Synthesis of boron nitride from triammoniadecaborane and hydrazine under pressure

Boron nitride (BN) of low crystallinity was synthesized from triammoniadecaborane (TAD) and hydrazine at 125 MPa below 650° C. TAD itself was pyrolysed at 600° C and 125 MPa to form a mixture of amorphous boron and boron nitride containing BH and NH bonds. The infrared spectrum of the pyrolysed product of TAD itself at 600° C and 125 MPa showed the BNB absorption at 800cm^–1 due to the formation of B₃N₃ structures. The X-ray diffraction (XRD) of the reaction product from TAD and hydrazine at 600° C had broad diffractions centred at 2=25.5° and 43.0° (CuK). The BH absorption at 2500cm^–1 decreased in intensity on increasing the N/B ratio from 0.3 to 0.85, and disappeared finally at a ratio of N/B=1.3. The reaction product at 125 MPa had a porous structure. The electron diffraction of the specimen changed from faint rings to spots on circular rings after heat treatment at 800° C for 10 h. The heat-treated specimen, however, did not give sharp reflections corresponding to hexagonal BN in the XRD profile. BN of low crystallinity was transferred to cubic BN at 1200° C and 6.5 GPa in a 90% yield, which was higher than that of well-crystallized BN in the presence of AIN.     

Preparation of TiB2 sintered compacts by hot pressing

A sintered compact of titanium diboride (TiB₂) was prepared by hot pressing of the synthesized TiB₂ powder, which was obtained by a solid-state reaction between TiN and amorphous boron. Densification of the sintered compact occurred at 20 MPa and 1800° C for 5 to 60 min with the aid of a reaction sintering, including the TiB₂ formation reaction between excess 20 at % amorphous boron in the as-synthesized powder (TiB₂ + 0.2B) and intentionally added 10 at % titanium metal. A homogeneous sintered compact of a single phase of TiB₂, which was prepared by hot pressing for 30 min from the starting powder composition [(TiB₂ + 0.2B) + 0.1 Ti], had a fine-grained microstructure composed of TiB₂ grains with diameters of 2 to 3 m. The bulk density was 4.47 g cm^–3, i.e. 98% of the theoretical density. The microhardness, transverse rupture strength and fracture toughness of the TiB₂ sintered compact were 2850 kg mm^–2, 48 kg mm^–2 and 2.4 MN m^–3/2, respectively. The thermal expansion coefficient increased with increasing temperature up to 400° C and had a constant value of 8.8 x 10^–6 deg^–1 above 500° C.     

A novel quarter‐wave retardation film for improving viewing angle properties in time‐sequential stereoscopic 3D‐LCDs

We have successfully developed a quarter‐wave retardation film (QWF) for wide viewing angle 3D liquid crystal displays (3D‐LCDs) that provides high luminance, low crosstalk, low color change, and low head‐tilt‐angle dependency. It was found that the out‐of‐plane retardation (Rth) of the QWF in the LCD needs to be close to 0 nm in order to improve the 3D display properties at an off‐axis position and that the in‐plane retardation (Re) needs to be adjusted from 120 to 130 nm to achieve low color change with head tilting. We adopted a coating process for making our QWF because of its potential for retardation control. 3D‐LCDs with this QWF whose Rth was nearly zero had high performance and allowed off‐axis other than on‐axis.     

Reaction control of TiB2 formation from titanium metal and amorphous boron

TiB₂ powder was synthesized by a controlled formation reaction from titanium metal and amorphous boron. Precursory TiB₂ formed by the pretreatment of the mixed powder (mole ratio: B/Ti=2.0) at 600° C for 60 min in an argon stream. Hollow TiB₂ powder with an average grain size of 15m was obtained by subsequent heat treatment above 900° C for more than 60 min in an argon stream. The formation reaction of TiB₂ powder was further controlled by pretreatment of the mixed powder at 600° C for 60 min in a hydrogen and argon stream and subsequent heat treatment at 1000° C for 360 min in an argon stream, when hollow-free TiB₂ powder was formed by a milder formation reaction between amorphous boron and the reformed titanium metal with hydrogen diffused lattice.     

