Millisecond-order response measurement for fast oxygen gas sensors

A novel method for the evaluation of fast response of oxygen gas sensors in terms of milliseconds is developed. Using the method of modulating oxygen partial pressure by changing the total pressure inside the test chamber, the millisecond-order measurement was succeeded. For the 100 Hz sign-wave operation, the measurement system generated the pressure changes from 180 to 220 kPa, corresponding to the change of oxygen partial pressure from 36 to 44 kPa. Using both jump-method and pressure modulation method, the response of the resistive oxygen sensors of cerium oxide thick films were evaluated at 1173 K and the kinetic mechanism of gas sensing was discussed. Their response times of t₉₀ obtained by square-wave change were measured to be 37 and 22 ms for high-to-low oxygen partial pressure and vice versa transition, respectively. The log–log plot of resistance of sensor and the frequency, pressure modulation spectra, was also evaluated at the same time and the kinetics of oxygen sensing was suggested to be diffusion-limited.     

Effects of phosphorus content on generation and growth of cracks in nickel–phosphorus platings owing to thermal cycling

We observed crack generation and structural changes in electroless nickel–phosphorus (Ni–P) plating layers formed on copper-metalized silicon nitride substrates both during thermal cycling from ? 40 to 250 °C and during storage (not cycling) at 250 °C in order to investigate the effect of the phosphorus contents on crack generation and growth in the Ni–P platings. The used platings contained phosphorus at three different contents: 2.1 wt% [Ni–P(low)], 6.5 wt% [Ni–P(med)], and 10.9 wt% [Ni–P(high)]. The generation time and the amount of cracks were strongly dependent on their phosphorus contents. More cracks appeared after thermal cycling than after storage at 250 °C. In Ni–P(low), cracks were generated after 200 thermal cycles, whereas no cracks were observed even after 250 h of storage at 250 °C. In Ni–P(med) and Ni–P(high), both during thermal cycling and storage at 250 °C, cracks formed during or after crystallization of the amorphous layers. These results suggest that the primary factors affecting the generation of cracks in electroless Ni–P platings are crystallization of the Ni–P platings and repeated changes in thermal stress.     

Oxygen release behavior of metastable tetragonal t′meta-(Ce0.5Zr0.5)2 phases prepared by reduction and successive oxidation of t′ phase

Tetragonal CaF₂-related-type t′-/Ce_0.5Zr_0.5)O₂ phase was reduced at 773 K ≤ T_red. ≤ 1073 K to prepare precursors with various oxygen compositions: Ce₂Zr₂O_712d /0.111 < δ < 0.379). Metastable tetragonal t^′_meta-(Ce_0.5Zr_0.5)O₂ phases were prepared by oxidizing in O₂ at 873 K the precursors, and subjected to evolved oxygen gas analysis by heating the samples at a constant rate. When the precursor was prepared at T_red: ? 773 K; i.e. δ ? 0:379; the oxygen release behavior of the tetragonal phase agreed approximately with that of the t^′. For δ < 0.29, distinct features of the t^′_meta-(Ce_0.5Zr_0.5)O₂ appeared in the XRD results and Raman spectra. The temperature exhibiting the maximum release rate of oxygen from the t^′_meta became lower with decreasing the d value. It could be concluded that the thermodynamic behavior of the t^′_meta is related closely to the precursor composition and becomes more unstable with decrease in the δ value. The t^′ and t^′_meta phases with disordered arrangement of Ce and Zr ions may belong to the same space group; nevertheless, difference in the random arrays of the Ce and Zr ions was suggested on the basis of the present experimental results.     

