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- Vol. 78 (1992), No. 1
Tetsu-to-Hagané Vol. 78 (1992), No. 1
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ONLINE ISSN: | 1883-2954 |
PRINT ISSN: | 0021-1575 |
Publisher: | The Iron and Steel Institute of Japan |
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Tetsu-to-Hagané Vol. 78 (1992), No. 1
How to Obtain the Next Generation of Ultra Heat Resistant Intermetallic Compounds
Pedro B. CELIS, Kozo ISHIZAKI
pp. 26-34
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Measurement of Surface Area for Dense Iron and Nickel Catalysts by Electrolytic Solution Method
Fengman SHEN, Toshio SATO, Reijiro TAKAHASHI, Jun-ichiro YAGI
pp. 42-49
Abstract
As for the estimation of the rates of gas-solid reaction and gas-gas reaction with solid catalysts, an accurate measurement is very important for determining the surface area of solids. Therefore, the measuring method of metal surface area should be standardized for the comparison of actual reaction rate. However, the surface area cannot be easily evaluated from geometric shape even in the case of dense metal, because the true surface area depends on the surface roughness. In this paper, the measuring method of dense metal surface area by electrolytic solution was developed for the dense metal of irregular shape and/or non-smooth surface.
According to the TAFEL's equation, a linear relationship exists between the current, Itotal, in circuit and the solid surface area, S, of the cathode under the given conditions. This principle was adopted as the measuring method. Optical glass was selected as the standard reference material for determining the surface area. By this method, the linear relationships were measured between Itotal and S for nickel and iron.
When the surface roughness and geometric surface area assuming that the surface is smooth were known, the surface area of catalytic metals could estimate by using the present results, and then, the surface area could be directly measured by this method even the surface roughness and/or geometric surface area were not known.
Combustion Behavior of Pulverized Coal in a Raceway Cavity of Blast Furnace and a Large Amount Injection Technology
Yotaro OHNO, Takeshi FURUKAWA, Masahiro MATSUURA
pp. 50-57
Abstract
For a large amount of pulverized coal injection into a blast furnace, the combustion of pulverized coal in a raceway cavity has been studied theoretically and experimentally.
The theoretical formula, which can estimate the combustion efficiency of pulverized coal in a raceway cavity, were derived. The effects of the injecting and operating conditions on the limit of pulverized coal combustion in a raceway cavity were evaluated.
The effect of the mixing of pulverized coal with oxygen on the combustion rate of pulverized coal was studied in a combustion test using both empty and coke packed furnace. From the results, the validity of the derived theoretical equation was verified, and it was also confirmed that the making sure of a raceway depth and the adoption of a injection technique which promotes the mixing of pulverized coal with oxygen are important to promote the combustion of pulverized coal.
Based on these discussions, the upper limit of pulverized coal injection rate in the hot blast furnace operation was estimated. To inject a large amount of pulverized coal more than the actually accomplished amount, it is necessary to increase the oxygen concentration in blast and to adopt a injection technique which promotes the mixing of pulverized coal with oxygen.
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Influence of Upper Shaft Profile and Burden Properties on Formation of Mixed Zone Near Wall and Gas Flow
Morimasa ICHIDA, Kenji TAMURA, Yoshio OKUNO, Kazushige YAMAGUCHI, Masaaki NAKAYAMA, Makoto NAKAMURA
pp. 58-65
Abstract
The influence of upper shaft profile and burden properties on gas velocity distribution and formation of mixed zone near wall was analyzed by using both a sector and a half section three-dimensional cold models of blast furnace. In the case of upper shaft profile with damage, the mixed zone near wall is formed, the gas velocity near wall increases 1.52.5 times and the high gas velocity region expands 1.52.0 times as compared with these in the case of normal upper shaft profile. This phenomenon is developed as the small ore ratio in the burden increases. The mixed zone near wall in upper shaft is formed by delaying of coke descent and percolation of small ore due to the drastic change of cross section area or the increase of friction angle between wall and burden. At Kimitsu No. 2 BF, the deviation of CO gas utilization ηco near wall decreased and the average of CO gas utilization ηco increased after the repair of upper shaft profile.
