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By W. A. Alexander, L. M. Pidgeon

Metallic magnesium and similar meta!s near the top of the electromotive series have been commercially produced by the electrolysis of a suitable molten salt. Despite the success of electrolysis, sufficient inherent objections exist to justify the search for a direct reduction method. Such a method would widen the choice of raw materials, relax the rigid electrolytic requirements of raw-material purity, and, by obviating direct current, over simplicity of plant equipment. This paper describes the pilot-plant development of one such method, which has subsequently formed the basis of operation of six commercial plants-—one in Canada and five in the United States. Unlike aluminum, magnesium is volatile at relatively low temperatures. This physical property, which produces its greater inflammability, also offers possibilities of direct reduction that are not available with aluminum. In the basic reaction MgO + X = XO + Mg if X is nonvolatile, the reaction may be forced to the right at high temperatures by the evolution of magnesium vapor, despite the large negative value of the heat of reaction which is almost bound to follow the use of any available commercial reducing agent. The cheapest X, of course, is carbon, but this notable advantage is modified by the production of a volatile oxide CO, so that both Mg and CO are evolved simultaneously. Elaborate devices are required to shock-cool the equilibrium mixture in order to prevent back reaction. At best, a pyrophoric powder is produced, requiring redistillation to provide marketable metal. The practical development of this process, is due to F. Hansgirg, and his methods have recently been given a trial on a grand scale in the plant at Permanente, California, and smaller plants were previously built in Austria, England and Japan. A second class of reducing agents is available, those which produce nonvolatile oxides. When XO and X are relatively nonvolatile, magnesium is the only volatile member of the system. It may be evolved in a simple distillation step and condensed without the formation of powder. Two basic requirements must bc fulfilled in order that such a reaction may proceed: I. The reducing agent when heated to a reasonable temperature in presence of MgO must cause the production of an appreciable equilibrium vapor pressure of magnesium. This magnesium must be removed continuously. z. A supply of heat must be maintained. In order to fulfill the first requirement, operations must be conducted in vacuo or in a stream of Hz. Owing to its greater efficacy and relative safety, vacuum has been employed in the work to be described. The choice of a suitable reducing agent formed the subject of an extensive series

