Structures and electronic properties of surface/edges of nanodiamond and nanographite

The structure, electronic and magnetic properties of nanodiamond and nanographite/nanographene are investigated. Detonation nanodiamond particles that are covered with amorphous graphitic composites are hydrothermally treated to remove the graphitic surface composites and to terminate the surface carbon atoms with hydrogen. The number of localized spins of dangling bonds and the hydrogen concentration increase upon the increase in the hydrothermal treatment time up to 40 h. Above 40 h, both drop discontinuously, a surface structural reconstruction was suggested. The creation of dangling bonds and an incomplete hydrogenation of the surface carbon atoms destabilize the surface, resulting in the structural reconstruction. Nanodiamond particles are thermally converted to nanographite/nanographene. A single nanographene sheet is successfully prepared by heat-treating nanodiamond particles. The edge of graphene sheet with its edge carbon atoms being hydrogen-terminated is investigated by UHV-STM/STS. Zigzag edges are found to have non-bonding π-state of edge origin, in good agreement with theoretical prediction.     

Low-Temperature Synthesis of ZrC Powder by Cyclic Reaction of Mg in ZrO2–Mg–CH4

We investigated the conditions for low-temperature synthesis of ZrC fine powder from ZrO₂–Mg–CH₄. The synthesis utilizes a thermite-type reaction, with Mg as the reducing agent, and a reaction between Mg and CH₄ gas as a carbon source. The Mg/ZrO₂ molar ratio as well as the heating rate were varied. Because C can be continuously fed into the reaction group by the cyclic reaction of Mg through the formation and decomposition of Mg₂C₃ (2Mg + 3CH₄→ Mg₂C₃+ 6H₂→ 2Mg + 3C), a molar ratio of 2.2 for Mg/ZrO₂ was sufficient for the synthesis of single-phase ZrC. ZrC powders were synthesized under the following conditions: Mg/ZrO₂ molar ratio = 2.2, heating rate = 20°C/min, and temperature maintained at 750°C for 30 min. The amount of reaction heat produced in the reduction reaction of ZrO₂ by Mg depended on the Mg/ZrO₂ molar ratio, specifically, the amount of ZrO₂ contained. Moreover, the cyclic reaction of Mg-Mg₂C₃–Mg was influenced by the amount of reaction heat described above and by the heating rate. The ZrC fine powder showed little aggregation and high dispersibility.     

Copolymerization of ethanesultam with 2-methyl-2-oxazoline

Summary This paper describes the so-called No Catalyst Copolymerization between dioxo-1,1-thiazetidine-1,2(Ethanesultam; ESm) and 2-methyl-2-oxazoline. The copolymerization took place without any added initiator to produce copolymers of MeOZO and ESm. The structure of the copolymer was determined by the IR and NMR spectra, elemental analysis, as well as by the result of an alkaline hydrolysis of the copolymer. The reaction scheme of the copolymerization via zwitterion mechanism (Eq 3–5) was proposed.     

Bromine addition and successive amine substitution of mesoporous ethylenesilica: Reaction, characterizations and arsenate adsorption

Bromination and subsequent ethylenediamine substitution of the CC double bond in mesoporous ethylenesilica were carried out to explore the characteristics of this periodic mesoporous organosilica. The structures of the products (BrPMO and EDA–BrPMO, respectively) were analysed by IR, Br K-edge EXAFS and NMR spectroscopies, as well as X-ray diffraction and nitrogen adsorption. We showed (1) that the formulae of the two products that formed were [CHBrSiO_1.5]_0.45[CHSiO_1.5]_0.55 and [NH₂CH₂CH₂NHCHSiO_1.5]_0.05 [CHBrSiO_1.5]_0.40[CHSiO_1.5]_0.55, respectively, (2) that the addition of Br₂ at room temperature occurred on the CC double bonds with disturbing the framework structure, (3) that IR absorption band of CC bonds that reacted with Br₂ is significantly different from that of inactive CC bond, (4) that the length of the C–Br bond was considerably longer than in conventional alkyl bromides, and (5) that a large proportion of the ν(C–Br) band remained at the same position in the IR absorption spectrum after the ethylenediamine (EDA) substitution, while a new ν(C–Br) absorption also appeared. The mechanisms of these reactions are discussed at both the micro and mesoscopic levels.

Arsenate adsorption on EDA–BrPMO, in which the EDA is directly bound to the “surface” of the mesopores, was compared with adsorption on EDA–Pr–PMO, which was prepared by the direct synthesis of 3-chloropropyl-functionalized mesoporous ethanesilica followed by the substitution of Cl with EDA. The strength of the adsorption, as measured with the distribution coefficient, was greater for the former adsorbent than the latter. The origin of this difference was attributed to the distance between amino group and the surface.     

