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ISIJ International Vol. 64 (2024), No. 15

ISIJ International
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オンライン版ISSN: 1347-5460
冊子版ISSN: 0915-1559
発行機関: The Iron and Steel Institute of Japan

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ISIJ International Vol. 64 (2024), No. 15

Preface to the Special Issue on “New Developments in High Temperature Processing of Steels and Related Materials Leading the Sustainable Society, and Key Properties of High Temperature Melts”

Masanori Suzuki

pp. 2085-2086

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Integrated Experimental Phase Equilibria and Thermodynamic Modelling Investigation of the FeO–Fe2O3–MgO and the FeO–Fe2O3–MgO–SiO2 Systems. Part I: Experimental Results in Air

Igor Babaian, Maksym Shevchenko, Evgenii Nekhoroshev, Evgueni Jak

pp. 2087-2097

抄録

Phase equilibria studies were undertaken on the FeO–Fe2O3–MgO–SiO2 and FeO–Fe2O3–MgO systems in air using an equilibration and quenching technique. Concentrations of Fe, Mg, Si in the coexisting phases were measured using electron probe X-ray microanalysis (EPMA) with a wavelength dispersive spectrometer (WDS) detector. The liquidus temperatures have been determined from 1400°C to 1740°C in primary phase fields of spinel, monoxide, olivine, pyroxene, tridymite, cristobalite and in two-liquids miscibility gap. Tielines between co-existing phases and the compositions of solid solutions have been determined. In the absence of a liquid phase which would facilitate mass transport, the subsolidus phase relations in the Fe2O3–MgO system were not studied directly. The measurements in the low-SiO2 area of pseudo-ternary “Fe2O3”–MgO–SiO2 system were used to derive phase equilibria of the “Fe2O3”–MgO pseudo-binary system with a special focus on the monoxide-spinel phase boundary. The present study is a part of the research program on the characterization of the MgO-containing refractory systems within the multicomponent Pb–Zn–Cu–Fe–Ca–Si–O–S–Al–Mg–Cr–Na–As–Sn–Sb–Bi–Ag–Au–Ni–Co system.

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Phase Equilibria of the Iron-rich Corner of the CaO–Fe2O3–Al2O3 System at 1240°C in Air

Hirokazu Sato, Maksym Shevchenko, Kazumasa Sugiyama, Siyu Cheng, Jiang Chen, Peter Charles Hayes, Evgueni Jak, Miyuki Hayashi

pp. 2098-2106

抄録

The compositional ranges of SFCA-I and other SFCA series and the phase equilibrium relationships were investigated in the iron-rich corner of the CaO–Fe2O3–Al2O3 system at 1240°C in air using powder and single crystal XRD as well as EPMA. To obtain the desired composition, reagent-grade CaCO3, Fe2O3, and Al2O3 powders were weighed, mixed, and equilibrated at 1240°C in air. Each of the obtained samples was divided into two parts: one was pulverized into a powder and analyzed by XRD, and the other was subjected to microstructural observation and compositional analysis using EPMA. The crystalline structures of the SFCA series for some samples were analyzed by a single XRD. The results revealed that not only SFCA-I but also SFCA-II and SFCA have been found in the compositional area of this study; the Al/(Al+Ca+Fe) concentration ranges are 7.89–20.33 mol% for SFCA-I, 17.62–24.55 mol% for SFCA-II and 20.93–27.60 mol% or even higher for SFCA. The compositions of SFCA are on the line satisfying M14O20, while those of SFCA-I and SFCA-II deviate from the lines satisfying M20O28 and M17O24, respectively, and are closer to the line satisfying M14O20. Since the compositions were derived based on the assumption that all Fe irons are Fe3+, the apparent compositions of SFCA-I and SFCA-II deviate from M20O28 and M17O24, respectively, owing to the presence of trace amounts of Fe2+.