Jan 1, 1944

By John W. Burd

A system is described for the simultaneous deposition of epitaxial layers on as many as eight substrates. A high degree of uniformity of both physical and electrical characteristics is achieved in the films. Variation of film thicknesses is consistently less than ±10pct within a wafer and from wafer to wafer within a run with the variation typically on the order of 55 pct. Composition variation of GaAs1-x PX layers within a wafer and from wafer to wafer within a run is consistently less than 51 pct. Electrical evaluation of the films by several techniques indicates excellent doping uniformity within a wafer and from wafer to wafer within a run. Mobilities for lightly doped GaAs films at 300°K are consistently >6000 cm2 v-1 sec-1 and mobilities > 7000 cm2 v- 1 sec-1 are regularly attainable. Techniques for the preparation of material with carrier concentrations from 1 x 1015cm-3 to 1 x 1019 cm-3 n-type and 5 x 1016 to 5 x 1018 cm-3 p-type are discussed. METHODS for the preparation of 111-V compounds by vapor phase reactions have been extensively reported in the literature.1-6 Almost all of the apparatus described for these various methods are suitable for processing one or at the most a very limited number of wafers simultaneously. With the recent rapid advances in the use of vapor grown GaAs for microwave oscillators and GaAs1-xPx as visible light emitters the requirements for these materials are steadily increasing. In order to satisfy these requirements it is necessary to move from a laboratory scale apparatus to one which is capable of processing a large number of wafers simultaneously. Desirable features would be a high degree of uniformity among the wafers and good reproducibility from run to run. The apparatus to be described fulfills these requirements very well. DISCUSSION The various methods reported in the literature can be classified under three headings: 1) closed tube, 2) open tube, and 3) the close-spaced method. Of these three the open-tube method is the most amenable for scale-up to a manufacturing process. It is the most versatile and the various operating conditions can be more precisely controlled than with the other two methods. A number of chemical reactions may be used to achieve vapor-phase growth of 111-V compounds. Sev-era1 of the more generally used reactions are shown in Fig. 1. All of these reactions have the following points in common: 1) generation of a volatile group III(Ga) species by the reaction of the transport agent (halide or HC1) with either Ga or GaAs, 2) introduction of the Group V(As and/or PI component, 3) a method of adding dopant, if desired, and 4) a region in which deposition from the vapor will occur and form as a single crystal epitaxial film on the substrates. The laboratory scale reactors permit the hot re-actant gases to flow into the relatively cooler deposition zone and pass successively over the several substrates which are arrayed along the long axis of the tube parallel to the gas flow. With this arrangement the composition of the reactant stream is continually changing as solid material is deposited on each successive substrate. As a result of this changing gas composition the reaction driving force also changes from substrate to substrate and the degree of uniformity of layer thickness, doping level, and so forth, is poor. This effect can be partially overcome by imposing a controlled temperature gradient along the deposition region to compensate for change in gas composition. However, even when this is done variations in layer thickness on the order of 30 to 40 pct are common and as high as 50 pct are frequently experienced between adjacent wafers in the tube. To expand this arrangement to a large number of wafers would only increase the nonuniformity from the first to last wafer in the line. From the above discussion the two undesirable features of changing gas composition and temperature gradient become evident. A reactor system which eliminates or minimizes these undesirable features is one in which the apparatus is mounted vertically as shown schematically in Fig. 2. The vertical mounting permits the disposition of a number of substrates on a suitable support so that all wafers are at the same vertical height in the furnace and hence at essentially the same temperature. By using only a single row of wafers the reactant gas mixture passes over only one substrate in its path through the reactor. Thus the two undesirable features of changing gas composition and temperature gradient are minimized. An additional design feature which further minimizes temperature variations is rotation of the substrate holder. Rotation serves to integrate any radial temperature gradient existing around the resistance heated furnace. A photograph of a reactor assembly at the completion of a run is shown in Fig. 3. MATERIAL PREPARATION Apparatus. Although any of the several chemical systems shown in Fig. 1 are adaptable for use in this apparatus the one generally used is System 2, the hydride synthesis system. This system has been de-

Jan 1, 1970

By John E. Conley, John A. Ruppert

W. B. Mather—A minor recommendation that may be offered to improve the paper is the inclusion of a map of Oregon showing the general location of the various deposits. This is of especial importance to persons like myself who are not familiar with the various areas and counties mentioned. N. S. Wagner and R. S. Mason (authors' reply)—We agree that an index map of Oregon showing the location of the various nonmetallic deposits would add to the paper (fig. 1).

Jan 1, 1951

By John A. Ruppert, John E. Conley

W. B. Mather—A minor recommendation that may be offered to improve the paper is the inclusion of a map of Oregon showing the general location of the various deposits. This is of especial importance to persons like myself who are not familiar with the various areas and counties mentioned. N. S. Wagner and R. S. Mason (authors' reply)—We agree that an index map of Oregon showing the location of the various nonmetallic deposits would add to the paper (fig. 1).

Jan 1, 1951

By Edwin H. Olson, Morton Smutz, Charles J. Baroch

IN 1949 an orebody containing some 10 billion lb of recoverable rare earth metals was discovered in the Mountain Pass district of San Bernardino County, California.1 The following year Molybdenum Corp. of America purchased a number of claims at the deposit and a mill on the property which had been constructed to process the district's gold ores. Average composition of ore from the San Bernardino deposit is less than 0.1 pct ThO2, 25 to 35 pet calcite, 10 pet rare earth oxides, 15 to 20 pet silica, and 30 to 40 pet barite.2 Rare earth content of the ore analyzes 50.7 pet CeO2, 4.2 pet Pr6O11, 11.7 pet Nd2O3, 1.3 pet Sm2O3, and 34.3 pet La2O3, and others.2

