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Glass-formation Range and Cooling Rate 玻璃形成范围和冷却速度
Pub Date : 1966-02-01 DOI: 10.2109/JCERSJ1950.74.846_52
M. Imaoka, H. Kurakata, S. Tai, Hiroshi Nonomiya
We have already studied the condition of glass-formation and the glass-formation range of borates, silicates and germanates. In these studies, however, we could not determine precisely the cooling condition which defines the glass-formation range, because the glassy stateis not a stable state, but a sub-stable one. These experiments were made under conditions which were determined for the sake of experimental convenience: namely, 1/80mols of specimen were melted and cooled naturally in a room. Therefore, it is necessary to examine to what extent the results of these experiments are effective in view of the glass structure. In this study experiments were carried out by changing the cooling rate, and the variation in the glass-formation range with various cooling rates was examined. These cooling processes included the followings: quick cooling by water, natural cooling in a room (cf. Curve I in Fig. 1), natural cooling in a furnace (cf. Curve II in Fig. 2) and slow cooling in a furnace controlled by a thermocontroller. These cooling rates are about 3×102, 10, 1.5×10-1 and 1.2×10-3°C/sec, respectively. The amount of molten glass is the same as that in the previous studies; crucibles employed are made of platinum or its alloy, which may have some effect especially in the case of the slow cooling in a furnace.Ternary borate systems have been chosen as the glass-forming system for the convenience of experiment, which have been divided into common systems and exceptional systems. The former include the B-type ternary system as the containing only the oxides of the a-group elements, the PbO-containing ternary system as the one containing both of the oxides of the a-group and the b-group elements, and the B2O3-Bi2O3-PbO system as the one containing only the oxides of the b-group elements. The results are shown in Fig. 1-19. These glass-formation ranges contain various critical lines of vitrification; the limit of the continuity of a network-structure (the AD-line in Fig. 2 and 3), the existing limit of necessary modifier ions for the network-formation (the B2O3-C line in Fig. 2 and 3), and the exchangeable limit of network ions represented by the number of b-group ions connecting B with B in the network-structure (the A1B2, A2B3, … lines in Fig. 8; cf. Table 1). The glass-formation range expressed by the above critical lines generally varies somewhat according to the variation in the cooling rate. Therefore the result of the glass-formation range under an arbitrary cooling condition has no absolute meaning. However, comparing Fig. 4 with Fig. 5, for example, we can see a similar variation in the glass-formation range in both cases. In the one case the modifier ions are not exchanged but the cooling conditions are changed, while in the other the modifier ions are exchanged but the cooling conditions are kept constant. This fact can be explained by assuming the 3-dimensional glass-formation range including the glass stability as shown in Fig. 7. When the m
