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By R. Scot Clark

The reactively sputtered silicon dioxide capacitor -was developed for use in the monolithic integrated circuit, thereby requiring the capacitor to be fabricated on an oxidized silicon slice. The silicon dioxide film is formed by reactively sputtering silicon in a 50 pct Ar-50 pct 0, atmosphere and the physical properties are indistinguishable from silica. A practical upper limit of capacitance per unit area of 0.25 pf per sq mil is reached with the capacitors fabricated from the Si0, film. Methods shown to enhance this value are double stacking the thin-film capacitors and addition of aluminum to the silicon cathode during sputtering to form an aluminosilicate dielectric. A major contribution to the field of diffused integrated circuits would be the addition of auxiliary passive devices for replacement of diffused passive devices which are currently being fabricated for many integrated circuits. This accomplishment would increase the flexibility of the diffusion process in order to concentrate more on transistor parameters rather than on fabricating diffused resistors and capacitors. To pursue this technique, a thin-film SiOz capacitor was developed which has _ proven applicable to many integrated circuits. Although the SiOl capacitor has an application, the major deterrent from extending the integrated circuit into many useful areas such as low-frequency linear application is the low dielectric constant of SiO, and the low usable capacitance in an integrated circuit. This paper will cover the sputtering techniques used for forming the SiO, film, the physical and electrical properties of sputtered SiO,, and yield information concerning the application of these capacitors to integrated circuits. REACTIVE SPUTTERING Reactive sputtering is simply the sputtering of a metal or semiconductor in glow discharge in the presence of a reactive gas. The material to be sputtered is seen in Fig. 1 as the cathode of the system and is bombarded with positively charged ions of the ambient gas. In this investigation, the ambient gas is composed of 50 pct Ar and 50 pct O2 at a pressure of approximately 2.5 X l0-' Torr. The ions are accelerated toward the cathode in the cathode dark space by the electric field and upon striking the cathode effect a momentum energy transfer to the surface atoms. The transferred energy is sufficient to dislodge a surface atom or atoms and these particles diffuse through the glow discharge to the collector or anode. Several mechanisms of oxidation in the reaction chamber can be considered during reactive sputtering. 1) The surface of the cathode is oxidized and the oxide is subsequently sputtered. 2) Oxidation and sputtering occur simultaneously. 3) Sputtering of the cathode material is followed

Jan 1, 1965

By H. C. Stumpf, L. A. Willey, V. L. Fink

Very few studies of the aluminum-sodium system have been reported. Heycock and Neville1 were unable to detect any solubility of sodium in liquid aluminum. Mathewson2 prepared an equilibrium diagram consisting of two horizontal lines at the melting points of the two metals. He was unable to detect solubility at either end of the system. Scheuer3 first developed a method for the chemical determination of sodium in aluminum and then studied the solubility of sodium in liquid aluminum. His method involved heating aluminum with excess sodium under hydrogen until the two liquids were at equilibrium, chilling the melt, and analyzing the aluminum-rich layer. He reported the solubility to be 0.10 pct sodium at 700°C, 0.115 pct at 750°C, and 0.128 pct at 800°C. This paper on the aluminum-sodium system is the twenty-first in a series from the Aluminum Research Laboratories describing equilibrium relations in aluminum alloy systems. Materials The alloys for this investigation were prepared from electrolytically refined aluminum (99.99 pct) and sodium of reagent quality conforming to specifications of the American Chemical Society. Chemical analysis of the aluminum showed the fol- lowing impurities: 0.002 pct Si, 0.002 pct Fe, 0.002 pct Cu, <0.001 pct Mn, 0.002 pct Mg and 0.001 pct Na. The sodium content of all alloys was determined by either chemical or spectro-graphic standard procedures5 No. IIA and No. SI I respectively. Determination of Miscibilitv The boundary of the miscibility gap was determined by a modification of the method of Scheuer3 and of that used by Henry and Cordiano. As finally developed the method was as follows: A fused alumina crucible 25 mm id with 75 mm depth and 1.5 mm wall thickness was placed on the bottom of a container made from a 4-in. length of 1 1/2-in. iron pipe and pipe caps. ?&apos;he space around the sides of the crucible was filled with 40 mesh crystalline alun-dum. A charge of 60 g of aluminum and 10 to 15 g of sodium was placed in the crucible, the sodium first being trimmed and rinsed with iso-pentane to remove kerosene. The container was tightly capped, filled with argon (99.6 pct pure), and heated to the desired temperature (between 670 and 800°C). A positive pressure of argon (about 8 mm of mercury) was maintained through a small pipe to the upper cap. After soaking for from 2 to 5 hr, the container was quenched by directing a stream of water onto the base, so that solidification of the aluminum-rich layer was rapid and essentially unidirectional. Analyses were made on drillings taken from the bottom of the ingots after machining off the surface layers. Pre-

