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THERMAL SPRAY OF STUHSPEERMALNSIONS S& PSORLAUYTIONS OF SUSPESYMPOSIUMNSIONS & S O(TS4)LUTIONS SYMPOSIUM (TS4) DECEMBER 2-3 , 2 0 1 5 MONTDECEMBERR E A L, 2- C3A,NAD 2 0 1A5 MONTR E A L, CA NADA

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TS415_InsidePages.indd 1 11/24/2015 10:33:16 AM ABOUT THE EVENT This special symposium is a chance for scientists and engineers interested in the emerging S&STS technologies to address both research challenges and development of industrial applications. The symposium will comprise a bal- anced group of speakers from industry, academia and national laboratories. Attendees will be coming from all over the world: Canada, United States, Japan, France, Germany, South Korea, Sweden, and Finland.

GENERAL INFORMATION REGISTRATION SCHEDULE Day/Date Hours Location Tuesday, December 1, 2015 4:00–6:00 p.m. Soprano Foyer, 4th Floor Wednesday, December 2, 2015 7:00 a.m.–5:00 p.m. Soprano Foyer Thursday, December 3, 2015 7:00 a.m.–4:00 p.m. Soprano Foyer

EXHIBIT DATES AND TIMES Soprano Foyer, 4th Floor Wednesday, December 2 Refreshment Break: 10:00–10:30 a.m. Lunch: 12:00–1:00 p.m. 2 Refreshment Break: 3:00–3:30 p.m. Networking Reception and Dinner: 6:00–8:00 p.m.

Thursday, December 3 Refreshment Break: 10:00–10:30 a.m. Lunch: 12:00–1:00 p.m. Refreshment Break: 2:30–3:00 p.m.

ORGANIZING COMMITTEE Brian Callen, Oerlikon Metco, Canada Ali Dolatabadi, Concordia University, Canada Brian Hazel, Pratt & Whitney, United States Luc Leblanc, GE- Cells, United States Rogerio Lima, National Research Council of Canada Christian Moreau, Concordia University, Canada Filofteia-Laura Toma, Fraunhofer Institute for Material and Beam Technology IWS, Germany

TS415_InsidePages.indd 2 11/24/2015 10:33:26 AM TECHNICAL PROGRAM SCHEDULE WEDNESDAY, DECEMBER 2, 2015

Time Activity Presenter Institution Room

Soprano AB, 8:00–8:15 a.m. Welcoming Remarks: Rogerio Lima/Christian Moreau 4th Floor Keynote Presentation: Suspension Spraying of TBCs for Industrial Turbines Ramesh Soprano AB, 8:15–9:00 a.m. Siemens Energy Inc. Chair: Rogerio Lima, National Research Subramanian 4th Floor Council of Canada SESSION 1: TBCs Engineered via Suspensions & Solutions Chair: Brian Hazel, Pratt & Whitney Influence of Morphology on Thermal Properties and Thermal Cyclic Lifetime Nicolaie 9:00–9:30 a.m. University West Soprano AB of Axial Suspension Plasma Sprayed Markocsan Thermal Barrier Low Conductivity GdZr/YSZr Bilayer Thermal 9:30– University of Barrier Coating Made by the Solution Eric Jordan Soprano AB 10:00 a.m. Connecticut Precursor Plasma Spray Process 10:00– Refreshment Break with Exhibitors Soprano Foyer 10:30 a.m.

SESSION 2: Suspension —Process Control & Reliability Chair: Luc Leblanc, GE-Fuel Cells 10:30– Engineering Coating Structure By Suspension Christian Moreau Concordia University Soprano AB 11:00 a.m. Plasma Spray 11:00– Rapid Formation of Fine Layers 3 Soshu Kirihara Osaka University Soprano AB 11:30 a.m. by Thermal Nanoparticle Spraying 11:30 a.m.– Numerical Simulation of Suspension Ali Dolatabadi Concordia University Soprano AB 12:00 p.m. Thermal Spray Processes Soprano C 12:00–1:00 p.m. Lunch with Exhibitors and Foyer SESSION 3: Suspensions & Solutions—Opportunities and Steps to Industrial Commercialization Chair: Brian Callen, Oerlikon Metco Industry Considerations in Spraying of 1:00–1:30 p.m. Brian Hazel Pratt & Whitney Soprano AB Suspensions 1:30–2:00 p.m. Is Suspension Plasma Spray a Solution? Luc Leblanc GE-Fuel Cells Soprano AB Lessons for Commercializing Suspension and 2:00–2:30 p.m. Kent VanEvery Progressive Surface Soprano AB Solution Plasma Spraying From Columnar Thermal Barriers to Dense 2:30–3:00 p.m. Coatings-Suspensions for Thermal Spray Nicholas Curry Treibacher Industrie AG Soprano AB Coating Applications 3:00–3:30 p.m. Refreshment Break with Exhibitors Soprano Foyer SESSION 4: Suspension Spraying Processing—Economical & Technical Challenges Chair: Christian Moreau, Concordia University Fraunhofer Institute Demands, Potentials and Economic Aspects of Filofteia-Laura 3:30–4:00 p.m. for Material and Beam Soprano AB Thermal Spraying with Aqueous Suspensions Toma Technology Development of Suspension Plasma Spray Processes Ghislain Univ. Bourgogne 4:00–4:30 p.m. Soprano AB at Atmosphere and at Low Pressure (100 Pa) Montavon Franche-Comté Axial Suspension Plasma Spraying: Northwest Mettech 4:30–5:00 p.m. Zhaolin Tang Soprano AB Its Development and Application Corporation Soprano C 6:00–8:00 p.m. Networking Reception and Dinner with Exhibitors and Foyer