我们已经研究了硼酸盐、硅酸盐和锗酸盐的玻璃形成条件和玻璃形成范围。然而,在这些研究中,由于玻璃态不是稳定状态,而是亚稳定状态,我们不能精确地确定定义玻璃形成范围的冷却条件。为了实验方便,我们确定了实验条件:1/80mol的样品在室内自然熔化冷却。因此,有必要考察这些实验结果在多大程度上对玻璃结构是有效的。本研究通过改变冷却速率进行了实验,考察了不同冷却速率下玻璃形成范围的变化情况。这些冷却过程包括:用水快速冷却、室内自然冷却(参见图1中的曲线I)、炉内自然冷却(参见图2中的曲线II)和由温控器控制的炉内缓慢冷却。这些冷却速率分别约为3×102, 10, 1.5×10-1和1.2×10-3°C/秒。玻璃液用量与以往研究相同;所使用的坩埚是由铂或其合金制成的,特别是在炉中缓慢冷却的情况下,它可能有一些效果。为方便实验,选择三元硼酸盐体系作为玻璃成型体系,并将其分为普通体系和特殊体系。前者包括只含有a族元素氧化物的b型三元体系,同时含有a族和b族元素氧化物的含pbo三元体系,以及只含有b族元素氧化物的B2O3-Bi2O3-PbO体系。结果如图1-19所示。这些玻璃形成范围包含各种玻璃化的临界线;网络结构连续性的极限(图2和3中的ad线),网络形成所需修饰离子的现有极限(图2和3中的B2O3-C线),以及网络结构中连接B与B的B族离子的数量所表示的网络离子的可交换极限(图8中的A1B2、A2B3、…线);参见表1)。以上临界线表示的玻璃形成范围通常会随着冷却速率的变化而有所不同。因此,任意冷却条件下的玻璃形成范围的结果没有绝对意义。然而,例如,将图4与图5进行比较,我们可以看到两种情况下玻璃形成范围的变化相似。在一种情况下,不交换改性剂离子但改变冷却条件,而在另一种情况下,交换改性剂离子但保持冷却条件不变。这一事实可以通过假设三维玻璃形成范围包括玻璃稳定性来解释,如图7所示。当B2O3-PbO-RO体系(图5)中的改性剂离子较小,使得其玻璃化体系更不稳定时,玻璃化只发生在高稳定段。在更稳定的玻璃化系统中,冷却速度较慢的情况也是如此。然后,我们将B2O3-MgO-BaO体系(图9)、B2O3-TiO2-BaO体系(图12)、B2O3-WO3-Li2O体系(图15)和B2O3-K2O-Bi2O3体系(图17)作为异常三元体系进行了研究,并讨论了这些体系异常的真实特征。在
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引用次数: 1
Diffusion in Oxides 氧化物中的扩散
Pub Date : 1966-01-01 DOI: 10.2109/JCERSJ1950.74.851_215
K. Hirano
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引用次数: 2
γ-酸化鉄 (III) のα-酸化鉄 (III) への転移の鉱酸による促進作用 γ-氧化铁(III)向α-氧化铁(III)转移的矿酸促进作用
Pub Date : 1965-03-01 DOI: 10.2109/JCERSJ1950.73.834_101
久保 輝一郎, 信一 白崎, 征明 御手洗
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引用次数: 0
On the Device of Rotary Kiln for the Calcination of Lime 石灰煅烧回转窑装置的研究
Pub Date : 1965-01-01 DOI: 10.2109/JCERSJ1950.73.838_C359
M. Takatsu
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引用次数: 0
Sintering in the Binary System MoSi2-WSi2 MoSi2-WSi2二元体系的烧结
Pub Date : 1964-01-01 DOI: 10.2109/JCERSJ1950.72.821_111
S. Matsuo, K. Homma
Molybdenum disilicide has recently been developed as an excellent heating element of high refractoriness and of high oxidation resistivity. The binary system of MoSi2-ZrO2 was studied for the purpose of improving the too low electrical resistivity of MoSi2 without changing the other favorable characteristics.ZrO2 used was previously stabilized by dissolving 10 mol % of Y2O3 at 1600°C. Samples of six different chemical compositions differing from each other by 20% in ZrO2 content, were formed under the pressure of 6ton/cm2 and sintered at five different temperatures between 1300° and 1650°C in H2 gas.The electrical resistivity, density and modulus of rupture were measured on sintered specimens and expressed as functions of sintering temperature, chemical composition and sintering time.The density becomes minimum at about 60% of ZrO2 content and the modulus of rupture varies approximately with the density.The electrical resistivity at a room temperature increases rapidly with the amount of ZrO2 above 60%. The change of the electrical resistivity was also investigated up to the surface temperature of 1700°C. The resistivity increases with temperature on the MoSi2 side, while decreases on the ZrO2 side.The thermal shock test by repeated rapid heating and cooling between a room temperature and 1400°C, showed that the samples of the medium composition had the least thermal shock resistance.