Jan 1, 1949

By Konrad Stern

The terms asphalt and bitumen have been applied interchangeably, although incorrectly on occasion, for centuries to various bituminous materials that were found in nature. Native bituminous materials of only the solid types, deposits of which are found on or near the surface of the ground, together with the principal asphaltic type petroleum bitumens will be considered in this chapter. The international dictionary compiled by the "Permanent International Association of Road Congresses" still gives the full name as "Asphaltic Bitumen" but of recent years the word "Bitumen" has been recognized as most appropriate and is defined by the American Society for Testing Materials as follows: "Mixtures of hydrocarbons of natural or pyrogenous origin, or combinations of both, frequently accompanied by their nonmetallic derivatives, which may be gaseous, liquid, semisolid or solid and which are completely soluble in carbon disulfide." Asphaltic pyrobitumens, as defined by Abraham,2 is a species of pyrobitumen, including dark-colored, comparatively hard and nonvolatile solids; composed of hydrocarbons, substantially free from oxygenated bodies; sometimes associated with mineral matter, the nonmineral constituents being infusible and largely insoluble in carbon disulfide. Deposits of native bituminous materials are found scattered over the entire world, but many are relatively unimportant as far as commerce is concerned. No attempt has been made to cover all of the known deposits. The principal bituminous materials of commercial interest are: 1. Native asphalts, solid or semisolid, associated with mineral matter such as Trinidad Lake asphalt, Rock asphalt and Selenitza, Boeton and Iraq asphalts. 2. Native Asphaltites, such as gilsonite, grahamite and glance pitch, conspicuous by their hardness, brittleness and comparatively high softening point. 3. Asphaltic bitumens obtained from nonasphaltic, semi-asphaltic and asphaltic crude petroleum by distillation, blowing with air and the cracking of residual oils. 4. Asphaltic pyrobitumens of which wurtzilite and elaterite are of chief interest industrially as they depolymerize upon heating, becoming fusible and soluble in contrast to their original properties in these respects.2 5. Mineral waxes, such as ozokerite, characterized by their high crystallizable paraffine content. Native Lake Asphalt At Brighton situated in the southwestern part of the Island of Trinidad is one of the largest deposits of native asphalt in the world.3 The lake is oval in shape, covering an area of 114 acres and having a depth of 285 ft at its center. The material forming this deposit is an emulsion of water and bitumen with a suspension of mineral matter consisting of impalpably fine clay dispersed by nature in the asphalt, and small quantities of silica and vegetable matter. The entire mass of asphalt is in slow but constant motion as evidenced by the migration of islands of vegetation from one place to an-

Jan 1, 1960

By R. P. Smith

Iron-carbon alloys containing a single-phase austenite region and a two-phase azcstenite + cementite region at the desired temperature were prepared by partial carburization of iron or partial decarburization of carburized iron. Each sample was held at a fixed temperature until equilibrium was achieved. Analysis of the austenite for carbon then gave the solubility of cementite in austenite. Solubility measzcrements were made for the temperature range 734° to 1012°C. These values together with other data give 7560 cal for the mean heat of solution of cementite in austenite, and 0.765 pct C for the eutectoid composition of austenite. They also indicate that graphite is the stable phase at all temperatures between the eutectoid and eutectic temperature. Measurements of the solubility of cementite in austenite at 927oand 1011 "C, using a method based on the equilibration of iron with boro-cementites, are reported. The solubility of cementite in austenite (?-iron) has been computed by Darken and Gurry1 from the observed solubility of graphite in austenite, and the thermodynamic properties of pure iron and of iron-carbon alloys. They have shown that the solubility of cementite is greater than that of graphite in the temperature range between the eutectoid and eutectic, and thus that cementite is metastable with respect to graphite and austenite saturated therewith. Since their computation is not in accord with the earlier experimental work of Mehl and wells,&apos; the present direct determination of the solubility of cementite in austenite was undertaken. EXPERIMENTAL PROCEDURE Each iron rod about 1/2 in. O.D. by 4 in. was first carburized at a temperature and with a H2-CH4 gas mixture such that the carbon content would be greater than that corresponding to the solubility of cementite in austenite at the desired (lower) temperature; sufficient carburizing time was allowed that the carbon content became substantially uniform, as illustrated by Curve A, Fig. 1. The sample was then partially decarburized with a hydrogen-water vapor mixture, giving a carbon distribution as schematically illustrated by Curve B. The sample was then held in a helium atmosphere at the temperature at which the solubility was to be determined until the decarburized portion of the sample came to equilibrium with that containing cementite. Curve C of Fig. 1 represents schematically the final carbon distribution; the horizontal portion corresponds to the carbon content of austenite saturated with cementite. To bring the sample to room temperature without change in the carbon distribution and in machinable condition, it was first quenched in a salt pot at 480°C, then in water at room temperature. Successive layers were machined from the center 2 in. of the sample and analyzed for carbon by the usual

Jan 1, 1960

Smoky Valley Mining Company, Round Mountain, Nevada, was the pioneer operation designed for large scale heap leaching of crushed gold ores. It is located in the Big Smoky Valley which stretches 160 km (100 miles) through central Nevada west of the Toiyabe Mountain Range. Gold was first-discovered at Round Mountain, 88 km (55 miles) north of Tonopah, in 1905; and mining in the area included placer operations, which ran from 1946 to about 1960. Smoky Valley Mining Company is a partnership of Felmont Oil Co., Case-Pomeroy & Co., and Copper Range Co., with the latter being wholly owned by Louisiana Land and Exploration Co. In 1969, an option on the Round Mountain property was acquired by Copper Range, and during 1974 a decision was reached to proceed with mine development and plant construction. Ore reserves were reported at 10,537,000 mt (1 1,617,000 st) of 2.09 g per mt (0. 061 oz per ton) gold using a cut- off grade of 0.69 g (0.02 oz). Silver content was approximately 2.4 g per mt (0.07 oz per ton) and the waste to ore ratio was about 1: 1. By the end of 1976 heap leaching was in operation. The ore is a rhyolite tuff, sometimes described as a gold porphyry with highly abrasive qualities but which does not break down into slimes upon contact .with cyanide solutions. Gold is unevenly distributed through the ore but as a whole it is in a very finely divided state. Climatic conditions are extreme in central Nevada. Summers are hot and dry while winters are windy and cold with subfreezing temperatures. Elevation of the property is about 1,920 m (6,300 ft). Precipitation averages 203 mm (8 in.) per year. Until February of 1980, leaching was continued until the temperature reached minus 2ºC (28º F), and about 10 months leaching was the average. Water for the operation is drawn from the Toiyabe Mountains through a 13. 7 km (8. 5 mile) pipeline, originally installed in 1915, or from wells in the valley bottom. The plant requires make-up water at the rate of about 1,500 liters per min (400 gpm). On a schedule of three shifts, seven days per week, the daily output at Round Mountain amounts ,to 12, 700 mt (14, 000 st) consisting of 6,350 mt (7,000 st) each of ore and waste. Ore is hauled with a fleet of 45 mt (50 st) trucks and dumped into the 1,0.70 by 1,650 mm (42 by 65 in. ) gyratory primary crusher located near the pit. The primary

