Authors: Hiroshi Yukawa, Shimpei Watanabe, Asuka Suzuki, Yoshihisa Matsumoto, Hideki Araki, Masataka Mizuno, Kazuki Sugita, Wataru Higemoto
Abstract: The temperature dependence of hydrogen solubility and diffusivity of Pd–53mol%Cu alloy membrane with the B2–type crystal structure has been investigated. The hydrogen permeation tests are performed using ultra–pure hydrogen (more than 9N) purified by a Pd–Ag alloy membrane to avoid any influences of impurities. It is found that the hydrogen permeability decreases significantly at low temperatures, especially near room temperature. The time dependence of hydrogen flux is monitored and found that the hydrogen flux decreases gradually during about 4 ~ 5 days after rapid cooling down to room temperature from 623 K.The results of the temperature dependence of the hydrogen permeability are analyzed in view of the consistent description of hydrogen permeation based on hydrogen chemical potential, where the hydrogen flux is proportional to the product of the mobility for hydrogen diffusion, B, and the PCT factor, fPCT. In this study, the pressure–composition–isotherms (PCT curves) for Pd–53Cu alloy with B2 structure are measured for the first time by the in–situ XRD–PCT method, and they are applied to estimate the PCT factors. Then, the temperature dependence of the PCT factor and the mobility for hydrogen diffusion is evaluated. It is revealed that the decrement in hydrogen permeability at low temperatures is mainly attributable to the decrement of the mobility for hydrogen diffusion.According to the positron annihilation experiments, the defects density is considered to be small in Pd–53Cu alloy with the B2 structure even at room temperature, suggesting that the excess Cu atoms in Pd–53Cu alloy occupy the positions of Pd sublattice, at which the Cu atoms form a local BCC–Cu unit. The diffusion of Cu atoms corresponds to the diffusion of BCC–Cu units in the B2 structure. Therefore the diffusion of Cu atoms and the configuration of BCC–Cu units in B2 structure could be a key to understand the gradual transition of hydrogen diffusivity at low temperatures.
31
Authors: Hiroshi Yukawa, Tomonori Nambu, Yoshihisa Matsumoto
Abstract: The concept for alloy design of Nbbased hydrogen permeable membrane is applied to NbWMo ternary system. The alloying effects of tungsten and molybdenum on the solubility of hydrogen, the resistance to hydrogen embrittlement, the hydrogen permeability and diffusivity are investigated in a fundamental manner. It is found that the addition of tungsten and molybdenum into niobium decreases the hydrogen solubility. As a result, the resistance to hydrogen embrittlement improves and higher hydrogen pressures can be applied to the NbWMo alloy membrane. It is shown that the designed Nb5mol%W5mol%Mo alloy membrane with single solid solution phase exhibits excellent hydrogen permeability together with strong resistance to hydrogen embrittlement. In addition, it is found that the alloying of tungsten and molybdenum with niobium enhances the hydrogen diffusivity. In fact, the activation energy for hydrogen diffusion decreases in the order, pure Nb > Nb5mol%W > Nb5mol%W5mol%Mo.
61
Authors: Hiroshi Yukawa, Tomonori Nambu, Yoshihisa Matsumoto
Abstract: The hydrogen solubility and the hydrogen permeability have been measured for Nb-based alloys in order to investigate the alloying effects on the hydrogen diffusivity during hydrogen permeation. It is found that the hydrogen solubility decreases by the addition of ruthenium, tungsten or molybdenum into niobium. The mobility for hydrogen diffusion during hydrogen permeation is estimated from the linear relationship between the normalized hydrogen flux, , and the product of the hydrogen concentration and the difference of hydrogen chemical potential, . It is found that the mobility for hydrogen diffusion during hydrogen permeation is larger for Nb-based alloys than pure niobium, especially at low temperature. The activation energy of the mobility for hydrogen diffusion decreases by the addition of ruthenium, tungsten or molybdenum into niobium.
506
Authors: Hiroshi Yukawa, G.X. Zhang, Masahiko Morinaga, Tomonori Nambu, Yoshihisa Matsumoto
Abstract: The hydrogen solubility and the hydrogen permeability have been measured for Nb-based alloys in order to investigate the alloying effects on the hydrogen diffusivity during hydrogen permeation. The hydrogen diffusion coefficient during hydrogen permeation is estimated from a linear relationship between the normalized hydrogen flux, , and the difference of hydrogen concentration, C, between the inlet and the outlet sides of the membrane. It is found that the hydrogen diffusion coefficient during the hydrogen permeation is increased by alloying ruthenium or tungsten into niobium. On the other hand, the activation energy for hydrogen diffusion in pure niobium under the practical permeation condition is much higher than the reported values measured for dilute hydrogen solid solutions. It is interesting that the activation energy for hydrogen diffusion decreases by the addition of ruthenium or tungsten into niobium.