Effective Kinematic Viscosity and Effective Diffusivity of Bubbles in Air-Water Bubbling Jet
Manabu IGUCHI, Zen-ichiro MORITA
pp. 66-73
Abstract
The effective viscosity νe and effective diffusivity De of bubbles in vertical bubbling jet in a cylindrical vessel were determined from governing equations based on the boundary layer approximation and the Boussinesq approximation. These conditions were satisfied in the buoyancy region in vertical bubbling jet. Gas holdup and mean bubble rise velocity needed in calculation of νe and De were measured with a two element electro-resistivity probe, and the mean velocity of water with laser Doppler velocimeter. The values of νe and De were almost the same on the jet axis in the buoyancy region and increased with an increase in injected gas flow rate. The radial profile of νe was parabolic and that of De was almost uniform across the bubbling jet. The profile of νe was different from the profile of νe in single-phase turbulent free jet.
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Development of On-line Analysis of Manganese in Molten Steel by EMF (Electromotive Force) Method
Kimitoshi YONEZAWA, Toshiya HARADA, Satoshi TABUCHI, Hisashi TAKAMOTO, Toshihiro OGURA, Ryuji FUJIWARA
pp. 74-81
Abstract
Many of experimental works for developing a suitable probe or sensor have widely been made with different methods in great demand for a rapid analysis of specific elements in molten steel.
The author had ever developed Si sensor of which measuring principle was based on the EMF method, and obtained the possible application of same principle to the rapid analysis of manganese in molten steel with foundational experiments.
After the affirmative conclusion on the examination, a new manganese sensor was built into a commercial sublance probe and evaluation tests were made to determine the end point value of manganese in the molten steel of the converter.
It is believed with the test results that this newly developed probes are well applicable to on-line analysis of manganese during the less-slag refining process of the converter.
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Decarburization Reaction of Molten Iron of Low Carbon Concentration with Solid Oxides
HAN Yetao, Tadashi SAWADA, Masakazu KATO, Masamichi SANO
pp. 82-89
Abstract
A kinetic study has been made on decarburization of molten iron of low carbon and oxygen concentrations with solid oxides. Electrolytic iron was melted in a MgO, Al2O3 or CaO crucible. The mass of iron and the initial carbon concentration were varied between 137 and 627 g and between 30 and 480 ppm. The initial oxygen concentration was below 50 ppm, and oxygen for the decarburization was supplied by the crucible oxide. Experiments were made with blowing argon gas (1000 Ncm3/min) onto the melt surface at 1580°C.
The rate of decarburization decreases in the order of MgO, Al2O3 and CaO and is almost independent of the stirring condition of the bath. For carbon concentration >100 ppm, the rate of decarburization does not change with the initial carbon concentration. From these results, it is considered that the rate is controlled by the dissociation reaction of oxide. For carbon concentration <100 ppm, the rate decreases with decreasing carbon concentration. In this case, the rate is presumed to be controlled by the dissociation reaction of oxide, formation reaction of CO at crucible-melt interface and CO mass transfer. A mathematical model is proposed to explain the rate of decarburization.
Decarburization Reaction of Molten Iron of Low Carbon Concentration with Vacuum Suction Degassing Method
HAN Yetao, Masakazu KATO, Shigeru SAKAMOTO, Masamichi SANO
pp. 90-96
Abstract
A kinetic study has been made on decarburization reaction of molten iron of low carbon and oxygen concentrations with solid oxides. A new degassing method, namely Vacuum Suction Degassing (VSD) method, was applied to decarburize molten iron to an ultra-low carbon concentration. A porous oxide tube, the inside of which was evacuated, was immersed into molten iron. The initial carbon concentration was varied between 110 and 30 ppm. The initial oxygen concentration was below 50 ppm. The experiments were performed under Ar atmosphere (1.01×105 Pa). The experimental temperature was 1853 K.
The VSD method can greatly increase the rate of decarburization of molten iron and the carbon concentration decreases to a very low value of a few ppm. The rate of decarburization with an Al2O3-SiO2 tube is higher than that with an Al2O3 tube. Increase in gas permeability of a porous tube enhances the decarburization reaction. The apparent rate constant of decarburization with evacuation in the porous tube is about 10 times larger than that without evacuation.