Jan 1, 1981

By G. Sachs, G. Espey

IT is well known that high residual stresses are created in tubing by the sinking process, in which no internal tool or mandrel is used.1-4 In this process, the wall thickness is usually slightly increased.4,5 In tube drawing with a plug, the residual stresses are gradually reduced with increasing reduction of wall, and, by the conventional approximation methods of stress measurement, no stress is detected in tubing in which the wall reduction is over 50 per cent of the total reduction in cross-sectional area.1-6, It has also been observed that higher stresses are set up by the use of wide-angle dies than by the use of acute dies.2 The actual stress distribution in drawn .tubing has been investigated by a few workers,7-9 but has not been related to the conditions of the drawing process: Some attempts have been made to correlate accelerated cracking tests for stresses in brass products with the magnitude of the circumferential stresses and the condition of the metal.1-10 MATERIALS AND PREPARATION The material used in this experiment was commercial cartridge-brass (70 per cent Cu, 30 per cent Zn) tubing in the straightened and annealed condition.‡ This tubing was of various outside diameters and had a wall thickness of 0.032 in. It was sunk to 1/2-in. outside diameter by means of an experimental 10,000-lb. hydraulic draw-bench, with a maximum drawing speed of 8 ft. per minute. All dies were of 1/2 -in. diameter. Various die materials and contours were used in order to study the effect of die design on residual stresses in the tubing; the specifications for the dies are given in Fig. I. Castor oil was used throughout as lubricant. Chattering occurred in sinking some of the tubing, particularly when dies having the more acute angles were used, but the tubes showing chatter marks did not differ markedly from those with a smooth surface regarding the magnitude of residual stress. The source of the chattering has not yet been revealed. The wall of the tubing becomes thicker during sinking, as previously observed 4,5 The increases in wall thickness were 3, 7 and 9.5 per cent on the average for 6, 20 and 33 per cent reductions in diameter, no effect of the contour being noticeable. The reductions mentioned throughout this investigation do not consider this fact, but are reductions of the outside diameter. For the evaluation of the residual stress two fundamentally different methods were used. The approximation method1,11 of splitting a certain length of tubing was employed to obtain a bird&apos;s-eye view of the effect of various drawing conditions on the circumferential stress measured by the diameter change occurring on splitting. For the determination of the complete stress

Jan 1, 1941

By R. R. Knuckey

Having been associated with the operation of the de Vooys process for coal, which has treated 13,000,000 tons per annum, and recognizing the process as of value in ore sorting, Huntington, Heberlein and Co. Ltd. (Great Britain) in 1936 made an examination of all other existing methods. In none of the pioneer applications had recognition been given to the necessity for maintaining certain conditions that are essential for sorting certain ores if a truly efficient separation by gravity alone is to be assured. Consequently, in 1936-1937 Huntington, Heberlein and Co. Ltd., with Pearson, employing certain ideas connected with the de Vooys application, commenced the development of a separator that would allow conformance with optimum conditions in the zone where separation is effected. Later, Holt and Wade added to the value of the original application by Wuensch, Rakowsky and others, whose conceptions are being successfully operated today. Meantime, Trostler had enhanced the value of the original H-H. process by improvements that are now embodied in operating plants, and today the process incorporates an improved apparatus and a stable medium that produce the optimum conditions for separation. These conditions are: 1. Elimination of disturbing currents in the separating zone; 2. Reduction to a minimum of medium-density differences throughout the separating zone; 3. Stable medium of minimum viscosity to permit the unretarded fall of mineralized particles; 4. Removal of products of separation with minimum disturbance to the separating zone. Design of Separator The H-H. sink-and-float separator consists of a pyramidal tank in which the separation actually takes place, connected at the bottom with an inclined bucket elevator. The tank and the elevator are filled with medium to within a few inches of the top of the tank. Medium is fed into the separator at a variety of points, according to the type of ore being treated, and it is withdrawn from the separator at two points: (1) together with the float product, by means of a variable-speed addle, at the surface of the medium, and (2) by flowing over an adjustable weir cut in the side of the elevator casing. The prepared ore is fed onto the surface of the medium. The intermediate paddles, which revolve at a slow speed of 2 to 5 r.p.m., move the floating ore across the bath from feed end to float-discharge end. The ore, which is heavier than the medium, sinks below the sweep of the addles and reaches the boot of the bucket elevator, which discharges it without disturbance of the separating zone. These arrangements for withdrawing medium from the separator allow the use of minimum flows, which connote minimum