Thickness dependence of H2 gas sensor in amorphous SnQx films prepared by ion-beam sputtering

Amorphous SnO_x films were deposited by ion-beam sputtering on sintered alumina substrates. Amorphous film sensors were prepared by annealing the films at 300° C for 2 h in air. The thickness dependence of resistivity and hydrogen gas sensitivity were measured at 150° C over the thickness range 1 to 700 nm. A resistivity maximum was observed in ultrathin films. Resistivity increased by three orders of magnitude with increasing film thickness from 0.9 to 7.4 nm and then decreased by five orders of magnitude from 7.4 to 35 nm. Ultrathin film sensors showed sensitivity maxima around a thickness of 10 nm. Sensitivity and resistivity of ultrathin films were significantly influenced by the thermal expansion coefficient and the surface state of the substrate.     

Properties of indium oxide/tin oxide multilayered films prepared by ion-beam sputtering

The preparation and characterization of indium oxide (InO _x )/tin oxide (SnO _y ) multilayered films deposited by ion-beam sputtering are described and compared with indium tin oxide (ITO) films. The structure and the optoelectrical properties of the films are studied in relation to the layered structures and the post-deposition annealing. Low-angle X-ray diffraction analysis showed that most films retained the regular layered structures even after annealing at 500° C for 16 h. As an example, we obtained a resistivity of 6×10^–4 cm and a transparency of about 85% in the visible range at a thickness of 110 nm in a multilayered film of InO _x (2.0 nm)/SnO _y (0.2 nm)×50 pairs when annealed at 300° C for 0.5 h in air. Hall coefficient measurements showed that this film had a mobility of 17 cm² V^–1 sec^–1 and a carrier concentration (electron density) of 5×10²⁰ cm^–3.     

Modification of mesophase pitch by blending Part 2 Modification of mesophase pitch fibre precursor with thermoresisting polyphenyleneoxide (PPO)

Polyphenyleneoxide was blended in amounts of 5 or 10 wt% into petroleum-derived mesophase pitch to reinforce the pitch fibre before the oxidative stabilization to achieve better handling properties. Although polyphenyleneoxide was fusible but hardly soluble in the mesophase pitch even at a spinning temperature of 350° C, blended pitch could be smoothly spun into pitch fibre 10m diameter, as could the parent pitch. Fibrous polyphenyleneoxide of less than 1m diameter was homogeneously dispersed in the pitch fibre, being arranged along the fibre axis. Such fibrous polyp henyleneoxide reinforced the pitch fibre considerably. The fibrous substances at the centre of the fibre disappeared in the carbonized fibre at 1300° C after oxidation at 250° C, although some short ones were observed in the skin region of the fibre, suggesting that polyphenyleneoxide was co-carbonized to be assimilated with mesophase pitch at the centre of the fibre, where the effects of oxidation may be rather limited. The oxidation reactivity and its mechanical strength after carbonization were slightly lower in comparison with those of the parent mesophase pitch.     

Synthesis of terpene alcohols from isoprene oligomers

Various terpene alcohols were prepared from isoprene oligomers via two steps: epoxidation with peracetic acid and isomerisation with aluminium triisopropoxide. For example, 2-methylene-6-methyl-7-octene-1-o1 was prepared from 2,6-dimethyl-1,7-octadiene. From 2,6-dimethyl-2,7-octadiene, 3,3,6-trimethyl-1,5-heptadiene, 2,7-dimethyl-2,6-octadiene, 2,6-dimethyl-1,3,6-octatriene, 1-methyl-4-isopropenyl-1-cyclohexene, and 1,5-dimethyl-1,5-cyclooctadiene, the corresponding alcohols were obtained, respectively.     

Role of Acetic Acid Added to the Reaction Media for the Enantio-differentiating Hydrogenation of Methyl Acetoacetate Over a Tartaric Acid-modified Nickel Catalyst

The role of acetic acid added to the reaction media for the enantio-differentiating hydrogenation of methyl acetoacetate over a (R,R)-tartaric acid-in-situ-modified nickel catalyst was studied from the viewpoint of the hydrogenation rate during repeated runs. The hydrogenation of methyl acetoacetate on the “enantio-differentiating sites” of a tartaric acid-modified nickel catalyst was specifically accelerated by the acetic acid added to the reaction media to increase the enantio-differentiating ability of the catalyst. In order to increase the enantio-differentiating ability, the addition of acetic acid to the reaction media was required in each run during the repeated use of the catalyst.     

Rapid Quenching Technique Using Thermal-Image Furnace for Glass Preparation

A new technique combining a thermal-image furnace and a twin roller is described for quenching the melt to form glass. The technique was applied to the simple system Li₂O-SiO₂, since its fundamental parameters in the estimation of critical cooling rate are available. Glass flakes were obtained in the composition Li₄SiO₄, for which a very large critical cooling rate (∼10⁹ K·s⁻¹) was needed for glass formation.