramics is advantageous, mainly due to
the greater thermal dynamics that allow a faster and more
precise control of the furnace and work load temperatures. For
these components, the operation under oxidizing atmospheres
is normally limited to temperatures of up to about 1450 K. It is
also known that molybdenum disilicide works well in a
temperature range from 950 to 1900 K under these conditions.
Therefore the aim of this work is the characterization and
optimization of molybdenum disilicide coatings for the hightemperature oxidation protection of metallic substrates.
Thermal spraying of agglomerated/sintered powder was
carried out by the APS process. Feedstock and coatings were
characterized by means of optical and scanning electron
microscopy. Coating porosity was determined by digital image
analysis.
Surfacing of metallic and ceramic components with MoSi2 is

possible by using different processes like PVD/CVD or
thermal spraying (Ref 7-8). The applicable spraying processes
are VPS, APS and HVOF (Ref 9-10).
Experimental
The powder production line contains the steps production of
suspension, spray drying and sintering. Within this
investigations the used powder fractions are 5 m < d < 20 m
and 20 m < d < 45 m. The powders are characterized in the
final sintered state. Thereby the particle distribution is
examined by laser diffraction. The measured particle size
distribution is shown in Fig. 1. A SEM micrograph of the
-45+20m powder is shown in Fig. 2.
Introduction
A lot of furnace linings consist of refractory materials like
Al2O3 or SiC with additional radiation shields, subdivisions or
muffles. These metallic parts are widely used in furnaces that
are operating in inert atmospheres. Especially because of the
better thermal dynamics, metallic components have
advantages over the conventional high-temperature-resistant
ceramics. Nevertheless these parts cannot be utilized when an
oxidizing atmosphere and high temperatures occur at the same
time.
The powders are processed by means of APS. The used

spraying system is a GTV F6 APS torch, using different
argon-hydrogen mixes. The parameter sets differ concerning
the different particle sizes of the powders because the surface
to volume ratio differs, the current remains constant at 600 A.
The coating process is carried out in meandering line scans
with line spaces of 3 mm. The spray distance is adjusted in the
range 100150 mm. The complete set of spray parameters is
shown in Table 1.
Molybdenum disilicide (MoSi2), which was discovered in

1907, has a unique profile of physical properties. Because of
its high melting point, its low electrical resistance up to high
temperatures and its excellent oxidation resistance it is
predestinated for applications in oxidizing atmospheres in the
temperature-range of 7001650 C.
47
Results
100
25
MoSi2 -45+20 m
20
15
MoSi2-layers are processed by means of APS with different

powder fractions by adjusting the spray parameters. As can be
seen in Fig. 3, the coatings sprayed with finer powder are
much denser than the ones produced with coarse powder. The
porosity strongly depends on the particle size. The measured
porosity is shown in Fig. 4 in relation to the parameters. The
coatings hardness depends on the particle size and the
processing parameters.
80
MoSi2 -20+5 m (cum.)

60
MoSi2 -45+20 m (cum.)
10
40
20
cumulated [%]
distribution density
MoSi2 -20+5 m
10
100
As shown in Fig. 5, the determined hardness rises with lower

heat input and higher spray distance. That may be the result of
the lower thermal energy of the impacting particles. The
adhesive pull strength is determined according to EN 582, the
results are shown in Fig. 6. The particle size and spray
parameters have not got a remarkable influence on the tensile
strength because delaminations mostly occur at the interface
between substrate and layer as can be seen in Fig. 7.
particle size [m]
Figure 1: Measured particle size distribution of MoSi2powders.
Figure 2: SEM micrograph of powder MoSi2 -45+20 m.

Investigations of produced coatings are carried out by means
of scanning electron microscopy, energy dispersive X-ray
analysis and X-ray diffractometry. SEM is carried out using a
SEM Leo 1455VP with integrated EDXS analysis unit. X-ray
diffractometry (XRD) is accomplished using Cu-K rays.
Light microscopical analyses and porosity measurements of
produced coatings are aided by a Jenoptic digital picture
examination system. The coating porosity is determined by
digital image analysis.
(a)
Table 1: Set of applied spray parameters.

particle size
-20+5 m
Ar [slpm]
H2 [slpm]
spray distance [mm]
-40+25 m
40
2,5
10
(b)
Figure 3: Optical micrographs of MoSi2-layers processed by
APS (a) MoSi2 -45+20 m (b) MoSi2 -20+5 m.
100, 125, 150
48
30
tensile stress [MPa]
porosity [%]
20
15
10
25
20
15
10
5
-45+20 m
5 slpm H2
0
-20+5 m
2.5 or 5
5 or 10
10 slpm H2
100
flow rate H2 [slpm]
125
150
spray distance [mm]
(a)
Figure 6: Determined adhesive pull strengths of MoSi2

coatings.
porosity [%]
20
15
10
5
2.5 slpm H2
0
5 slpm H2
100
125
150
spray distance [mm]
(a)
(b)
Figure 4: Measured porosity of the coatings:
(a) MoSi2 -45+20 m;
(b) MoSi2 -20+5 m.
600
HV 0.3
500
400
(b)
300
Figure 7: Fractured surface of the coatings:

(a) MoSi2 -45+20 m;
(b) MoSi2 -20+5 m.
200
100
5 slpm H2
0
10 slpm H2
100
125
Summary and Conclusions
150
spray distance [mm]
MoSi2-coatings were applied by APS process using

agglomerated and sintered powders of different particle sizes.
The powder particles exhibited globular shapes and thereby
feeding properties were not observed. Processing of the
powders was done using an APS F6 torch.
Figure 5: Determined hardness of the coatings MoSi2

-45+20 m.
49
The influence of the powder size and spray parameters on

porosity, hardness and adhesive pull strength was determined.
While coatings produced with coarse powder fraction
exhibited a relatively high porosity of about 10-15 %, the finer
powder can be applied resulting in low porosity range around
5 %. Especially the finer powder fraction is susceptible to low
processing temperatures, which result in a strong increase of
porosity.
References
1. Y.A. Chang, Oxidation of Molybdenum Disilicide, J.
Mater. Sci., 1969, 4, p. 641-643
2. W. Schulle, Feuerfeste Werkstoffe, Deutscher Verlag fr
Grundstoffindustrie, 1991
3. Y.L. Jeng and E.J. Lavernia, Processing of Molybdenum
Disilicide, J. Mater. Sci., 1994, 29, p. 2557-2571
4. K. Bundschuh and M. Schtze, Materials for Temperatures
above 1500 C in Oxidizing Atmospheres - Part I: Basic
Considerations on Materials Selection, Mater. Corr.,
2001, 52, p. 204-212
5. N.S. Stoloff, C.T. Liu and S.C. Deevi, Emerging
Applications of Intermetallics, Intermetallics, 2000, 8, p.
1313-1320
6. Z.J. Yao and T.S. Stiglich, Molybdenum Silicide Based
Materials and Their Properties, J. Mater. Eng. Perf, 1999,
8, p. 291-304
7. J.K. Yoon, J.Y. Byun, G.H. Kim, J.S. Kim and C.S. Choi,
Growth Kinetics of Three Mo-Silicide Layers Formed by
Chem. Vapor Deposition of Si on Mo Substrate. Surf.
Coat. Techn., 2002, 155, p. 85-98
8. S. Govindarajan, J.J. Moore, B. Mishra and D.L. Olson,
Physical Vapor Deposition of Molybdenum and Silicon
Thin Films. Surf. Coat. Techn., 1994, 68-69, p. 45-50
9. M. Fukumoto, T. Ueda and I. Okane: Gas Permeability of
Plasma Sprayed MoSi2 Coating. J. Mater. Sci. Lett., 1994,
13, p. 656-657
10. S. Motojima, A. Fujimoto, and K. Sugiyama, Molybdenum
Disilicide Coating on Steel and its Oxidation Resistance, J.
Mater. Sci. Let., 1982, 1, p. 19-22
The hardness of the coatings exhibits a contrary effect. It rises

with lower heat input caused by lower hydrogen flow rates or
larger spray distances. The value of the adhesive pull strength
was about 25 MPa, which should be sufficient for the most
applications. The fracture at the interface of coating and
substrate was not significantly influenced by the spray
parameters.
Further investigations will deal with the development of a
diffusion barrier coating between substrate and coating.
Additionally the chemical characterization of the coating will
be carried out.
Acknowledgement
Part of the research was carried out within the scope of the
project # 16858 BG/1 funded by the Bundesministerium fr
Wirtschaft
und
Technologie
(BMWi)
via
the
Arbeitsgemeinschaft fr Industrieforschung (AiF). The
authors thank the BMWi for financing this project and the
Fraunhofer IKTS for supplying the powders.
50


All rights reserved
Friction and Wear Properties of (Ti,Mo)(C,N) Hardmetal Coatings Prepared

by Gas and Liquid Fuel HVOF Processes
L.-M. Berger
Fraunhofer Institute Material and Beam Technology (IWS), Dresden, Germany
J. Kitamura*, F. Kasahara, J. Yamada, K. Sato
*E-mail: kitamuraj@fujimiinc.co.jp
P. Vuoristo, A. Milanti, K. Niemi
Tampere University of Technology, Department of Materials Science, Tampere, Finland
. Houdkov
Vzkumn a zkuebni stav Plze s.r.o (VZU), Plzen, Czech Republic
J. Savkov
New Technology Research Centre, University of West Bohemia, Plzen, Czech Republic
HVOF coatings is needed. The main commercial feedstock

hardmetal compositions are based on tungsten carbide, WC
(WC-Co, WC-CoCr, WC-(W,Cr)2C-Ni traded as WC-CrCNi or similar), or chromium carbide, Cr3C2 (Cr3C2-NiCr).
HVOF coatings prepared from these powders are
characterized by their excellent mechanical properties. They
also represent an environmentally friendly alternative to hard
chrome plating. (Ref 3, 4)
Abstract
Materials based on the cubic hard phase TiC are a highly
promising extension and alternative to existing hardmetal
coating solutions, such as WC-Co, WC-CoCr and Cr3C2-NiCr.
TiC-based compositions, alloyed with Mo and N, consist of
two core-rim-structured hard phases embedded in metal binder
phase of Co and/or Ni, for example. These materials can be
sprayed with various methods, such as plasma spray,
detonation gun and HVOF, resulting in competitive coating
properties. For example, HVOF sprayed (Ti,Mo)(C,N)hardmetal coatings show variable friction properties where the
coefficient of friction (CoF) is lower when sprayed by gas fuel
type whereas liquid fuel type gives higher CoF. However, this
conclusion needs to be confirmed, since feedstock powders
and measurement equipment have been different that makes
prevent simple comparison. In this work, comprehensive
studies have been conducted by preparing powder feedstock
with Ni and Co binders retaining same manner for various
HVOF methods as well as unified measurement conditions for
CoF and wear properties.
Among the carbides of the transition metals of the IVB-VB