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Reduction and Carburization Behaviors of Iron Oxide Composite with Iron Carbide and Free Carbon

Ryota Higashi, Daisuke Maruoka, Yuji Iwami, Taichi Murakami

pp. 2107-2114

抄録

The blast furnace ironmaking process relies heavily on fossil fuels, posing challenges to achieving carbon neutrality. New methods, like hydrogen reduction ironmaking, face limitations such as the need for high-grade iron ore and issues with DRI melting. To address these, biomass char has been explored as a carbon-neutral carburizing agent, yet practical application is difficult due to biomass supply limitations in East Asia. Thus, Carbon Capture and Utilization, CCU becomes essential. Examples include iACRES and carbon recycling blast furnaces, which recycle CO2 for reducing agents but have limited scope.

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Reduction and Melting Behaviors of Iron Oxide Composite with Carbon Deposited Using CO–CO2–H2 Mixed Gas

Ryota Higashi, Daisuke Maruoka, Yuji Iwami, Taichi Murakami

pp. 2115-2122

抄録

The ironmaking industry consumes significant fossil fuel-derived carbon as a heat source, reducing agent for iron ores, and carburizing agent for reduced iron. Despite the demand for reduction of carbon dioxide emission, carbon is essential for smelting molten iron. A carbon recycling ironmaking process using circulating CO has been proposed to achieve carbon neutrality. However, this process does not consider molten hot metal production because CO does not dissolve sufficient carbon in iron to be melt. Our group has suggested a new carbon recycling ironmaking process capable of producing hot metal. This process utilizes free carbon and iron carbides produced via carbon deposition reactions using metallic iron as a catalyst. CO gas produces only Fe3C, whereas adding H2 gas also produces Fe5C2. The composite, agglomerated with these carbonaceous materials and fine iron ore (Deposited Carbon-Iron Oxide Composite: DCIC), is reduced and melted in a furnace. This study focuses on the effects of iron carbides and free carbon on the melting behavior of DCIC.

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Refining of High-Carbon Steel and Reduction of CO2 Emissions by Using Lignite Upgraded Coal Briquettes

Hideichi Matsuoka, Yoshiyuki Matsui, Wataru Adachi, Yuri Shibuya, Koichiro Semura

pp. 2123-2133

抄録

This study investigated the use of sustainable coal (lignite) that can simultaneously satisfy three requirements: [1] Environmental issues (CO2), particularly Carbon dioxide Capture and Utilization (CCU) that reduces CO2; [2] Resource issues, particularly Enhancement of dephosphorization function in the refining process; and [3] Enhancement of refining high-carbon steel. This study confirmed that use in the steel making process of lignite upgraded coal briquettes gives possibility to functionally differentiate the reaction site of decarbonization and dephosphorization and to reduce CO2 emissions.

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Measurement of Bubble Size Distribution and Generation Position of Bubbles Generated during Smelting Reduction of Iron Oxide-containing Slag

Ko-ichiro Ohno, Taiga Eguchi, Tatsuya Kon

pp. 2134-2143

抄録

Slag foaming is a phenomenon caused by the generation of CO bubbles due to the reaction between iron oxide in slag and carbon in pig iron. The purpose of this study is to explore the controlling factors of slag foaming by observing the bubble formation behavior caused by the chemical reaction between iron oxide and Fe–C alloy in slag. 0.06 g of Fe–C alloy was charged to the bottom of the BN crucible, and 6.0 g of slag (SiO2:CaO:Fe2O3 = 40:40:30) was charged on top of it. The crucible was placed in an infrared image heating furnace, and the temperature was rapidly raised to 1370°C at a rate of 1000°C/min in a N2 stream, then held for a predetermined time and rapidly cooled. After rapidly cooling, the internal structure of the sample was observed using a high-resolution X-ray CT device. The spherical equivalent volume is calculated based on the number of bubbles observed and their equivalent circle diameter, and the relationship between the volume ratio of small bubbles in the slag volume and the distance from the bottom of the crucible is calculated, and the bubble density and volume ratio are calculated. It was suggested that the value tends to increase as the distance from the bottom of the crucible increases.

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Effect of Iron Oxide on Sulfide Capacities of CaO–SiO2–FeO and CaO–Al2O3–FeO Ternary Systems

Masakatsu Hasegawa, Keijiro Saito, Kosuke Awaya, Domu Mitsuyama

pp. 2144-2148

抄録

Towards steelmaking processes which are compatible with the sustainable society, re-sulfurization reaction in hot metal pre-treatments needs to be suppressed as much as possible. To evaluate the effects of iron oxide on the sulfur distribution ratio between FeO-containing slag and hot metal, sulfide capacities and FeO activities were measured in CaO–SiO2–FeO and CaO–Al2O3–FeO ternary liquid slags. Although the FeO activity and oxygen potential increased, the addition of FeO raised sulfide capacity drastically and resulted in an increase in the calculated value for distribution ratio of sulfur.

