In low-pressure plasma spraying, a plasma jet generator with a supersonic expansion nozzle is useful for spray coating hard and large-area films adhering strongly to substrates. In the expansion nozzle, the pressure and the electron density drastically decrease downstream, and therefore the plasma is in thermodynamic nonequilibrium state. Additionally, the supersonic expanding plasma jet is expected to be in chemical nonequilibrium state in which excited plasma particles are carried downstream in chemically-active state. In this study, titanium nitride (TiN) reactive spraying was carried out under a low-pressure environment using a DC arc plasma jet generator with a supersonic expansion nozzle. Titanium powders were injected using a hollow cathode with argon gas, and the plasma gas was nitrogen or nitrogen and hydrogen mixture. Microstructure and properties of the coatings were examined using scanning electron microscope (SEM) and X-ray diffraction (XRD). A dense and high-quality TiN coating with a Vickers hardness of 2000 was formed at a low substrate temperature of 700 °C with a low input power of 5.3 kW. All results showed that the supersonic plasma jet in thermodynamic and chemical nonequilibrium state had high potentials for reactive spraying.

In magneto-plasma-dynamic (MPD) arc jet generators, plasma is accelerated by electromagnetic body forces. Silicon nitride reactive spraying was carried out using an MPD arc jet generator with crystal silicon rods and nitrogen gas. Because higher-velocity, higher-temperature and higher-density and larger-area plasmas are produced with the MPD arc jet generator than those with conventional thermal plasma torches, nitriding of silicon can be enhanced. A dense and uniform β-Si 3 N 4 coating 30 µm thick was formed after 200 shots at a repetitive frequency of 0.03 Hz with a discharge current of 9 kA and a substrate temperature of 700 °C. The Vickers hardness reached about 1300. Furthermore, silicon carbide and aluminum nitride sprayings were conducted with the same spraying system. Surface modification is under study with lots of chemically reactive gases. All results showed that the MPD arc jet generator had high potential for spraying and surface modification.

Since Dye sensitized solar cell (DSC) is a solar cell which uses anatase film as photo voltaic device, production cost of DSC can be very low in comparison with that of silicon solar cell. Besides, according to some theoretical discussion on DSC, the electric power conversion efficiency can be raised to 30%. Therefore, DSC will be mainly used in future. In this study, in order to develop a low cost fabrication process for photo voltaic device of DSC, photo-catalytic titanium oxide film depositions were carried out by thermal plasma CVD (TPCVD) and thermal spraying. As working gas for plasma jet, and substrate, Ar gas and 20mm×40mm×1mm copper plate were used. Feedstock materials were titanium tetra butoxide in TPCVD and rutile powder in thermal spraying. In the DSCs using these films, cathodes (titanium oxide coated electrodes) were located beneath the transparent anodes. Consequently, in the case of TPCVD, anatase dominant film could be deposited and the DSC using this TPCVD film could generate 50 mV in electro motive force. Furthermore, even in case of thermal spraying, though rutile powder was used, photo-catalytic coating (anatase and rutile mixture coating) could be obtained by cooling substrate during coating and post heat treatment. It was confirmed that the electromotive force of the DSC using this thermal spray coating was almost the same as that of the DSC using the TPCVD film. From these results, these thermal plasma processes was found to have high potential for DSC fabrication.

In order to develop a functional film deposition process with high deposition rate, as a basic study, deposition of zinc oxide film by thermal plasma CVD (TPCVD) in the air was carried out. As ingredient, working gas and substrate, ethanol diluted zinc acetate solution, Ar and 430 stainless steel were used. As for deposition condition, Ar gas flow rate was fixed at 20SLM, deposition distance (distance between substrate surface and nozzle outlet of plasma torch) was varied 50 to 200 mm, zinc acetate concentration in the ingredient was varied 20 to 50 vol%, and ingredient feed rate was varied 30 to 200 ml/h. Consequently, with varying deposition distance, not only crystallized film but also amorphous film could be deposited. In the case of crystallized film, photo-catalytic properties could be confirmed in the films by methylene blue decoloration testing and wettability testing. Besides, in this case, film structure could be changed from lamellar to columnar by decreasing zinc acetate/ ethanol ratio. From these results, this process was found to have high potential for high rate functional film deposition process conducted in the air.