groups of the periodic table, TiC is the most promising
alternative to WC and Cr3C2 due to its properties and
abundance (Ref 5). Based on alloying concepts for cutting
tools, special Mo- and N-alloyed feedstock powders have been
developed where two core-rim-structured hard phases are
embedded in metal binder phase of Co and/or Ni, for example.
(Ref 6-8) These materials can be sprayed with various
spraying methods, such as plasma spray, detonation gun, and
HVOF, resulting in competitive coating properties. In
particular, (Ti,Mo)(C,N) hardmetal coatings have unique
friction properties compared with conventional carbide
coatings. They show variable friction properties where
coefficient of friction (CoF) is lower in coatings sprayed by
gas fuel tHVOF systems compared to those sprayed by liquid
fuel spray systems (Ref 4, 7-13). A lower CoF can be also
retained under high temperature test conditions than common
carbide materials, implying that is suitable for sliding
applications under high temperature.
Introduction
Thermal spray coatings have been continuously advanced,
enabling the expansion of their practical applications in a
range of industries. High velocity oxy-fuel (HVOF) spraying
technology has played an important role in the development of
functional surfaces with a high wear resistance. (Ref 1) This is
a critical factor for many machinery parts in industrial
applications. (Ref 1, 2) Their required wear resistance is
continuously increasing, and a matched improvement of
However, this conclusion needs to be confirmed, since

(Ti,Mo)(C,N) hardmetal as feedstock powders and
measurement equipments have been different which prevents
51
simple comparison. In this work, comprehensive studies have

been conducted by preparing powder feedstock of Ni and Co
binders retaining same manner. Three kinds of HVOF
processes, K2, Diamond Jet and JP-5000 have been used to
prepare the coatings. Three kinds of wear test, dry rubberwheel (3-body, ASTM G65), dry abrasion (2-body, ASTM
D6037) and pin-on-disk (ASTM G99), as well as CoF
measurement have been conducted under uniform conditions.
Basic characterization has been also carried out, such as
microstructure, hardness and adhesive strength.
porosity was estimated by image analysis from OM images.

Coating hardness was evaluated by micro Vickers hardness tester
(HV0.2). Adhesion test for the coatings (ASTM C633-79) was
also carried out.
Three kinds of wear tests were conducted: 3-body dry rubber
wheel test (ASTM G65), 2-body dry abrasion test (ASTM
D6037) and Pin-on-Disk (PoD, ASTM G99). In G65,
modified apparatus tested five samples simultaneously. Total
duration of the test was 60 min (wear length of 5904 m).
Samples were pressed against the rubber wheel with a force of
22 N. The surface speed of the rubber wheel was 1.64 ms-1.
Specimens had dimensions of 50 20 5 mm. Dry quartz
sand (SiO2) with a grain size of 0.1-0.6 mm was used as an
abrasive. Wear area was approximately 30 20 mm.
Experimental
(Ti,Mo)(C,N) Hardmetal Powders and HVOF Spraying
Four kinds of (Ti,Mo)(C,N) powders were produced by
agglomeration and sintering by Fujimi Incorporated (Japan) as
summarized in Table 1. Ni and Co were used as binder metal,
whose content was around 26~28wt%. Their volume ratio of
metal and ceramics was almost same as WC-12wt%Co (Ref 5).
Two different particle size distributions (PSD) of -45+15 and 30+10 m were prepared for kerosene- and gas-fuel HVOFs,
respectively. Scanning electron microscopic images of typical
powders are shown in Fig. 1.
The D6037 abrasion test, shown in Fig. 2 was tested under the
following conditions. The abrasive was silicon carbide (SiC)
sand paper (F180, +63 m, D50% of around 90 m). Specimens
had dimensions of 50 70 5 mm. The load was 30.1 N.
Reciprocating velocity and total reciprocation at one test cycle
(run) was 40 DS/min and 400 DS, respectively. After weight
measurement, specimens were tested again. Wear area was
approximately 30 12 mm. Wear length was estimated to be
24 m/run. Each specimen had 5 run (total wear length of 120
m).
Three HVOF spray processes were used: kerosene-fuel type of

K2 (GTV, Germany) and JP-5000 (Praxair, USA) as well as
gas-fuel type of Diamond Jet 2700 (DJ-2700, Sulzer Metco,
Switzerland) for comprehensive study. A PSD of -45+15 m
powders was used with K2 and JP-5000, while -30+10 m was
used with DJ-2700. Low carbon steel was used as a substrate.
Detailed conditions of PoD test of unidirectional sliding wear

(CSM high temperature tribometer) are as follows. Steel
100Cr6 and Al2O3 (alumina) ball of 6 mm in diameters were
used as counter part. Diameter of wear track was 6 and 12 mm
for steel and alumina, respectively. Load was 10 N. Sliding
velocity was 10 cm/s and the test was stopped at 30000 cycles.
Coefficient of friction (CoF) was also measured during the test.
Table 1: (Ti,Mo)(C,N)-Ni and Co powders

Product name
PSD
[m]
DTS-T10-45/15
DTS-T11-30/10
DTS-T14-45/15
DTS-T15-30/10
-45+15
-30+10
-45+15
-30+10
(a) T10
Chemical composition (wt%),

Ti as balance
Mo
C
N
O
Ni
10.4 8.4
4.7
0.3
26.5
10.5 8.6
4.5
0.5
26.0
10.5 8.3
4.5
0.5
10.3 8.2
4.5
0.6
-
Co
27.8
27.1
reciprocation
Load: 3.15kgf (30.9N)
Coating
SiC abrasive paper (F180)
(b) T11
Figure 2: 2-body dry abrasion test, ASTM D6037

Microstructure, Adhesion and Hardness
Cross sectional images by OM are shown in Fig. 3. Porosity
by image analysis is inserted in the figure. Coating thickness
of K2 and JP is about 200 m and of DJ is thicker about 600
m. Images and porosities indicate both Co-K2 and Ni-K2
coatings have denser structure, which seems to be similar to
conventional WC- and Cr3C2-based HVOF-sprayed hardmetal
coatings. Co-DJ coating are also dense whereas Ni-DJ has
higher porosity. Coatings by JP-5000 are porous, which is
apparently different from conventional hardmetal coatings as
well as the previous reports on (Ti,Mo)(C,N)-based coatings.
Figure 1: (Ti,Mo)(C,N)-Ni powders of (a) -45+15 m and (b) 30+10 m

Evaluations of Coating Properties
Microstructural investigation of the coatings was carried out by
optical and scanning electron microscopy (OM and SEM). Coating
52
(Ref 4, 8-10) Porosity of Ni-JP coating has been difficult to

evaluate due to large scaled lateral crack that tend to
overestimate. Adhesion testing (ASTM C633-79) has shown
that all specimens have failed at adhesives, whose strength is
about 80 MPa.
identified as core-rim-structured hard phase embedded in

metal binder phase as bright region is clearly seen from all
coatings. No clear difference of microstructure can be seen
from the images implying that (Ti,Mo)(C,N)-based
composition is relatively insensitive to decomposition and
oxidation during spraying compared to WC-Co for example
(Ref 14, 15). The hardness of the coatings prepared in this
study ranges from 550 to 730 HV0.2. The K2 coatings have
similar hardness as the coatings sprayed by JP-5000 in
previous study (Ref 8). However, hardness of the JP coating in
this study is significantly lower. As for DJ, present specimens
also show lower hardness than that presented in previous
report. (Ref 16) As a result, K2 attains harder coatings than
others within this study. JP and DJ should have much room to
increase hardness by optimization.
Large lateral cracks are seen in Ni-JP coating. This suggests

that optimization of spray parameters is required. Since these
coatings have been prepared with slow movement of spray
gun, substrates have been overheated. This thermal stress may
be the cause of lateral cracks and porous structure. Spray
parameters for K2 and DJ as well as powders for them are also
insufficiently customized. Therefore, coatings are expected to
be improved, which will be studied in the future.
(a) Co-K2, 3.6%
(b) Ni-K2, 4.3%
200m
(c) Co-DJ
Another possible reason of lowering hardness is particle

strength (particle compactness) of the powders. Particle
strength of agglomerated powder becomes higher with
increasing sintering temperature during production process in
general. The powders in this study may be soft and porous
than those of previous ones in previous study (Ref 7, 8) that
may affect lowering hardness in DJ process. It can be said that
K2 process generating higher particle velocity than DJ
overcomes the difference in particle strength. Influence of
powder properties on coating hardness and other functional
properties will be one of the topics to be studied in the future.
200m
(d) Ni-DJ
500m
(e) Co-DJ, 6.1%
(a) Co-K2, 731HV
(b) Ni-K2, 680HV
(c) Co-DJ, 549HV
(d) Ni-DJ, 524HV
500m
(f) Ni-DJ, 3.0%
200m
(g) Co-JP, 11.6%
200m
(h) Ni-JP
(e) Co-JP, 639HV

200m
200m
20 m
Figure 3: Cross sectional optical microscopic images of

coatings: (a) Co-K2, (b) Ni-K2, (c, e) Co-DJ, (d, f) Ni-DJ, (g)
Co-JP and (h) Ni-JP
Back scattered electron (BSE) images by SEM are shown in
Fig. 4. The Ni-JP coating was not studied. Microhardness
values HV0.2 are inserted in the figure. The dark region
Figure 4: Cross sectional SEM (BSE) images of coatings: (a)