Kinetics of Nitrogen Desorption from Liquid Fe-Cr Alloys under Reduced Pressure
Akihito KIYOSE, Kazuumi HARASHIMA, Kazuo ONUKI, Ryoji ARIMA
pp. 97-104
Abstract
The kinetics of nitrogen desorption from liquid Fe-Cr alloys under reduced pressure have been studied at 1600°C.
The nitrogen desorption rate was described by the 2nd order reaction with respect to nitrogen content under these conditions.
The overall nitrogen desorption rate constant, kov decreased with the increase in sulfur and chromium contents.
Assuming the mixed control model, the apparent interfacial reaction rate constant, k[N], is proportional to ƒN1.2ƒN3.2.
The rate of nitrogen desorption seemed to be controlled by the interfacial chemical reaction under the present conditions.
Control of Uneven Solidified Shell Formation of Hypo-peritectic Carbon Steels in Continuous Casting Mold
Hiroshi MURAKAMI, Mikio SUZUKI, Toru KITAGAWA, Shinobu MIYAHARA
pp. 105-112
Abstract
Surface cracks tend to occur in continuously cast slab of hypoperitectic carbon steels. The surface cracks are originated by an uneven solidified shell formation in the continuous casting mold. Mechanism of uneven solidified shell formation at the initial stage of solidification was investigated by dipping of water cooled chill plates in the molten steel. The dip test showed that, (1) the shell of hypo-peritectic carbon steel has a hexagonal depression pattern and these depressions form air gap between the shell and the chill plate and results in the uneven solidified shell formation, (2) the chill plate with a fixed interval lattice grooves was most effective to prevent the uneven solidified shell formation. Nextly, the casting tests using a small-scale continuous caster were performed to investigate the measures for prevention of the uneven solidified shell formation. The mold with a controlled uneven heat extraction method was essential to form the even solidified shell at the initial stage of solidification.
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Effect of Mold Oscillation Curves on Heat Transfer and Lubrication Behaviour in Mold at High Speed Continuous Casting of Steel Slabs
Mikio SUZUKI, Shinobu MIYAHARA, Toru KITAGAWA, Shigetaka UCHIDA, Takashi MORI, Kazutaka OKIMOTO
pp. 113-120
Abstract
High-speed continuous casting is prerequisite to realize the hot direct rolling. It is necessary to understand the phenomena of solidification and lubrication in the mold for the prevention of the troubles on the operation of high-speed casting.
In this work, the effects of mold oscillation curves on the heat transfer rate and lubrication behaviour in the mold are investigated by means of the measurement of temperature in the copper plate of mold, and hydraulic pressure of the cylinder for oscillating the mold, and the behaviour of lubrication in the mold at high-speed casting are discussed. The results obtained are as follows:
(1) The heat transfer rate near the meniscus for the non-sinusoidal oscillation curve is reduced approximately 10% in comparion with that for the conventional sinusoidal oscillation curve.
(2) The frictional force in the mold is proportional to the relative velocity of mold to casting speed, and the non-sinusoidal oscillation curve can reduce the frictional force drastically.
(3) The lubrication mechanism in mold at high-speed casting can be assumed to be liquid lubrication for the reason that the measured frictional force has a good agreement with the values calculated from the liquid lubrication model.
(4) The upper limit of casting speed in the continuous casting process with oscillating mold can be predicted to be 5 to 8 m/min on the basis of the comparison of the frictional force and the tensile strength of solidified shell beneath the meniscus.