Oxygen release behaviour of Ce(1−x)ZrxO2 powders and appearance of Ce(8−4y)Zr4yO(14−δ) solid solution in the ZrO2–CeO2–CeO1.5 system

To clarify the existence of metastable phases in the ZrO₂–CeO₂–CeO_1.5 system, evolved-oxygen gas analyses, (EGA), by heating a single phase of t′ and t″ (Ce_(1−x)Zr_xO₂) with various compositions, x, in a reducing gas and successive oxidation were carried out repeatedly. The oxygen release behaviour of the t′ and t″ phases was very complicated. The single κ phases, (Ce_(1−x)Zr_xO₂) with the composition, x=0.5 and 0.6, which were obtained by oxidizing the resulting pyrochlore as a precursor in O₂ gas at 873 K, exhibited a sharp oxygen release at the lowest temperature; the composition range of κ phase may be x=0.450.65. A new tetragonal phase t*, (Ce_(1−x)Zr_xO₂), which was attained by cyclic redox process together with annealing in O₂ gas at 1323 or 1423 K, exhibited a sharp oxygen release at the highest temperature; the composition range of t* phase may be as wide as x=0.200.65. A metastable solid solution expressed by a chemical formula of Ce_(8−4y)Zr_4yO_(14−δ) (y=01) possessing a CaF₂-related structure appeared on deoxidation of the t* phase. A ternary phase diagram containing the t* and Ce_(8−4y)Zr_4yO_(14−δ) solid solution was proposed.     

Formation mechanism of monodispersed spherical core-shell ceria/polymer hybrid nanoparticles

Very unique core-shell ceria (cerium oxide)/polymer hybrid nanoparticles that have monodispersed spherical structures and are easily dispersed in water or alcohol without the need for a dispersant were reported recently. The formation mechanism of the unique nanoparticles, however, was not clear. In order to clarify the formation mechanism, these nanoparticles were prepared using a polyol method (reflux heating) under varied conditions of temperature, time, and concentration and molecular weight of added polymer (poly(vinylpyrrolidone)). The size of the resultant nanoparticles was strongly and complicatedly dependent on the set temperature used during reflux heating and the poly(vinylpyrrolidone) molecular weight. Furthermore, the size of the nanoparticles increased by a 2-step process as the reflux heating time increased. The IR spectral changes with increasing reflux time indicated the increase in the number of cross-linked polymers in the shell. From these results, the formation mechanism was discussed and proposed.     

Development of a new seminested PCR method for detection of Legionella species and its application to surveillance of legionellae in hospital cooling tower water

The presence of PCR inhibitors in water samples is well known and contributes to the fact that a practical PCR assay has not been developed for legionella surveillance. In this study, we devised a new seminested PCR assay for detection of Legionella spp. in water samples as a means of overriding the PCR inhibitors without loss of sensitivity. The seminested PCR assay utilized primers to amplify the 16S rRNA gene (LEG primers) of 39 Legionella spp. The assay was specific to legionellae, and the sensitivity was 1 fg of extracted Legionella DNA in laboratory examination. To evaluate the feasibility and sensitivity of the PCR assay in identifying the presence of legionellae, it was used to survey Legionella contamination in the water of 49 cooling towers of 32 hospitals. A commercially available EnviroAmp Legionella kit and a culture method were also used in the survey for comparison with the seminested PCR assay. The detection rates of legionellae in the samples were 91.8% (45 of 49) by the PCR assay and 79.5% (39 of 49) by the culture method. The EnviroAmp kit revealed that 30.6% of the water samples (15 of 49) contained inhibitors of the PCR amplification. However, the seminested PCR assay could produce the Legionella-specific DNA bands in 14 of the 15 samples. Although 8 of the 14 samples were positive in the first-step PCR, 6 of the 14 samples became positive in the second-step PCR. These results suggest that the effect of PCR inhibitors in samples, if any, can be reduced because of the dilution of the sample in the second-step PCR and that sensitivity of detection can be increased by the second-step PCR. Thus, the seminested PCR assay with LEG primers to amplify the 16S rRNA gene of 39 Legionella spp. was a practical and sensitive method to detect Legionella spp. in water samples.     