TS415_InsidePages.indd 3 11/24/2015 10:33:30 AM THURSDAY, DECEMBER 3, 2015

Time Activity Presenter Institution Room

8:00–8:15 a.m. Opening Remarks Soprano AB Keynote Presentation: High Velocity Flame Spraying of Nano-structured Materials and University of 8:15–9:00 a.m. Rainer Gadow Soprano AB Related Industrial Applications Stuttgart Chair: Laura Toma (Fraunhofer IWS) SESSION 5: Suspension Engineered TBCs—Processing & Properties Chair: Brian Hazel, Pratt & Whitney National Suspension Plasma Spray (SPS) as an Emerging Institute for 9:00–09:30 a.m. Seiji Kuroda Soprano AB Process for Thermal Barrier Coatings Materials Science Columnar & Porous SPS YSZ Thermal Barrier National 9:30– Coatings Deposited at Traditional Air Plasma Research Dina Goldbaum Soprano AB 10:00 a.m. Spray Distances—A Study on Microstructural Council of Evolution and Canada 10:00– Refreshment Break with Exhibitors Soprano Foyer 10:30 a.m.

SESSION 6: Suspension Engineered TBCs—Performance & Evaluation Chair: Ali Dolatabadi, Concordia University Comparison of APS, SPS and EB-PVD YSZ 10:30– Coating Characteristics for Advanced Brian Callen Oerlikon Metco Soprano AB 11:00 a.m. Thermal Barrier Coatings 11:00– Evaluation of SPS YSZ Coating Performance Progressive 4 Kent VanEvery Soprano AB 11:30 a.m. in Thermal Barrier Applications Surface 11:30 a.m.– Performance of Columnar 7–8wt% YSZ SPS Christopher Praxair Surface Soprano AB 12:00 p.m. Coatings as a Function of Heat-Treatment Petorak Technologies 12:00–1:00 p.m. Lunch with Exhibitors Soprano C and Foyer SESSION 7: Suspension/Solution Applications & System Development Chair: Luc Leblanc, GE-Fuel Cells Use of Suspension and Solution Precursor University of 1:00–1:30 p.m. Plasma Spraying for Solid Fuel Cell Olivera Kesler Soprano AB Toronto Applications Effects of SPPS Deposition Conditions on University of 1:30–2:00 p.m. the Structure and Wetting Behaviour of a Thomas Coyle Soprano AB Toronto Superhydrophobic Ceramic Coating National Institute of Advanced Microstructure Control of SPS Ceramic Coating 2:00–2:30 p.m. Masato Suzuki Industrial Soprano AB with an Axial Feed Plasma Spray Gun Science and Technology (AIST) 2:30–3:00 p.m. Refreshment Break with Exhibitors Soprano Foyer Round Table Discussion Moderators: Rogerio Lima, National 3:00–4:00 p.m. Soprano AB Research Council of Canada and Christian Moreau, Concordia University 4:00 p.m. Conclusion

TS415_InsidePages.indd 4 11/24/2015 10:33:30 AM ABSTRACTS with time at high temperature. The results showed SUSPENSION PLASMA SPRAYING OF significant influence of coating morphology on ther- mal conductivity and thermal-cyclic performance of TBCS FOR INDUSTRIAL GAS TURBINES the coatings. Also, significant microstructural changes Siemens Energy Inc. Ramesh Subramanian, were noticed during the heat treatment such as pore- Siemens Industrial Turbomachinery Xin-Hai Li, rearrangement and . The push to higher firing temperatures, increased efficiencies, reduced emissions and multiple fuel capa- bility continues to demand more out of de- LOW CONDUCTIVITY GdZr/YsZr sign and materials systems capabilities. Thermal bar- BILAYER rier coatings are an integral part of many hot section turbine components, contributing one of the key func- MADE BY THE SOLUTION PRECURSOR tions of thermal protection, especially with increas- ing firing temperatures. Strain tolerance is one of the PLASMA SPRAY PROCESS key TBC characteristics necessary for increasing high Eric H. Jordan, Chen Jiang, and Maurice Gell University of Connecticut temperature operations. Suspension plasma spray Storrs, CT, USA processes offer a unique path to manufacturing strain tolerant, low thermal conductivity TBCs. Thermal con- The, low thermal conductivity, high temperature ductivity and cyclic lives depend strongly on the micro- stability and good CMAS resistance of gadolinium structures, which are different from conventional plas- zirconate (GZO) are well-documented. Gadolinium zi- ma sprayed TBCs. Furthermore, it has been seen that conate is more expensive than yttria stabilized zirconia spallation life times depend on bond-coat type, chem- (YSZ) and has lower fracture toughness. The advan- istry, and surface roughness. Results from efforts in SPS tages of GZO can be achieved and the disadvantage TBCs, performed by Siemens Gas Turbines division in minimized by fabricating a bilayer TBC consisting of an Sweden, will be presented and future outlook will be inner layer of YSZ and outer layer of GSO. A low thermal discussed for this emerging manufacturing approach. conductivity (0.62 W/mK) YSZ coating with structured porosity was deposited using the solution precursor plasma spray process (SPPS) then an SPPS GZO layer 5 INFLUENCE OF COATING was put on top. Cyclic furnace tests, two types of CMAS MORPHOLOGY ON THERMAL resistance tests and steam environment tests were run. No failures were observed at the GZO to YSZ interface PROPERTIES AND THERMAL in any of the tests. It was also found that GZO top layer coatings had greatly superior CMAS resistance when CYCLIC LIFETIME OF AXIAL the CMAS was put on all at once at the start of a cyclic SUSPENSION PLASMA SPRAYED furnace testing but performed no better than YSZ in tests where CMAS precursor was applied every cycle. THERMAL BARRIER COATINGS Nicolaie Markocsan, Ashish Ganvir, and Per Nylén Axial Suspension Plasma Spraying is a relatively ENGINEERING COATING STRUCTURE new thermal spaying technique to produce advanced BY SUSPENSION PLASMA SPRAY thermal barrier coatings. This technique enables the pro- C. Moreau, A. Dolatabadi, N, Sharifi, duction of a variety of microstructures from highly dense, M. Aghasibeig, M., Pugh, and R. Wuthrich highly porous, segmented or columnar coatings. These Concordia University, Canada coatings can provide extremely low thermal conductivity Suspension plasma spraying (SPS) is an emerg- and better thermal-cyclic lifetime. In this work, five differ- ing coating process that has been the object of exten- ent types of suspension plasma sprayed coatings were sive research and development efforts over the last 15 sprayed using axial injection and different set of process years. The process involved the deposition of ultrafine parameters. The influence of coating microstructure and droplets (typically from 0.5 to 5 microns) that permits the various microstructural defects on their thermal and the production of coatings with unique microstruc- functional properties were studied. tures, one or two orders of magnitude finer than those Experimental tests carried out to study this rela- achieved typically in other thermal spray processes. tionship include microstructural analysis with SEM, In this presentation, we will discuss how SPS can thermal conductivity measurements using laser flash be used to tailor the structure of spray coatings to en- analysis and lifetime using thermal-cyclic fatigue test. hance their performance in specific applications. In The samples were also heat treated at 1150°C for 200 particular, surfaces structured at the micron and/or and 400 hours to study the microstructural changes nanoscales are produced to optimize the properties of