Jan 1, 1947

By R. R. Knuckey

Having been associated with the operation of the de Vooys process for coal, which has treated 13,000,000 tons per annum, and recognizing the process as of value in ore sorting, Huntington, Heberlein and Co. Ltd. (Great Britain) in 1936 made an examination of all other existing methods. In none of the pioneer applications had recognition been given to the necessity for maintaining certain conditions that are essential for sorting certain ores if a truly efficient separation by gravity alone is to be assured. Consequently, in 1936-1937 Huntington, Heberlein and Co. Ltd., with Pearson, employing certain ideas connected with the de Vooys application, commenced the development of a separator that would allow conformance with optimum conditions in the zone where separation is effected. Later, Holt and Wade added to the value of the original application by Wuensch, Rakowsky and others, whose conceptions are being successfully operated today. Meantime, Trostler had enhanced the value of the original H-H. process by improvements that are now embodied in operating plants, and today the process incorporates an improved apparatus and a stable medium that produce the optimum conditions for separation. These conditions are: 1. Elimination of disturbing currents in the separating zone; 2. Reduction to a minimum of medium-density differences throughout the separating zone; 3. Stable medium of minimum viscosity to permit the unretarded fall of mineralized particles; 4. Removal of products of separation with minimum disturbance to the separating zone. Design of Separator The H-H. sink-and-float separator consists of a pyramidal tank in which the separation actually takes place, connected at the bottom with an inclined bucket elevator. The tank and the elevator are filled with medium to within a few inches of the top of the tank. Medium is fed into the separator at a variety of points, according to the type of ore being treated, and it is withdrawn from the separator at two points: (1) together with the float product, by means of a variable-speed addle, at the surface of the medium, and (2) by flowing over an adjustable weir cut in the side of the elevator casing. The prepared ore is fed onto the surface of the medium. The intermediate paddles, which revolve at a slow speed of 2 to 5 r.p.m., move the floating ore across the bath from feed end to float-discharge end. The ore, which is heavier than the medium, sinks below the sweep of the addles and reaches the boot of the bucket elevator, which discharges it without disturbance of the separating zone. These arrangements for withdrawing medium from the separator allow the use of minimum flows, which connote minimum

Jan 1, 1947

By R. D. Vaughn

The limiting cases of non- Newtonian fluids flowing inside a concentric annular duct are developed without using a model of the fluid behavior. The solutions provide limits with which to test the various models of fluid behavior such as the power law and Bingham plastic models. The results of previous theoretical work are discussed in terms of limiting cases. This limiting case study also shows that experimental work on flow of non-Newtonian fluids in annular ducts should be confined to ducts for which the ratio of the radius of the inner wall to that of the outer wall is less than 0.3 and preferably less than 0.2. INTRODUCTION During the last 10 years the problem of laminar flow of non-Newtonian fluids in concentric annuli has received much attention large1y because of its application to the hydrodynamics of the wellbore. Recently solutions utilizing the power law1,2 and Bingham plasticl,3,4 models have been published. In this paper the method of limiting cases, which has been successfully applied to laminar-flow heat transfer516 will be applied to the problem of flow of non-time dependent, non-Newtonian fluids through annuli. This method permits solutions for the limiting cases to be made without using a model of unknown validity. The solutions, therefore, provide limits with which to test the various models which have been or will be proposed. A pertinent conclusion concerning the region of experimental work is also provided. DEVELOPMENT OF LIMITING CASES The limiting cases for the axial flow of fluids in concentric annuli may be defined with reference to Fig. 1. It is possible to define two limiting cases which pertain to the physical dimensions of the annulus. First, the annulus must degenerate to a circular pipe as the radius of the inner wall decreases or, as k = (k R/R) ? 0. Second, the annulus must approach the limit of parallel plates of infinite extent as the spacing between the inner and outer tubes becomes small in comparison with the radius R of the annulus, or as k?1. It is also possible to ascertain three limiting cases which pertain to fluid behavior. With reference to Fig. 2, as a fluid becomes progressively more pseudoplastic, the shear stress-shear rate relationship progressively approaches the indicated horizontal line more closely. At this limit the shear stress becomes independent of the shear rate. At the other extreme of increasingly dilatant behavior, the vertical asymptote is approached. Intermediate between these two limiting cases lies the case of the Newtonian fluid. Fluids which exhibit a yield shear stress also approach the limiting case of "infinite" pseudoplastic behavior. The remainder of the theoretical development is concerned with the description of and the solutions

By L. Grånäs, B. Aronsson

In a recent study of Fe-Si alloys Walter and Koch&apos; observed pairs of dislocations in Fe-6.25 pct Si crystals rolled to reductions of 10 pct and subsequently annealed for 1 hr at 650°C. They interpreted these pairs as being due to stacking faults. From the spacing of the dislocations a stacking-fault energy of 15 to 19 ergs per sq cm was calculated. These authors did not pay any attention to the order -disorder phenomena in Fe-Si alloys. It is the purpose of this communication to report some preliminary results from a study of ordering and its influence on the plastic deformation of Fe-6.0 pct Si alloys. Our results suggest that the dislocation pairs observed by Walter and Koch may have been due to long-range order rather than to stacking faults. The alloys used in this investigation were prepared from pure electrolytic iron and silicon and were melted in argon. After hot working, strip tensile specimens were machined to a gage length of 70 mm and a thickness of 1 mm. The specimens were heat- treated for 2 hr at 1000°C, furnace-cooled, and subsequently deformed 2 pct in tension at 400°C. The strain rate was 5.6 X lo-&apos; sec-&apos;. Thin foils of the deformed specimens were prepared by means of the Bollman technique and examined in a Siemens Elmis-kop I at an accelerating voltage of 100 kv. In the Fe-Si system long-range ordering occurs at a silicon content of about 6 pct Si. In our alloys evidence for ordering is given by selected-area diffraction patterns which show extra reflections consistent with a super lattice of the D0 9 type. In addition, the dislocation arrangement in deformed specimens indicates that long-range order is present. A typical mi-crophotograph of a thin foil is shown in Fig. l. The dislocations are usually straight and parallel and laying in distinct directions. In the commonly observed (111) zone the projections of the dislocations are close to (113) and (oil). Observation of the image position indicates that the two dislocations in a pair have the same Burgers vector and hence constitute a superlattice dislocation.~ According to theory3 a superlattice dislocation in the DO3 structure consists of four ordinary dislocations connected by two types of antiphase boundaries as shown in Fig. 2. In our specimens only two dislocations in each pair have been observed, Fig. 1. The problem is to decide whether the area between these is a NN or a NNN antiphase boundary. Dark-field images using the (200) reflexion (the indices are defined with respect to the DO3-type superlattice) can

