窯業協會誌
Online ISSN : 1884-2127
Print ISSN : 0009-0255
ISSN-L : 0009-0255
84 巻, 973 号
選択された号の論文の12件中1~12を表示しています
  • 持田 統雄, 高橋 健太郎
    1976 年 84 巻 973 号 p. 413-420
    発行日: 1976/09/01
    公開日: 2010/04/30
    ジャーナル フリー
    In AsO3/2-BO3/2 glass system molar volume (V), molar refractivity (R) and thermal expansion coefficient (α) increased linearly with AsO3/2 content (Fig. 1, 2, 3). Infrared spectra of these glasses showed good agreement with the summed curves for As2O3 and B2O3 glasses with the mole percents of the components taken into account (Fig. 7). These facts reveal that the structure of these glasses consists of As4O6 molecules and boroxol rings randomly distributed each other without forming As-O-B bonds. The increase in transformation temperature (Tg) of the glasses containing more than 70mol% BO3/2, shown in Fig. 5, is due to the structural change into a layer network of boroxol rings interlaced with As4O6 molecules.
    The change in ratio of infrared absorption intensities of the BO4 band at 930cm-1 and BO3 band at about 1300cm-1, shown in Fig. 10, revealed that the fraction of four-coordinated B3+(N4) increased rapidly up to 25mol% BiO3/2 and reduced to zero at 65-70mol% BiO3/2. This change of boron coordination estimated from infrared spectra corresponds fairly to the changes of the other properties, that is, the maxima in Tg and Vickers microhardness (Hv), and the minima in V and α at 20-25mol% BiO3/2 (Fig. 5, 6, 3, 4), and a maxima in α and breaks of Tg- and Hv- composition curves at 65-70mol% BiO3/2 (Fig. 4, 5, 6).
    In binary SbO3/2-BO3/2 glasses, α decreased slightly, and Tg and Hv increased with SbO3/2 content, dangling in a minimum in α, a maximum in Tg and a break of Hv-composition curve at about 30mol% SbO3/2 (Fig. 4, 5, 6). Introducing SbO3/2 into B2O3 glass weak absorption peaks due to BO4 groups appeared at 850-1050cm-1 (Fig. 11). These are obviously due to the change of coordination number of B3+ from 3 to 4, but N4 in these glasses is much smaller than that in BiO3/2-BO3/2 glasses.
    The difference in the tendency of the coordination number change of boron in three binary borate glasses was interpreted as follows. As3+ and Sb3+ are coordinated trigonal-pyramidally because of stronger covalent characters of As-O and Sb-O bonds. In the region rich in BO3/2 content owing to stronger ionic character of Sb-O bond compared to As-O bond, a small amount of Sb3+ behaves as NWM, resulting in the coordination number change of a small portion of B3+. As Bi-O bond is stronger in ionic character than Sb-O bond, Bi3+ behaves as NWM in the same region, resulting in the coordination number change of B3+. The coordination number of Bi3+, however, decreases with increasing BiO3/2 content because of increase in the covalent character of Bi-O bond.
  • 高塩 治男
    1976 年 84 巻 973 号 p. 420-426
    発行日: 1976/09/01
    公開日: 2010/04/30
    ジャーナル フリー
    Translucent aluminum oxide-to-niobium metal seals were formed by using an oxide solder and interfaces between the materials were examined by an optical microscope and an electron probe microanalyzer.
    The oxide solder used for this experiment was a crystalline solder and was composed of crystals of CaO, Al2O3, MgO and B2O3, and contained no alkali.
    The results were as follows:
    (1) Vacuum tight seals were formed by this technique.
    (2) The solder which turned into a glass-ceramic composite by sealing operation contained 3CaO⋅Al2O3, CaO⋅Al2O3 and MgO⋅Al2O3 as main constituent phases.
    (3) B2O3 in the solder was very useful in improving adhesion.
    (4) The intermediate layer about 10μ thick was formed at translucent aluminum oxidesolder interface.