TS415_InsidePages.indd 5 11/24/2015 10:33:30 AM superhydrophobic coatings and electrode coatings for and evaporation, the molten and semi-molten fine evolution. The coating structure is engineered particles are deposited on a substrate. Although the by using air plasma spray (APS), SPS and combination of coatings produced by STS have shown enhanced char- APS/SPS processes. Some challenges for optimizing and acteristics, further understanding of the complex phe- controlling the SPS process will also be discussed. nomena of the entire process from suspension injec- tion to the sub-micron solid particles conditions upon impact can help us to overcome the technological chal- RAPID FORMATION OF FINE lenges associated with SPS systems. CERAMIC LAYERS BY THERMAL In this work a three-dimensional compressible NANOPARTICLE SPRAYING Eulerian framework along with Volume of Fluid (VOF) Soshu Kirihara surface-tracking method coupled with the Large Eddy Associate Professor Simulation (LES) turbulence model are used to directly Joining and Welding Research Institute model the primary suspension breakup. Effect of vary- Osaka University ing the suspension properties i.e. viscosity, density and surface tension, on the structure of internal flow and Thermal Nanoparticle spraying techniques were consequently, the external flow are studied and com- newly developed to create fine ceramic layers and pared against the validation experiments. nanometer sized composite structures. The alumina and zirconia nanoparticles of 200 to 500 nm in aver- In parallel, secondary droplet breakup, solvent age diameter were dispersed into acrylic resins evaporation, as well as solid particle heating, melting, at 40 to 60 % in volume contents, and the obtained and boiling are studied using a two-component (solvent high viscosity slurries were blown by compressed air and solid particle suspension) droplet in the Lagrangian jet of 2 to 4 atm in pressure as micro mists of 10 to 50 framework. Kelvin-Helmholtz Rayleigh-Taylor (KHRT) μm in drop size into an and gas flame breakup model is utilized to predict the secondary torch for a coaxial direction. On SUS-304 breakup of suspension. Particle conditions upon impact substrates of 50×50×5 mm in size placed at 100 mm in (i.e. trajectory, velocity, and temperature) as well as the distance from the flame gun, the alumina and zirconia substrate location and curvature have key influences on coated layers of 50 to 300 μm in thickness were formed the deposition and quality of the coatings. successfully with 50 μm/s in deposition late. Micro- 6 structures were observed by using scanning electron microscopy. X-diffraction spectroscopy was used to an- INDUSTRY CONSIDERATIONS alyze the residual carbon elements produced by imper- IN SPRAYING OF SUSPENSIONS fect combustions of the liquid resin. Effective dielectric Brian Hazel constants of the layers were measured suc- Pratt & Whitney cessfully to calculate the porosities of air defects vol- Thermal spraying utilizing suspension feedstock is ume contents by using time domain spectroscopy of a relatively new method for applying coatings. Suspen- electromagnetic waves in a terahertz frequency range. sion plasma spraying specifically has demonstrated the Dr. Soshu Kirihara is Associate Professor of Join- ability to produce a range of coating microstructures. ing and Welding Research Institute in Osaka Univer- The suspension plasma sprayed strain tolerant verti- sity, Japan. Recent investigation topics are utilization cally segmented and columnar structures are of par- of nanoparticle slurries for thermal spraying and three ticular interest for application of thermal barrier coat- dimensional printing technologies. Fine ceramic layers ings used in gas turbine engines. These strain tolerant and components with nanometer sized composite pat- structures are expected to have the ability to withstand terns and micrometer sized geometric structures were the high temperatures and thermal cycling inherent in processed successfully to modulate energy and mate- gas turbine operation. Therefore, two applications of rial flows. a suspension plasma sprayed thermal barrier coating can be imagined. First, as an alternative to coatings made by electron-beam physical vapor deposition and, NUMERICAL SIMULATION OF second, as an improvement over traditional dry pow- SUSPENSION THERMAL SPRAY der air plasma sprayed coatings. As an alternative to electron-beam physical vapor deposition, suspension PROCESSES plasma spraying is expected to have a significantly A. Dolatabadi, C. Moreau, M. Jadidi, and K. Pourang lower operating cost due to reductions in capital, labor Concordia University, Canada and raw material costs while having near similar per- Suspension thermal spraying (STS) is an emerging formance. As an alternative to traditional dry powder process for producing coatings with enhanced proper- air plasma spraying, suspension plasma spraying is ex- ties. Sub-micron up to few micron-sized particles are pected to have marked performance improvement at a suspended in a solvent and injected into a plasma or modestly higher cost. The risks, tradeoffs, and progress HVOF plume. After the suspension undergoes breakup along these paths will be considered.