Jan 1, 1968

By Walter Crafts, C. M. Offenhauer

In a previous study of the carbide phase of chromium steels, it was shown that chromium carbide (Cr7C3) is 2 more stable carbide than cementite (Fe3C) at tempering temperatures above about 500°C. in quenched steels containing from about I to 7.5 per cent chromium. Below this temperature the carbide phase was found to consist of cementite in all of the steels examined. In the present investigation it was found that a similar change in the carbide phase takes place in molybdenum and in chromium-molybdenum steels at approximately the same tempering temperatures. The approximate ranges of occurrence of the alloy carbides Cr7C3, Cr4C, and Mo2C have been determined in steels containing up to 5 per cent chromium, I per cent molybdenum and 0.60 per cent carbon. The experimental steels were made in small high-frequency furnaces from Armco ingot iron, low-carbon ferrochromium and calcium molybdate and were poured into 2-in. ingots, which were forged to I-in. round bars. Sections of the bars were heated to the carbide-solution temperature and cooled rapidly to induce austenite transformation at relatively low temperatures. The steels were subject to some segregation, therefore comparatively high temperatures were necessary to dissolve all of the carbides. The microstructure of the quenched specimens was examined to verify the belief that the carbides had been dissolved, and also to determine the nature of the nonmartensitic structure of incompletely hardened steels. Ferrite and pseudo-martensite were present in some of the specimens, but all specimens were quenched at such a rate that pearlite was not formed, in order to ensure the formation of the carbides at temperatures lower than about 500°C. It had been found previously1 that in chromium steels the chromium carbide could be produced by transformation of austenite in the pearlite range above 500°C., and, in order to start the tempering treatment with the carbide present as cementite, the absence of pearlite was considered to be essential. The specimens were tempered for 64 hr. to permit the formation of the stable carbide. After tempering, the specimens were submitted to microscopic and X-ray examination. The carbides were separated either electrolytically in a 5 per cent HCl electrolyte or with an acidified copper-potassium chloride solution. The crystal structure of the carbide phases was determined by the Debye-Scherrer type of X-ray patterns. The X-ray patterns obtained from specimens near the boundaries between two types of carbides were generally weak and diffuse as compared with the other patterns. For this reason, and because the more soluble components may be masked, the boundaries between the phases could not be determined precisely. However, the X-ray analysis of electrolytically separated carbides has given consistently reproducible results

Jan 1, 1943

By Walter Crafts, C. M. Offenhauer

In a previous study of the carbide phase of chromium steels, it was shown that chromium carbide (Cr7C3) is 2 more stable carbide than cementite (Fe3C) at tempering temperatures above about 500°C. in quenched steels containing from about I to 7.5 per cent chromium. Below this temperature the carbide phase was found to consist of cementite in all of the steels examined. In the present investigation it was found that a similar change in the carbide phase takes place in molybdenum and in chromium-molybdenum steels at approximately the same tempering temperatures. The approximate ranges of occurrence of the alloy carbides Cr7C3, Cr4C, and Mo2C have been determined in steels containing up to 5 per cent chromium, I per cent molybdenum and 0.60 per cent carbon. The experimental steels were made in small high-frequency furnaces from Armco ingot iron, low-carbon ferrochromium and calcium molybdate and were poured into 2-in. ingots, which were forged to I-in. round bars. Sections of the bars were heated to the carbide-solution temperature and cooled rapidly to induce austenite transformation at relatively low temperatures. The steels were subject to some segregation, therefore comparatively high temperatures were necessary to dissolve all of the carbides. The microstructure of the quenched specimens was examined to verify the belief that the carbides had been dissolved, and also to determine the nature of the nonmartensitic structure of incompletely hardened steels. Ferrite and pseudo-martensite were present in some of the specimens, but all specimens were quenched at such a rate that pearlite was not formed, in order to ensure the formation of the carbides at temperatures lower than about 500°C. It had been found previously1 that in chromium steels the chromium carbide could be produced by transformation of austenite in the pearlite range above 500°C., and, in order to start the tempering treatment with the carbide present as cementite, the absence of pearlite was considered to be essential. The specimens were tempered for 64 hr. to permit the formation of the stable carbide. After tempering, the specimens were submitted to microscopic and X-ray examination. The carbides were separated either electrolytically in a 5 per cent HCl electrolyte or with an acidified copper-potassium chloride solution. The crystal structure of the carbide phases was determined by the Debye-Scherrer type of X-ray patterns. The X-ray patterns obtained from specimens near the boundaries between two types of carbides were generally weak and diffuse as compared with the other patterns. For this reason, and because the more soluble components may be masked, the boundaries between the phases could not be determined precisely. However, the X-ray analysis of electrolytically separated carbides has given consistently reproducible results

Jan 1, 1943

By Gerald A. Munson, Fremont F. Clarke

DURING recent years the use of lithium has expanded greatly in industrial, chemical, and metallurgical fields, while at the same time modernized methods of mining and refining lithium have increased production. Technical literature includes many papers describing the geology and mineralogy of lithium deposits. Mining and beneficiating problems, however, have not been thoroughly described. Published reports have failed to emphasize that one of the chief reasons lithium minerals were not extensively mined until recently is the difficulty of beneficiation. Four lithium minerals of pegmatites and the lithium-sodium-phosphate byproduct from the brines at Searles Lake, Calif., have been sources of lithium. Among the pegmatite minerals, only spodu-mene and petaline are known to occur in deposits large enough to support large tonnage operations. Spodumene, a lithium-aluminum-silicate, is the principal lithium mineral mined in the U. S. Lithium Corp. of America, during its rapid development and growth, has successfully employed three different methods of concentration: 1) hand sorting, 2) Heavy Media separation, and 3) froth flotation. Each method, though economic in its sphere, is becoming outdated as extractive techniques improve. The most recent development has taken place at Lithium Corp.&apos;s new operation in North Carolina, where the extractive process yields lithium compounds directly from mined rock without an intervening concentrating step. Until 1954 Lithium Corp. mined only in the southern part of the Black Hills of South Dakota, where the various types of lithium-bearing pegmatite could be used to develop untried processes of beneficiation. Concentrates from these operations are shipped to the corporation&apos;s chemical plant in St. Louis Park, Minn., where actual extraction of lithium and production of commercial compounds takes place. Nature of Deposits The geology of the southern Black Hills pegmatite deposits is admirably presented by a U. S. Geological Survey publication.&apos; Only the factors pertinent to exploitation need be mentioned here. Lithium Corp. has been interested primarily in three deposits, the Edison, the Mateen, and the Longview-Beecher No. 2. The history of these deposits dates back to the mining boom of 1880 to 1900 in the Black Hills, when most of the deposits were prospected for tin by the ill-fated Harney Peak Tin Mining Co. The three deposits described here, however, lay idle and unwanted until Lithium Corp. opened the Edison mine in 1943 and the Mateen and Longview-Beecher No. 2 in 1951. Edison Deposit: The Edison deposit is about a mile southeast of Keystone, S. D., on the northeastern flank of the Harney Peak uplift. The deposit consists of no less than four and probably at least six separate pegmatites that coalesce in a central mass from which the individual pegmatites finger outward and downward in complexly folded schist and gneiss beds of the country rock.