Jan 3, 1959

By R. C. Good

Slag control for any kind of steel, rimming, straight carbon or alloy, should start with the charge and be developed well in advance of the tap because its composition, viscosity and temperature will unquestionably govern the physical and chemical properties of the steel when tapped. In the majority of plants producing alloy steels, primary consideration is given to the chemical specifications; physical characteristics usually occupy secondary place in the melter's mind. Recently, however, buyers have indicated limits of machinability, hardenability, grain size and, of course, always wanted steel free from foreign nonmetallic inclusions. It is these latter specifications that require the attention of the operator to the slag and its control. The slag must act as a vehicle for oxidized elements originating from the metallic portion of the charge; it should hold the oxides of phosphorus, silicon, manganese, iron and chromium that come into contact with it either before or after the refining and finishing stage of the heat. It must be used as a transferring medium of oxygen from the atmosphere or oxide additions to the metal and should permit a free escape of gas generated within the charge. Finally, the slag is the principal controlling factor in regulating the rate of oxidation which in turn eventually determines the quality of the steel as measured for the various characteristics mentioned above. With pig iron of uniform composition, the iron oxide in the slag increases as the limestone is increased but with the same addition of stone in every heat, the iron oxide decreases as the silicon is increased in the charge, and vice versa.

Jan 1, 1935

By R. C. Good

Slag control for any kind of steel, rimming, straight carbon or alloy, should start with the charge and be developed well in advance of the tap because its composition, viscosity and temperature will unquestionably govern the physical and chemical properties of the steel when tapped. In the majority of plants producing alloy steels, primary consideration is given to the chemical specifications; physical characteristics usually occupy secondary place in the melter's mind. Recently, however, buyers have indicated limits of machinability, hardenability, grain size and, of course, always wanted steel free from foreign nonmetallic inclusions. It is these latter specifications that require the attention of the operator to the slag and its control. The slag must act as a vehicle for oxidized elements originating from the metallic portion of the charge; it should hold the oxides of phosphorus, silicon, manganese, iron and chromium that come into contact with it either before or after the refining and finishing stage of the heat. It must be used as a transferring medium of oxygen from the atmosphere or oxide additions to the metal and should permit a free escape of gas generated within the charge. Finally, the slag is the principal controlling factor in regulating the rate of oxidation which in turn eventually determines the quality of the steel as measured for the various characteristics mentioned above. With pig iron of uniform composition, the iron oxide in the slag increases as the limestone is increased but with the same addition of stone in every heat, the iron oxide decreases as the silicon is increased in the charge, and vice versa.

Jan 1, 1935

By B. W. Frazier

At a recent meeting of the North of England Institute of Min ing and Mechanical Engineers, during a discussion upon the com pression of air, attention was called to an apparent anomaly in the phenomena attending the compression. At a subsequent meeting this apparent anomaly was explained by Prof. Herschel, and all the facts observed shown to be strictly in accordance with the laws of thermodynamics. Upon reading the report of the discussion in the published transactions of the society, it occurred to me that an attempt to determine mathematically the amounts of energy (whether in the form of heat or of work) expended and absorbed in compressing air, and causing it to perform work by expansion, might prove of use to some who have not access to any treatise upon the application of the laws of thermodynamics to the compression of air, and who have not the time or the inclination to make such application for themselves. The apparent anomaly noticed was this: If air be compressed, and at the same time, by the sufficient application of a cooling medium, kept at a constant temperature, the indicator diagrams in the