TS415_InsidePages.indd 6 11/24/2015 10:33:31 AM bers or chrome oxide for the print and paper industry IS SUSPENSION PLASMA demand coatings with vastly different microstructures and properties compared to thermal barriers. The use SPRAY A SOLUTION? of suspension has enabled a much larger range of coat- Luc Leblanc ing microstructures to be produced compared to tradi- GE-Fuel Cells tional powder spraying techniques. While a variety of Suspension spray has the ability to produce a wide coating types can be achieved through process param- variety of coating microstructures as well as different eter manipulation alone; suspensions require tailored surface textures, ranging from thin functional layers for properties tied to final coating application in order to applications such as solid oxide fuel cells, to columnar reach their full potential. thermal barrier coatings for gas turbines, or highly tex- tured surfaces with superhydrophobic properties. We In this paper, the influence of a number of suspen- will discuss the development of suspension plasma sion and spray process parameters on the resulting spray in the context of industrial research where the coating microstructures will be presented. Further- final goal is to develop coatings that will eventually be more, some possible suspension spray routes to the used on actual parts for cost and/or performance ben- manufacture of dense, porous or columnar microstruc- efits, or lead to applications not previously in the realm tures for various applications will be discussed. of thermal spray technology. DEMANDS, POTENTIALS AND LESSONS FOR COMMERCIALIZING ECONOMIC ASPECTS OF THERMAL SUSPENSION AND SOLUTION SPRAYING WITH AQUEOUS PLASMA SPRAYING SUSPENSIONS Dr. Kent VanEvery Filofteia-Laura Toma1, Christoph Leyens1, 2, and Progressive Surface Annegret Potthoff3 For several years ongoing work has been conduct- 1. Fraunhofer Institute for Material and Beam Technology (IWS), ed at Progressive Surface towards developing suspen- Dresden, Germany sion and solution plasma spray coating solutions to 2. Technische Universität Dresden (TUD), Dresden, Germany 3. Fraunhofer Institute for Ceramic Technologies and Systems (IKTS), various industries. Compared to using dry powders, Dresden, Germany producing coatings via suspension or solution plasma 7 In this contribution, the main aspects of thermal spraying presents challenges which are either new or spraying with suspensions, which have to be consid- of increased importance. This talk will discuss lessons ered in order to produce suspension sprayed coatings learned on feedstock performance, process dynamics, in an economical way, are presented. The economic coating formation, and equipment considerations. efficiency of the process depends on the availability of suitable additional system components (suspension FROM COLUMNAR THERMAL feeder, injectors), on the development and handling of stable suspensions, as well as on the high process sta- BARRIERS TO DENSE COATINGS bility for acceptance at industrial scale. -SUSPENSIONS FOR THERMAL Special focus is made on the development and SPRAY COATING APPLICATIONS processability of -based suspensions of ceramic Nicholas Curry . The use of water as a liquid media for prepar- Treibacher Industrie AG ing suspensions is often critically discussed due to the necessity of a higher heat input during spraying com- Suspension spraying of ceramics has become a pared to alcoholic suspensions. In fact, the safe and highly innovative field in recent years. As production environmental friendly manufacturing as well as lower level equipment has become available for coating de- production and transport costs clearly speak for the velopment in the form of specially adapted high power industrial use of aqueous suspensions. Recent devel- plasma guns and HVOF equipment; advances have opments have demonstrated successful production been made in bringing suspension spraying to the in- and processing of highly concentrated aqueous sus- dustrial level. pensions (of 50 wt. % or more). The economic aspects The first field to adopt the use of suspension in terms of deposition efficiencies and feed rates in spraying has been the gas turbine industry; where the relation to the solids content of aqueous suspensions ability to generate segmented or columnar thermal of different ceramic oxides are discussed. In the case barrier coatings without the high processing cost of EB- of alumina S-HVOF coatings feed rates between 15 to PVD, has generated a great deal of interest. Suspension 35 g/min and deposition efficiencies up to 65–70% spraying also has the potential to be utilized in fields could be reached with aqueous suspensions. The coat- where dense, hard ceramic coatings are required. Appli- ing (850 HV0.3) did not change with increase of cations such as yttrium oxide for plasma etching cham- the suspension concentration from 35 to 50 wt. %. For