In this paper, spectroscopic and electrostatic probe measurements are made to examine the characteristics of a supersonic dc plasma jet near the surface of titanium plate during a nitriding treatment. The low-pressure nitriding process is done using a mixture of ammonia, nitrogen, and hydrogen gasses. Heating effects from the plasma are evaluated with nickel slug and thermocouple attached to the plate. The authors present the results of their study along with observations, insights, and suggestions on how to improve plasma nitriding processes. Paper includes a German-language abstract.

This work evaluates the microstructure and composition of zirconia films produced by thermal plasma chemical vapor deposition (TPCVD). The results show that TPCVD has the potential to produce durable ceramic films with columnar structure, even in open air. Paper includes a German-language abstract.

To improve wear resistance of the atmospheric thermal plasma sprayed molybdenum coating, diamond deposition on the molybdenum plate and the atmospheric plasma sprayed molybdenum coating by the combustion flame chemical vapor deposition (CVD) was carried out. Diamond has excellent properties such as low surface energy, hardness, chemical corrosion resistance ability and so on. Besides, since the combustion flame CVD is the process carried out in the air, diamond/ molybdenum complex coating can be deposited without any vacuum facilities by using this technique if molybdenum coating is deposited by atmospheric thermal spray. In this study, acetylene welding torch was used as diamond synthesis apparatus and mass flow ratio C 2 H 2 /O 2 was varied from 0.9 to 1.3. Consequently, many diamond particles which were 10 micrometer in diameter respectively were deposited on the molybdenum plate by only 20 minutes combustion flame irradiation in the case of 1.2 in mass flow ratio of C 2 H 2 /O 2 . Especially, the molybdenum coating was covered with diamond films consists of 10 micrometer diameter particles in the case of over 1373K in deposition temperature. Besides, according to the results of wear testing, wear mass loss of diamond deposited coatings were much lower than that of original thermal sprayed molybdenum coatings. From these results, this process was found to have a high potential in order to improve wear resistance of thermal sprayed coating.

Spectroscopic and electrostatic probe measurements were carried out to understand the plasma feature inside and outside a 10-kW-class direct-current arc plasma jet generator with a supersonic expansion nozzle. Ammonia and a mixture of nitrogen and hydrogen were used as the working gas. The NH3 and N2+3H2 plasmas in the throat were expected to be nearly in a temperature-equilibrium condition, although the plasmas in the expansion nozzle and in the downstream plume without substrate plates were in thermodynamical nonequilibrium states. As a result, the H-atom excitation temperature and the N2 rotational excitation temperature decreased from 7000-11000 K in the throat to about 4000 K and to 1000-1500 K, respectively, on the nozzle exit at 0.1-0.2 g/s, although the NH rotational temperature did not show an axial decrease even in the nozzle. On the other hand, each temperature was almost kept a small range in the downstream plume without substrate plates under an ambient pressure of 130 Pa except for the NH rotational temperature for NH, working gas, although in the case with a titanium plate the nonequilibrium plasma came to a temperature-equilibrium one as approaching the plate.

Since plasma jets, which have been used as heat sources of thermal plasma spraying process, expand adiabatically under a low pressure environment, the plasma temperatures drastically fell down to 2000K at the nozzle out let at 30Pa chamber pressure. However, the plasma jets still had enough reactivity to form hard nitride layer on the surface of the titanium samples by only a few minutes treatment. In this study, in order to obtain useful information for the practical applications of this plasma as low temperature and high rate surface modification processes, nitriding of nitriding steel and carbon steel using supersonic expanding hydrogen/ nitrogen mixture plasma jets were carried out. Consequently, though surface hardening was occurred slightly in the case of carbon steel, surface hardening was obviously promoted in the case of nitriding steel. In both cases, surface hardening was promoted with increasing hydrogen flow rate and thermal damages of the samples due to heat transfer from plasma jets weren't observed. Besides, according to the results of wear testing, wear mass loss of nitrided samples were much lower than that of non-nitrided samples. From these results, this process was found to have a high potential even in the case of surface modification of steel materials.