二硅化钼是近年来发展起来的一种具有高耐火度和高抗氧化性的优良加热元件。研究了MoSi2- zro2二元体系,目的是在不改变MoSi2电阻率过低的同时,改善其其他有利特性。先前使用的ZrO2通过在1600℃下溶解10mol %的Y2O3来稳定。在6ton/cm2的压力下形成6种不同化学成分的样品,ZrO2含量相差20%,并在H2气体中在1300°~ 1650°C的5种不同温度下烧结。测量了烧结试样的电阻率、密度和断裂模量,并将其表示为烧结温度、化学成分和烧结时间的函数。在ZrO2含量为60%左右时,密度达到最小,断裂模量随密度近似变化。当ZrO2含量超过60%时,材料的室温电阻率迅速升高。研究了表面温度达到1700℃时的电阻率变化。MoSi2侧电阻率随温度升高而升高,ZrO2侧电阻率随温度升高而降低。在室温至1400℃之间反复快速加热和冷却的热冲击试验表明,该介质成分的样品具有最低的抗热冲击性能。
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引用次数: 1
Casting Properties of Pottery Body due to Specific Base-Exchange Cations 特定碱交换阳离子对陶体铸造性能的影响
Pub Date : 1964-01-01 DOI: 10.2109/JCERSJ1950.72.821_117
Y. Shiraki
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引用次数: 0
Some Observations on Cracking of Clay during steady Heating in a saturated Atmosphere 饱和大气中稳定加热过程中粘土开裂的一些观察
Pub Date : 1964-01-01 DOI: 10.2109/JCERSJ1950.72.827_169
Y. Shiraki
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引用次数: 1
Studies of the Glass-formation Range of Silicate Systems : Investigations on the Glass-formation Range, 2 硅酸盐体系玻璃形成范围的研究:玻璃形成范围的研究,2
Pub Date : 1963-12-01 DOI: 10.2109/jcersj1950.71.816_215
M. Imaoka, T. Yamazaki
Following a previous report “Studies of the Glass-formation Range of Borate Systems” (This Journal, 69, 282 (1961)), we studied the glass-formation range of silicate systems. Although silicate glasses have long been used, sufficient systematic studies of the glassformation ranges of silicate systems have not yet been made.In this experiment, 1/80 mole (about 1g.) of materials were melted in crucibles made of pure platinum or platinum containing 20% rhodium at temperatures from 1400° to 1750°C. The oxides used besides SiO2 were 16 kinds of the oxides of a-group elements namely Li, Na, K, Be, Mg, Ca, Sr, Ba, Al, La, Ti, Zr, Th, Nb, Ta and W.The glass-formation ranges of binary silicate systems are shown in Table 1. These ranges differ in some points from those of borate systems. For instance, the La-silicate system has no vitrified range, while the Mg-silicate system has a wider glass-formation range than the borate. Whether a component ion enters into the glass structure as a modifier or as a network-former depends on the acidity of the glass-former and on the electronegativity of the component ion. In silicate systems, however, the actual range of glass-formation equals the difference between the glass-formation range and the immiscible range. If the latter is equal to the former or somewhat wider, the vitrified range will disappear.The glass-formation ranges of ternary systems are shown in Fig. 1-34. The whole number of the studied systems reached about one hundred. The Experimental results show that the actual glass-formation ranges agree with the range (hatched areas in the figures) to be expected from the “Conditions of Glass-formation” (This Journaj, 67, 364 (1959)). Among these systems, the systems containing TiO2 (cf. Figs. 12 and 13) are remarkably different from the corresponding borate systems. In the borate systems, a glass-fromation range spreads on the right side of the SiO2-D line (cf. Fig. 10), and therefore it has been estimated that the co-ordination number of Ti4+ is 6. (In order for the Ti4+ ion to take 6-co-ordination as a network-former, the modifier of divalency must also be present, therefor, in the area on the left of the SiO2-D line glass-formation is impossible.) However, in the silicate system the limited line of SiO2-D is lacking. Consequently, it is concluded that the Ti4+ ion as well as the Si4+ ion takes the 4-co-ordination. The glass-formation range of the TiO2-containing systems are shown in the hatched areas of Figs. 12 and 13, which are limited by the AD line.The WO3-containing silicate systems have a remarkably narrow glass-formation range compared with borate systems. The vitrified range of the B2O3-WO3-alkali oxide system has two feet, but the silicate system, we suppose, lacks the left foot. Moreover, it is considered that the left foot consists of WO3 and alkali borate in borate systems, but that this part becomes immiscible in silicate systems.According to the devitrification of the binary system, La2O3 sy