TS415_InsidePages.indd 7 11/24/2015 10:33:33 AM high melting temperature S-HVOF coatings like chro- If atomization requires more developments since mia, yttria, or yttria-stabilized zirconia the deposition optimization of the twin-fluid nozzle geometry is man- efficiencies (15–30%) and coating thicknesses depos- datory, it offers the main advantage of decoupling the ited per pass (2–5 µm/pass) were lower than in the case injected suspension flow rate and the injection param- of alumina. Cr2O3 S-HVOF coatings with microhardness eters from the plasma torch power parameters, a main values in the range 1150–1450 HV0.3, which were higher drawback encountered with mechanical injection. than those of the conventional APS coatings, were pro- The first part of this paper will address the devel- duced with different aqueous Cr O suspensions. 2 3 opment of a twin-fluid nozzle suitable for suspension plasma spraying and describe the different steps im- DEVELOPMENT OF SUSPENSION plemented: suspension atomization (by shadowscopy and droplets size measurements), droplets injection PLASMA SPRAY PROCESSES AT in the plasma flow (by shadowscopy), droplets/par- ATMOSPHERE AND AT LOW ticles velocity in the plasma flow (by particle imagery velocimetry), collected flattened particles analysis (by PRESSURE (100 PA) optical interferometry), coating void content (by US- Ghislain Montavon1, Marie-Pierre Planche1, AXS), etc. Various atomizing conditions, correspond- Emilie Aubignat1, Hanlin Liao1, He Pengjian1, ing to variable gas-to-liquid ratios (GLR) have been Frédéric Lapostolle1, Dominique Billieres2, studied with two types of suspensions: alcohol-based and Alain Allimant3 and water-based and two feedstock materials: alu- 1. Univ. Bourgogne Franche-Comté, IRTES-LERMPS, France mina and yttria. 2. Saint-Gobain Coating Solutions, France 3. Saint-Gobain C.R.E.E., France Beside, the energy required for vaporizing the Suspension plasma spraying (SPS) is an emerging liquid during suspension processing limits the spray route aiming at processing a suspension made energy available for processing later on the particles of micrometer, sub-micrometer or nanometer-sized by the plasma flow: the interaction time significantly particles suspended in a suspension. Compared to a decreases. Additionally, the low inertia and thermal conventional plasma spray route processing particles inertia of processed particles requires decreasing the of diameters ranging from 15 to 50 µm (for ceramic ma- spray distance from about 100 mm, average value, to terials), SPS allows processing much smaller particle about 35 mm, average value. In turn, the heat flux im- 8 sizes and hence manufacturing coatings exhibiting a parted by the plasma flow to the substrate drastically finer structural scale with a unique void network. In increases (it is multiplied by 10 in a first approxima- turn, the decrease in the coating structural scale modi- tion). Increasing the interaction time and/or decreasing fies its properties. As an example, their elastic property the heat load imparted by the plasma to the substrate and toughness increase whereas their thermal conduc- could be mandatory for some applications. For those tivity decreases. reasons, the SPS process has been implemented under low pressure to explore the benefit it could provide, re- The injection of the suspension in the plasma flow gardless of the cost of implementation. is particularly challenging since it tailors the particles trajectory, and their processing. Two techniques have The second part of this paper will address the been considered by the scientific community: implementation of SPS at a pressure of 100 Pa of pure . Nanometer-sized yttria-stabilized zirco- •  an axial injection requiring adapted plasma torch nia (YSZ) particles were considered as feedstock. A designs, most of the time with multiple cathodes, three-cathode plasma torch and axial injection with a •  a radial injection adapted on most existing stick mechanical injector was considered. Optical emission mono-cathode plasma torches, but requiring more spectroscopy demonstrated a partial vaporization of robust and optimized conditions. feedstock particles in the plasma flow. Coatings were manufactured with different sets of spray operating Since radial injection can be very easily imple- parameters. Their structure was analyzed and some mented on most existing plasma torches, it is primarily of their mechanical properties measured. It was found developed by the community: that the Young modulus of those coatings and their •  either by considering mechanical injection for which hardness were 30% and 50%, respectively, higher the suspension is forced through a capillary injector than the values of SPS YSZ coatings reported in pub- to form a continuous stream which penetrates the lished data. Condensation of vaporized vapors during plasma flow where it is atomized in droplets by the coating manufacturing could explain the increase in plasma shear forces, the coatings stiffness. •  or by considering atomization for which the suspen- sion is atomized in droplets in a twin-fluid nozzle prior their injection in the plasma flow.

TS415_InsidePages.indd 8 11/24/2015 10:33:37 AM conventional spray materials preparation. The HVSFS AXIAL SUSPENSION PLASMA suspension flame spray process represents a novel process for the direct processing of nano-powder sus- SPRAYING—ITS DEVELOPMENT pensions in a workplace safe closed system technol- AND APPLICATION ogy, which opens new application fields even for es- Z. Tang, G. Masindo, D. Barentzen, tablished materials since nanoscale coating structures D. Dolomont and Z. Celler can improve properties and performance compared to Northwest Mettech Corp. the respective standard coatings. Especially in case of Axial suspension plasma spraying (ASPS) is gain- suspensions, their preparation, storage and handling ing considerable interest in commercial applications require distinct expertise. Flame interaction of where advanced ceramic coatings are required. The and suspensions with different heat and mass transfer presentation is aimed at describing complexities of the as well as coating formation phenomena are key issues process and gaining a better understanding of the coat- to gain the necessary process knowledge. ing mechanisms. The effect of powders, suspension, This is required to control the liquid feedstock atomization, plasma parameters, and coating process based spray process and raise the technology to an in- on properties of coatings were investigated. The coat- dustrial production and stability level. Especially in the ing microstructures and properties can be tailored for field of thermally sprayed tribo-functional coatings, emerging applications such as solid oxide fuel cells nano materials show enhanced characteristics regard- (SOFCs), plasma erosion resistant coatings, and ad- ing coating microstructure, porosity and surface topog- vanced thermal barrier coatings (TBCs). With ASPS by raphy as well as improved lifetime, and spraying liquid suspension containing fine powders, resistance. The potential of direct use of nanoscale dense YSZ and Y2O3 coatings were achieved with high thermal spray feedstocks as suspension will be demon- functional properties for SOFC and plasma erosion re- strated in various industrial applications, e.g., internal sistance applications, respectively. By contrast, very combustion engines, gear and train systems, industrial porous and columnar structured TBCs, similar to those engineering and special tools. deposited by electron beam-physical vapor deposition (EB-PVD) have also been demonstrated with ASPS. This was possible thanks to modification of process param- SUSPENSION PLASMA SPRAY eters including selection of powders, make-up of sus- AS AN EMERGING PROCESS FOR pensions, and plasma conditions. ASPS technology has 9 been proven to be an economical route for TBCs on ad- THERMAL BARRIER COATINGS vanced turbine components. Xiaolong Chen, Seiji Kuroda, Takuma Ohnuki, Hiroshi Araki, Makoto Watanabe, and Yoshio Sakka HIGH VELOCITY FLAME SPRAYING National Institute for Materials Science Thermal barrier coatings (TBCs) fabricated either OF NANOSTRUCTURED by atmospheric plasma spraying (APS) or electron MATERIALS AND RELATED beam physical vapor deposition (EB-PVD) are widely used in the metallic hot-section components of gas INDUSTRIAL APPLICATIONS turbines to provide thermal and corrosion protections. R. Gadow and A. Killinger Due to the powder size (20–120μm) limitation in APS University of Stuttgart process, SPS as an emerging process which can be used Institute for Manufacturing Technologies of for TBC fabrication by using directly the powder size Ceramic Components and Composites (IFKB) less than 5 μm has been widely and intensively inves- HVSFS processing is a promising method to pro- tigated recently in the thermal spray field. The starting duce novel structural and functional coatings, by the di- powder size impart the final SPS TBCs with finer micro- rect processing of nano and micro ceramic suspensions structures and improved thermophysical properties. in thermal spray systems. The potential of these coat- It is more interesting that both highly segmented with ings is well known and has gained vital interest among higher density and columnar microstructural TBCs can the scientific and industrial community. It is expected, be prepared in the same SPS process. However, SPS as that thermal spraying with liquid feedstocks will give a new process is still beyond precisely control due to substantial contributions in numerous industrial key its processing complexity. In this paper, dependences applications like biomedicine, energy conversion, ca- of SPS TBC microstructures on processing parameters, talysis, automotive, and aerospace. Fabrication routes and the resultant properties of the SPS TBCs such as and processing of solutions and suspension feedstocks thermomechanical properties, and high temperature containing fine primary particles strongly differ from stability has been investigated.