By B. W. Frazier

AT a recent meeting of the North of England Institute of Mining and Mechanical Engineers, during a discussion upon the compression of air, attention was called to an apparent anomaly in the phenomena attending the compression. At a subsequent meeting this apparent anomaly was explained by Prof. Herschel, and all the facts observed shown to be strictly in accordance with the laws of thermodynamics. Upon reading the report of the discussion in the published transactions of the society, it occurred to me that an attempt to determine mathematically the amounts of energy (whether in the form of heat or of work) expended and absorbed in compressing air, and causing it to perform work by expansion, might prove of use to some who have not access to any treatise upon the application of the laws of thermodynamics to the compression of air, and who have not the time or the inclination to make such application for themselves. The apparent anomaly noticed was this: If air be compressed, and at the same time, by the sufficient application of a cooling medium, kept at a constant temperature, the indicator diagrams in the

Jan 1, 1874

By John V. Beall

When the mineral seekers came, they brought romance, excitement and, too often, transitory riches. It has been so for uncounted centuries. While the rich ore lasted, living was high and money flowed-mostly out of town. The whole creation was like a circus. The headframe went up like the center pole of the big top. The reduction works was an ingenious affair; an opportunity for self-expression by the mining engineer on the job. When the high grade gave out or the bottom dropped out of the market, the whole show folded. Machinery was scavenged for the next location. About all that was left were the raw footings, like giantsteps on the hillside; and the headframe above the silent diggings. Mostly, the people went away too. Arizona Territory was like that at the turn of the century. It can still happen. But, in copper, the age-old pattern has been disrupted. From Mineral Park in the northwest to Chino in the east and Cananea in the South, a growing number of companies have emerged-large, stable, productive. Southwest copper is truly a mighty industry, accounting for one fifth of world new copper production. In this period of scientific development, changes are fast, often dramatic. But even mining engineers, or possibly more so because they have an intimate knowledge of the industry, fail to appreciate the evolutionary changes that have shaped Southwest copper into what it is today.

Jan 10, 1965

By Nicholas J. Grant, Italo S. Servi

SPECIAL polishing and etching techniques were developed during an investigation of the high temperature mechanical properties of high purity aluminum (99.995 pct Al).* Electrolytic polishing was done successfully in the following electrolyte: 5 ml perchloric acid (72 pct), and 95 ml glacial acetic acid. No special precautions need be taken during the preparation of the electrolyte since no appreciable heat of mixing is evolved. Although the electrolyte is not an explosive, it is recommended that Jacquet's safety rules' be followed during the polishing operation. A voltage of 25 to 60 v gives a good polish in about 2 min at room temperature after preparation on 3/0 metallographic paper. Most of the grain boundaries are visible under the microscope after polishing. Since the current is controlled essentially by the resistance of the bath, it is necessary to keep the anode-to-cathode distance as constant as possible. Accordingly, polishing of irregularly shaped pieces will be difficult. A cooling bath and a stirring system are advisable in order to keep the temperature of the bath uniform and constant. Coarse-grained samples can be macroetched in a few seconds by lowering the voltage below 10 v. This is done after electrolytic polishing, without removing the sample from the bath, Fig. 1. The specimen can be repolished in less than 1 min by raising the voltage above 25 v. The "galvanic etching" technique, which has been described elsewhere,' was found to be helpful not only for macroetching, but also for microetching coarse-grained specimens. In fact, the different orientations of adjacent grains provide good contrast at the grain boundaries, when the sample is observed under polarized light. If the specimen is only partially etched, Fig. 2a, the grain boundaries can be located without completely destroying the appearance of the surface of the specimen. The unetched surface appears black under polarized light. Excellent color contrast is obtained by using a "sensitive tint" plate in the optical system of the microscope. In this case, the unetched surface has a magenta color, while the etched part of the sample assumes different colors varying from green to brown, according to the orientation of the grains. Etch pits were produced on high purity aluminum by using the technique suggested by Lacombe and Beaujard." Good results also were obtained by substituting 70 pct nitric acid for the fuming nitric acid recommended. This gave an etching reagent of the following composition: 70 ml nitric acid (70 pct), 50 ml hydrochloric acid (37.5 pct), and 3 ml hydrofluoric acid (48 pct). An example of the results is shown in Fig- 2b. The outline of the etch pits is revealed sharply if the specimen is observed under polarized light, as shown in Fig. 2c. These metallographic techniques are not suitable for the examination of commercially pure (2s) aluminum. References 'P. A. Jacquet: Metal Finishing (Nov. 1949) 47, p. 62. 21. S. Servi: Metal Progress (1950) 58, p. 732. 3 P. Lacombe and L. Beaujard: Journal Inst. of Metals (1947) 74, p. 1._________________________