继之前的报告“硼酸盐体系的玻璃形成范围的研究”(the Journal, 69, 282(1961))之后,我们研究了硅酸盐体系的玻璃形成范围。虽然硅酸盐玻璃早已被使用,但对硅酸盐体系的玻璃形成范围还没有足够系统的研究。在本实验中,将1/80摩尔(约1g)的材料熔化在由纯铂或含20%铑的铂制成的坩埚中,温度从1400°到1750°C。除SiO2外,还使用了Li、Na、K、Be、Mg、Ca、Sr、Ba、Al、La、Ti、Zr、Th、Nb、Ta、w等16种a族元素的氧化物,二元硅酸盐体系的玻璃形成范围见表1。这些范围在某些方面与硼酸盐体系有所不同。例如,la -硅酸盐体系没有玻璃化范围,而mg -硅酸盐体系比硼酸盐具有更宽的玻璃化范围。组分离子是作为改性剂还是作为成网剂进入玻璃结构,取决于成网剂的酸度和组分离子的电负性。然而,在硅酸盐体系中,玻璃形成的实际范围等于玻璃形成范围与不混相范围之差。如果后者与前者相等或稍宽,则玻璃化范围将消失。三元体系的玻璃形成范围如图1-34所示。所研究的系统总数约达100个。实验结果表明,实际的玻璃形成范围与“玻璃形成条件”(This journal, 67,364(1959))所期望的范围(图中孵化的区域)一致。在这些体系中,含有TiO2的体系(参见图12和图13)与相应的硼酸盐体系有显著差异。在硼酸盐体系中,在SiO2-D线的右侧有一个玻璃化范围(参见图10),因此可以估计Ti4+的配位数为6。(为了使Ti4+离子以6-配位作为网络形成剂,还必须存在二价修饰剂,因此,在SiO2-D线左侧区域不可能形成玻璃。)然而,在硅酸盐体系中,缺乏二氧化硅- d的限制线。结果表明,Ti4+离子和Si4+离子均为4配位。含tio2体系的玻璃形成范围如图12和13的孵化区域所示,该区域受AD线限制。与硼酸盐体系相比,含wo3硅酸盐体系的玻璃形成范围非常窄。b2o3 - wo3 -碱氧化物体系的玻璃化范围有两个脚,但我们认为硅酸盐体系没有左脚。在硼酸盐体系中,认为左脚由WO3和碱硼酸盐组成,但在硅酸盐体系中,这部分变得不可混溶。根据二元体系的反玻化作用,La2O3体系可归为c型三元体系,其玻璃形成范围比硼酸盐体系窄。SiO2-Al2O3-La2O3体系的玻璃化范围(参见图29)与相应的硼酸盐体系的玻璃化范围一致,但不混相范围的极限线kl低于硼酸盐体系,因此前者的玻璃化范围比后者窄。其他的la -硅酸盐体系也是类似的。在含th2或Al2O3的c型三元体系中,在相应的硼酸盐体系中有玻璃化范围,我们发现只有SiO2具有玻璃化状态
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引用次数: 20
X-Ray Study of Behaviors of Sesquioxides Depositing in a Chromite Grain 铁铁矿中倍半氧化物沉积行为的x射线研究
Pub Date : 1963-01-01 DOI: 10.2109/JCERSJ1950.71.810_109
Eiji Anbo
It is well known that sesquioxides, Cr2O3, Al2O3 and Fe2O3, are liberated from chromite ore by heat treatment in air. But behaviors of the sesquioxides in ores fired at temperatures below 1000°C have not been studied systematically.In this report, influences of behaviors of the sesquioxides on lattice spacing of the chromite fired below 1300°C and diffusion phenomena of the sesquioxides in the fired chromite grain were examined by X-ray diffraction and fluorescent X-ray analysis. The followings were observed (1) The lattice spacing (440) of the chromite decreased with elevation of heating temperature up to 700°-900°C in air and increased over these temperatures. The diffracted line (440) was most broadened at 700°-900°C. The X-ray pattern of the sesquioxides in α-type appeared over 700°C, and the relative intensity of the diffracted line (014) increased with decrease of its lattice spacing (014) between 700° and 1300°C. (2) By fluorescent X-ray analysis of the chromite grain, ratio of Fe2O3/Cr2O3 on the surface of the grain fired was determined. The ratio increased in the temperature range between 700° and 1100°C, and over this range decreased. So diffusion of the liberated sesguioxides in the spinel phase which presumably consists of a single crystal, was ascertamed.It was concluded that by the liberation of the sesquioxides the chromite phase was made unstable at the heating temperature of 700°-900°C, but was brought into a stable state over 700°-900°C by isolation of two different crystal phases of the sesquioxides and the spinel, with formation of a solid solution of the sesquioxides. The degree of crystallization of the two different phases was raised by heating over 700°-900°C.The author considers that the behaviors, as described above, of the sesquioxide deposited on the surface of the chromite crysta will give a valuable explanation of reactions with the chromite grain.