    (5) Thickness of the intermediate layer at niobium metal-solder interface was less than 1μ. This was in contrast to the case of solder containing Na2O and K2O which had formed intermediate layer 10μ thick in the author's previous experiment.
    (6) Transition layers with concentration gradients of Al and Nb were formed in the solder at the ceramic-solder and metal-solder interfaces, respectively. These layers were expected to be useful in reducing sealing stress and in improving adhesion.
  • 清水 紀夫, 柳田 博明, 橋本 甲四郎
    1976 年 84 巻 973 号 p. 426-431
    発行日: 1976/09/01
    公開日: 2010/04/30
    ジャーナル フリー
    With DTA, TGA and X-ray diffraction analysis of the phases obtained in a closed vessel in the temperature range 300-600°C, it was postulated that the dissociation sequence of chromium trioxide into intermediate chromium oxides was CrO3→Cr3O8→X-phase→Cr2O5→CrO2→Cr2O3. Although the X-phase was not characterized enough, it was considered to be a new intermediate phase (Cr:O=1:2.49) different from Cr2O5.
    Seed crystal (HCrO2), water and oxygen pressure had effects on the reaction. With water, phase of Cr2O5 was stabilized At elevated oxygen pressure beforehand (up to 10kg/cm2), phase of Cr3O8 was stabilized and formation of Cr2O3 was retarded.
    Adding HCrO2 for seed crystals gave rise to change in the reaction sequence, the sequence being CrO3→Cr2O5→CrO2→Cr2O3. Further, seed crystals decreased the effects of water and oxygen pressure on the reaction.
  • 飯村 勉
    1976 年 84 巻 973 号 p. 431-435
    発行日: 1976/09/01
    公開日: 2010/04/30
    ジャーナル フリー
    The effects of V2O5 addition on the magnetic properties of Li-Zn ferrites have been studied. Samples were fired at 1050-1150°C for 2 hours in air. The squareness ratio, sintered density, saturation magnetization, Curie temperature, and order-disorder transition of Li-Zn ferrites were determined as functions of V2O5 addition.
    The results obtained are summarized as follows.
    (1) The maximum squareness ratio (Br/Bm) were obtained by the addition of 0.1 wt% V2O5, but further increase in V2O5 content decreased Br/Bm.
    (2) The improvement of squareness ratio was due to the combination of small grain size and homogeneous grain size distribution.
    (3) It was found from saturation magnetization, Curie temperature and lattice constant that a portion of V2O5 dissolved into ferrite. The result support the B-site ordering which decreased with increasing V2O5 content. It was shown that the decrease in octahedral site ordering by the addition of V2O5 is attributed to the incorporation of V ions in the spinel lattice and also to the separation of α-Fe2O3.
  • 広田 慎一郎, 泉谷 徹郎
    1976 年 84 巻 973 号 p. 435-439
    発行日: 1976/09/01
    公開日: 2010/04/30
    ジャーナル フリー
    Up to date, refractive index of optical glasses has been discussed in the Drude-Voigt dispersion formula in terms of the inherent wavelength of absorption λ0 and the number of molecules in unit volume N1 on the assumption that the oscillator strength f0 is constant. In this study, the influence of oscillator strength on the refractive index was investigated. It was found that the Drude-Voigt equation in which only a single oscillator is considered,
    nλ2-1=(e2mc2)N1f0/(1/λ02-1/λ2),
    is applied very well to the measured dispersions of almost all optical glasses. λ0, N1 and f0 of about two hundred kinds of optical glasses were calculated from above equation, and the following conclusions were obtained;
    1) As N1f0λ0 of crystals of the same structure are constant, those of each series of optical glasses such as SK-, La-series etc. are also found to be roughly constant.
    2) Refractive index nd is approximately expressed as a linear function of N1f0λ02. While Abbe's number νd is approximately expressed as a linear function of 1/λ02 but is independent of N1 and f0.
    3) Refractive index was surely affected by oscillator strength values f0 as seen in those glasses which have nearly equal λ0 and N1 but different f0 values.