Jan 1, 1956

By R. R. Knuckey

HAVING been associated with the operation of the de Vooys process for coal, which has treated 13,000,000 tons per annum, and recognizing the process as of value in ore sorting, Huntington, Heberlein and Co. Ltd. (Great Britain) in 1936 made an examination of all other existing methods. In none of the pioneer applications had recognition been given to the necessity for maintaining certain conditions that are essential for sorting certain ores if a truly efficient separation by gravity alone is to be assured. Consequently, in 1936-1937 Huntington, Heberlein and Co. Ltd., with Pearson, employing certain ideas connected with the de Vooys application, commenced the development of a separator that would allow conformance with optimum conditions in the zone where separation is effected. Later, Holt and Wade added to the value of the original application by Wuensch, Rakowsky and others, whose conceptions are being successfully operated today. Meantime, Trostler had enhanced the value of the original H-H. process by improvements that are now embodied in operating plants, and today the process incorporates an improved apparatus and a stable medium that produce the optimum conditions for separation. These conditions are: 1. Elimination of disturbing currents in the separating zone; 2. Reduction to a minimum of medium-density differences throughout. the separating zone; 3. Stable medium of minimum viscosity to permit the unretarded fall of mineralized particles; 4. Removal of products of separation with minimum disturbance to the separating zone. DESIGN OF SEPARATOR The H-H. sink-and-float separator consists of a pyramidal tank in which the separation actually takes place, connected at the bottom with an inclined bucket elevator. The tank and the elevator are filled with medium to within a few inches of the top of the tank. Medium is fed into the separator at a variety of points, according to the type of ore being treated, and it is withdrawn from the separator at two points: (1) together with the float product, by means of a variable-speed paddle, at the surface of the medium, and (2) by flowing over an adjustable weir cut in the side of the elevator casing. The prepared ore is fed onto the surface of the medium. The intermediate paddles, which revolve at a slow speed of 2 to 5 r.p.m., move the floating ore across the bath from feed end to float-discharge end. The ore, which is heavier than the medium, sinks below the sweep of the paddles and reaches the boot of the bucket elevator, which discharges it without disturbance of the separating zone. These arrangements for withdrawing medium from the separator allow the use of minimum flows, which connote minimum

Jan 1, 1943

By David A. Thomas, Eugene S. Meieran

MECHAMCAL, electrical, and other property measurements are often more easily made on wires than on sheets. In order to carry out transmission electron microscopy on the same material used for property determinations, we have developed a method for preparing thin foil specimens of wires. The technique was developed for 0.030 in. diam tungsten wires, and is a modification of the thinning techniques used by Wilsdorf, et al 1 A length of wire is first ground to about 0.010 in. thick by mounting the wire in low melting temperature wax, hand grinding a longitudinal flat, removing and reversing the wire in the mount, and then grinding a second parallel flat. The 0.030 in. wide and 0.010 in. thick strip is cut into 1/8 in. lengths to fit in the specimen holder of the electron microscope. Next the specimen is gripped in platinum-tipped tweezers (the anode) and placed 2 mm below a hol- low copper cathode with a 0.010 in. ID nozzle. Electrolyte, 10 pct NaOH, flows by gravity feed through the nozzle onto the specimen, as shown in Fig. l(a). Polishing is carried out until a shallow impression is made on one surface, and then the specimen is turned over and the opposite surface indented. The metal between the two impressions should be about half the specimen thickness, as is shown by the heavy line in the cross section in Fig. l(b). The entire specimen is then electropolishedin 2 pct NaOH until a hole appears at the location of the indentations. The apparatus is shown in Fig. 2, and is essentially the same as that used by Wilsdorf et al. at The Franklin Institute. Light is reflected by a mirror onto the bottom surface of the specimen! which is viewed by a stereoscopic microscope placed above it. Polishing is carried out until light is seen, indicating that a hole has formed, and then immediately stopped. The specimen is washed in water. alcohol, and ether, and is then ready for examination. The specimen should be reversed in its platinum clip during electropolishing to insure equal polishing on both sides of the impression. For tungsten, indenting at 120 v and 0.04 amp takes less than 1 min, and final polishing, at 10 v and 1 amp, less than 5 min. The portion of the specimen available for transmission microscopy surrounds the hole, as is seen by the dashed lines in Fig. l(b). Slight electroetch-ing accompanying electropolishing reveals the mi-crostructure, as seen in Fig. 3(a) by light microscopy. Low-magnification electron microscopy, as in Fig. 3(b), enables the same areas and grains to be viewed and identified when subsequently examined at high magnification. Fig. 4 is a typical structure of