Jan 1, 1952

By W. A. Riggs

In a single year the total transportation cost equals nearly 30 pct of the value of mineral commodities, the largest single cost from the deposit to consumer. The magnitude of this economic factor calls for more complete understanding of cost and operational problems between producer and carrier than now exists. Details are given of the costs of providing transportation as well as freight rates for selling transportation. In 1958, transportation of mineral commodities in the United States required 600 billion ton-miles to move 1 3/4 billion tons of products of mines comprising solid fuels, crude oil, industrial minerals and rocks, and ores. Possibly 17 pct was handled by more than one mode of transport, since combinations of several modes of transport may, at times, achieve better service/cost results than any single mode. Total transportation cost of nearly $5 billion equaled roughly 30 pct of the value of the mineral commodities, the largest single cost from the mineral deposit to the consumer. The tremendous magnitude of this transportation undertaking demands much more complete understanding than now exists between mineral producers and carriers about the economic and operational problems of each other. A substantial portion of the daily work of the writer is spent in trying to act as a combination interpreter and catalyst between potential shippers and carriers, hoping to direct both to points of mutual understanding and advantage. For the purpose of this paper, it is necessary to ask mining people to accept some terminology and to try to appreciate the mental approach of the freight rate making people of the carriers. This paper will consider costs of providing transportation as well as freight rates for selling transportation—although these are fields of limited certainty. There are no accurate statistical breakdowns for all modes of transport and types of carriers indicating commodities, volume of traffic, distances, costs, and rates. Much information is available for railroads, and some for the regulated portions of air, motor, pipeline, and water transportation. Unregulated carriers, handling about half of the transportation of products of mines, are not required to report, and very little is known of their activities. Figures used herein are national in scope, unless otherwise indicated, and have generally been derived from Interstate Commerce Commission reports and files. Tonnage figures have been reduced to net tons of 2000 lb. The very generalized comparison of average mileage freight rate levels for various modes of transport provided by Fig. 1 affords advantageous perspective for the entire field of transportation costs. Dashed guide lines show cents per ton-mile, and dotted guide lines show percentage of first class railroad freight rate. While costs of other than railroad transportation more nearly follow constant cents per ton-mile functions, costs of railroad transportation show characteristic taper, or decrease in cents per-ton mile with increasing length of haul. This fundamental difference in cost is due largely to the fact that railroads and pipelines provide their own fully taxed roadway facilities while highway, waterway, and air carriers use government-provided tax-free roadway at no cost other than fuel, license, and certain excise taxes. Thus railroad and pipeline transportation might be said to carry heavy threshold costs in addition to those transportation costs which are directly variable with ton miles of transportation produced. The original basis of railroad freight rate structures lies in the classification of all articles of commerce into railroad class ralings ranging from 7 to 40 pct of first class (100 pct) rate level, dependent on value, hazard, loading characteristics, service requirements, and whether carload or less than carload. Classification tables and mileage-based (but arbitrarily grouped), rate scales are published as tariffs subject to approval by regulatory bodies. Used together, these determine class rates in cents per 100 lb between points in the U. S. Where local commercial or operating conditions render it advantageous for carriers to depart from

