Reaction of sodium perborate with a chlorinated cyclic hindered amine (TMP-Cl): I. Quantitative evaluation of active oxygen species in fabric bleaching

The reaction of N-chloro-4-hydroxy-2,2,6,6-tetramethylpiperidine (TMP-Cl) with sodium perborate (PB) was investigated with special reference to the generation of singlet oxygen and the possible application to a new oxidative bleaching process. Generation of the singlet oxygen (¹O₂), the hydroxyl radical (HO·) and superoxide anion radical (O₂·⁻) in the PB/TMP-Cl mixed solution was confirmed by the trapping reagent method. From the results of another experiment, in which the bleaching abilities of each active oxygen species were confirmed, the main active oxygen species contributing to the bleaching of purpurogallin, the skeleton of black tea pigment, in the PB/TMP-Cl system was concluded to be¹O₂.     

Segmented conjugated polymer based on poly(α-thiophenediyl)benzylidine

Summary Segmented polymers with random sequences of conjugated and non-conjugated blocks are produced by partial dehydrogenation of poly(-thiophenediyl)benzylidene. The fraction of conjugated block was controlled by the elimination time. The polymers gave photoluminescence. Absorption coefficients of the polymers increased with the rate of dehydrogenation, and the highest fluorescence intensity were achieved around 9 % conjugation conversion. The polymers were characterized by ¹H- and ¹³C-n.m.r. and infrared spectra, and were soluble in common organic solvents, which suggests a good processability.     

Relation between crystal structure and lattice oxygen content of sintered reaction-bonded silicon nitride

When reaction-bonded silicon nitride containing MgO/Y₂O₃ additives is sintered at three different temperatures to form sintered reaction-bonded silicon nitride (SRBSN), the thermal conductivity increases with sintering temperature. The β-Si₃N₄ (silicon nitride) crystals of SRBSN ceramics were synthesized and characterized to investigate the relation between the crystal structure and the lattice oxygen content. The hot-gas extraction measurement result and the crystal structure obtained using Rietveld analysis suggested that the unit cell size of the β-Si₃N₄ crystal increases with the decrease in the lattice oxygen content. This result is reasonable considering that the lattice oxygen with the smaller covalent radius substitutes nitrogen with the larger one in the β-Si₃N₄ crystals. The lattice oxygen content decreased with increasing sintering temperature which also correlated with increase in thermal conductivity. Moreover, it is noteworthy from the viewpoint that it may be possible to apply the lattice constant analysis for the nondestructive and simple measurement of the lattice oxygen content that deteriorates the thermal conductivity of the β-Si₃N₄ ceramics.     

Negative ion etching of Al−Si−Cu by employing a magnetic filter in halogen plasmas

Al etching was studied employing negative ions generated in downstream Cl₂ plasma. The Al etch rate by the alternate irradiation of positive and negative ions was two times higher than that by usual positive ions. In order to etch the Al film practically on an insulator covered electrode coupled with RF power, reduction of the negative self bias voltage (Vdc) was examined using a magnetic filter which traps electrons. The reason for the high etching reactivity is that the dominant negative ions F in SF₆ and Cl⁻ in Cl₂ plasmas are atomically very similar to the radicals. Addition of SF₆ and H₂ to a Cl₂/BCl₃ mixture reduced Vdc significantly. However, fluorine and hydrogen atoms inhibited Al etching in spite of sufficient ion energy.     

碳基钨涂层在退火过程中的组织和结构变化

用真空等离子体喷涂(VPS)技术在C／C复合材料基体上制备了厚度为0．5mm的钨(W)涂层，涂层的表面通过物理气相沉积(PVD)预沉积钨、铼(Re)多层作为碳(C)的扩散势垒。涂层经过1200℃--2000℃的电子束退火，其微观结构和化学构成发生变化。经测量涂层的再结晶温度约为1400℃，再结晶的活性能为63kJ／mol。当退火温度高于1300℃时，涂层表面的多层W、Re结构将由于W、Re和C之间的相互扩散而发生改变，并在1600℃以上退火lh后由于脆性碳化钨在界面的形成而完全失效，碳化钨层的厚度将随着退火漏度的升高和退火时间的延长而迅速增加。     

Optimum combination of operating parameters in abrasive cut-off

For optimization of abrasive cut-off operation, wheel wear equation must be identified before the operation is optimized. The equation is obtained by using GMDH algorithm with successive determination of trends containing interactive terms. In the model equation factors of grinding fluid are taken into consideration in addition to the factors of wheel, work material, feed (table speed) and wheel speed. For the identification of the model wheel wear tests are performed under the experimental design treating the above-mentioned factors as independent variables. The grinding ratio (output in the model) can be predicted for combinations of various factors using the model. With the wheel wear equation and machining cost model, the optimum combination of wheel, fluid, feed and wheel speed can be selected for a given work material. The relationships between these variables and the costs are investigated.     