Jan 1, 1963

By R. I. Jaffee, H. R. Ogden, D. J. Maykuth

Phase diagrams for the Ti-W and Ti-Ta systems were determined. The Ti-W system is characterized by a wide, two-phase region of ß plus tungsten which is derived from a peritectic reaction between the liquid and tungsten solid solutions. The ß field terminates in a eutectoid reaction between a titanium and tungsten terminal solid solution. Tantalum and ß titanium form a complete series of solid solutions. Other features of this system are the extensive a-ß field at low temperatures and an appreciable solubility of tantalum in a titanium. BOTH tungsten and tantalum were first thought to form ß-isomorphous systems with titanium as a result of early work&apos; using powder-metallurgical techniques. Later work2 on arc-melted Ti-Ta alloys, made using a commercial titanium base, showed that, in the range of 0 to 10 pct, tantalum was soluble in ß titanium and that the a solubility extended to between 2 and 5 pct Ta at 790 °C. The present investigation covered the entire alloy range in both systems and was chiefly concerned with high-purity alloys at the titanium-rich end. The constitution of titanium-rich alloys made with a commercial titanium base was reported by Holla-day, Kura, and Jackson.3, 4 As will be shown in detail later, the early prediction of a isomorphism was true for the case of the Ti-Ta system, but not for the Ti-W system. The results of this investigation will be presented first. The experimental methods used are described in the Appendix. Ti-W System The entire Ti-W phase diagram is shown in Fig. 1. Details of the titanium-rich side are shown in Fig. 2. The chief features of the system are a ß eutectoid and a high-temperature peritectic between liquid and tungsten solid solution. Melting Range: Examination of cast structures of low and medium-tungsten-content ingots showed cored ß phase as the primary constituent. Fig. 3a illustrates a typical cast structure for alloys in the range of 20 to 30 pct W. From 30 to 72 pct W, coring was very severe. Alloys containing 72 through 88 pct W, however, showed definite evidence of a peritectic reaction between the liquid and a terminal solid solution of titanium in tungsten. Fig. 3b shows the cast structure for an 80 pct W alloy. A 95 pct W alloy, shown in Fig. 4, consisted primarily of primary tungsten solid solution plus a small quantity of ß probably rejected during cooling. Incipient-melting experiments located the peritectic temperature between 1850" and 1900°C and indicated that the reacting phases are liquid containing about 25 pct W and tungsten terminal solid solution containing about 8 pct Ti. Figs. 5 and 6

Jan 1, 1954

By E. A. Peretti

BEFORE embarking on a detailed investigation of the system indium-antimony-bismuth, experiments were carried out to determine the existence of quasi-binary sections. The bordering binary systems are known1 and show the occurrence of three intermetallic binary species corresponding closely to InSb, InBi and In2Bi. Attention was focused on the low-indium end of the ternary diagram where the possible quasi-binary sections, excluding ternary compound formation, would involve the pairs: InSb-Bi, InBi-Sb and InSb-InBi. The latter pair revealed itself as a true quasi-binary, so it was investigated fully by thermal analysis, x-ray and microscopic examinations. All compositions were made by proper combination of three elements involved. The indium had a guaranteed purity of 99.97 pet; the antimony contained 99.99 pet Sb, and the bismuth had a purity of 99.99 pet. Alloys were made by melting together antimony, bismuth and indium in evacuated, sealed pyrex-glass tubes at a temperature of 600°C with vigorous agitation. The melts, weighing about 80 grams, were allowed to freeze in the sealed tubes and finally were transferred to glass tubes for the taking of cooling and heating curves. A protective atmosphere of helium was used, and the melts were stirred mechanically while cooling at rates of from 0.5 to 3°C per min. Temperatures were measured with a calibrated chromel-alumel thermocouple and were recorded graphically on a Minneapolis-Honeywell extended-range recorder working in conjunction with a Leeds and Northrup type K-2 potentiometer. Conventional polishing techniques gave satisfactory results in preparing specimens for microscopic examination. Etching was carried out with Vilella&apos;s reagent or aqueous mixtures of chromic oxide with either nitric acid or sulfuric acid plus dichromate. Conclusions deduced from the thermal analysis and microscopic examinations were confirmed by X-ray photograms using Co-K alpha radiation. The phase diagram is shown in Fig. 1. The liqui-dus consists of an uninterrupted line running from the freezing point of InSb (525°C) to a eutectic point experimentally indistinguishable from the freezing point of InBi (110°C). X-ray patterns of the InSb show a slight expansion of the lattice with the addition of InBi, and microscopic work indicated the solid solubility of InBi in InSb to be less than 0.5 pet at room temperature. Acknowledgment We wish to thank the Indium Corporation of America for the loan of the indium used in this investigation. References 1 E. A. Peretti and S. C. Carapella, Jr.: Trans. ASM., 1949, vol. 41, P. 947. T. S. Liu and E. A. Peretti: Trans. ASM, 1952, vol. 44, p. 539. Metals Reference Book, vol. 1, 2nd ed., AIME, p. 345.