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Modification of the Activities of Components in Ca2SiO4–Ca3P2O8 Solid Solution at 1573 K

Keijiro Saito, Masakatsu Hasegawa

pp. 2149-2155

抄録

The activities of components in Ca2SiO4–Ca3P2O8 solid solutions have been reported by preceding studies as the basic thermodynamic data for phosphorus removal in the steelmaking process. Since the reported activities contained the uncertainties accumulated from thermodynamic data, this study aimed to reevaluate the experimental results in the preceding studies. Firstly, the equilibrium constant of the following reaction used to calculate the P2O5 activities was measured at 1573 K through a gas equilibrium method.

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Structure Design and Phase Stability Analysis of Ca2SiO4-Based Solid-Solution Crystal in Molten Slag

Masanori Suzuki

pp. 2156-2166

抄録

It is known that dephosphorization of molten iron is promoted by Ca2SiO4 precipitates in molten slag because they form a solid solution with Ca3P2O8. Crystal structure of the Ca2SiO4 precipitate is important because it strongly affects phosphorus solubility. Although the α phase of the solid solution shows extremely high phosphorus solubility at high temperatures, its phase transition easily occurs to the α’ phase that has low phosphorus solubility when iron oxide is incorporated in slag. Phase stability of Ca2SiO4 crystal strongly depends on the solubility of foreign components, which influence the ionic configuration. To explore the optimum composition for enhancing structural stability of the α phase, this study conducted a structure design of Ca2SiO4-based solid-solution crystal by first-principles calculation based on density functional theory. The effect of foreign component solubility on the α phase stability was evaluated by free energy change of solid-solution formation. It was found that Ca2+ substitution with Fe2+ in α-Ca2SiO4 crystal makes the structure unstable, whereas Ba2+ incorporation enhances stability. In the latter case, oxygen ion configuration becomes distorted and the structure is relaxed. High-temperature in-situ X-ray diffraction analysis was performed to observe precipitation of the Ca2SiO4-based solid solution in a molten slag and its phase transition with decreasing temperature. The α phase of the Ca2SiO4-based solid solution initially precipitated at 2073 K, while the αα’ phase transition and precipitation of the calcium ferrite phase occurred at temperatures lower than 1673 K. It was verified that the Ba-bearing Ca2SiO4 precipitates in slag contained significant phosphorus content.

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Viscosity Measurement of CaO–SiO2–FexO Foaming Slag at 1673 K

Yoshiyuki Egashira, Noritaka Saito, Kunihiko Nakashima

pp. 2167-2175

抄録

Foaming slag generated in the steelmaking process, especially in hot-metal pretreatment and electric arc furnaces, is a gas-liquid coexistent fluid with CO gas generated by the interfacial reaction between slag containing iron oxide and hot metal or carbonaceous materials. In addition, it is essential to understand the flow behavior of foaming slag during slag-tapping and the sedimentation behavior of iron particles, which affects iron yield, and to expand our knowledge of the viscosity of gas-liquid coexisting fluids for CFD modeling of these phenomena. In the present study, the apparent viscosity of a foaming slag was systematically investigated, which was generated by reacting CaO–SiO2–FexO slag with Fe–C alloy and varying the composition, gas phase ratio, and shear rate of the slag. By adding Fe–C alloy powder to the slag, bubbles were continuously generated in the molten slag, and foaming slag suitable for viscosity measurement could be prepared. It was found that the higher the amount of Fe–C alloy powder, the larger the gas phase ratio of the foaming slag due to an increase in the number of bubbles generated. The relative viscosity of the foaming slag was found to increase with the gas phase ratio. The higher the rotation speed, the smaller the relative viscosity of the foaming slag indicating shear-thinning characteristics. The relationship between shear rate and shear stress calculated from the viscosity of the foaming slag did not show general non-Newtonian fluid behavior.