TS415_InsidePages.indd 9 11/24/2015 10:33:40 AM substrates with MCrAlY (M=Ni, Co, Fe) bond COLUMNAR AND POROUS SPS coats. The YSZ coatings are produced by either Air Plas- ma Spray (APS) and/or Electron Beam Physical Vapor YSZ THERMAL BARRIER COATINGS Deposition (EB-PVD). Design considerations for selec- DEPOSITED AT TRADITIONAL tion of the coating method are component size, cost and performance requirements. Each method has its AIR PLASMA SPRAY DISTANCES—A own advantages and disadvantages. Conventional STUDY ON MICROSTRUCTURAL APS is relatively inexpensive but limited to porous or dense YSZ coatings, whereas EB-PVD produces fila- EVOLUTION AND THERMAL mentary strain tolerant coatings at much higher cost. To offset the high capital cost of EB-PVD, researchers CONDUCTIVITY have looked at developing strain tolerant coatings Dr. Dina Goldbaum and Dr. Rogerio S. Lima through microstructure changes produced by alterna- National Research Council of Canada tive processes. Suspension Plasma Spray (SPS) moves Suspension plasma spray (SPS) technology has towards more sophisticated segmented/columnar the potential to provide a valuable alternative to elec- structures using dual or multilayer approaches where tron beam physical vapour deposition (EB-PVD) for the coatings structures can be adjusted for specific appli- production of ZrO2-Y2O3 (YSZ) thermal barrier coatings cations and components. The goal of this work is to (TBCs) on the blades of gas turbine engines. The co- better understand the similarities and differences of lumnar and porous microstructures of SPS TBCs com- these YSZ microstructures in terms of their character- bine the vertically-oriented columnar microstructures istics through using equal material selections and test found in EB-PVD TBCs, with the typical high coating conditions. porosity of TBCs engineered via air plasma spray (APS). The vertically-oriented columnar microstructure of the YSZ SPS TBC contributes to the coating strain tolerance, EVALUATION OF SPS YSZ COATING whereas, the high coating porosity contributes to lower- PERFORMANCE IN THERMAL ing its thermal diffusivity and conductivity values. The combined effect imparts high temperature resistance BARRIER APPLICATIONS and strain tolerance to SPS TBCs with potential turbine Kent VanEvery, Ph.D.1, Nicholas Curry, Ph.D.2, blade applications. One of the engineering challenges and Todd Snyder1 10 of SPS coating processing is the typical short spray dis- 1. Progressive Surface tances required to deposit these coatings (e.g., 5 cm). 2. Treibacher AG These short spray distances increase the residual stress The thermal cycling, shock, and conductivity data levels in the coatings and reduce torch maneuverability of suspension plasma spray (SPS) yttria-stabilized zir- around the turbine part. Current work successfully en- conia (YSZ) coatings will be presented. These data will gineered columnar and porous SPS YSZ TBCs sprayed be compared to similar properties from conventional at traditional APS distances of 7.5 and 10 cm. The effect air plasma spray (APS) YSZ coatings. The differences of the deposition conditions on the coating microstruc- in SPS and APS properties will be connected to micro- ture, porosity, thermal diffusivity and thermal conduc- structural and atomic differences in the coatings. tivity is investigated. A conventional APS YSZ TBC was employed as a comparison. PERFORMANCE OF COLUMNAR COMPARISON OF APS, SPS 7-8WT% YSZ SPS COATINGS AS A FUNCTION OF HEAT-TREATMENT AND EB-PVD YSZ COATING Christopher Petorak CHARACTERISTICS FOR ADVANCED Praxair Surface Technologies Suspension plasma spray (SPS) columnar coatings THERMAL BARRIER COATINGS have demonstrated the ability to adhere to smooth Brian W. Callen1, Mitchell Dorfman2, Jing Liu2, bondcoated substrates, and perform for hundreds of Alex McLane2, and Riston Roccio-Heller2 1. Oerlikon Metco (Canada) Inc. hours in FCT. The performance and properties of SPS 2. Oerlikon Metco (US) Inc. 7wt% YSZ coatings are linked to their unique colum- Legacy 7–8 wt% YSZ (Yttria-Stabilized Zirconia) nar microstructure, where the individual columns are materials have been used over the last thirty years for comprised of fine micron sized resolidified particles various turbine applications, namely as TBCs (Thermal and lamellae. Consequently, the intra-columnar micro- Barrier Coatings). The benefits of 7–8 wt% YSZ TBC structure is associated with high specific surface area materials are well-known in the literature, with key and porosity. The following work examines the stabil- features of low thermal conductivity, high temperature ity of these microstructures at elevated temperatures phase stability and compatible thermal expansion to where the driving force for sintering provides potential