Evolution of patinas on copper exposed in a suburban area

Copper plates were exposed under sheltered outdoor conditions for up to one year, starting in September 2001 in Musashino City, Tokyo, a suburban area. Following various periods of exposure, the patinas on the plates were characterized to investigate their evolution by using X-ray fluorescence analysis, X-ray diffraction, field emission scanning electron microscopy, and glow discharge optical emission spectroscopy. The difference in the roles of sulfur and chlorine in the early stages of copper patination were identified by analyzing the depth profiles of these two elements. Sulfur was found on top of the patina as cupric sulfates such as posnjakite (Cu₄SO₄(OH)₆ · H₂O) or brochantite (Cu₄SO₄(OH)₆). Brochantite appeared only after 12 months of exposure. In contrast, chlorine was found on the surface after only one month of exposure. It gradually penetrated the patina as the exposure period lengthened, forming copper chloride complexes. Chloride ions accumulated at the patina/copper interface, forming nantokite (CuCl), which promoted corrosion.     

The multiphase effect on crystal structure, hydrogen absorbing properties and electrode performance of Sc---Zr based Laves phase alloys

The crystal structure, hydrogen absorbing properties and electrode performance of Laves phase alloy systems, Sc---Zr---Ni---Mn and Sc---Ni---V systems, were studied by optical and scanning electron microscopy, X-ray powder diffraction, pressure-composition isotherm and electrochemical measurements. C14 and C15 Laves phases and minor ScNi-related phase were found in the Sc---Zr---Ni---Mn alloy system. The ScNi-related phase was composed of Sc, Zr and Ni elements. Two kinds of minor phase, BCC and ScNi-related phases, were identified in addition to the C15 phase in the Sc---Zr---Ni---V alloy system. The BCC contained mainly the element V. The ScNi-related phase contributed to an increase in the hydrogen capacity, but those in the V alloy system did not. The multiphase anode with a large amount of the ScNi-related phase showed a low durability against the KOH electrolyte. The substitution of Zr by Sc led to an improvement in the initial activation of the anode, but there was not a clear correlation between the presence of the multiphase in the anode and the rate capability.     

High-power hybrid plasma spraying of large yttria-stabilized zirconia powder

To testify to the advantage of large ceramic powder spraying, numerical simulations and experimental studies on the behavior of large yttria-stabilized zirconia (YSZ) powder in a high-power hybrid plasma spraying process have been carried out. Numeric predictions and experimental results showed that, with the high radio frequency (RF) input power of 100 kW, the most refractory YSZ powder with particle sizes as large as 88 μm could be fully melted and well-flattened splats could be formed. A large degree of flattening (ξ) of 4.7 has been achieved. The improved adhesive strength between the large splat and the substrate was confirmed based on the measurement of the crack density inside of the splats. A thick YSZ coating >300 μm was successfully deposited on a large CoNiCrAlY-coated Inconel substrate (50×50×4 mm in size). The ultradense microstructure without clear boundaries between the splats and the clean and crack-free interface between the top-coat and the bond-coat also indicate the good adhesion. These results showed that highpower hybrid plasma spraying of large ceramic powder is a very promising process for deposition of highquality coatings, especially in the application of thermal barrier coatings (TBCs).     

Differences between corrosion products formed on copper exposed in Tokyo in summer and winter

We analyzed the copper corrosion products that formed during a month in summer and a month in winter at three sites in Tokyo using several analytical techniques. The X-ray diffraction patterns revealed that cuprite Cu₂O and posnjakite Cu₄SO₄(OH)₆·H₂O formed on copper exposed in summer. By contrast, only cuprite was found in winter exposed copper. The X-ray fluorescence results indicated that the amounts of sulfur and chlorine on the copper plates exposed in summer were much greater than those in winter. This could be explained by the change in particulate sulfate and sea salt concentrations. Depth profiling analysis by Auger electron spectroscopy revealed that the oxide layer formed in summer was thicker than that in winter. This difference in oxide layer thickness could have been due to the differences in temperature, relative humidity, and the amount of sulfur and chlorine on the copper plate.