Jan 1, 1959

By J. W. Taylor, E. G. Zukas

THE results of shock-loading studies on copper were reported several years ago by smith. In his experiments, Smith found that there was a correlation between the shock direction and the orientation of twins which the shock produced. By using free-surface-type shots in which the free surface of the specimen was not normal to the shock direction, he showed conclusively that twinning of copper in impulsive loading was caused by the rarefaction wave. Similar tests with iron, however, showed that it twinned during compression. More recent studies of iron2 and on Fe-Si single crystals3 have shown that twinning can be suppressed in these materials by shock loading at pressures high enough so that the velocity of the shock wave exceeds the elastic-wave velocity. From these observations, it appeared that twinning was caused by the shear stresses present in the zone undergoing adjustment from one-dimensional to three-dimensional loading. At high pressures, such a zone becomes so thin that there is insufficient time for the relatively ordered motion of atoms involved in twinning to occur. Twinning in copper, therefore, cannot be produced by a single compressive shock wave because resolved shear stress large enough to create twins exists only for a very short time (0.01 psec or less) before the pressure increases suddenly and loading becomes essentially hydrostatic. (A typical pressure vs time record for a copper shot, illustrating the short rise time of the compression wave, is shown in Fig. 1.) If, on the other hand, a second shock wave can be created in a precompressed sample, then the new elastic limit is several kilobars,4 and a resolved shear stress sufficient to cause twinning should be maintained for an adequate time period (0.1 psec or more). This experimental situation can, in fact, be realized. The experimental arrangement used to do so is shown in Fig. 2. By utilizing the pressure transformation in Fe-V alloys, it was possible to shock-load the copper in compression while the copper was already precompressed. In the first test, an 8 wt pct V-Fe sample was used as a driver for loading the copper, and the copper was exposed to the following series of compressive shocks: 1) an elastic wave of about 8 kbars, which is usually ignored in shock studies; 2) the pressure transformation wave for the driver of 200 kbars; and 3) the driving shock wave of 270 kbars pressure. Metallurgical determination of the angular twin distribution, shown in Fig. 3, with respect to the shock direction and the shock rarefaction direction (which was 23 deg from the shock direction) showed that twinning took place

Jan 1, 1965

By Howard Clarke, Cyril Stanley Smith, Clarence Zener

THE importance of cold-working in the fabrication of metals is in marked contrast with our ignorance as to the nature of the accompanying internal changes. The failure of the usual methods of testing to provide a consistent picture of these internal changes has given the incentive for the present program of investigating the effect of cold-working upon the internal friction of metals measured at small strain amplitudes. It has previously been shown1,2,3, that the internal friction introduced by cold-work is removed by annealing at comparatively low temperatures. In the present paper the following additional factors are investigated: (I) frequency of measurement, (2) amount of cold-work, (3) temperature of measurement. Special care was taken to minimize the internal friction due to causes other than cold-work. The present paper is purely experimental, the authors believing that any conclusions drawn from this work as to the nature of the internal changes accompanying cold-work would be premature." PREPARATIONS OF SPECIMENS In this study of cold-work it was desirable to eliminate as far as possible all other sources of internal friction. One disturbing source is the lack of temperature equilibrium between adjacent crystallites of a vibrating specimen.4 Temperature equilibrium is aided by small grain size and by the use of low-frequency vibrations. Unless unduly long specimens are used, low frequencies can be obtained only in transverse vibrations. But in transverse vibrations a second source of internal frictions is present, that arising from transverse thermal currents.5 The effect of these may be reduced by increasing the transverse dimensions. The grain size and transverse dimensions of the specimens were thus so chosen as to render the vibrations simultaneously nearly isothermal with respect to intercrystalline thermal currents, and nearly adiabatic with respect to transverse thermal currents. The material for this investigation was a 70-30 brass, part of the same lot of material that was used for some earlier studies on the effect of strain on proportional limit.10 It had the following composition: copper, 70.59 per cent; zinc, 29.39; lead, 0.01; iron, 0.01. This material was received from the brass mill in the form of 3/4-in. rod, cold-drawn to final size by a 65 per cent reduction of area from material that had been annealed to give a grain size of 0.060 mm. Rods of appropriate length were annealed for 2 hr. at 400°C. and cooled in air. The annealed rods (grain size, 0.012 mm.) were then stretched in a tensiontesting machine, using special grips10 to ensure axial application of the load. The rate

Jan 1, 1941

By S. Weinig, E. S. Machlin

THE mechanism of the martensitic transformation has been the subject of a remarkable number of papers in recent years.&apos; Because the task of evaluating all the available theories is a formidable one, the authors will confine themselves merely to the presentation of results of an experimental investigation of the habit orientation, lattice relations, magnitude and direction of average transformation shear strain, and orientation of subband markings for a single variant of the possible habit systems in an 11 pct Mo-Ti alloy. It is hoped that these data will assist in the establishment of a rigorous theory for the mechanism of the martensitic transformation. Experimental Procedure Specimen Preparation: A sample, approximately 1/2 x 1/4 x 1/4 in., was cut from a double arc-melted ingot composed of commercial-process A titanium and high purity molybdenum (nominally, 11 pct Mo). It was capsuled in evacuated Vycor at 10.-3 mm Hg subsequent to a double argon wash and homogenized for 48 hr at 1100°C. After a direct quench into H2O at room temperature, a large-grained specimen resulted, which, by X-ray diffraction and metallographic means, was subsequently shown to be in the body-centered-cubic phase, ß. Two adjacent, approximately perpendicular faces were polished and the ends of the specimen were ground parallel in a V-block. Fiducial lines were inscribed at 45" to the common edge of the polished surfaces in order that they would be perpendicular to the habit traces of the subsequently formed a plates.2 The specimen was then compressed between the ground ends in a Buehler press to stress induce the transformation ß to a&apos;. Experimental Measurements: The habit-plane orientation, the orientation of subband markings, the orientation relation between the parent ß and the product a&apos;, and the transformation strain for the same plate were determined. To further establish the nature of the subbands, one surface was repol-ished and etched. The bands in the a&apos; were still visible and were found to be optically anisotropic under polarized light. Back-reflection Laue patterns were obtained from the ß matrix and from a region comprising both a&apos; plates and adjacent ß matrix (a Cu target was used). By superposition of the two X-ray diffraction patterns, it was possible to obtain a tentative orientation relationship between the two phases. This result was confirmed by a pattern taken after the specimen was rotated to make the basal-plane pole of the hexagonal a&apos; phase strike the film. This necessitated cutting the specimen to expose the a&apos; plate in the new position relative to the X-ray beam. Analysis of Experimental Measurements On the basis of the aforementioned X-ray patterns, the orientation between parent and product

Jan 1, 1955