TS415_InsidePages.indd 10 11/24/2015 10:33:40 AM effects on coating properties and performance. Spe- costly to employ at an industrial scale. Here, we pres- cifically, a focused understanding of the effects of heat- ent a novel coating technique to manufacture ceramic treatments on the thermal conductivity and erosion re- superhydrophobic coatings rapidly and economically. sistance are evaluated due to their critical connection A rare earth oxide (REO) was selected as the coating with engine performance and lifetime. material due to its hydrophobic nature and strong me- chanical properties, and deposited on stainless steel substrates by solution precursor plasma spray (SPPS). USE OF SUSPENSION AND SOLUTION Effects of spraying conditions including: standoff dis- PRECURSOR PLASMA SPRAYING tance, arc current, plasma gas velocity, and number of torch passes on the coatings’ microstructure and hy- FOR SOLID OXIDE FUEL CELL drophobicity were investigated. A wide range of coat- APPLICATIONS ing microstructures was produced, and among them, Olivera Kesler a water as high as 165° and a contact University of Toronto angle hysteresis as low as 2° were achieved. Compared The talk will present an overview of several case to smooth REO surfaces, the SPPS superhydrophobic studies making use of suspension plasma spray (SPS) coating improved the water contact angle by as much and solution precursor plasma spray (SPPS) processing as 65%. The excellent wetting behaviour of the SPPS techniques for the fabrication of solid oxide fuel cells superhydrophobic coatings resulted from the combi- (SOFC) and their components. Advantages and chal- nation of the hydrophobic material and a hierarchically lenges of the techniques for the production of SOFCs structured coating topography, which closely resem- will be presented, including challenges related to the bles superhydrophobic surfaces in nature. fabrication of dense, crack-free electrolyte layers and porous, high-surface area electrode layers. Methods to increase deposition efficiency will be reported, as well MICROSTRUCTURE CONTROL OF as methods to minimize surface roughness and seg- SPS CERAMIC COATING WITH AN mentation cracking. Comparisons of electrode micro- structures and gas transport properties resulting from AXIAL FEED PLASMA SPRAY GUN SPS, SPPS, and powder plasma spraying (PPS) will be M. Suzuki presented and correlated to fuel cell performance. Fi- National Institute of Advanced Industrial nally, high performance fuel cell testing results for cells Science and Technology (AIST) 11 made by SPS and SPPS will be presented, and future Tsukuba, Ibaraki, Japan research directions will be discussed. Deposited particle size in the SPS coatings is much smaller, since liquid phase materials are used as spray- ing materials, while ceramic powders are sprayed in EFFECTS OF SPPS DEPOSITION conventional plasma spray process. So that it is pos- CONDITIONS ON THE STRUCTURE sible to control the coating micro structure in finer range such as nano-micron. This is thought to be a very AND WETTING BEHAVIOUR OF important point for the production of the high perfor- A SUPERHYDROPHOBIC mance coatings. A very unique plasma spray system “Twin Cathode CERAMIC COATING Type Plasma Spray System,” is used for the fabrication Y. Cai, T.W. Coyle, J. Mostaghimi, and G. Azimi of the coating in this study. This plasma gun is con- Centre for Advanced Coating Technologies sisted of three plasma torches; one main torch and two Superhydrophobic surfaces exhibit superior wa- sub torches. The voltage in operation is higher than the ter repellent properties, and they have great potential conventional plasma spray system, so that the usage to improve current energy infrastructure. Substantial of argon is enough for melting the spraying materials; research has been performed on the production of su- no needs of nitrogen or hydrogen. The most important perhydrophobic coatings. However, superhydrophobic feature of this system is that axial feeding of spraying coatings have not yet been adopted in many industries materials is available with a hollowed electrode in the where potential applications exist due to the limited main torch. It was found that the control of particle size durability of the coating materials and the complex and is the most important aspect from the microstructure- costly fabrication processes. were extensively control point of view, and the axial feeding is more suit- studied in the past because of their low , able for a manner of spraying material injection. Some but their low hardness and strength make the resulting current progress of R&D on SPS will be reviewed. coatings vulnerable to scratching and wear. Recently, biomimetic, nano-patterned superhydrophobic surfac- es were fabricated by lithography and laser ablation. However, these techniques are time consuming and

TS415_InsidePages.indd 11 11/24/2015 10:33:40 AM TS415_InsidePages.indd 12 11/24/2015 10:33:46 AM THERMAL SPRAY OF SUSPENSIONS & SOLUTIONS SYMPOSIUM (TS4) SHOW DIRECTORY

EXHIBIT DATES AND TIMES 13 Soprano Foyer, 4th Floor Wednesday, December 2 Refreshment Break: 10:00–10:30 a.m. Lunch: 12:00–1:00 p.m. Refreshment Break: 3:00–3:30 p.m. Networking Reception and Dinner: 6:00–8:00 p.m.