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Apparent Viscosity Measurement of Gas–liquid Multiphase Fluids by the Falling Ball Method

Yusaku Mita, Takayuki Iwama, Huafang Yu, Shin’ichi Shimasaki, Noritaka Saito, Ryo Inoue, Shigeru Ueda

pp. 2176-2185

抄録

The recovery rate of iron is reduced if iron particles suspended in the refining slag do not sediment. The sedimentation rate of particle iron in the foaming slag is slower than in the slag in the single-phase liquid. Iron particles are especially likely to remain in the foaming slag. To predict the sedimentation rate of iron particles in the slag, it is necessary to derive an accurate viscosity of the foaming slag. However, it is difficult to estimate an appropriate value because the state of gas-liquid multiphase fluid changes the condition with time. Its apparent viscosity varies depending on the measurement method because it is a non-Newtonian fluid. In this study, to understand the sedimentation behavior of iron particles in foaming slag, a gas-liquid multiphase fluid was generated by glycerin solution. Its apparent viscosity was estimated by the Stokes equation using the falling-ball method. The sedimentation rate of stainless steel, titanium, and glass balls with a diameter of 2 mm were measured in a glycerin aqueous solution gas-liquid fluid. The sedimentation rate was non-uniform because the gas-liquid fluid’s state differed depending on the position. The apparent viscosity of the fluid increased with an increase in the gas phase ratio. The variation of apparent viscosity with the conditions of the falling-ball method was also discussed. Furthermore, a comparison was made between the present results and the apparent viscosity measured by the rotational technique.

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Terminal Settling Velocity of Particle in Suspension

Shin’ichi Shimasaki, Shigeru Ueda, Noritaka Saito

pp. 2186-2194

抄録

In the steelmaking process, most slags and fluxes often contain a solid phase, such as CaO. The suspension in which solid phases are suspended has higher viscosity than that of a pure matrix liquid. Therefore, it is expected that the viscosity of slag containing solid phases will increase. In this study, the terminal settling velocity of particles in a suspension has been measured. The suspensions consist of a silicone oil matrix and polyethylene beads, and the settling particles are bearing balls made of stainless steel. As a result of the higher viscosity of suspension, the terminal settling velocity of the bearing ball becomes slower than that in the pure silicone oil. It was clarified that the retardation of the terminal velocity and the increase in the drag coefficient depend only on the volume fraction of the solid phase (polyethylene beads) of the suspension, and they are independent of the size of the suspended beads and the viscosity of the matrix liquid. A correlation equation for predicting the drag coefficient of particles in a suspension was proposed.

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Settling of Particle in Foaming Slag

Shin’ichi Shimasaki, Shigeru Ueda, Noritaka Saito, Kenji Katoh

pp. 2195-2202

抄録

During steel-manufacturing, molten slag is foamed through gas injection and gas generation reactions. However, molten iron droplets are trapped in the slag. The settling velocity of an iron droplet in the foaming slag is important because the residence time of an iron droplet in the slag is used to directly calculate the settling velocity. Previous studies have shown that the rate of settling velocity is lower than that observed in regular non-foaming slag. However, this has not been quantitatively determined. This study measured the settling velocities of particles through a foaming glycerin-water solution. A dimensionless correlation equation for particle settling velocity in the formed liquid was proposed by conducting a dimensional analysis of the experimental data. Using the obtained equation, the settling velocity of iron particles in the foaming slag was predicted. The settling velocity of iron particles was significantly affected by the volume fraction of the gas phase in the foaming slag. A threshold for the velocity was observed; the velocity of particles below this threshold was zero.

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Slag-steel Reactions in the Refining of Advanced High-Strength Steel

Panwen Su, Petrus Christiaan Pistorius, Bryan Arthur Webler

pp. 2203-2209

抄録

The high aluminum concentration in advanced high-strength steels lowers the oxygen activity at the steel-slag interface, compared with conventional low-carbon aluminum-killed steels. The lower oxygen activity affects the rate and equilibrium extent of steel-slag reactions. One result of the lower oxygen activity is a higher concentration of dissolved magnesium, leading to faster conversion of alumina inclusions to spinel inclusions, and spinel to periclase – as demonstrated in previous work. The current study concerns the dissolution of nitrogen in ladle slag as nitride ions. Laboratory results of the rate and extent of nitrogen removal are compared with model predictions, confirming that substantial nitrogen removal is possible. While aluminum nitride was found in some steel samples after solidification, aluminum nitride does not appear to play a role in nitrogen removal from liquid steel to liquid slag.

