Search Documents

By K. T. Aust

It is proposed that the intergranular corrosion of austenitic stainless steels is associated with the presence of continuous grain houndary paths of either second phase, or solute segregate resulting from solute-vacancy interactions. Experimental observations of structural changes and crrosion behavior of different types of austenitic stainless steel provide support for this poposal. On the basis of this model, it is shown that the intergranular -corrosion susceptibility of austenitic stainless steels in nitric-dic hromate solution may be substantially reduced either by suitable heat treatments or by impurity control. AUSTENITIC stainless steels, such as Type 304, generally have excellent corrosion resistant properties when properly solution heat-treated and used at temperatures where carbide precipitation is slow. However, several corrosion environments have been found which produce intergranular corrosion of solu-tion-treated stainless steels, that is, those steels with no detectable carbide precipitation.''2 Of the various corrosion environments, the most widely used test solution has been the boiling nitric-dichromate solution. In these acid solutions, stainless steels have been found to be susceptible to intergranular attack despite the addition of carbide-forming elements such as titanium or columbium, or despite lowering of the carbon content or use of high-temperature solution treatments. Studies of the electrochemical mechanism of corrosion attack have been made by several worke1s3'4 who found that oxidizing ions such as crt6 depolarize the cathodic reactions and consequently raise the open-circuit potential of stainless steel immersed in nitric acids. As a result of this, the anodic reaction is accelerated. The reason for the localization of anodic activity at the grain boundaries, and resulting intergranular corrosion, has not been conclusively determined. Several workers, e.g., Streicher,3 and Coriou et al.,4 have suggested that the strain energy associated with grain boundaries provides the driving force for the accelerated intergranular corrosion. This argument would predict that alloys of high purity would still be susceptible to intergranular attack. However, work by chaudron5 and by ArmijO,6 has shown that high-purity alloys are immune to attack, in disagreement with this argument. An alternative suggestion is that chemical concentration differences exist between grains and grain boundaries, that is, impurity segregation at boundaries, and that these chemical differences provide the driving force for localized attack. It is this impurity segregation which can lead to accelerated dissolution of grain boundaries when the alloy is exposed to a suitable corrodant. This mechanism would predict the immunity of high-purity alloys to inter-granular attack, which is in agreement with experi-mental observations. In the present paper, some recent studies on inter-granular corrosion of austenitic stainless steels which were conducted by coworkers and myself will be re-tibility A simple model will be described in which it is proposed that the intergranular corrosion of aus-tenitic stainless steel is associated with the presence of continuous grain boundary paths of either second phase or solute-segregated regions.* On the basis of this model, it is suggested that the intergranular corrosion rate can be markedly reduced by the formation of a discontinuous second phase at the grain boundaries if the discontinuous second phase incorporates the major part of the segregating solute, drained from the grain boundary region. Results are presented of corrosion tests and electron microscopic studies of different types of austenitic stainless steel after various heat treatments which provide experimental support for this model. Finally, a solute clustering mechanism, based on a solute-vacancy interaction, is shown to be consistent with the results obtained for inter-granular corrosion of solution-treated austenitic stainless steels. EXPERIMENTAL Corrosion tests using weight loss measurements were made on sheet specimens, which were lightly electropolished, washed, and immersed in boiling (115°C) 5 N HN03 containing 4 g crt+6 per liter added as potassium dichromate. Studies in which the inter-granular penetration depth was measured both by electrical resistance and metallographic methods have shown an empirical correlation between the rate of intergranular penetration and the weight loss per unit time for identically treated specimens of stainless steel." As a result, although all the corrosion data reported here are in terms of simple weight loss measurements, these data are considered to reflect primarily the rate of intergranular dissolution. Fig. 1 shows a typical result of intergranular attack of a solution-treated Type 304 stainless steel after 4 hr in a boiling nitric-dichromate solution. The wide grain boundary grooving at the surface, and the attack at incoherent twin boundaries, are evident; very little corrosion attack is seen at the coherent twin boundaries. INTERGRANULAR CORROSION MODEL