Jan 1, 1961

By Leonard Waldo

PROBABLY some of the views advanced in this paper will appear, from a metallurgical standpoint, little less than revolutionary. It is with considerable hesitancy that I venture to offer a few thoughts concerning what, seems to me to be perhaps the most important development of metallurgy since the introduction of Bessemer steel. Dr. John Percy, with that rare insight which characterizes the epoch-making man, described in a communication to the Royal Society, about 1855, an alloy of duminum and copper which he called aluminum-bronze. The name has "stuck." The term "bronze" has been so variously used that I confess I do not know exactly what constitutes a bronze; but I know that in the great materials of engineering simplicity of composition is a cardinal excellence; and I wish to venture the suggestion that aluminum-bronze is not an alloy of aluminum and copper in any such sense as the compounds of tin and zinc with copper (except the copper-tin compound SnCn3) are alloys. There are several reasons which lead me to this view. In the first place, if a series of bars be prepared containing varying percentages of aluminum and copper, and the electrical conductivity of these bars be carefully determined, a curve of conductivity will be obtained, as shown in Fig. 1, which represents the result of such experiments. While I am not sure, at this time, that the values of conductivity shown in this diagram are wholly dependent upon the percentage of aluminum added, the assumption is a probable one; and the curve indicates that an extremely small percentage of aluminum affects the conductivity in a ratio out of all proportion to the amount of that metal. Another reason is drawn directly from experience in the foundry. If we take from the furnace a crucible containing melted aluminum and one containing melted copper, both at a little more than a red heat, and pour them together, the reaction is so intense that the

Jan 1, 1895

By E. T. Stephenson

Wert and Marx1 pointed out that a straight-line relationship exists between the activation energy of a relaxation process and the temperature at which the maximum relaxation occurs. The data available at the time indicated that this relationship held for a number of Snoek peaks, several grain boundary peaks, and pair relaxation in a brass. Theoretical justification for the observed relationship was found in the following equation, which Wert and Marx derived from the theory of interstitial atomic diffusion coefficients:' where AH is activation energy, R is the gas constant, T is the internal friction peak temperature, v is the interstitial atomic frequency, f is the frequency of the applied stress, S is entropy of activation. More accurate internal-friction data on interstitial diffusion in bcc metals have become available since Wert and Marx's paper. Table I gives activation energies calculated by several authors from a combination of elastic aftereffect data and the peak temperatures at several frequencies of measurement. (In the case of Fe-C and Fe-N, the referenced authors5'7'8'10 also used high-temperature diffusion data.) However, diffusion experiments at 150°C and above1'-13—rather than anelastic techniques—were used to determine the activation energy of hydrogen diffusion in Fe-H. In order to plot this recent data as a AH vs T graph we calculated the peak temperatures of the systems listed in Table I (with the exception of Fe-C, Fe-N, and Fe-H) by using published values3'' of AH and Do. These calculated peak temperatures varied by only a few degrees from experimentally determined peak temperatures. The calculated values were felt to represent the better average. A number of investigators have found the peak temperatures in Fe-C and Fe-N to be 38 to 40°C and 20° to 24°C, respectively. The values of 39" and 22°C (312° and 295°K in Table I) were determined by carefully executed experiments.6'8 The hydrogen peak temperature has been measured at 1 cps,12 20 cps,14 and 35,000 cps.15 All hydrogen peak temperatures were adjusted to 1 cps for Table I using AH = 3000 cal per mole. As Fig. 1 shows, the data of Table I fit a straight line at least as well as the earlier data used by Wert and Marx. Linear-regression analysis was applied to the data in Table I. The Fe-H data was omitted because the activation energy has not been experimentally determined in the temperature range of the peak. The analysis yields the equation: with a standard error of 860 cal per mole. The agreement of the data in Table I with the Wert-Marx equation is excellent. Strict application of Eq. [I] forces the linear regression analysis through the origin. In this case, the analysis gives a slope of 62.1 cal per mole per deg, and a standard error of *890 cal per mole. With this value, it follows from internal-friction theory that Hence, Do varies by only 30 pct among these bcc-interstitial systems. Thus, a concept suggested originally by Wert and Marx1 is confirmed by recently published data. The