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Surface Tension Measurement of SiO2–Na2O–NaF System by Maximum Bubble Pressure Method

Osamu Takeda, Naoki Yamashita, Yuting Chen, Ryuki Higure, Xin Lu, Hongmin Zhu

pp. 2210-2216

抄録

The surface tension of the mold flux is important because it governs the interfacial phenomena between the mold and molten/solid steel. The maximum bubble pressure (MBP) method is often used to determine the surface tension of molten slags. However, for liquid samples with high viscosity, such as molten silicate, the MBP is overestimated. In this study, a simple relaxation function was applied to determine the MBP using the gas flow-rate as a parameter. Consequently, a static MBP was obtained, and the surface tension was reliably measured. The surface tension of the SiO2–Na2O–NaF melts were measured over a wide composition range using the developed method. When SiO2-40 mol% Na2O was added to NaF, the surface tension of the melts gradually increased with increase in SiO2–Na2O concentration. When the NaF in SiO2-40 mol% NaF was replaced by Na2O, the surface tension of the melts did not change significantly at the beginning of the addition. It was considered that F ion was exposed in the surface of melts instead of O2− ion. This result is consistent with the discussion of the relative strength of the bonding force between the constituent particles. The increase in the surface tension upon further replacement of NaF with Na2O was gradual, indicating that F was relatively exposed more than O2− on the surface of the investigated melts.

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Effect of Fluoride Ions in Slag on the Dynamic Change of the Interfacial Tension between Liquid Iron and Molten Slag

Masanori Suzuki, Kenta Iwakura, Yuichi Tsukaguchi, Kazuaki Mishima

pp. 2217-2225

抄録

The interfacial tension between the liquid steel and molten slag is one of the key properties to control the entrapment of mold flux in molten steel in the continuous casting process. A dynamic change of the interfacial tension is observed when deoxidized iron and silicate slag are in contact, which can be explained by the oxygen absorption and desorption at the iron/slag interface. However, the dynamic change of the interfacial tension is influenced by other surfactant components of the molten iron and slag. Fluoride ions are fundamental component of mold flux, and recognized as the surface active component of molten slag. The effect of fluoride ions in slag on the interfacial tension has not been critically evaluated. Here, the effect of fluoride ions in slag on the interfacial tension between molten iron and molten silicate slag was evaluated at 1823 K, where the fluoride-containing slag compositions were designed to exhibit the same SiO2 activity and slag viscosity as those of the fluoride-free slag. Compared with the case of molten iron and fluoride-free slag, the interfacial tension between the molten iron and fluoride-containing slag was initially lower. Except the effect of oxygen adsorption, fluoride ion was considered to directly decrease the interfacial tension. However, as the fluoride content in slag was higher, the interfacial tension tended to show the higher value at the final state. This behavior was attributed mainly to fluoride vaporization as SiF4, which reduce the SiO2 activity in slag and thus equivalent oxygen content at the iron/slag interface.

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Molecular Dynamics Simulation of Viscosity of the CaO, MgO and Al2O3 Melts

Alexander Moiseev, Alex Kondratiev

pp. 2226-2237

抄録

Viscosity of oxide melts is a fundamental physicochemical property that plays a critical role in important technological and natural processes like slag flow, slag/metal separation, volcano eruptions etc. Unfortunately, many oxides melt at extremely high temperatures and are highly corrosive in the liquid state, which makes experimental measurement of viscosity by conventional experimental techniques a difficult, expensive, and sometimes impossible task. In this case it might be helpful to use other methods to determine viscosity, such as modelling or simulation. In the present paper the shear viscosity coefficients of the liquid CaO, MgO, and Al2O3 have been simulated via the classical molecular dynamics and compared to the available viscosity data (e.g. experimental viscosities, other model predictions) collected and stored in a databank by one of the authors. Different viscosity calculation techniques (e.g. the Green-Kubo equation, the Einstein relation, and the non-equilibrium molecular dynamics methods) coupled with MD have been employed to ensure a more reliable viscosity calculation. It has been shown that the simulated viscosities of the CaO and MgO melts are close to those calculated by phenomenological viscosity models and represent a plausible estimation for viscosity of these unary systems. It has also been shown that the simulated viscosity of the Al2O3 melt is lower than the majority of the available experimental data. In general, it has been demonstrated that the molecular dynamics simulation could provide a reasonable estimation of viscosity, especially if no other viscosity data is available.