Jan 1, 1970

By Hollis L. Caswell

The present status of integrated circuits utilizing. superconductive switching. elements is reviewed with special attention given to fabrication techniques, methods for interconnecting completed circuits, and refrigeration requirements. Cryoelectronics has been largely an "inte- grated-circuit" technology since its conception because the switching speed of superconductive devices is attractive only when these devices are fabricated with thin-film techniques. It is true that cryotron circuits can be constructed from wires of appropriate materials (as indeed was done by Dudley Buck 1 in his early investigations) but these circuits will switch in times characteristic of milliseconds whereas similar circuits fabricated by thin-film methods have potential switching times of nanoseconds. Furthermore, cryo-electronic devices such as the cryotron lend themselves readily to fabrication by thin-film techniques since these components may be made from polycrys-talline thin films and are relatively insensitive to the presence of impurities (as measured by semiconductor standards). Therefore, during the past decade considerable effort has been devoted to developing techniques for batch fabricating circuit arrays containing superconductive switching elements. Technology had developed to the point several years ago that fabrication of cryoelectronic arrays containing up to one hundred devices was rather straightforward. However, larger arrays containing between lo4 and 106 components which are required for commercial development of cryoelectronics still pose very severe yield problems. Thus in a sense cryoelectronics found itself in 1962 at the point semiconductor technology finds itself today; namely, individual devices and small groups of integrated devices could be fabricated with acceptable yield and the outlook for building larger integrated-circuit arrays was bright. Unfortunately, problems associated largely with yield have made fabrication of these larger arrays difficult. Unlike semiconductor technology, cryoelectronics had to solve the problems of large-scale integration before it could become economically attractive. This has proven to be a sizable burden to bear. Since several reviews exist on superconductivity,2 superconductive devices,3 and cryoelectronic technology, no attempt will be made in this paper to summarize these areas. Instead a few specific topics will be dealt with in more detail. First, a brief description is given of selected superconducting switching and storage devices with special attention to several metallurgical techniques which improve the performance of these devices. Second, techniques used to fabricate cryoelectronic devices are described with emphasis on problems affecting yield. Third, techniques for interconnecting a number of cryoelectronic planes are described. And last, refrigeration of cryoelectronic components is discussed briefly since the low operating temperature of superconductive devices is an important consideration in this technology. SUPERCONDUCTING STORAGE AND SWITCHING DEVICES The basic superconductive switching device is the thin-film cryotron. The geometry of this device is attractively simple, since it involves only the intersection of two lines that are electrically insulated from each other. The switching element (gate) and control element (control) of a crossed-film cryotron are arranged as illustrated in Fig. 1. The material for the gate is selected to permit the gate to be switched from the superconducting to the normal (resistive) state by the application of a control current. Tin, which has a critical temperature (T,) of 3.7°K, is commonly used for the gate and the cryotron is operated at a temperature just below T, (for example, 3.5°K). The control material (normally lead, with T, = 7.2°K) is chosen so that the control is never driven normal during circuit operation. To improve cryotron operation, a ground plane, also of lead, is placed under all of the circuitry to act as a diamagnetic shield and improve the current-density uniformity across the width of various thin-film elements. Normally, line widths vary from 0.005 to ^ 0.020 in. and film thicknesses from 300 to 10,000A, although new fabrication techniques make narrower lines feasible. In fabricating cryotrons it is important that the edges of the gate elements be geometrically sharp to avoid undesirable switching characteristics associated with a thinner edge region, Fig. 2. One technique which has been used extensively to form patterns consists of placing a physical mask containing the film pattern between the evaporation source and the substrate and depositing through the mask. Film strips formed in this manner possess a penumbra at the film edges due to shadowing of the evapor-ant under the mask. Several techniques have been proposed for minimizing effects due to this penumbra. One of the more promising metallurgical techniques

Jan 1, 1967

By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim'cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors' knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad's analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier's conclusion.

Jan 1, 1964

By Rclssell Gibson, F. S. Turneaure

The tin deposit of Monserrat; Bolivia, consists of one major vein 1600 m in length. The ore is unusual because of the notable quantity of teallite, even though cassiterite is the principal tin mineral. The deposit, formed at shallow depth under a wide range in temperature, may be classed as xenothermal. Polished sections reveal a complex history of replacement, with low-temperature minerals deposited before high-temperature minerals.

Jan 1, 1950

By AIME AIME

AT the annual .meeting of the Minnesota Section in December, Dr. Leith characterized as a question still open the exact method of origin of Lake Superior iron ores and emphasized it as an important practical problem for the future. He welcomed the step taken last year by Dr. Gruner in presenting a new hypothesis, and asked Lake Superior geologists to meet the challenge of such multiple hypotheses by unbiased, study.

Jan 1, 1932

By AIME AIME

TECHNICAL achievement in mining will be rewarded at the forthcoming Annual Meeting of the Institute when the William Lawrence Saunders Gold Medal will be presented to Herman C. Bellinger. Mr, Bellinger was unanimously selected on the first ballot of the Medal Committee. Mr. Bellinger has had notable technical success as vice-president in charge of operations for the Chile Exploration Co., a position he has held since 1920.