Co-K2, (b) Ni-K2, (c) Co-DJ, (d) Ni-DJ and (e) Co-JP
53
Wear Properties
Results of wear tests G65 (dry rubber wheel with quartz sand
0.1-0.6 mm), D6037 (dry abrasive with SiC F180 sand paper)
and G99 (PoD, against alumina ball) are shown in Fig. 5.
Wear track in G99 against steel ball is too small to estimate
the wear rate. Volume loss of G65 and D3067 has been
estimated using weight loss and theoretical density of the
material about 6.16 g/cm3.
G65, Volume loss [mm3]
40
30
Co-K2
Ni-K2
Co-DJ
Ni-DJ
Co-JP
Ni-JP
The K2 coatings show the best wear resistance in all tests. K2Ni has better wear resistance in D6037 and G99 than K2-Co.
The DJ samples have comparable properties to K2 only in
G99. In G65 these have slightly lower resistance. The JP
samples are the worst in G99 and G65 in this work. Co-JP is
the worst. Although large lateral crack is seen in Ni-JP,
mechanical properties of Co-JP coating are much lower than
Ni-JP, suggesting that Co-JP should have weaker bonding
between lamellae in the coating totally.
Worn out
around 4.7 km
Considering that the trend in all samples, G65 and G99 seems
to be quite similar: K2 is the best, DJ is not far from K2 and
JP is the worst. On the other hand, D6037 shows different
tendency that JP is better than DJ. The result of D6037 seems
to be consistent with hardness where harder coating simply
increase D6037 wear resistance. That suggests G65 and G99
are influenced by not only hardness but other factors, such as
toughness. Another possible factor is size of counter materials.
When large sized particles attack coating surface, these should
affect large area. Bonding among particles (lamellar
boundary) may be strongly affected than inside particles.
Media size in G65 and G99 seems to have significantly larger
than splat size that may enhance the wear from the lamellar
boundaries dominantly. In D6037, on the other hand, its media
size is smaller than other tests and is probably comparable to
splats and Vickers indent size of about 20 m. Small SiC
particle should attack smaller region, probably inside particles.
This difference of major factor on wear may affect the
tendency.
20
10
(a)
0
0
3
4
Distance [km]
15
Co-K2
Ni-K2
Co-DJ
Ni-DJ
Co-JP
10
G99, Volume loss [mm3]
D6037, Volume loss [mm3]
20
Comparing with other conventional carbides, the best

(Ti,Mo)(C,N) hardmetal of Co-K2 has almost same wear
resistance as Cr3C2-NiCr HVOF coatings in G65. Its wear rate
is 4-5 times higher than WC cermet coatings (Ref 10). Same
tendency is seen in D6037 that the best Ni-K2 has slightly
better than Cr3C2-NiCr and about 4-5 times worse than WC12Co. Difference of the resistance between (Ti,Mo)(C,N) and
WC is smaller in G99 than that of G65 and D6037 as shown in
Fig. 6. The wear rate of the best K2-Ni is less than twice than
that of WC-12Co. According to the previous work (Ref 4),
Cr3C2-NiCr has wear rate of more than one order of magnitude
higher than (Ti,Mo)(C,N). From them, (Ti,Mo)(C,N) can be
suitable for sliding at temperature above 600 C where WCCo or WC-CoCr coatings are inapplicable.
(b)
0
0
0.003
(c)
2
3
Run [times]
0.128
0.002
0.001
Dry Sliding Properties

Progression of coefficient of friction (CoF) during PoD G99
test of the coatings at room temperature is shown in Fig. 7. All
specimens of Co and Ni binder show similar CoF about 0.70.8 at 30000 cycles when applying steel ball as counterpart.
This is in good agreement with previous study, where CoF
about 0.6-0.8 was found. (Ref 8) It can be considered that
oxidation of steel ball creates tribo-film on the ball and the
film is transferred to coating surface. And thus, only tribo-film
becomes a dominant contacting material in every specimens
that mainly affects CoF. All specimens show lower CoF at the
beginning around 0.2 against steel ball. CoF of JP increases
Ni-JP
Co-JP
Ni-DJ
Co-DJ
Ni-K2
Co-K2
Figure 5: Volume loss of 3 kinds of wear test: (a) ASTM G65,

3-body dry rubber wheel, counter material of quartz, 0.1-0.5
mm, (b) ASTM D6037, 2-body dry abrasion, counter material
of SiC (F180, about 90 mm), and (c) ASTM G99, pin-on-disk,
counter material of alumina ball.
54
1.2E-07
1.1E-06
JP-steel
0.8
0.7
JP-alumina
0.6
COF
2.1E-07
1.5E-07
(a) Co binder
0.9
3.9E-08
1.E-07
6.9E-08
1.6E-07
1.E-06
K2-steel
0.5
DJ-alumina
K2-alumina
0.4
0.3
DJ-steel
0.2
WC-12Co/JP
Ni-JP
Co-JP
Ni-DJ
Co-DJ
Ni-K2
1.E-08
Co-K2
G99, Specific wear rate [mm3/N/m]
1.E-05
0.1
JP-Co-steel
DJ-Co-steel
K2-Co-steel
JP-Co-Al2O3
DJ-Co-Al2O3
K2-Co-Al2O3
0
0
1
Figure 6: Specific wear rate at G99 of (Ti,Mo)(C,N) coatings

and conventional WC-12Co HVOF coating.
5000
10000
15000
No. of cycles
20000
25000
30000
(b) Ni binder
0.9
JP-steel
0.8
0.7
sharply from 0.2 to 0.7 at an earlier stage and K2 followed.

Duration of low friction of DJ is the longest. Ni binder tends
to have longer duration of low friction than Co binder. This
tendency can be explained by the influence on coating
hardness, shown in Fig. 4. Hard coating reduces duration of
low CoF at the beginning.
K2-steel
COF
0.6
JP-alumina
DJ-alumina
0.5
0.4
K2-alumina
0.3
DJ-steel
0.2
0.1
When applying alumina as counterpart, DJ and K2 show lower

CoF about 0.5 for Co binder and 0.4 for Ni binder at 30000
cycles. JP specimens have higher CoF of 0.8 for Co binder and
0.6 for Ni binder. DJ has much mild progression than others as
maximum CoF is still lower of about 0.6 for Co binder and 0.5
for Ni binder. According to previous report under almost same
conditions of PoD against alumina ball (Ref 7, 10), CoF of
WC-17Co and Cr3C2-25NiCr and (Ti,Mo)(C,N)-39NiCo by
JP-5000 have shown about 0.8, 0.6 and 0.8 at 30000 cycles
respectively. WC-17Co is less stable that it is reduced about
0.4 after 50000 cycles. Therefore, Ni-DJ and Ni-K2 seems to
have better sliding properties in the study. Considering that
CoF values and their progression, Ni-DJ is the best as its CoF
is gradually increased from 0.2 to 0.4 with a small peak of
about 0.5. Ni-K2 also has better sliding properties as well as
higher wear resistance than other (Ti,Mo)(C,N) coatings.
JP-Ni-steel
DJ-Ni-steel
K2-Ni-steel
JP-Ni-Al2O3
DJ-Ni-Al2O3
K2-Ni-Al2O3
0
0
5000
10000
15000
No. of cycles
20000
25000
30000
Figure 7: Progression of the CoF of the coatings against steel

and alumina balls at room temperature: (a) Co binder and (b)
Ni binder
0.8
Ni binder, Alumina counter
0.7
JP-RT
0.6
K2-RT
DJ-600
K2-600
COF
0.5
JP-600
0.4
DJ-RT
0.3
Progression of the CoF of selected coatings of Ni-DJ, Ni-K2

and Ni-JP against alumina ball at room temperature and 600
C in the air is shown in Fig. 8. It is clear that DJ and K2
coatings are quite stable CoF around 0.45~0.55 from room
temperature to 600 C around 30000 cycles. At 600 C, both
coatings show very stable CoF of around 0.5~0.55 from the
begging of the test, which is quite different from the
progression at room temperature. Although higher CoF around
0.6-0.7 at room temperature, Ni-JP also shows stable CoF of
about 0.5 at 600 C, slightly lower than other coatings.
Figure 8: Progression of the CoF of the Ni-DJ, Ni-K2 and NiJP coatings against alumina ball at room temperature and
600 C in the air
Other carbides have higher CoF at room temperature of 0.8 in

WC-17Co and 0.6 in Cr3C2-NiCr. Their values have decreased
to about 0.7~0.5 and 0.5 at 500 C (Ref 7). Comparing among
the CoF, less dependence of CoF on temperature can be one of

the advantage of (Ti,Mo)(C,N) hardmetal at least from room
temperature and 600 C, where WC-Co is inapplicable due to
0.2
Ni-DJ-600
Ni-DJ-RT
0.1
Ni-K2-600
Ni-K2-RT
Ni-JP-600
Ni-JP-RT
0
0
55
5000
10000
15000
20000
No. of cycles
25000
30000
lower thermal stability. As mentioned above, wear resistance

of Cr3C2-NiCr is one order less than (Ti,Mo)(C,N) hardmetal
at room temperature. Considering that sliding properties and
wear resistance, (Ti,Mo)(C,N) hardmetal will be one of the
promising candidate for sliding applications due to its
properties of high wear resistance, relatively lower friction
which is less dependent on temperature and high temperature
stability.
6.
7.
In future work, chemical compositions of the coatings should

be clarified to suggest the influence of the element on sliding
properties, in particular, oxygen. Analysis wear track of PoD
and wear rate at high temperature will be also important to
understand the wear behavior.
8.
Conclusion
Comprehensive studies have been carried out by preparing
powder feedstock of (Ti,Mo)(C,N) hardmetal with Ni and Co
binders retaining same manner for three HVOF methods of K2,
Diamond Jet and JP-5000. Coating specimens are evaluated by
microstructure, hardness, bonding strength, wear and friction.
K2 coatings showed higher hardness than others. All coatings
have higher bonding strength more than adhesives of 80 MPa.
In all wear tests, K2 showed the higher wear resistance, which
is comparable to Cr3C2-NiCr in G65 and D6037 as well as 10
times better than Cr3C2-NiCr in G99. Ni binder coatings by DJ
and K2 have stable CoF around 0.45-0.55 from room
temperature to high temperature of 600 C, where drastic
difference between the coatings are unclear. Considering that
wear and sliding properties, Ni binder by K2 is the best within
this study.
10.
References
12.
1.
2.
3.
4.
5.
9.
11.
J.R. Davis, Thermal Spray Processes and Selected

Applications, Handbook of Thermal Spray Technology,
ASM International, 2005, p54-76 and p175-213
B.A. Kushner and E.R. Novinski, Thermal Spray
Coatings, Friction, Lubrication, and Wear Technology,
Vol 18, ASM Handbook, ASM International, 1992, p829833
R.V. Burg and D. Liu, Chromium and Hexavalent
Chromium, J. Appl. Toxicol. 1993, 13, 225230
. Houdkov, F. Zahlka, M. Kaparov and L. -M.
Berger, Comparative Study of Thermally Sprayed
Coatings Under Different Types of Wear Conditions for
Hard Chromium Replacement, Tribol. Lett. 2011, 43,
p139154
L.-M. Berger, W. Hermel, P. Vuoristo, T. Mntyl, W.
Lengauer, and P. Ettmayer: Structure, Properties and Potentials of WC-Co, Cr3C2-NiCr and TiC-Ni-Based Hardmetal-Like Coatings, Thermal Spray: Practical Solutions
13.
14.
15.
16.
56
for Engineering Problems, ASM International, 1996, p