Microgenerator Using BiSbTe-Pt Thermopile and Pt-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Ceramic Combustor

The performance of a microcombustor thermoelectric generator device based on a thermopile using p-type Bi_0.3Sb_1.7Te₃ (BST) and n-type Pt films has been investigated. The BST films were prepared by two different methods—pulsed laser deposition (PLD) and sputter deposition—on Si₃N₄/SiO₂ multilayers on Si substrate. The ceramic catalyst combustor was patterned on the thermopile end on a thin membrane fabricated by back-side bulk etching of the silicon substrate. At 138°C the thermoelectric power factors of the PLD and sputter-deposited films were 3.6 × 10⁻³ W/mK² and 0.22 × 10⁻³ W/mK², respectively. The power from the generator with the sputter-deposited film was 0.343 μW, which was superior to that of the device with the PLD film, which provided 0.1 μW, for combustion of a 200 sccm flow of 3 v/v% hydrogen in air.     

Electrical conductivity of metastable κ-CeZrO4 phase possessing ordered arrangement of Ce and Zr ions

Electrical conductivity σ_t of metastable κ-CeZrO₄ possessing ordered arrangement of Ce and Zr ions in a manner similar to a pyrochlore-type was measured as a function of temperature and time, and compared with tetragonal metastable t′-(Ce_0.5Zr_0.5)O₂ and t′_meta-(Ce_0.5Zr_0.5)O₂ phases possessing random arrangement of the cations. The κ disk was prepared by reoxidizing a pyrochlore-type precursor in O₂ gas at 873 K. The σ_t as measured for the κ-CeZrO₄ was reproducible as a function of temperatures between 957 and 1190 K. At increasing temperatures above 1233 K, the σ_t decreased gradually with time due to the phase transition: κ→t′, and became consistent with the t′. Although the κ-CeZrO₄ phase is thermodynamically less stable than the t′-(Ce_0.5Zr_0.5)O₂, it was virtually stable up to around 1233 K. It was found from the change in the σ_t due to the phase transition that the σ_t for the metastable κ-CeZrO₄ was an order of magnitude higher than that for the t′ and was similar to that for the t′_meta. It was previously reported that a phase transition, t′_meta→t′, occurred above 1143 K. The phase transition, κ→t′, accompanied by redistribution of the cations appeared to occur at higher temperatures than that for t′_meta→t′ leaving random cation arrangement.     

Roll-to-roll plasma deposition machine for the production of tandem amorphous silicon alloy solar cells

A roll-to-roll plasma deposition machine for depositing multilayered amorphous alloys has been developed. The plasma deposition machine has multiple deposition areas and processes a stainless steel substrate 16 in wide continuously. Amorphous photovoltaic thin films (less than 1 μm thick) with a six-layer structure (p-i-n-p-i-n) are deposited continuously in a single pass onto a roll of stainless steel substrate 16 in wide and 1000 ft long. Mass production of low cost tandem solar cells utilizing roll-to-roll processes is now possible. A commercial plant utilizing this plasma deposition machine for manufacturing tandem amorphous silicon alloy solar cells is now in operation.     

Development of Resistive Oxygen Sensors Based on Cerium Oxide Thick Film

It is important to shorten the response time of resistive oxygen sensor in order to reduce harmful emission of automobiles. The diffusion and surface reaction theory tells us that reducing particle size leads to shortening the response time. The fine ceria powder was prepared a by new precipitation method and the oxygen sensors having ceria thick film with the particle size of 120 nm were fabricated using fine ceria (cerium oxide) powder. The thick film exhibited good adhesion to alumina substrate. The value of n in R P(O₂)^1/n at 1073 and 1173 K were 6.2 and 6.4 in the oxygen partial pressures range from 10^{– 13} to 10⁵ Pa, respectively. The response time for the sensor was 22 and 12 ms at 1073 and 1173 K, respectively. The sensor fabricated in this study showed fast response.