众所周知,从铬铁矿中通过空气热处理可以释放出倍半氧化物Cr2O3、Al2O3和Fe2O3。但在低于1000℃的温度下,对倍半氧化物在矿石中的行为还没有系统的研究。本文通过x射线衍射和荧光x射线分析,研究了倍半氧化物的行为对1300℃以下焙烧铬铁矿晶格间距的影响,以及倍半氧化物在焙烧铬铁矿颗粒中的扩散现象。结果表明:(1)在空气中加热温度为700℃~ 900℃时,铬铁矿的晶格间距(440)随着温度的升高而减小,在此温度范围内晶格间距增大。衍射线(440)在700°-900°C时展宽最大。α型倍半氧化物在700°C以上出现x射线衍射,在700°~ 1300°C之间,衍射线(014)的相对强度随着晶格间距(014)的减小而增大。(2)通过对铬铁矿晶粒的荧光x射线分析,确定了焙烧晶粒表面Fe2O3/Cr2O3的比例。该比值在700 ~ 1100℃范围内增大,在此范围内减小。因此,释放的半氧化物在尖晶石相(可能由单晶组成)中的扩散被确定。结果表明,在700°-900°C的加热温度下,半氧化物的分离使铬铁矿相变得不稳定,但在700°-900°C的加热温度下,通过分离半氧化物和尖晶石的两种不同晶相,形成半氧化物的固溶体,使铬铁矿相处于稳定状态。在700°-900°C以上加热,提高了两种不同相的结晶程度。作者认为,如上所述,沉积在铬铁矿晶体表面的倍半氧化物的行为将对与铬铁矿颗粒的反应提供有价值的解释。
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引用次数: 0
On the Influence of the Gamma-Irradiation upon the Electric Conductivity of Glasses 辐照对玻璃电导率的影响
Pub Date : 1962-01-01 DOI: 10.2109/JCERSJ1950.70.122
T. Sugiura, K. Murakami, Hirobumi Tanaka
Influence of gamma-irradiation upon properties of glasses have scarcely been studies excepting phenomena such as coloration and fluorescence caused by the irradiation. In this study, therefore, not only the influence of gamma-irradiation upon the electric conductivity of glasses, but applicability of glasses exposed by gamma-rays to semi-conductive glass or radiationdosimeter was studied.The electric conductivity for ten kinds of glasses were measured after irradiating gamma-rays up to the maximum dosage of 107r. using Co60.For the measurement of the electric conductivity, a vacuum tube voltmeter was used for the range of low resistance values and a vibration reed electrometer for the range of high resistance.The result of the measurement showed that no change in electric conductivity of the glasses occured by the irradiation of 107r. and consequently the gamma-irradiation to the glasses was found to be unapplicable in making semi-conductive glass and glass-dosimeter.
除了辐照引起的变色和荧光等现象外,很少研究γ辐照对玻璃性质的影响。因此,本研究不仅研究了伽玛辐照对玻璃电导率的影响,还研究了伽玛射线照射下的玻璃对半导电玻璃或辐射剂量计的适用性。对10种玻璃进行了最大剂量为107r的γ射线辐照后的电导率测定。使用Co60。对于电导率的测量,在低电阻值范围内使用真空管电压表,在高电阻值范围内使用振动簧静电计。测量结果表明,在107r辐照下,玻璃的电导率没有发生变化。因此,发现对玻璃的辐照不适用于制造半导电玻璃和玻璃剂量计。
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引用次数: 0
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Journal of the Ceramic Association, Japan
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