89-96.
L.-M. Berger, M. Nebelung, P. Vuoristo, and T. Mntyl:
Coating Powder and Method for its Production, DE 196
40 788 (filing date: 02. 10. 1996), WO 98/14630, US
6.162.276, EP 0948659, CA 2 267 960, BR PI 9711858-3,
NO 321957, JP 4282767
L.-M. Berger, S. Thiele, P. Vuoristo, T. Mntyl, H.
Keller, E. Pro and R. Scholl, Titanium Carbide-Based
Powders and Coatings Compositions, Processability and
Properties, Proc. International Thermal Spray Conference
2002, DVS, 2002, p727-732
L.-M. Berger, S. Zimmermann, H. Keller, G. Schwier, R.
Scholl, S. Thiele, M. Nebelung and R. Enl,
Microstructure and Properties of HVOF-Sprayed TiCBased Coatings, Thermal Spray 2003: Advancing the
Science & Applying the Technology, ASM International,
2003, p793-799
L.-M. Berger, M. Woydt, S. Zimmermann, H. Keller, G.
Schwier, R. Enl and S. Thiele, Tribological Behavior of
HVOF-Sprayed Cr3C2-NiCr and TiC-Based Coatings
under High-Temperature Dry Sliding Conditions, Proc.
International Thermal Spray Conference 2004, DVS,
2004, CD
. Houdkov, F. Zahlka, M. Kaparov and L. -M.
Berger, Tribological Behavior of Thermally Sprayed
Coatings at Elevated Temperatures, Proc. International
Thermal Spray Conference 2008, DVS, 2008, CD
L.-M. Berger, S. Saaro, and M. Woydt Reib/Gleitverschlei
von
thermisch
gespritzten
Hartmetallschichten, Jahrbuch Oberflchentechnik 2007,
Vol. 63, Ed.: R. Suchentrunk, Eugen G. Leuze Verlag,
2007 p 242-267 (in German)
L.-M. Berger, C.C. Stahr, S. Saaro, S. Thiele, M. Woydt
and N. Kelling, Dry Sliding Up to 7.5m/s and 800C of
Thermally Sprayed Coatings of the TiO2Cr2O3 System
and (Ti,Mo)(C,N)Ni(Co), Wear, 267, 2009, p954-964
L.-M. Berger, M. Woydt and S. Saaro, Comparison of
Self-Mated Hardmetal Coatings under Dry Sliding
Conditions Up to 600c, Wear, 266, 2009, p406-416
J.M. Guilemany, J.M. de Paco, J. Nutting, and J.R.
Miguel, Characterization of the W2C Phase Formed
during the High Velocity Oxygen Fuel Spraying of a WC
+ 12 Pct Co Powder, Metall. Mater. Trans. A, 1999, 30(8),
p 1913-1921
C. Verdon, A. Karimi, and J.L. Martin, A Study of High
Velocity Oxy-Fuel Thermally Sprayed Tungsten Carbide
Based Coatings, Part 1: Microstructures, Mater. Sci. Eng.
A, 1998, 246(1-2), p 11-24
P. Vuoristo, T. Mntyl, L.-M. Berger and M. Nebelung,
Sprayability and Properties of TiC-Ni Based Powders in
the Detonation Gun and HVOF Processes, Thermal
Spray: A United Forum for Scientific and Technological
Advances, ASM International, 1997, p 910-915


All rights reserved
Dense MoB/CoCr Coatings to Apply to Pot-Roll

of Galvanizing Lines in Steel Industries
J. Kitamura*, T. Tosaki, H. Mizuno,
FUJIMI INCORPORATED, Gifu, Japan
*E-mail: kitamuraj@fujimiinc.co.jp
Abstract
considered that rolls coated by Co-based self-fluxing alloy has

insufficient durability in spite of relatively longer life
compared to the common roll made from stainless cast steel.
(Ref 6, 7)
MoB/CoCr coating has high durability against molten Zn,

widely used in galvanizing lines in steel industries. (Ref. 1)
However the coatings have been sometimes damaged without
showing its intrinsic properties in lab test. It has been found
out that damaged specimens tend to have higher porosity that
enhances penetration of molten Zn through the connected
pores that erodes substrate steel and detach coatings as a result.
This suggests denser coating in the application is essentially
critical to exhibit its durability and quality assurance
practically. In this paper, dense MoB/CoCr coatings have been
prepared by optimization of powder properties and HVOF
spray conditions using JP-5000. Salt spray test has been
conducted to evaluate the coating density qualitatively.
Optimized dense coatings showed no rust from the low carbon
steel substrate after around 300 hours of salt spray test. Porous
coatings, on the other hand, showed the rust around 24-48
hours. Optimized coatings confirmed by salt spray test have
no damaged after 90 days (>2000 hours) immersion in the
industrial galvanizing bath (Zn-0.2%Al at 460C).
HVOF sprayed WC/Co coatings show higher durability than

the Co-based alloy coating in molten pure Zn (Ref. 6) and ZnAl (low Al content) alloys. (Ref. 7) Inclusion of double
carbides of -phase (Co3W3C and Co6W6C) is found to be
effective to improve the durability, where -phase reduces
reactive metal cobalt. (Ref. 6-9) Technological advance of the
steel manufacturing processes still highly requires further
improvement of surface properties without alloy adhesion and
dissolution.
Durable MoB/CoCr against molten Al and Zn-Al alloys has
been developed by Fujimi Incorporated (Japan) to utilize for
die casting parts and CGL parts. (Ref. 1, 10-12) Immersion
test has revealed that the MoB/CoCr coating has much higher
durability in the molten Al and Zn-Al alloys than conventional
spray coatings. No damage and dissolution are observed in the
MoB/CoCr coating after long-term immersion test of molten
Zn-55wt%Al alloy, where both the conventional cermet and
ceramic coatings are damaged by dissolution and crack
generation, respectively.
Introduction
Thermal spray coatings offer various customized surface
properties, such as resistance to corrosive atmosphere,
abrasion, erosion, high temperature and high heat flux.
Recently, these properties of the spray coatings have been
greatly progressed by development of spray processes, such as
high-power plasma spraying and high velocity oxygen-fuel
(HVOF) spraying, (Ref. 2, 3) as well as by development of
feedstock (Ref. 2) including customization for the equipments.
Durable spray coatings in molten metals are one of the
important applications practically. (Ref. 4)
The MoB/CoCr coated small specimens sometimes have been

damaged without showing its properties in internal lab scaled
test. It has been found out that damaged specimens tends to
have higher porosity that enhances penetration of molten Zn
through the connected pores that erodes substrate steel and
detach coatings resultingly. This suggests denser coating is
essentially critical to exhibit its durability and quality
assurance practically.
In continuous galvanizing and galvalume lines (CGL),

galvanizing rolls, such as sink roll and stabilizing roll, with
higher erosion resistance against molten zinc (Zn) and zincaluminum (Zn-Al) alloys is one of the key technologies in
steel manufacturing process to improve quality of steel sheet
and expanding time between maintenance. (Ref. 5) It is
In this paper, dense MoB/CoCr coatings have been prepared

by optimization of powder properties and HVOF spray
conditions using JP-5000 (Praxair, USA) with combination of
parameters among particle size, chamber pressure, spray
distance and barrel length. Salt spray test has been conducted
57
Table 2: HVOF coating specimens. Combustion conditions are (a)

1900, 5.1, (b) 2000, 6.0, (c) 2000, 6.5 and (d) 2100, 6.5 of oxygen
[scfh] and kerosene flow rate [gph], respectively. Specimens
labeled s are sealing treated.
to evaluate the coating density qualitatively as well as used for

screening to select better specimens without rust observation,
which can be proceeded to next trial of immersion test. Static
immersion test has been conducted in the CGL (Zn-0.2%Al at
460C, galvanizing, GI) for 90 days to investigate the
performance of dense MoB/CoCr coatings.
Name
Powder
Combustion
conditions
1
1s
2
2s
3
4
4s
5
6
6s
7
8
8s
9
10
11
11s
12
13
14
14s
(a)
Experimental
MoB/CoCr Powders
Three sized MoB/CoCr powders were produced by Fujimi
Incorporated as summarized in Table 1. Since HVOF coatings by
DTS-B49-45/15 (A) used in previous work (Ref. 1) were
sometimes damaged in our internal research, finer particles (B,
DTS-B46-38/10 and C, DTS-B47-30/5) were prepared to attempt
for making denser coatings.
Table 1: MoB/CoCr powders in the study
A
B
C
DTS-B49-45/15
DTS-B46-38/10
DTS-B47-30/5
Particle size
distribution (m)
-45+15
-38+10
-30+5
Preparation of HVOF Specimens for Salt Spray Test

HVOF spraying using JP-5000 was conducted with combinations
among several parameters of powders, oxygen and fuel feeding
rates, barrel length and spray distance. Substrates were low carbon
steel (JIS SS400) of 50 mm 70 mm 2t mm, which were grit
blasted by alumina media prior to HVOF. Coating was ground and
final thickness was adjusted from 100 to 120 m. The ground
surface was necessary to observe rust clearly during salt spray test.
Clog &
spit
380
No
340
300
(c)
(b)
Slight
No
380
340
300
6
(c)
Slight
380
340
380
No
340
(d)
300
2200
Oxygen flow rate [scfh]
2100
Table 2 summarizes thecoating specimens. Specimens labeled s,

such as 1s and 2s, are sealed onto the coating surface using MR100 sealant (Okitsumo, Japan). Sealant layer on the surface was
removed by polishing and thus sealant penetrated into pores was
only remained. Combustion conditions labeled from (a) to (d) are
as follows: (a) 1900, 5.1, (b) 2000, 6.0, (c) 2000, 6.5 and (d) 2100,
6.5 for oxygen [scfh] and kerosene flow rate [gph], respectively. As
shown in Fig. 1, a map describing combustion conditions for JP5000. Condition d produces the highest chamber pressure
whereas a the lowest. High pressure is expected to generate
higher particle velocity effective for producing dense coating.
2000
Ch
am
be
rp
res
su
re
(c) 2000, 6.5

(b) 2000, 6.0
11
1900
(a) 1900, 5.1
0p
si
1800
10
0
1700
1600
1500
1400
4.5
Coarse A particle was sprayed with an 8 inches long barrel

without clogging trouble in all conditions. Commonly, clogging
and spitting generate inhomogeneous coating microstructures,
which will be easy to make open pores, become routes of Zn
penetration. Thus, it should be avoided for the purpose. Specimen
No. 1 is defined as reference, same as previous paper. (Ref. 1).
Middle B particle caused clogging and spitting using 8 inches.
Shorter barrel of 6 inches with optimized spray parameters of (b)
attained no clogging. Short barrel of 4 inches was better
(d) 2100, 6.5
ps
i
Product name
SD
[mm]
(c)
80
s to
ich
io
m
et
ri
Name
Barrel
length
[inches]
8
ps
i
5.0
5.5
90
6.0
ps
i
6.5
7.0
7.5
Kerosene flow rate [gph]
Figure 1: Combustion conditions for JP-5000

to deposit finest C particle without clogging and highest chamber
pressure of (d) could be conducted. Changing spray distance was
also attempted to change coating density. Shorter distance is well
known to form denser coating effectively in spite of lowering
deposition efficiency.
58
Salt Spray Test

Salt spray test of the ground and sealed specimens was conducted
under the conditions referred as ISO 9227: 2006, where
concentration of NaCl, temperature, spray rate and its pressure were
5 wt% (pH7), 35 C, 1~2 ml/h and 0.098 MPa, respectively. The
specimens was checked every 24 hours. Lifetime has been
defined by visual observation of rust. Microstructural analysis
and Vickers hardness testing were also conducted.