Thursday, December 3 Refreshment Break: 10:00–10:30 a.m. Lunch: 12:00–1:00 p.m. Refreshment Break: 2:30–3:00 p.m.

We appreciate and acknowledge the following sponsors:

TS415_InsidePages.indd 13 11/24/2015 10:33:46 AM EXHIBITOR LIST & FLOOR PLAN The ASM TS4 Exposition designations are: Green listing indicates Sponsor.

Tabletop # Exhibitor Tabletop # Exhibitor 1 Progressive Surface, Inc. 6 AMT AG 2 Northwest Mettech Corp. 7 TECNAR Automation Ltd. 3 Oerlikon Metco 8 Howard Inc. 4 INNOVNANO Advanced Materials 5 Treibacher Industrie AG

1 2 3

Entrance Soprano Foyer 7 6 5 4 14 8

Progressive Surface, Inc. 1

Northwest Mettech Corp. 2

Oerlikon Metco 3

INNOVNANO Advanced Materials 4

Treibacher Industrie AG 5

AMT AG 6

TECNAR Automation Ltd. 7

Howard Alloy Inc. 8 Entrance

TS415_InsidePages.indd 14 11/24/2015 10:33:55 AM EXHIBITOR LIST & FLOOR PLAN COMPANY DESCRIPTIONS AMT AG Oerlikon Metco Table # 6 Sponsor AMT AG, Dottingen, Switzerland, designs & manufac- Table # 3 tures thermal spray guns, equipment and turn-key sys- Oerlikon Metco enhances surfaces that bring benefits tems. This includes air plasma spray, plasma to customers through a uniquely broad range of surface and low pressure coating systems (LPCS), HVOF, and technologies, equipment, materials, services, special- wire arc equipment. AMT builds plasma and HVOF guns. ized machining services and components. The surface Plasma guns include F4, 03C, 9MB/3MB, F1 and F2 ID technologies such as Thermal Spray, , Plasma guns, and a high-power F5000 gun. AMT builds HVOF Heat Treatment and Laser Cladding improve the per- guns including JP 5000, DJ, and Jet Kote. AMT offers a formance and increase efficiency and reliability. Oer- unique hybrid liquid fuel (kerosene)—gaseous fuel gun, likon Metco serves industries such as aviation, power HV200. Advanced Materials and Technology Services, generation, automotive, oil & gas, industrial and other Inc. (AMTS), Los Angeles, CA is the USA representative specialized markets worldwide. for AMT AG, and stocks guns & parts in USA. www.oerlikon.com/metco/ www.amt-ag.net/ Progressive Surface, Inc. Howard Alloy Inc. Table # 1 Table # 8 Progressive Surface designs and builds integrated ther- Howard Alloy Inc. prolongs the service life of critical mal spray systems and surface treatment equipment. components by supplying specific wear/heat resistant We build turnkey systems for conventional plasma, coatings and materials tailored to different applica- HVOF, combustion and our 100HE High Enthalpy plas- tions. We provide industrial solutions to the clients in ma. The 100HE is exceptional at spraying standard the mineral, recycling, oil & gas and other industries plasma coatings as well as suspension plasma spray with the competitive price and desired quality. (SPS) and solution precursor (SPPS) coatings. www.howardalloy.com www.progressivesurface.com/ INNOVNANO Advanced Materials TECNAR Automation Ltd. Table # 4 15 Innovnano is a specialist manufacturer of nanostruc- Sponsor tured zirconia-based powders, specifically designed Table # 7 for thermal barrier coatings. As a subsidiary of CUF TECNAR is THE world leader in the field of advanced and certified to ISO 9001 standards, Innovnano manu- sensors for thermal and cold spray processes. In par- factures and supplies industrial scale quantities of its ticular, its Accuraspray is the most effective instrument powders from a purpose-built production technology to characterize and monitor the suspensions-based centre in Coimbra, Portugal. thermal spray processes. www.innovnano-materials.com www.tecnar.com Northwest Mettech Corp. Treibacher Industrie AG Table # 2 Table # 5 Mettech manufactures its advanced Axial III plasma Treibacher Industrie AG is a global advanced raw mate- torch with suspension plasma spray coating equip- rial producer with over 120-years of history in chemical ment and offers expert service, support and product and metallurgical innovation. Treibacher is a leading development. We partner with our commercial and in- developer and industrial producer of a wide range of stitutional clients to provide superior solutions (e.g., an engineered ceramic powders; many of which are avail- alternative to EB-PVD) in aerospace, printing, pulp and able as spray powder or suspensions for Suspension paper, mining and other industries. Plasma Spray www.mettech.com www.treibacher.com

Because there may have been some late changes in booth assignments, some exhibitors may have a different booth number than was shown on their invitations and advertising. Please check this Directory for the most-up-to-date listings, as well as onsite signage. Reasonable precautions have been taken to avoid errors in and omissions from this Directory, but ASM International does not guarantee listings herein and shall not be responsible for errors in or omission in this Directory.

TS415_InsidePages.indd 15 11/24/2015 10:33:55 AM All Your Suspension Plasma Spray Needs from a Single Source!

The Simple Choice for a Perfect Surface

The right material…the best application technology…the most experience. Oerlikon Metco’s unique formulations for suspension plasma spray of thermal barrier coatings are a cut above the rest...Our best-selling plasma spray guns are readily supplied with modified gun hard- ware for suspension plasma spray...Our long history of development and co-development of conven- tional and advanced ceramics for TBCs. This is what you want from your suspension plasma spray supplier and what Oerlikon Metco offers our customers.

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TS415_InsidePages.indd 16 11/24/2015 10:33:56 AM