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Characteristics of Electrolytic Chromate Films Formed on Zinc or Zinc Alloy Plated Steel Sheet in Low Concentration CrO3-Heavy Metal Ions-Halogen Bath
Hisao ODASHIMA
pp. 121-126
Abstract
Chromate technique in CrO3-halogen bath has been investigated on zinc and zinc alloy plated steel sheet. The colorless chromate film is formed stably by electrolysis in the bath that CrO3, Cl- and Co2+ content are controlled. Deposition efficiency of chromate film in CrO3-Co2+-Cl- bath is six times as much as in CrO3-SO42- bath. The amount of chromate film increases almost linearly in response to quantity of electricity on Zn or Zn-Ni plated steel sheet, and thus can be controlled by quantity of electricity. The chromate film formed on zinc plated steel sheet in CrO3-Co2+-Cl- bath dissolves in 5%NaOH aqueous solution a little more easily than that formed in CrO3-SO42- bath, and the film formed on Zn-Ni plated steel sheet in CrO3-Co2+-Cl- bath dissolves more easily in 5%NaOH. However, chromate materials formed in CrO3-Co2+-Cl- bath show very excellent corrosion resistance and fairly low extension velocity of rust. Furthermore, adhesion property of painted film on the chromate materials is excellent. Meanwhile, improvement effect on corrosion resistance of Ni plated EG by chromate film is more excellent than that of EG, and that of Zn-Ni plated steel sheet is the most excellent among them.
Effect of Coating Weight and Corrosive Environment on Under-film Corrosion of Zn and Zn-Fe Alloy Coated Steel Sheets
Kimitaka HAYASHI, Yoichi ITO, Yasuhiko MIYOSHI
pp. 127-133
Abstract
Thus far the formulae shown the physical shape of coating corrosion circuit are reported. These are required to describe (1) the effective length (lc) of steel substrate contributing the formation of corrosion circuit between coating and steel substrate and (2) the distribution ratio (α) of corrosion current by way of circuit on coating to total coating corrosion current.
In this study, the effect of coating weight and corrosive environment on under-film corrosion of Zn, Zn-Fe alloy coated steel sheets is investigated quantitatively to use these formulae.
In Zn coated steel sheet, lc was independent on coating weight and constant, and a increased with an increase of coating weight on under-film corrosion in exposure environment. In Zn-Fe (15%) alloy coated steel sheet, lc was decreased and α increased with an increase of coating weight.
On the contrary, the coating corrosion rate and lc increased and α decreased with an increase of wet time in corrosive environment.
Low-cycle Fatigue Properties of TiAl Intermetallic Compounds
Koji YAMAGUCHI, Masuo SHIMODAIRA, Satoshi NISHIJIMA
pp. 134-140
Abstract
Axial strain-controlled fatigue tests were carried out for an annealled Ti-34.7Al-1.74 V (wt%) intermetallic compound at RT and 800°C. It showed cyclic strain hardening behaviors at both temperatures. The fatigue strength at 800°C was higher than that at RT.
The fracture surface tested at RT was a mixture of three modes: (1) crystallographic fracture with linear steps, (2) intergranular fracture with smooth facets of grain boundaries and (3) transgranular cleavage fracture with river patterns. The fatigue cracks were found to be initiated by several mechanisms including slip-off steps or cracking under stress concentrations due to coarse slip or double slip lines.
The fracture mode at 800°C also consisted of the same three types, but the initiation was found to be controlled by grain boundary cracking, with striped patterns on the facets, under stress concentrations due to large twin-deformations across a grain.
Effect of Prior Deformation on Diffusional Reversion of Deformation Induced Martensite in Metastable Austenitic Stainless Steel
Kouki TOMIMURA, Seishin UEDA, Setsuo TAKAKI, Youichi TOKUNAGA
pp. 141-148
Abstract
Effect of prior deformation on the microstructure of diffusionally reversed austenite from lath martensite and the mechanical properties of the reversed austenite have been investigated in a metastable austenitic 18.08 mass% Cr-8.65% Ni steel by means of transmission electron microscopy and tensile test. The steel used transforms to almost full lath martensitic structure through 50% cold rolling. Further cold rolling changes the martensite microstructure from lath to cell.
The reversion occurs with two different processes, depending on prior microstructure. The austenite reversed from martensite lath structure are nucleated at the lath boundaries and grow along them. The morphology is platelike and looks like martensite lath structure. They gather to form austenite block, which is composed of austenite lath with the same crystallographic nature. On the other hand, the austenite reversed from martensite containing cell structure are fine equiaxed in shape and random in orientation.
The 0.2% proof stress of reversed austenite is higher with increasing deformation rate. This increase can be explainable in terms of a refinement of effective grain size. The effective grain size of austenite reversed from martensite lath structure corresponds to austenite block one. The effective grain size of equiaxed austenite is smaller than that of austenite block.