Jan 1, 1941

By L. L. McDaniel

During the past few years a nuinber of improvements in smelting and power equipment have been made at the Douglas smelter of the Phelps Dodge Corporation at Douglas, Ariz. In the summer of 1935 work was started on the first unit of a new reverberatory waste-heat boiler plant which ultimately was to furnish steam for a modern high-pressure power pIant. A second reverberatory waste-heat boiler unit

Jan 1, 1944

Illinois Mining Institute, 224 South Michigan Ave , Chicago, Ill. B. E Schonthal, Secretary. In 1929, 1930 and 1931, the Institute published the Proceedings of its meetings The volumes of the Proceedings are a record of the papers and discussions presented at the two meetings each year and deal with coal mining in Illinois. The Proceedings will be sent to those particularly interested on receipt of sufficient postage to cover mailing

Jan 1, 1933

For the benefit of those of our members who are considerable holders of securities, but owing to their isolated situations are not in-close touch with the metropolitan market and current quotations, we are publishing two very interesting graphs, showing the course of the bond and stock markets in New York over a long period. These graphs are furnished through the courtesy of the financial department of the New York Tribune.

Jan 5, 1919

For the benefit of those of our members who are considerable holders of securities, but owing to their isolated situations are not in close touch with the metropolitan market and current quotations, we are publishing two very interesting graphs, showing the course of the bond and stock markets in New York over a long period. These graphs are furnished through the courtesy of the financial department of the New York Tribune.

Jan 7, 1919

By Pierre R. Hines

Diphenyl guanidine is used as an accelerator in vulcanizing rubber. Other rubber accelerators are also flotation collectors, e.g., dithiocarbamate, thiazole, and the xanthates. Urea and its derivatives are good flotation collectors,1 and guanidine is the nitrogen analog of urea. These two characteristics suggested testing diphenyl guanidine as a flotation collector. Diphenyl guanidine has been tried in flotation work previously, but references give no details.2-4

Jan 2, 1959

Successful preliminary experiments at the University of North Carolina indicate that computers can provide speedy, accurate identification of the mineral content of rock samples. In just two minutes, the University's Univac 1105 computer solves the complex equations that would often require more than four hours using conventional methods. In addition, the computer is frequently spotting minerals that a geologist might miss simply because he wasn't looking for them.

Jan 6, 1964

E. G. Spilsbury, Trenton, N. J.: Mr. Case's paper possesses much interest for me, because my attention was called many years ago (early in the seventies) to the deposit he describes, and his explorations seem to have confirmed the predictions I then made as to the form of the deposit, namely, that the ore would be found to occur, not, as was then imagined, in loose boulders, distribnted

Jan 1, 1894

For the benefit of those of our members who are considerable holders of securities, but owing to their isolated situations are not in close touch with the metropolitan market and current quotations, we are publishing two very interesting graphs, showing the course of the bond and stock markets in New York over a long period. These graphs are furnished through the courtesy of the financial department of the New York Tribune.

Jan 12, 1919

For the benefit of those of our members who are considerable holders of securities, but owing to their isolated situations are not in close touch with the metropolitan market and current quotations, we are publishing two very interesting graphs, showing the course of the bond and stock markets in New York over a long period. These graphs are furnished through the courtesy of the financial department of the New York Tribune.

Jan 6, 1919

For the benefit of those of our members who are considerable holders of securities, but owing to their isolated situations are not in close touch. with the, metropolitan market and current quotations, we are publishing two very interesting graphs, showing the course of the bond and stock markets in New York over a long period. These graphs are furnished through the courtesy of the financial department of the New York Tribune.

Jan 9, 1919

By W. C. Knopf, I. M. LaBaron

In the Carlsbad area potash is dry-mined and wet- concentrated. Wet concentration involves recirculation of saturated brines, with resultant difficulties of brine disposal and inherent losses in recovery through solution of the KC1. A dry beneficiation process for potash minerals would offer many advantages over present methods. International Minerals & Chemical Corp. has been working on development of a dry process for some time. This article is a progress report.

Jan 10, 1958

MANY members of the National Societies died in service overseas during the World War. No memorial to these engineers has been set up but a unique and interesting suggestion has been made. While Edward Dean Adams, Fellow of the American Society of Civil Engineers, and Associate of the Ameri-can Institute of Electrical Engineers, ,vas in Belgium last June as delegate of the National Societies, En-gineering Foundation, and Engineering Societies

Jan 12, 1927

By Roshan B. Bhappu, Zeki M. Dogan

Two magnesite ores containing 3.15% and 8.73% SiO2 and a calcined magnesite product assaying 2.6% Si02 were first reduced in size to -20 mesh by roll crushing. 'They were then treated dry on a high intensity magnetic separator to reduce their silica content by rejecting iron-stained silicate minerals in the magnetic fraction and obtaining marketable magnesite or calcined magnesite as a nonmagnetic product.

Jan 1, 1975

By Denis Yeung, B. H. G. Brady

A hybrid finite element-boundary element code with eight noded isoparametric finite elements and three noded boundary elements is described for plane strain and linear isotropic elasticity. In the direct formulation of the Boundary Flement Method, quadratic variation of geometry and displacements, and linear variation of tractions with respect to the element intrinsic coordinates are used. The boundary element region is treated as a "super-element" in the finite element sense.

Jan 1, 1982