Pulsed Electric Current Sintering of Silicon Nitride

Pulsed electric current sintering (PECS) has been used to densify α-Si₃N₄ powder doped with oxide additives of Y₂O₃ and Al₂O₃. A full density (>99%) was achieved with virtually no transformation to β-phase, resulting in a microstructure with fine equiaxed grains. With further holding at the sintering temperature, the α-to-β phase transformation took place, concurrent with an exaggerated grain growth of a limited number of elongated β-grains in a fine-grained matrix, leading to a distinct bimodal grain size distribution. The average grain size was found to obey a cubic growth law, indicating that the growth is diffusion-controlled. In contrast, the densification by hot pressing was accompanied by a significant degree of the phase transformation, and the subsequent grain growth gave a broad normal size distribution. The apparent activation energy for the phase transformation was as high as 1000 kJ/mol for PECS, almost twice the value for hot pressing (∼500 kJ/mol), thereby causing the retention of α-phase during the densification by PECS.     

Semiconductor Passivation and Insulation Properties for Hydroxyl- and Fluoride-Free ZnO-SiO2-B2O3-Al2O3 Glasses Stabilized by Increased P2O5

F⁻- and OH⁻-free ZnO-B₂O₃-SiO₂-Al₂O₃-P₂O₅ glasses used for semiconductor-device passivation or insulation are investigated with regard to compositional dependencies for thermal expansion, viscosity points, and metal oxide semiconductor (MOS) capacitor properties. The experimental data show that thermal expansion increases, and flow points decrease, when P₂O₅ is substituted for B₂O₃. MOS capacitors passivated by OH⁻- and F⁻-free ZnO-based glasses exhibit normal capacitance-voltage curves.     

Liquid crystalline side-chain polysiloxanes containing mesogenic groups attached by esterification

Summary Liquid crystalline side-chain polysiloxanes were prepared without metal complex catalyst. Mesogenic groups such as cholesteryl, 4-cyano-4-biphenyl and 4-methoxy-4-biphenyl group were introduced into polysiloxane by esterification and from DSC measurements they were compatible with other liquid crystalline polysiloxanes reported previously.     

Transmission of correct gaze direction in video conferencing using screen-embedded cameras

In this paper, we propose a new video conferencing system that presents correct gaze directions of a remote user by switching among images obtained from multiple cameras embedded in a screen according to a local user’s position. Our proposed method reproduces a situation like that in which the remote user is in the same space as the local user. The position of the remote user to be displayed on the screen is determined so that the positional relationship between the users is reproduced. The system selects one of the embedded cameras whose viewing direction towards the remote user is the closest to the local user’s viewing direction to the remote user’s image on the screen. As a result of quantitative evaluation, we confirmed that, in comparison with the case using a single camera, the accuracy of gaze estimation was improved by switching among the cameras according to the position of the local user.

     

退火对Inconel718合金氢脆特性的影响

通过实施不同的退火热处理工艺，调整合金中强化相的析出状态，制备具有不同退火状态的几组拉伸试样。对每组试样在未充氢和充氢后按相同的条件进行拉伸试验对该组试样的脆化作用。通过比较不同组试样的脆化表现通过比较未充氢试样和充氢后试样的强度和塑性，评价氢考察退火状态对Inconel 718氢脆倾向的影响。试验结果表明，随着退火程度的加强，强化相体积分数减少，氢引起的塑性损失下降，即抗氢脆性能改善。该结果说明，强化相γ″和γ′对Inconel 718合金的氢脆有促进作用。因此，根据不同工业应用要求，在符合强度要求的前提下，可以通过热处理改善零件的抗氢脆性能。     

Chromium-nitride in situ composites with a compositional gradient formed by reactive DC plasma spraying

Nitrides of transition metals have good wear- and corrosion-resistant properties because of their high hardness and chemical stability. Chromium-nitride coatings can be deposited by ion plating; however, the thin thickness due to the slow deposition rate must be improved for severe wear-resistant applications. The main objective in this paper is to realize good structural control in the processing of chromiumnitride in situ composite coatings formed at a high deposition rate. They were synthesized by reactive low-pressure plasma spraying using elemental chromium powder as a spray material. The transferred arc between the gun electrode and the substrate was used to accelerate the nitriding reaction. The sprayed coatings consist of chromium, Cr₂N, and CrN, which have a composition gradient from the substrate interface to the surface. The volume fraction of Cr₂N increases with transferred arc current, and nonreacted chromium concurrently decreases, except close to the substrate. The CrN phase, however, only exists as a surface layer of 20 to 30 μm because it is decomposed to Cr₂N above 1420 K. The hardness of the composite coatings depends on the volume fraction of Cr₂N, and it increases to 1300 HV at a Cr₂N volume fraction of 0.98. The seizure stress with lubricant depends on the coating hardness. The maximum seizure stress of 24.9 MPa is obtained at a hardness of 1300 HV. The composite coatings also show a superior wear resistance. Hence, the Cr₂N in situ composite coatings synthesized by reactive plasma spraying with transferred arc are expected to be good candidates for wear-resistant applications.