Changes of X-ray Photoelectron Spectra for Oxides by Ion Sputtering
Satoshi HASHIMOTO, Kichinosuke HIROKAWA, Yasuo FUKUDA, Ken-ichi SUZUKI, Toshiko SUZUKI, Noriaki USUKI, Norio GENNAI, Shizuo YOSHIDA, Mitsuru KODA, Hiroshi SEZAKI, Hiroshi HORIE, Akihiro TANAKA, Takashi OHTSUBO
pp. 149-156
Abstract
Round-robin experiments have been performed in order to establish the correction of binding energy shift of XPS spectra in oxides by the chargeup which results from the radiation of X-rays or ion sputtering and to determine the criteria for the change of chemical state by Ar ion sputtering. Samples of Al2O3, SiO2, MgO, TiO2 and NiO, in plate and powder form, were used for the experiments. We determined that the difference in energy between the Al 2p (Si 2p or Mg 1s) line and the O 1s line gives a better correction of the measurements of the binding energy shift of Al2O3 (SiO2 or MgO) than that between the Al 2p (Si 2p or Mg 1s) line and the C is line. After Ar ion sputtering, TiO2 and NiO are reduced and damage is induced in the case of Al2O3 and SiO2, while MgO remains stable, as examined using the binding energy and FWHM of XPS spectra. We revealed that the changes caused by ion sputtering of oxides depend on the change of free formation enthalpy and the ionicity. We also showed that both plate and powder samples are useful as standards for determining the binding energy from XPS spectra.
Quantitative Analysis of Oxide Samples by Means of X-ray Photoelectron Spectroscopy
Noriaki USUKI, Kichinosuke HIROKAWA, Yasuo FUKUDA, Ken-ichi SUZUKI, Satoshi HASHIMOTO, Toshiko SUZUKI, Norio GENNAI, Shizuo YOSHIDA, Mitsuru KODA, Hiroshi SEZAKI, Hiroshi HORIE, Akihiro TANAKA, Takashi OHTSUBO
pp. 157-164
Abstract
We report results of a joint research about the quantitative analysis of SiO2, Al2O3, MgO and forsterite plates by X-ray photoelectron spectroscopy (XPS). At first, we obtained the relative sensitivity factors (RSFs) using the standard oxides in order to clarify the difference in instrumental responses among instruments and analytical conditions. Then, we carried out the quantitative analysis of a forsterite sample using the above-mentioned RSFs to determine the deviation in quantitative values among laboratories.
The RSFs obtained with the standard oxides depend on analyser mode ( ΔE=const. or ΔE/E=const.). In the case of measuring with the same analyser mode, the deviation in RSFs among instruments was within ±20% on the high kinetic energy side but this became large on the low kinetic energy side. On the other hand, the theoretical RSFs which were calculated using instrumental functions, inelastic mean free paths and photo-ionisation cross sections were 1.3 times as large as the experimental RSFs.
The quantitative analysis of a forsterite plate showed that the deviation in quantitative values among laboratories was within ±10%. However, the quantitative value of magnesium measured with XPS was lower than the chemical composition.
These results demonstrate that the quantification using the experimental RSFs leads to the small deviation in quantitative values among laboratories, but the these quantitative values include the difference from chemical composition.
Correction of the Instrumental Factor in Quantitative Analysis of Auger Electron Spectroscopy
Norio GENNAI, Kichinosuke HIROKAWA, Yasuo FUKUDA, Ken-ichi SUZUKI, Satoshi HASHIMOTO, Toshiko SUZUKI, Noriaki USUKI, Shizuo YOSHIDA, Mitsuru KODA, Hiroshi SEZAKI, Hiroshi HORIE, Akihiro TANAKA, Takashi OHTSUBO
pp. 165-172
Abstract
This report is the result of a joint experiment on the quantitative analysis in Auger electron spectroscopy. The Auger intensity ratios of a high energy to a low energy for Al, Ni and Au varied by a factor of 2-3 among instruments, and as these ratios did not show a linear behavior with electron energy it was difficult to provide a universal expression for this behavior. Also, the variation of these ratios by the movement of an electron beam or the misplacement of a sample was not large enough to prove the spread among instruments. On the other hand, the voltage supply to a sample had a large influence on the low energy Auger intensity, and it was possible to reduce the spread of the data among instruments by selecting suitable voltages. But we could not obtain good results in the application of this method to the Fe-B-P alloy measurements.