Salt Spray Test
Fig. 4 shows the result of the salt spray test for as sprayed
specimens. Lifetime has been defined by visual observation of
rust from the low carbon steel substrate through open
connected pores. Pictures of specimens with rust are also
inserted in the figure. It can be considered coatings with high
density open pores result in short lifetime. Porous coatings
should not suitable because molten Zn will be easily
penetrated that destroys the substrate steel.
Static Immersion Test at Industrial Galvanizing (GI) Line

Specimens for the immersion test are illustrated in Fig. 2. Coatings
have been prepared onto grit blasted stainless steel 316L bar and
grinded. Target coating thickness after grinding was 100 m. MR100 was sealed onto the ground surface. Two specimens were
prepared: modified No 5 with particle B, changing spray distance
from 380 mm to 300 mm, and No. 14 with particle C in Table 2.
Three samples were prepared for both specimens to check after 30,
60 and 90 days immersion. The test was conducted at industrial GI
line at Nucor Crawfordsville, IN, USA in the ZCO-57 of
Galvanizing Autobody Partnership (GAP) program 2011-2013.
Specimens during the immersion test are shown in Fig. 3.
Coatings with powder A (specimen Nos. 1-4) have quite lower

lifetime showing higher porosity than others. In particular,
Reference No. 1 (Ref. 1) is the worst with high amount of the
rust only after 24 hours. Therefore, they should be avoided in
selecting next trial of the immersion test.
Lifetime of coatings with powder B (specimens Nos. 5-8), is
longer than that with powder A. This means finer particle is
effective in producing dense coating. No. 8 is the best without
observation of rust after about 300 hours. Comparing with Nos.
6 and 7, shorter spray distance is effective for coating
densification. No. 5 is better than No. 6, showing that higher
chamber pressure is also effective, however, its lifetime is
insufficient probably due to longer spray distance. Since
clogging in No. 5 is less serious, modified No. 5 has been
selected for the immersion test. Here, spray distance was
changed shorter from 380 to 300 mm.
300 mm
50 mm
Coated area: 250 mm
Coatings with powder C (specimens Nos. 9-14) shows much

longer lifetime than powders A and B. In spite of clogging, no
rust has been observed from Nos. 9 and 10 after about 300
hours. Comparing with Nos. 13 and 14, higher chamber
pressure is critical for coating densification. No. 14 is selected
for the immersion test because of no rust and no clogging.
Hole: 12 mm
Figure 2: Specimens for immersion test at industrial GI line
No rust was observed from all sealed specimens of Nos. 1s, 2s,
4s, 6s, 8s, 11s and 14s. This shows sealing is quite effective to
avoid penetration of salt water at least. However, it is unclear
this is also effective to avoid molten Zn penetration under high
temperature of around 450 C. Regardless of the effect of
sealing, it can be said that denser coating is critical for
MoB/CoCr coating to perform its intrinsic properties because
porous MoB/CoCr coating with sealant has short lifetime
under molten Zn immersion test in our previous study.
Microstructure and Hardness
Cross sectional images of typical specimens are shown in Fig.
5. Their Vickers hardness is also inserted in the figure. Both
coatings of modified No. 5 and No. 14 are quite denser with
small size pores than the No. 1 that is consistent with the salt
spray test. Dense coatings also have higher hardness of more
than 1000HV, whereas 840HV for porous coating.
Figure 3: Specimens during the immersion test at industrial GI line
59
Powder A (B49)
300
Powder B (B46)
Powder C (B47)
250
Lifetime
Life time[hrs]
[hrs]
200
150
100
50
Name
SD
Combustion
Barrel
380
a
340
c
300
380
c
340
b
300
10
11
12
380
340
380
c
340
13
14
300
d
4
Figure 4: Result of the salt spray test. Lifetime has been defined by visual observation of rust from the low carbon steel substrate.
(a) No. 1, powder A, 840HV
Mod. No.5, powder B
(b) mod. No. 5, powder B, 1100HV
No. 14, powder C
bottom
bottom
center
(c) No. 14, powder C, 1040HV
200 m
top
30 days
60 days
90 days
60 days
90 days
Analyzed by SEM/EDX
Figure 5: Cross sectional images of specimens (a) No. 1, (b)

modified No. 5 and (c) No. 14
Figure 6: Specimens after the Zn immersion test at GI line
Immersion test at Industrial GI line

Fig. 6 shows the photograph of the specimens after the
immersion test. One sample was accidentally dropped off in
the GI bath during the test. No apparent change of specimens
is seen within this visual inspection. Only a thin Zn layer is
adhered onto the surface without dramatic change of shape
such as thinning and thickening both of overall and locally.
Adhered Zn layer of all specimens is easily removed by hand
as shown in Fig. 7. The coatings without large change are
observed after the removal visually. No substrates of stainless
steel 316L are exposed in almost entire area.
Microanalysis with scanning electron microscopy/energy
dispersive x-ray spectrometry (SEM/EDX) has been done for
60 and 90 days samples. 2 positions of center and bottom of
Fig. 7: Adhered Zn layer is easily removed by hand.
60
the sample were selected as shown in Fig. 6. Table 3

summarizes the result of the analysis. Almost of all areas in
entire samples shows excellent performance. A little Zn
diffused into the coatings as shown in Figs. 8(a) and (b),
which are typical results.
(a) No. 14, powder C, center, 60days
Fe
Table 3: Summary of SEM/EDX to identify damage by Zn

Posistion
Center
Bottom
No. 14
60 days
Good
Good
90 days
Good
Locally NG
Mo
Mod. No. 5
90 days
Good
Good
Good: A little Zn diffusion

Locally NG: Zn reached substrate, locally
Microanalysis has revealed the coatings remain without large

change, such as no change of microstructure, less cracks and
no dramatic change of thickness. Chemical composition is still
mainly MoB/CoCr and a few Zn is detected in entire coating.
A slightly high amount of Zn but still a few wt% is detected at
coating surface. It may be adhered Zn on the surface and/or
diffused Zn near surface. A little Zn diffusion is observed in
entire coating from the surface to almost close to interface as
their intensity is slightly higher than background as shown in
Fig. 8(a). Comparing with 60 and 90 days data, Zn diffusion in
entire coating is almost same suggesting saturation of Zn
diffusion. Although it is unclear how Zn exists, such as
forming compound with other element, solid solution in
MoB/CoCr and so on, saturation of Zn diffusion is expected to
extend lifetime.
Magnification of Zn
Zn diffusion or
adhesion
Diffused Zn
background
Zn
(b) Mod. No.5, powder B, center, 90 days
As described above, dense coating is expected in this

applications to avoid Zn penetration through open pores. On
the other hand, it is well known that too dense coating tends to
generate cracks easily than porous coating that might be
another possible route of molten Zn. Through SEM
observation of a number of places (>20), Zn penetration is
seen through the cracks from No. 14 as shown in Fig. 9. The
cracks will be generated by heat shock during HVOF spraying
and/or GI bath immersion. After arrival of Zn to substrate,
damage of steel substrate will cause peeling off.
Mo
Magnification of Zn
In order to avoid such a defect retaining high density, careful

HVOF spraying is necessary at first, such as substrate
temperature, torch traverse speed, and so on. Thinner coating
will be easier solution to avoid cracks during immersion
and/or before immersion, which will be done in the future
work. Actual coating thickness was about 120 and 140 m
around center and bottom, respectively, which were thicker
than the target of 100 m. And relatively strong Zn adhesion
can be frequently seen around bottom. That implies thick area
tends to have high density cracks that causes strong Zn
adhesion Therefore improving homogeneity of thickness
retaining less than 100 m is one possible solution to
overcome the problem. Since MoB/CoCr itself has quite stable
in GI bath, thinner coating will be realistic.
Zn diffusion
Zn
Fig. 8: SEM/EDX analysis of cross section at (a) center of No.
14 after 60 days and (b) center of modified No. 5 after 90 days.
61
References
No. 14, powder C, bottom, 90days
1.
H. Mizuno, J. Kitamura, MoB/CoCr cermet coatings by