Jan 1, 1965

By E. Maxwell, C. J. Bechtoldt, H. C. Vacher

IN the course of an investigation of the properties of metals at low temperature there was occasion to determine the constitution of four iridium-osmium alloys. There is very little information in the literature1 on the constitution of synthetic Ir-0s alloys. Zvyagintzev' s has made a comprehensive study of different natural Ir-0s alloys and concludes that alloys containing more than 32 pct 0s have the close-packed hexagonal structure of osmium, whereas those containing less than 32 pct 0s have the face-centered cubic structure of iridium. The alloys studied in this work were prepared by the American Platinum Works, Newark, N. J., and were received in the form of fragments approximately 1.5 mm average diameter. The fragments had been obtained by crushing ingots made by fusing charges of iridium and osmium under an arc and air cooling. The ingots were not given a homogenizing heat treatment. Sample fragments Table I. Results of X-Roy Diffraction and Microscopic Examinations Phases Present as Determined by X-ray Diffraction Osmium Alloy Close- Iridium Face- Packed Centered Osmium, Iridium, Hexagonal Cubic Mlcro- WtPot Wt Pct Structure Structure scope 0 99.9 None Present 1 23.6 76.4 None Present 1 38.7 61.3 Present Present 2 59.4 40.6 Present Present 2 79.0 21.0 Present Not detected 2 99.9 0 Present None 1 Note: Chemical analyses of the iridium, osmium, and alloys were furnished by the American Platinum Works. of the iridium and osmium used in making the alloys also were included. Several fragments of each metal and alloy were examined microscopically and by X-ray diffraction. For the X-ray method the fragments were crushed further to pass a 270-mesh screen, then sealed in evacuated fused-silica tubes, heated to 1100°C for 18 hr, and allowed to cool in the furnace. Powder X-ray diffraction patterns were obtained from the annealed fragments by means of a Norelco camera having a diameter of 114 mm, and unfiltered cobaIt radiation. For the microscopic examination several fragments in the as-received condition were mounted in Melmac, (American Cyanamid Co.) and ground using the conventional series of abrasive papers. The polishing was done with 0-2 diamond abrasive on a Microcloth (Buehler Ltd.) lap, wet with xylene. After polishing, the surface was etched electrolytically in a 10 pct solution of chromic acid or in a 10 pct solution of potassium cyanide. Both reagents attacked the osmium-rich constituent, whereas the iridium constituent was attacked slightly by the chromic acid reagent and not noticeably by the potassium cyanide reagent. The results of the X-ray diffraction and microscopic examinations are summarized in Table I. Fig. 1 shows the microstructure of a 21 pct Ir-79 pct 0s alloy. The results indicate an appreciable solid-solu-bility range of osmium in iridium as was reported by Zvyagintzev.' The solid-solubility range of iridium in osmium is more restricted, apparently less than 21 pct Ir. This implies a large range of composition in which two phases can coexist that was not reported by Zvyagintzev.