    4) Oscillator strength f0 are small in F-series glasses, while they are large in BK-, SK-, La- and Ta-series glasses. In La- and Ta-series glasses, N1 are also large.
  • 頓行 宏
    1976 年 84 巻 973 号 p. 439-443
    発行日: 1976/09/01
    公開日: 2010/04/30
    ジャーナル フリー
    The nature of Al-O bonds in K2O-Al2O3-B2O3 glasses has been studied by using the optical absorption spectra of VO2+ ions dissolved in the glasses. It has been found that the Al-O bonds in the glasses involve a double-bond character found only in the Al-O bonds in a structure unit containing a four-coordinated Al atom. The bonding mode of Al atoms in the glasses has been discussed in the light of the information obtained from the X-ray emission spectra for some aluminoborate glasses. Two modes have been suggested to be considered. In a mode, the only K+AlO4- group is formed independently of the glass composition and, in the other, the K+(K+AlO6-)- group, together with an AlO4, is formed in the low K2O region and the K+AlO4- group is dominantly formed at the high K2O content.
  • 笹本 忠, 原 宏, 佐多 敏之
    1976 年 84 巻 973 号 p. 444-447
    発行日: 1976/09/01
    公開日: 2010/04/30
    ジャーナル フリー
    高温での蒸発現象を利用した純度向上法がどこまで適用可能であるのかを, 市販のマグネシアクリンカーを用いて1800および2000℃の真空加熱処理を行った場合について, 検討を行った. 対象不純物はAl2O3, SiO2, CaO, B2O3, Na2O, K2O, TiO2, Cr2O3, MnO, Fe2O3の10種類の酸化物であり, それらのマグネシア中での濃度はスパーク・ソース型質量分析器で測定された.
    その結果, B2O3, Na2O, K2O, MnOについては数十ppm wtまでその濃度を減少しえたが, 一方CaO, Fe2O3, SiO2については濃度低減が困難であり, Al2O3, Cr2O3にいたっては全く蒸発精製効果が認められなかった. 全般的にみて, ペリクレースの粒界に存在し, かつ蒸気圧の大きい酸化物ほど高温真空中での加熱処理によって除去されやすい傾向が認められた.
  • 毛利 尚彦
    1976 年 84 巻 973 号 p. 447-449
    発行日: 1976/09/01
    公開日: 2010/04/30
    ジャーナル フリー
    Cobalt-aluminum spinel (CoO⋅Al2O3) was synthesized by sintering the equimolar mixture of Co(OH)2 and γ-Al2O3 in at temperature range from 1000 to 1500°C under different atmosphere. When heating the sample in air, the grain size of the spinel was 0.07μ at 1000°C, 11μ at 1500°C. The color of the products was changed from light to violet blue with raising temperature which results larger grain size. Under O2 atmosphere, a defect spinels (CoO)1-x⋅Al2O3 were formed below 1200°C, and the stoichiometric spinel above 1200°C. Lattice constants of the spinels synthesized below 1200°C under O2 atmosphere were smaller than those of the samples synthesized at the corresponding temperature in air.
    In air, the solid solutions between CoO⋅Al2O3 and Al2O3 were formed above 1200°C. The amount of dissolved Al2O3 in spinel increases with increasing temperature.
  • 田中 稔, 石間 健市, 元山 宗之, 橋詰 源蔵
    1976 年 84 巻 973 号 p. 450-452
    発行日: 1976/09/01
    公開日: 2010/04/30
    ジャーナル フリー
  • 西川 友三
    1976 年 84 巻 973 号 p. 452-454
    発行日: 1976/09/01
    公開日: 2010/04/30
    ジャーナル フリー
  • 元井 操一郎, 佐藤 好毅
    1976 年 84 巻 973 号 p. 454-455
    発行日: 1976/09/01
    公開日: 2010/04/30
    ジャーナル フリー
  • 1976 年 84 巻 973 号 p. A73-A78
    発行日: 1976/09/01
    公開日: 2010/04/30
    ジャーナル フリー
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