HVOF spraying against erosion by molten Al-Zn alloy, J.
Thermal Spray Technol, 2007, 16(3), p404-413
2. R. e.g. Handbook of Thermal Spray Technology, J. R.
Davis Ed., ASM International, 2004, p. 56-60, 62-70, and
133-168
3. R.B. Heimann, Plasma-Spray Coating, Principles and
Applications, VCH Verlagsgesellschaft mbH, Germany,
1996
4. K. Hamashima, Y. Shinozaki, and M. Sasaki, Thermal
Spraying of Mo2NiB2-Ni Cermet, Advances in Powder
Metallurgy & Particulate Materials, part2, 1997, p.43-48
5. H. Yamaguchi, and T. Hisamatsu, Reaction Mechanism
of the Sheet Galvanizing, J. Iron and Steel Institute of
Japan, 1977, 63(7), p.1160-1169, in Japanese
6. T. Tomita, Y. Takatani, Y. Kobayashi, Y. Harada, and H.
Nakahira, Durability of WC/Co Sprayed Coatings in
Molten Pure Zinc, J. Iron and Steel Institute of Japan
International, 1993, 33(9), p.982-988
7. K. Tani, T. Tomita, Y. Kobayashi, Y. Takatani, and Y.
Harada, Durability of Sprayed WC/Co Coatings in Aladded Zinc Bath, J. Iron and Steel Institute of Japan
International, 1994, 34(10), p.822-828
8. A.J. Stavros, Behavior of Some Tungsten Carbide
Coatings in Molten Zinc, Proc. of 9th National Thermal
Spray Conference, C.C. Berndt Ed., Oct 7-11 (Cincinnati,
OH), ASM International, 1996, p.141-146
9. D. Nolan, P. Mercer, and M. Samandi, Reactivity of WC12% Co Thermal Spray Powders with Molten Zinc Alloys
as a Function of Phase Content, Surface Modification
Technologies XI, T.S. Sudarshan, M. Jeandin, and K.A.
Khor Eds., The Institute of Materials, 1998, p. 312-317
10. H. Mizuno, J. Kitamura, S. Osawa, and T. Itsukaichi,
Development of Durable Spray Coatings in Molten
Aluminum alloy, Proc. International Thermal Spray
Conference 2005, ASM International, 2005, CD
11. H. Mizuno, J. Kitamura, S. Tawada, and T. Itsukaichi,
Development of Durable Spray Coating in Molten Al and
Al-Zn alloys, Proc. 1st Asian Thermal Spray Conference,
Asian Thermal Spray Committee, 2005, p.81-82
12. H. Mizuno, J. Kitamura, S. Tawada, and T. Itsukaichi,
MoB/CoCr Spray Coating with Higher Durability in
Molten Al and Al-Zn Alloys, Proc. International Thermal
Spray Conference 2006, ASM International, 2006, CD
Cracks
Al
Fe
Co
Zn
Cr
Mo
Fig. 9: SEM/EDX analysis of cross section for at bottom of No.

14 after 90 days to investigate influence of cracks on Zn
penetration
Conclusions
Dense MoB/CoCr coatings have been prepared by optimizing
particle size and HVOF spray conditions. Denser coatings
showed high sealing performance found out by salt spray test,
applicable to galvanizing (GI) bath immersion test. Salt spray
is easy and suitable method for screening of specimens. Two
best coatings by both medium (-38+10m) and fine (-30+5m)
particles with optimized HVOF spray conditions have been
applied to Zn immersion test of 90 days at industrial GI line.
These showed excellent durability in GI bath, where adhered
Zn was easily removed by hand and almost no change of the
coatings.
Acknowledgement
The Authors thank the sponsors of the Galvanizing Autobody
Partnership (GAP) Program for financial support. Mr. Scott
Sexton from Nucor Corporation supported to conduct
immersion test at industrial galvanizing line, Crawfordsville,
IN, USA.
62


All rights reserved
Effect of WC-Co-Cr Powder Properties on

Coating Characteristics by Recent HVAF Spraying
Kazuto Sato1*, Hidenori Miyajima2, Masami Kato2, Junya Kitamura1 and Kazuhiko Sakaki2
1 Fujimi Incorporated, Gifu, Japan*2 Shinshu University, Nagano, Japan
*E-mail:satouk@fujiniinc.co.jp
Abstract
Spray process
From the appearance of HVOF thermal spray system on

1980s, WC cermet coatings have been used as anti-wear
coatings in many industrial applications. Recently, WC cermet
spray materials were applied to new thermal spray method
such as Warm Spray and Cold Spray for improvements of
coating performance, spray efficiency and so on. Gas velocity
values of the latest models of HVAF torches are higher than
those of the previous ones. Therefore, dense WC coating can
be fabricated by using the latest HVAF process.
WC-Co like cermet

/ Hard materials
1940
In this study, agglomerated and sintered WC-Co-Cr powder

properties and spray conditions were investigated to
understand the influence on HVAF spraying. From the results,
it was clear that coating wear performance was improved by
using higher gas speed conditions and powder composed of
fine CoCr particles. It is also clear that coating hardness was
improved by employing fine particles.
Spray powder
1960
APS
1980
HVOF
HVAF
CS
2000
WS
Optimizing the
powder production,
powder size,
WC size,
and etc
for thermal spray
Figure 1: Development of spray process and spray powders

on WC cermet coatings
Introduction
Thermal sprayed tungsten carbide (WC) cermet coatings are
widely applied to facilities and machines to achieve the long
time maintenance-free operation because of high wear
resistance. Its trend has been accelerated by invention of high
velocity oxygen fuel (HVOF) spraying on 1980s (Ref 1),
which can produce dense coatings with high bond strength as
well as low degradation of WC cermet materials compared
with plasma spraying. However, degradation of WC cermet,
such as oxidation, decarburization and dissolution of WC to
metal binder, still occurs using HVOF that is quite different
from and inferior to sintered hard metal, which can be defined
as an ideal material. Therefore, low temperature processes,
such as cold spray, warm spray and high velocity air fuel
(HVAF) are actively researched to achieve WC cermet
coatings, similar to sintered one, where denser and harder
coatings have been prepared better than HVOF (Ref 2-6).
commercial powder materials (Ref 7, 8). The HVAF system is

a high velocity combustion spray process that uses fuel gas or
kerosene and compressed air (not oxygen) for combustion. It
was originally development to reduce the cost of operation,
replacing pure oxygen by compressed air. And flame
temperature of HVAF is lower than that of HVOF, which lead
to less dissolution of WC and decomposition of coating (Ref
9). It is well known that denser and harder WC coating than
HVOF can be fabricated by latest HVAF process.
Figure 1 shows that spray powders have been improved to
adjust spray process progressed historically, such as powder
production methods, particle size, WC size, particle strength
and so on. In HVAF process, optimized powder is considered
to be different from powder used in HVOF. In this study, WC
size, particle structure, particle size distribution and spray
condition were investigated for optimized HVAF coating.
HVAF coatings were studied comparison with WC12mass%Co HVOF coating which is widely used in industry.
HVAF spraying is seen as the pre-eminent process for

deposition of metallic and carbide-based cermets coatings of
63
Table 1: HVAF coatings fabricated by WC-CoCr powder

Powder
Chemical components
Particle size
distribution
Benchmark
2.0m
High speed
Fine WC
Fine CoCr
WC size
WC-10mass%Co
-4mass%Cr
-30+5m
Particle
porosity
Spray condition
A
2.5m
0.2m
12%
1.0m
2.0m
Porous particle
Fine particle
CoCr size
-15+3m
2.5m
26%
15%
Table 2: HVAF spray conditions
Experimental
Spray condition
HVAF Coatings
HVAF coating specimens are summarized in Table 1. Benchmark
coating was fabricated by using WC-10mass%Co-4mass%Cr
powder with spray condition A which is listed in Table 2. WC size
and nominal particle size distribution were 2m and -30+5m,
respectively. The coating named high speed was fabricated by
using same powder in benchmark with spray condition B which is
predicted to be higher gas speed condition compared with spray
condition A. Figure 2 shows the SEM images of the powder used
in this study. The coatings named Fine WC, Fine CoCr,
Porous particle and Fine particle were fabricated by using
powder in Table 1 and Figure 2 with spray condition A.
Chamber type
52mm (#2)
74mm (#3P)
Nozzle type
Primary fuel gas
Coating Evaluations
Coating structure was investigated using SEM. Porosity was
measured by image analysis with optical micrographs of cross
section of coatings. Micro Vickers hardness at cross section of
coatings were measured under the load conditions of 1.96 N
(200 gf) and 10 s. Abrasive wear properties were studied using
Suga-abrasion tester (ASTM D6037) where abrasive paper of
SiC F180 as a counter material was selected under the load of
30.9 N (3.15 kgf). Volume loss of carbon steel (JIS SS400)
was set to reference to estimate volume wear ratio. X-ray
diffraction (XRD) was conducted for the powders and asfabricated coatings with the Cu K radiation.
Propane ( C3H8 )
Air pressure
0.59MPa
0.62MPa
Primary fuel gas

pressure
0.45MPa
0.51MPa
Gun traverse speed
1000mm/s
Spray distance
200mm
Substrate
Mild steel / Grit blasted (Al2O3, F24)
Preheat substrate
temperature
140
Benchmark
Fine WC
Fine CoCr
Porous particle
The target value of cross sectional hardness and volume wear

ratio of HVAF coatings were 1100HV and 0.02, respectively,
which are value of coatings of HVOF (TAFA/ JP-5000) WC12mass%Co (Ref 10).
Fine particle
HVAF Coatings Properties

SEM images of HVAF coatings are displayed in Figure 3. Figure 4
shows the coating porosity. HVAF coatings were similar and/or
denser than HVOF coatings. The results of Suga abrasion test
Figure 2: Agglomerated and sintered powder of WC10mass%-4mass%CoCr
64
HVOF
Benchmark
Fine WC
Fine CoCr
High speed
Porous particle
Fine particle
Figure 3: Cross sectional SEM images of HVOF and HVAF coatings

2.5%
shown in Figure 5. HVAF coatings composed of fine CoCr and

coatings fabricated by high speed condition were similar and/or
better than HVOF coating. On the other hand, HVAF coatings
composed of fine WC and fine particle were much worse than
benchmark and HVOF coatings. Figure 6 shows the result of
Vickers hardness. Almost HVAF coatings were little harder than
HVOF coating. HVAF coating composed of fine particle was the
hardest in this study (Ref 11). From these results, it is considered
that HVAF coatings have enough potential to be alternative of
HVOF coating.
2.0%
HVOF
Porosity
1.5%
1.0%
0.5%
The Effects of Spray Condition

HVAF coating fabricated by high gas speed condition was much
denser than benchmark. It is estimated that strong peening effect
was main reason. In addition, wear property relate with bonding
strength of lamella was also improved by strong peening effect.
However, advantage in hardness of the coating was minor despite
dense coating. In the discussion of coating hardness and coating
porosity, plastic deformation associated with indentation
should be investigated more detail.
0.0%
Benchmark
High speed
Fine WC
Fine CoCr
Porous particle
Fine particle
Figure 4: Porosity of HVAF coatings

