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 magneto-plasma-dynamic (MPD) arcjet generators, plasma is accelerated by electromagnetic body forces. The MPD arcjet generator can produce higher-velocity, higher-temperature, higher-density and larger-area plasmas than those of conventional thermal plasma torches. Two types of MPD arcjet generator were developed for applications to ceramic spray coatings. One generator was installed with a cathode covered with mullite or zirconia ceramics and the other with a titanium cathode. The former was operated with Ar for mullite or zirconia coating by an ablation process of the cathode cover and the latter with N 2 for titanium nitride coating by a reactive process between ablated titanium particles and nitrogen plasma. Silicon nitride reactive spraying was also carried out. The MPD spray process could successfully form dense, uniform and hard ceramic coatings. In titanium nitride reactive spraying, plasma diagnostic measurement and flowfield analysis were conducted. A large amount of N and N + was expected to be exhausted with a high velocity from the MPD generator. Both the electron temperature and the electron number density were kept high at a substrate position compared with those for conventional low-pressure thermal sprayings. A chemically active plasma with excited particles of N + , Ti, Ti + and Ti 2+ was considered to contribute to better titanium nitride coatings. All coating characteristics showed that the MPD arcjet generators had high potentials for ceramic spray coatings.

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.

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.

Electromagnetic acceleration plasma generators, which are called Magneto-Plasma-Dynamic (MPD) arcjet generators, can produce higher-velocity, higher-temperature and higher-density plasmas than those of conventional thermal plasma torches, because MPD arcjet plasma is efficiently accelerated by electromagnetic body forces in MW-class input power operation. These properties are effective for deposition of rigid coatings adhering strongly to substrate surfaces. In the present study, we newly developed an ablation type MPD arcjet generator for titanium nitride (TiN) reactive spray coatings. The coatings were deposited onto steel substrate. The phase structure and the composition of the coatings were analyzed by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD), and their Vickers hardness were measured. These analyses showed that the MPD spray process could successfully form dense and uniform titanium nitride coatings. The properties of the titanium nitride coatings were highly sensitive to the titanium cathode diameter and discharge current.

In this paper, as a basic study of the plasma jet process under a low pressure, the nitriding of titanium plates and atmospheric plasma sprayed titanium coatings are carried out using nitrogen and hydrogen added nitrogen plasma jets at 30Pa. The plasma torch used in this paper is equipped with a supersonic expansion nozzle to improve the acceleration efficiency of plasma jets. The effects of ambient pressures and supersonic expansion nozzles on transformation of plasma particles are examined from gas-dynamical viewpoints. It was observed that from the results, the supersonic plasma jet process under a low pressure was proved to have a high potential for nitriding. Paper includes a German-language abstract.

The quasi-steady magneto-plasma-dynamic (MPD) arcjet generator is a promising plasma accelerator, which has a coaxial electrode structure similar to those of conventional plasma torches. The MPD arcjet generator utilizes principally electromagnetic acceleration of the interaction between the discharge current of kiloamperes and the azimuthal magnetic field induced by the discharge current, although the working gas is accelerated aerodynamically through a nozzle in a thermal arcjet generator. In this paper, ablation-type MPD arcjet generators are developed for ceramic coatings. Discharge voltages and ablation rates of ceramic materials are examined, and front velocities of ablated atoms of ceramic component are also estimated using a streak camera. The Vickers hardness of coating is measured. Their cross sections are observed with a scanning electron microscope, and their surfaces are analyzed by means of x-ray diffraction and x-ray photoelectron spectroscopy. Paper includes a German-language abstract.

Ammonia and a mixture of nitrogen and hydrogen are used for material processing. Since these gases are chemically active, the processing efficiency is enhanced. This article describes a study to understand the physical properties of ammonia and a mixture of nitrogen and hydrogen plasmas inside and outside an arcjet generator. Spectroscopic measurement is made, and several plasma properties are determined from the data. The result shows that the H-atom electronic excitation temperature and the nitrogen rotational excitation temperature decreased from 7000-11000 K in the constrictor to about 4000 K and to 1000-1500 K, respectively, on the nozzle exit with mass flow rates of 0.1-0.2 g/s at input powers of 7-12 kW. However, the NH rotational excitation temperature did not show a significant axial decrease even in the downstream plume. Paper includes a German-language abstract.