1091
Authors: Viviane M. Azambuja, Dílson Silva dos Santos, Daniel Fruchart
Abstract: . The Pd0.97Zr0.03, Pd0.97Ce0.03 and Pd0.97Ce0.015 Zr0.015 alloys were produced and studied in the present paper with respect to the hydrogen diffusivity and solubility. These alloys in the conditions as melted and cold worked, heat treated and also internally oxidized were submitted to hydrogen permeation tests. It was observed that the hydrogen diffusivity is strongly affected by the internal oxidation due to nano-oxides formation in the samples. On the other hand, the hydrogen solubility increases with introduction of defects as dislocations and vacancies introduced by cold working as well as the precipitates due to the internal oxidation. The nature, size and distribution of the precipitates and their influence on the hydrogen permeation parameters are discussed in this work.
81
Authors: Hiroshi Yukawa, G.X. Zhang, N. Watanabe, Masahiko Morinaga, Tomonori Nambu, Yoshihisa Matsumoto
Abstract: The hydrogen diffusion coefficients are investigated during the hydrogen permeation through Nb-based hydrogen permeable membranes at high temperature. It is found that the hydrogen diffusion coefficient for pure niobium under practical conditions is much lower than the reported values measured for dilute hydrogen solid solutions. Surprisingly, the hydrogen diffusion is found to be faster in Pd-Ag alloy with fcc crystal structure than in pure niobium with bcc crystal structure at 773K during the hydrogen permeation. It is also found that the addition of Ru or W into niobium increases the hydrogen diffusion coefficient under the practical conditions.
225
Authors: E.A. Pastukhov, N.I. Sidorov, Valery A. Polukhin, V.P. Chentsov
Abstract: Molecular dynamics simulation was used for investigating hydrogen migration in Pd-Si alloy at a temperature Т = 300 K. The strong affect of hydrogen dynamics and its defects creation to structure of palladium matrix is stated. The partial radial distribution function calculation for silicon specifies a preferable arrangement of silicon atoms relative to each other in the second coordination sphere. Model calculations have shown that not only silicon atoms can affect hydrogen mobility. Hydrogen itself also can significantly change the diffusion of the other components in the alloy.
149
Authors: N. Watanabe, G. Zhang, Hiroshi Yukawa, Masahiko Morinaga, Tomonori Nambu, K. Shimizu, S. Sato, K. Morisako, Yoshihisa Matsumoto, Isamu Yasuda
Abstract: The alloying effects of Pd on the hydrogen solubility and the resistance to hydrogen
embrittlement are investigated for Nb-xmol%Pd-ymol%Zr (x=0~19; y=0, 1) alloys. The hydrogen
solubility at 673 K is found to decrease with increasing Pd content in the alloys. Both pure Nb and
Nb-Pd alloys possessed ductility in vacuum at 673 K. However, severe hydrogen embrittlement
occurs in pure Nb when it is tested under the hydrogen pressure even as low as 0.01 MPa. In view of
the small punch (SP) absorption energy, the addition of Pd into Nb improves the resistance to
hydrogen embrittlement by decreasing the hydrogen solubility in the alloy, although brittle fracture is
still observed in the Nb-15mol%Pd alloy tested under a hydrogen pressure of 0.015 MPa at 673 K.
873
Authors: J.S. Park, Soong Keun Hyun, Masakazu Tane, Hideo Nakajima
Abstract: We investigated the pore morphology in lotus-type porous copper fabricated by continuous
casting technique as a function of transference velocity range from 1 to 100 mm・min-1 under
hydrogen gas pressure of 1.0 MPa. Lotus-type porous copper with long cylindrical pores aligned in
one direction parallel to the transference direction was fabricated, which posses a sufficient
uniformity of the porosity and pore size. The pores formed at transference velocity of 1 mm・min-1
were larger than other condition. Necks were observed in these pores, whose formation may be
attributed to bubbling in the melt. The pore size decreased with increasing transference velocity,
while the porosity was not varied much by transference velocity.
1725
Authors: Dílson Silva dos Santos
219