0.10
Volume wear ratio (Reference SS400)
0.09
From the results of XRD pattern of HVAF coatings shown in

Figure 7, W2C crystal phase and dissolution of WC to Co (Ref
12) were not avoid in this study. These are defects of
degradation the coating toughness related to wear property. It
is considered that gas temperature should be low but enough
to deposit the WC-CoCr powder (Ref 12,13).
The Effects of Powder Properties
From the result of XRD pattern, it is considered that the
coatings composed of fine WC and fine particle were inferior
to wear property compared with benchmark because of
increased W2C crystal phase which is hard but brittle (Ref 14).
0.08
0.07
0.06
0.05
0.04
0.03
0.02
HVOF
0.01
0.00
Benchmark
High speed
Fine WC
Fine CoCr
Porous particle
Fine particle
Figure 5: Abrasive wear resistance of HVAF coatings
65
1600
WC
W2C
Co
1400
Vickers hardness Hv0.2
1200
HVOF
1000
Fine particle
800
Porous particle
Fine CoCr
600
Fine WC
400
High speed
Benchmark
200
WC-CoCr powder
(Benchmark)
Benchmark
High speed
Fine WC
Fine CoCr
20
Porous particle
Fine particle
Figure 6: Vickers hardness of HVAF coatings
30
40
50
Diffraction angle, 2(Cu K)
60
70
Figure 7: XRD pattern of HVAF coatings
HVAF coatings composed of fine CoCr and porous particle

were superior to wear property compared with benchmark.
The bonding strength between WC and CoCr was predicted to
be strong because of good wettability and large contact area
by fine CoCr. In the case of using porous particle, promoting
the lamella deformation was estimated to leads to good wear
property.
References
1. Browning, J.A., U.S. patent 4416421, 1983
2. Chivavibul P., et al., Development of WC-Co Coatings
Deposited by Warm Spray Process, Journal of Thermal
Spray Technology, Vol.17, No.5, (2008), pp.750/56
3. Lima, R.S. et al., Microstructural Characteristics of ColdSprayed Nanostructured WCCo Coatings, Thin Solid
Films, Vol.416, Issues 1-2, (2002), pp. 129/35
4. Kim, H-J., et al., Fabrication of WCCo Coatings by Cold
Spray Deposition, Surf. Coat. Technol., Vol. 191 (2005),
pp.335/340
5. Kim, H-J., et al., Superhard Nano WC12%Co Coating by
Cold Spray Deposition, Mater. Sci. Eng., Vol. A391
(2005), pp.243/248
6. Li, C-J., et al., Characterization of Nanostructured WC-Co
Deposited by Cold Spraying, J. Thermal Spray Technol.,
16 (2007), Issue 5-6, pp. 1011/1020
7. A. Verstak., et al., Activated Combustion HVAF Coatings
for Protection Against Wear and High Temperature
Corrosion, Thermal Spray 2003, pp. 559/565
8. A. Verstak., et al., Deposition of Carbides by Activated
Combustion HVAF Spraying, Thermal Solution: Advances
in Technology and Application, DVS-German Welding
Society (2004), pp. 551/555
9. K. Sakaki., et al., Improvement of Mechanical Properties
of WC-Cermet Coatings Prepared by High Velocity Air
Fuel Spraying, CD-R of proceedings of the JSME/ASME
2011 International Conference on Materials and
Processing (2011).
10. J.Kitamura., et al., Mechanical Properties of WC/Co
Coatings Prepared by Cold Spraying, CD-R of Proc. of
International Thermal Spray Conference (2008),
pp.1246/1250
11. C. Verdon., et al., A Study of High Velocity Oxy-Fuel
Thermally Sprayed Tungsten Carbide Based Coatings, Part
These results indicate the tendency of optimized powder for

HVAF coating. Coarse WC and fine metal binder are
considered to be suited raw material. Porous particle was also
considered to be suited particle structure. Particle size should
be select regarding in order of priority on demand
characteristics. For example, coarse particle would be better in
the case of anti-wear coating.
Conclusions
This study indicates the effects of spray conditions and
powder properties in coatings sprayed by HVAF. These were
the main observations:
1
The wear performance levels of the HVAF coatings
fabricated by using high gas speed conditions and fine CoCr
particles were superior to those of HVOF coatings.
2 The hardness values of HVAF coating composed of fine
particle were the highest in this study.
3 High gas speed conditions and fine CoCr particles led to
the production of dense coatings.
Acknowledgments
The authors thank Toshiki Takamatu of New Metals and
Chemicals Corporation, Ltd. for supplying the HVAF spray
equipments and advices.
66
1: Microstructures, Materials Science and Engineering A

(1998), 246, pp.11/24
12. P.Chivavibul., et al., Effect of Powder Characteristics on
Properties of Warm-Sprayed WC-Co Coatings, Journal of
Thermal Spray Technology (2010), Vol. 19(1-2), pp.81/88.
13. K. Sato., et al., Application Study of Spray Efficiency on
WC Cermet Coating Using Cold Spray, Japan Thermal
Spray Society 92nd Autumn Meeting (2010), pp57/58, in
Japanese
14. K. Sato., et al., Comparative Study on The Mechanical

Properties of WC-12Co between HVOF Coatings and
Hard Material, Tribology Online (2008), pp.137/141
67


All rights reserved
Investigation of HVOF-Sprayed Hardmetal Coatings for

Static Friction Applications
L.-M. Berger,* J. Spatzier
Fraunhofer Institute IWS, Dresden, Germany
*E-mail: lutz-michael.berger@iws.fraunhofer.de
M. Grfensteiner, J. Vidner, E. Leidich
Chemnitz University of Technology, Department of Engineering Design, Chemnitz, Germany
S. Schiefer, S. Grger, M. Gerlach
Chemnitz University of Technology, Institute of Production Measuring Technology and Quality Assurance, Chemnitz,
Germany
standard deviation. This is dependent on both material and

geometry of the surface.
Abstract
Frictionally engaged joints are widely used in mechanical
engineering and require a high static friction. Thermally
sprayed hardmetal coatings have a high potential to fulfil this
requirement. However, almost all research activities are
traditionally focused on the decrease of the dynamic
coefficient of friction. In this paper the static coefficient of
friction of as-sprayed Cr3C2-NiCr coatings in torsion
experiments with different contact pressures was studied. The
form, orientation and the geometric characteristics of the
friction surface have been investigated. The slipping curves
have been determined and a static coefficient of friction max
up to 0.80 was measured. The results show a standard
deviation depending on the nominal contact pressure.
For the first experiments of a systematic study, Cr3C2-NiCr

coatings sprayed with a liquid-fuelled HVOF gun have been
selected, due to the fact that high dynamic coefficients of
frictions were found against sintered alumina and in selfmated pairs (Ref. 1,2) and their relatively large carbide grain
size.
Experimental
Coating Preparation
The coatings were prepared with a liquid-fuelled HVOF spray
process (K2, GTV mbH, Luckenbach, Germany) using a
commercial Cr3C2-NiCr feedstock powder (Amperit 584.054,
H.C. Starck GmbH, Germany). The substrate material was
steel 42CrMo4+QT of specimen specially designed for the
investigation of the static coefficient of friction (see Fig. 1).
The effective ring-shaped friction surface at the top of the
specimens has an inner diameter of di= 15 mm and an outer
diameter of da= 30 mm. The coatings were sprayed onto the
friction surface with an optimized spray parameter set and a
thickness of about 300 m. Fifteen specimens were prepared
and were studied as-sprayed. Average roughness values Ra of
6.0 m and Rz of 32.2 m were measured.
Introduction
Hardmetal coatings sprayed by high velocity oxy-fuel (HVOF)
spraying are intensively studied for wear applications, in
particular for lubricated and dry sliding applications, where
usually a low coefficient of friction is required (Ref 1-3).
However, these coatings have also a high potential for static
friction applications requiring an opposite property profile
an increase of friction to a maximum value (Ref 4). It is
supposed that for these applications an excellent bonding to
the substrate, as typical for HVOF-sprayed coatings, and a
high coating roughness is required. Coating roughness is
depending on the carbide grain size. However, current
feedstock materials for HVOF processes are optimized to
small carbide grain sizes. Thus, such a development is
challenging.
Thermally sprayed WC-based hardmetal coatings are reported
to be used as friction pads in large joint flanges (Ref 4). A
calculated static coefficient of friction is given with 0.65. In
the current development, the general focus is to further
increase of the static coefficient of friction and decrease of its
Figure 1: Hardmetal coated specimen (left) and uncoated

counterpart with face grinded surface (right) after testing.
68
Geometric Characterization
The interaction of two surfaces in a tribological system
requires a holistic approach that includes the characterization
of all geometrical properties such as form, waviness and
roughness with a 3D evaluation method. The friction surface
of the specimen has been extracted holistically to derive
parameters for the complete friction surface in the same
reference system. The form, waviness and roughness are
extracted by a precision form measuring instrument Mahr
MFU 100 with a roughness stylus (Fig. 2a).
Before the friction test, four selected specimen were

characterized.
Microstructural Characterization
In addition, the as-sprayed coating surface and the coating
surface after testing was studied by SEM, as well as the
metallographically prepared cross section.
Procedure of the Static Coefficient of Friction Measurements
The friction measurements were performed on a standardised
static friction test bench as shown in Figure 4.
hydraulic normal
force actuator
force transducer
stamp
a)
b)
strain gauges for

torque measurement
Figure 2: a) Form measuring instrument with a roughness

Stylus. b) Form measuring instrument with a form stylus
flexible coupling
The values for the static coefficient of friction are depending

on the form and orientation of the friction surface in contact
with the counterpart. Therefore, minor deviations from the
nominal form and orientation can decrease the contact area.
Thus, they have to be controlled before testing. This is
performed with a regular form stylus on the same precision
form measuring instrument (Fig. 2b).
hydraulic torque
actuator
Figure 4: Test bench for determination of static coefficient of

friction.
The principle of the torsion test and the design of the specimen
are shown in Fig. 5. The normal pre-load was set according to
the predetermined surface pressure of 30, 100 and 300 MPa.
From the dimension of the friction surfaces, pre-load forces of
15.9, 53.0 and 159 kN respectively were applied. The
coefficient of friction was than calculated according to eq. (1).
a)
2 TR
.......................................................(1)
FN Dm
2 d 3 di3
.......................................................... (2)
Dm a2
3 d a di2
b)
Figure 3: a) Scheme of the marking system. b) Top view on

the hardmetal coating with the indentions
For the present specimen geometry, the effective friction

diameter is Dm = 23.33 mm.
For repeatable results of the geometrical characterization,

including the detection of surface changes, a marking system
was developed to create a Cartesian coordinate system on the
sprayed surface. Vickers indentations are used to mark the
surface for the definition of the Cartesian coordinate system
(Fig. 3a, b).
69
a)
b)
Figure 6: Principle of the evaluation for a static torsion load
and determination of the slipping moment (slipping curve).
Figure 5: a) Principle of the friction test with planar surface

b) Specimen design
Before testing, the specimens were pretreated in a standard
cleaning process in an ultrasonic bath with n-hexane (C6H14)
for 20 minutes (Ref 7). After cleaning, the specimens were
cooled down to 20C for four hours and tested in the test
bench within the next three hours.