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Temperature Dependence and Prediction of Density of Alkali Silicate Slag Melts

Kenshi Fujino, Hiromichi Takebe

pp. 2238-2244

抄録

We measured the density of eight types of molten alkali silicate slag within the range of 1673–1823 K using the Archimedean double-bob method. The melt density of binary alkaline silicate glass linearly increased with a decrease in temperature. The temperature coefficient of the density ranged from −21.5 to −13.2 × 10−5 g·cm−3·K−1, and its order corresponded to the order of the ionic radii of the alkali oxide components. We applied Doolittle’s free volume theory by combining the reported values of melt viscosity with the measured densities and volume expansion coefficients of melts and glass solids to propose an equation for predicting melt density from slag composition and temperature. Melt densities in the range of 1273–1823 K were predicted and compared with experimental values.

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Phonon Mean Free Path of Silicate Glasses: A Useful Parameter to Distinguish between Framework and Nonframework Cations

Sohei Sukenaga, Bunta Ozato, Yohei Onodera, Shinji Kohara, Masahiro Shimizu, Tsuyoshi Nishi, Rie Endo, Takaaki Tomai, Akira Yoko, Sakiko Kawanishi, Hiroshi Fukaya, Hiromichi Ohta, Hiroyuki Shibata

pp. 2245-2252

抄録

Assuming that heat is transported by lattice vibrations (phonons) in silicate glasses, their thermal conductivity is correlated with the product of sound velocity, volumetric heat capacity, and phonon mean free path (MFP). The sound velocity and heat capacity have been studied extensively, but the origin of the composition-induced variation in the MFP remains unclear. The present study investigated MFP in M2/nO–SiO2 (Mn+: Li+, Na+, Ca2+, Sr2+, or Pb2+) glasses with a variation of M2/nO content. The MFP of the silica glass decreased with the addition of M2/nO. The effect of the type of metallic cation on the MFP was minimal for the selected alkali and alkaline-earth silicate glasses. By contrast, the MFP of lead silicate glasses was higher than those of alkali or alkaline-earth silicate glasses when the metallic cation contents were comparable. Previous studies have demonstrated that alkali and alkaline-earth cations act as nonframework species that break the silicate network structure, whereas lead cations have inconclusive structural roles. Our data indicate that lead cations partly act as framework cations and that phonons tend to be scattered near nonframework cations in silicate glasses. Thus, the phonon MFP is a useful parameter for determining the structural role of metallic cations in silicate glass via phonon propagation.

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Thermophysical Properties of Molten Fe–Cu Alloy Measured Using the Electrostatic Levitation Furnace Aboard the International Space Station (ISS-ELF) under Microgravity Conditions

Yusaku Seimiya, Hidekazu Kobatake, Kazuki Tono-oka, Riku Sugahara, Shuya Kurosawa, Suguru Shiratori, Ken-ichi Sugioka, Takehiko Ishikawa, Chihiro Koyama, Yuki Watanabe, Rina Shimonishi, Shumpei Ozawa

pp. 2253-2261

抄録

The thermophysical properties of molten Fe–Cu alloys, including density, surface tension, and viscosity, were measured using the electrostatic levitation furnace aboard the International Space Station (ISS-ELF) under microgravity conditions, which provided an environment that facilitated accurate measurements. The densities of the molten Fe–25at%Cu and Fe–50at%Cu alloys decreased linearly with increasing temperature, and higher copper compositions resulted in increased density. The surface tension of the molten alloys exhibited a unique up-convex temperature dependence curve that initially increased and then decreased as the temperature increased. Viscosity measurements indicated that the viscosity of the molten Fe–Cu alloys decreased with increasing temperature, following a quadratic curve, and that an increase in the copper composition resulted in lower viscosity.

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