Next, we discussed the method for correcting Auger peak intensity by utilizing the background intensity obtained from N(E) spectrum, and it was clarified that this method was effective for reducing the spread of the data among instruments and measuring conditions. We could obtain good results in the Fe-B-P alloy measurements by this method.
Determination of Al in Sample of Zn Hot Dip Galvanizing Bath by X-ray Fluorescence Spectrometry
Yoshiro MATSUMOTO
pp. 173-177
Abstract
In the production of Zn hot dip galvanized steel sheets, the concentration of Al in the galvanizing bath must be maintained within a limited range to ensure optimum performance. For this purpose, an accurate determination of Al by X-ray fluorescence spectrometry was studied.
The results were as follows:
(1)The AlKα line intensity increased with the lapse of time after sample preparation because of the enrichment of Al in the near surface of the samples.
(2)An accurate analysis was performed by peparing a sample with an SiC abrasive paper of coarse grit size 40 and starting the X-ray intensity measurement at a short time elapsed of 3 min after sample preparation.
A Quantitative Analysis of Solution Nitrogen in Cr-Ni-Mo Austenitic Steels by Electron Probe Microanalysis
Nagato ONO, Itaru TAJIMA, Shigeru SAWADA, Masanori KAJIHARA, Makoto KIKUCHI
pp. 178-185
Abstract
Five 2025Cr-Ni-Mo austenitic steels were prepared with a nickel concentration range between 5 and 28 mass% and a molybdenum concentration range between zero and 4 mass%. Five series of Cr-Ni-Mo austenitic steels with different nitrogen concentrations ranging from 0.01 to 0.76 mass% were prepared by nitrogenizing under different nitrogen gas pressures at 1 523 K without changing the matrix composition. They were used to make calibration curves between the nitrogen concentrations and NKα intensities. A coated multi-layer X-ray dispersion element, specifically designed for measuring NKα intensities, was used as an analyzing crystal. Correlation between the nitrogen concentrations and the NKα intensities was represented by a straight line. Gradients and background intensities for five calibration curves are all the same within the present experimental accuracy. Nitrogen partitioning between ferrite and austenite in duplex stainless steels was determined by utilizing the calibration curves for five Cr-Ni-Mo austenitic steels. Nitrogen in solution both in ferrite and austenite was analyzed with an accuracy of ±0.02 mass%.
A Quantitative Analysis of Nitrogen in Chromium Nitrides by Electron Probe Microanalysis
Nagato ONO, Shigeru SAWADA, Masanori KAJIHARA, Makoto KIKUCHI
pp. 186-193
Abstract
Homogeneous single phase di-chromium nitrides, ε-Cr2N1-x, with nitrogen concentrations from 9.8 to 11.4 mass% were produced by nitriding pure chromium under different nitrogen gas pressures at temperatures between 1373 K and 1 523 K. A correlation between the nitrogen concentrations and NKα intensities was represented as a straight line. This can be used as a calibration curve. A coated multi-layer X-ray dispersion element, specifically designed for NKα, was used as an analyzing crystal. A nitrogen concentration of ε phase which appeared as a second phase in a Cr-40Ni-5N alloy equilibrated at 1 523 K, was determined by utilizing the calibration curve.
A ZAF correction method developed for light elements by RUSTE and GANTOIS was confirmed to be better suited for nitrogen. Nitrogen concentrations of π phase: a nitride with the metal-atom arrangement of β manganese, which appeared as one of two or three phases in both Cr-40Ni-5N and Cr-35Ni-5Fe-5N alloys equilibrated at 1273 K, were determined by selecting Cr2N0.91 as a standard specimen for nitrogen and applying the ZAF correction by RUSTE and GANTOIS. The nitrogen concentrations of the π phase determined by EPMA were confirmed by average nitrogen concentrations in the specimens determined by an inert gas fusion method.
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