Surface Texture Measurement and Microstructure
The extracted evaluation area of the coating surface marked by
the indentations was used to derive the geometrical parameters
(Fig. 7).
After the preliminary treatment, the specimens were clamped

into the test bench. All coated specimens were tested against
uncoated counterparts of face grinded steel 42CrMo4+QT.
The average roughness of the grinded friction surface was in
the range Rz = 3.2 -3.6 m.
m
110
100
90
80
70
60
50
40
The specimens were pressed together, using the axial load

force actuator FN. In the static slippage test, the twisting angle
was increased continuously (0.5/s) until the tested joint
slipped or a relative twisting angle of approximately 5 was
achieved. One experiment of each contact pressure has been
interrupted at lower twisting angles in order to produce
specimens for detailed investigations of the surface. During
the test, the axial load FN, the torque T and the twisting angle
were recorded continuously.
30
20
10
0
Figure 7: Extracted friction surface and evaluation area for

surface characterizing
Currently, the parameters proposed to influence the static
coefficient of friction are the number of islands, the mean
surface of the islands and the volume of the material for a
specific evaluation height c. Figure 8a explains the calculation
of the number of islands and Fig. 8b schematically depicts the
calculation of the mean surface of islands. The sum of all the
mean surfaces of all islands in the evaluation area is the
resulting geometrical parameter.
From the data recorded and the resulting twisting angle torsion
moment diagrams (so called "slipping curves"), the slipping
torque TR can be derived as shown in Fig. 6. Most notably,
elastic deformation of the test bench (linear increase) and
partial micro movements in the joint (alignment of surface
asperities) were recorded during global adhesion of the joint.
Since it might be difficult to distinguish between the sticking
and slipping range, the evaluation method according to (Ref 8)
was applied. This method specifies the static friction
coefficient according to a specific twisting angle. The
maximum coefficient of friction value can be calculated from
the known friction area geometry and preload force, using eq.
(1).
a)
The coefficient of friction was analysed at a twisting angle

= 0.1 and at the maximum of torque max.
b)
Figure 8: Geometrical characterization

The evaluation height c was derived to calculate the surface
parameters for the interaction of the two surfaces. Current
70
analysis shows that the contacting surface of the counterpart

interacts with the friction surface. Based on current results it is
proposed that the two surfaces interact to a depth maximum of
20% by the Abbott curve depending on the preload. For
hardmetal coatings, the evaluation height c therefore correlates
to the material ratio of 20% based on the Abbott curve (Ref 9,
10). The new parameters and the threshold as the evaluation
height c of a HVOF-sprayed hardmetal coating surface are
shown in Fig. 9.
Cr3C2 grains are located for direct contact with the

counterpart.
Torsion Experiments
The typical slipping curves of the tribological system are
displayed in for 30 MPa, 100 MPa and 300 MPa nominal
contact pressure in Figu. 11a, 11b, and 11c, respectively.
a)
27.90 m
Anzahl vonNumber
Inseln
of islands
1262
1138m
VolumederofInseln
material (m/m) 0.9554
Durchschnittshhe
1262
Durchschnittsoberflche der Inseln
1138 m
Mean surface
of islands
Durchschnittsvolumen
der Inseln
6849 m
4.238 m
b)
Durchschnittliches
Verhltnis Hhe
/ Flche
m/m
Figure
9: Geometrical
parameters
of the coating0.003726
surface
The geometrical characterization parameters have been

calculated with the Mountains Map software. The average
number of island of the four specimens is 1936 and the
average mean surface is 720 m. The small range for the
number of islands and the mean surface of the islands shows
approximately the same geometrical characteristic for all
HVOF-sprayed hardmetal coated surfaces.
The measurement of form and orientation deviations showed
deviations from flatness and perpendicularity. Flatness
deviations result from the coating roughness. Some
perpendicularity deviations leading to a decrease of total
contact area of the friction surface were detected. They results
from the spray process and will be optimizied in future sample
preparation.
c)
Figure 10: SEM micrograph of the coating (a) and surface

region (b), coating deposited with same spray parameters on
low carbon steel.
Figure 11: Slipping curves for nominal contact pressures of
30 MPa (a), 100 MPa (b) and 300 MPa (c).
The typical microstructure of the coatings is depicted in the

SEM micrograph in Figure 10a. Figure 10b shows the typical
appearance of the surface region of the coating, where mostly
71
The slipping curves of the tests at 30 and 100 MPa contact

pressure indicate a similar friction characteristic without
presence of a distinctive static friction coefficient (except testno. B 04 01). At 300 MPa contact pressure the slipping curves
show the classical friction characteristic with a distinctive
static friction maximum and a lower kinetic friction
coefficient. The parameters of the friction tests are compiled
in Table 2. Fig. 12 indicates the influence of the nominal
contact pressure to the static friction coefficients 0.1 and max.
With higher contact pressure the scatter of the static friction
coefficient decreases. Compared to the friction tests at 30 MPa
nominal pressure, the coefficient of friction max increases
about 12% at 100 MPa and about 20% at 300MPa nominal
contact pressure.
material areas transferred to the surface of the coating are

increasing with the contact pressure. At 300 MPa a large part
of the coating area is covered by the transferred counterpart
material. The coating surface itself appears unchanged in
result of testing.
Table 2: Overview of friction test results at 30, 100 and

300 MPa contact pressure.
test-no.
pressure
nominal
[MPa]
B 04 06
B 04 05
30
slipping
torque TR0.1
[Nm]
friction
coefficient
0.1
friction
coefficient
max
29.6
93
0.51
0.65
30.0
100
0.54
0.64
axial load FN
[kN]
contact
pressure P
[MPa]
15.7
15.9
B 04 01
15.9
30.0
124
0.67
0.71
B 04 15
53.0
100.0
351
0.57
0.70
52.9
99.8
439
0.71
0.77
B 04 11
53.0
100.0
389
0.63
0.74
B 04 03
158.8
299.5
1270
0.69
0.79
159.2
300.3
1280
0.69
0.80
159.2
300.3
1214
0.65
0.79
B 04 09
B 04 08
B 04 12
100
300
Figure 13: SEM micrographs of the coating surface in the assprayed state (a) and after the friction experimen: (b) at 30
MPa, (c) 100 MPa and (d) 300 MPa nominal contact
pressure.
Figure 14 shows an SEM micrograph of a face grinded

counterpart surface and an optical micrograph of the
counterpart surface after the friction test at 300 MPa contact
pressure. The hard phase particles of the coating induce
typical grooves on the grinded counterpart surface. Even at
300 MPa contact pressure, no significant deformation of the
roughness asperities could be detected.
200 m
Figure 12: Static friction coefficients 0,1 and max according

nominal contact pressure
Figure 14: SEM micrograph of the face grinded counterpart

surface (left), surface of the counterpart after the friction test
300 MPa nominal contact pressure.
Microstructural Investigation of the Surface after the Friction

Experiment
Figure 13 shows SEM micrographs of the as-sprayed surface
and the coating surface after the friction tests. With increasing
contact pressure an increasing material transfer from the face
grinded counterpart to the surface of the Cr3C2-NiCr coating
was observed. Both the size and amount of counterpart
Conclusion
Measurements of the static coefficient of friction of as-sprayed
Cr3C2-NiCr coatings has shown their high potential for use in
frictionally engaged joints. The coatings were deposited on the
72

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ITSC 2013: Innovative Coating

Solutions for the Global Economy

Mr. John Hayden, Chair

Mr. Albert Kay

Mr. Charles Kay, Past Chair

Mr. Komal Laul

Mr. Luc Pouliot

Dr. Rogerio Lima

Dr. Aaron Hall, Board Liaison

Mrs. Simone Mahlstedt

Mr. Robert Miller, Board Liaison

Dr. Basil Marple

Prof. Kirsten Bobzin

Dr. Christian Moreau

Prof. Thomas Coyle

Dr. Kazuhiro Ogawa

Mr. Mitchell Dorfman

Dr. Robert Tucker

Prof. Masahiro Fukumoto

Dr. Julio Villafuerte

Dr. Robert Gansert

Prof. Petri Vuoristo

Mr. Peter Heinrich

Mr. Greg Wuest

Mr. Jens Jerzembeck

Dr. Dongming Zhu

Dr. Jeganathan Karthikeyan

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Effects of Dry-Ice Blasting On Plasma-Sprayed Thermal Barrier Coatings .................... 22

Mechanical Properties of Plasma Sprayed YSZ Coatings

Y2O3 and Yb2O3 Co-Doped Strontium Hafnate as a

A Novel Modification for Twin Wire Arc Spraying to

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Investigation of HVOF-Sprayed Hardmetal Coatings for

Thermally Sprayed Ti3SiC2 and Ti2AlC MAX-Phase Coatings ........................................... 74

Development of Thermal Spray Coating Solution for Ceramic Substrates ..................... 79

Applications and Case Study

Macroporous Titanium Coatings by Thermal Plasma Spray ............................................. 91

High Performance Arc Sprayed Coatings for

Fabrication of Wire Mesh Heat Exchangers for

The Definition of Power in Plasma Spraying:

Superhydrophobicity and Water Repelling Characteristics of

High Temperature Oxidation Behavior of a

Characterization of Cold-Sprayed Copper Coatings with

Comparison of the Mechanical and Electrochemical Properties of

Effects of Spark Plasma Sintering Treatment for

Investigation on Microstructural & Mechanical Properties of

Mechanical Properties of Cold-Sprayed Ti-6Al-4V Coatings ........................................... 155

Study on the Restoration of Aluminum Aerospace IVD Coatings Using

Comparison of Microstructures and Mechanical Properties between

Shockwave Induced Spraying Process:

Preparation and Characterization of TiO2 Scattering Layer for

Dust Explosion Properties of Aluminum, Titanium, Zinc and

Design and Development of High-Pressure Warm Spray Gun ........................................ 196

Mechanical Properties of Cold Sprayed Al Coatings Reinforced by Ceramics ............. 200

Influence of Carrier Gas Composition on Microstructures and

Anisotropic Mechanical Properties of Cold Sprayed Copper Coatings .......................... 210

High-Pressure Cold-Sprayed Ni and Ni-Cu Coatings

Fundamental Cost Analysis of Cold Spray ....................................................................... 221