Jan 1, 1955

By F. J. Radd, R. L. McGlasson

The mechanisms of corrosion and corrosion fatigue damages to sucker rods are examined from a fundamental electrochemical viewpoint, and the relationships of sucker rod microstructures to these damaging effects are defined. The common corrosive agents in crude oil production and storage are discussed as to types of attacks that they cause. The variations of fatigue strength with alloy content, surface preparation, and stress ranges are analyzed. Finally, conclusions are drawn as to how microstructures largely influence and control sucker rod performance. INTRODUCTION Greater than 90 per cent of the crude oil produced by artificial lift methods is produced through sucker rod pumping systems. In the USA each year more than $14 million is spent for sucker rods in new and old pumping installations. It is important to make this investment a wise one. Essentially, the sucker rod system is a long series of steel rods, operating under alternating stress loadings and under mechanical vibrations, which connect the surface power source with the subsurface pump. These rods often operate in a variety of corrosive media, including water, brines, carbon dioxide, hydrogen sul-fide, and air. Basically, this paper is concerned with the problem of the behavior of certain steels in various corrosive media under high and dynamic stress patterns. The main objective of this paper is to show how, once the stress effects and the corrosive environments are defined, one can still realize structural control and beneficial influence upon corrosion and corrosion fatigue. FUNDAMENTAL DEFINITIONS AND ANALYSIS In the corrosion and stress behavior of this solid state mixture of iron and iron carbide called steel, one must analyze upon what major factors does its service life depend and of what, exactly, is steel composed. The former question can be referred to two external factors and two internal factors. The two major external factors are: 1. the nature of the stress patterns — size and range of stresses present 2. the nature of the corrosion — erosion environment — the corrodent and/or wear involved The two fundamental internal factors that govern the strength and useful life of a steel both in normal duty and in heavy-duty corrosion service are: 1. the nature of the steel volume properties 2. the nature of the steel surface properties For the latter question normal steel is defined as a solid mixture of iron and iron carbide particles, generally with certain accidental and intentional elements present. (The amount of iron carbide present is determined by the carbon content of the steel.) These additional elements generally dissolve into either the iron (ferrite) or the iron carbide (cementite) components.

Jan 1, 1955

Jan 1, 1950

By R. A. Graham, R. W. Rohde

The effect of hydrostatic pressure upon the austenite start temperature of a commercial Fe-28.4 at. pct Ni-0.5 at. pct C alloy has been determined. For pressures to 20 kbar, the austenite start temperature decreased from its atmospheric pressure value of 380°C at the rate of about 4°C per kbar. These data are analyzed by two different thermodynamic approaches; first, considering the transformation as an isothermal process, and second, considering the transformation as an isentropic process. It was found that both these approaches fit the experimental data equally well. The effect of hydrostatic pressure upon the austenite start temperature is best described by considering the mechanical work done during the transformation as that work obtained by multiplying the applied pressure with the gross volume change of the transformation. It is widely recognized1 that strain has an important effect on the initiation of martensitic transformations.* For example, the martensite start tempera- *In this paper, use of the term martensitic transformation implies the reversal of martensite to austenite as wen as the formation of martensite from austenite. ture, M,, may be increased by plastic deformation. Similarly, plastic deformation is observed to lower the austenite start temperature, A,. The effect of uniaxial stress on the M, of iron-nickel alloys has been studied by Kulin, Cohen, and Averbach.2 They found that the martensite start temperature was significantly changed by stresses well within the elastic region. Moreover, the effect of tensile and compres-sive stresses differed. These effects were explained in terms of the interaction of the applied stress with both the dilational and shear components of the transformation strain. The magnitudes of the influence of uniaxial tension, compression and hydrostatic pressure on Ms were measured in 30 pct Ni 70 pct Fe by Pate1 and Cohen.3 Their thermodynamic calculations and similar calculations by Fisher and Turnbull4 predicted the experimental results when the transformation was assumed to occur isothermally at some fixed driving force. This driving force was assumed to be supplied by a combination of the chemical free energy difference between the austenitic and martensitic phases and the work performed during transformation by the applied stress. More recently, Russell and winchel15 reported the effect of rapidly applied shear stress on the reversal of martensite to austenite in iron-nickel-carbon alloys. They performed a thermodynamic analysis of this transformation based upon the assumption that the re- versal occurred adiabatically. They concluded that the applied shear stress did not significantly interact with the transformation strain and thus did not assist in inducing the reversal. Rather they concluded that the reversal was effected by localized strain heating which resulted from the gross local shear deformation of the experiment. In either the adiabatic or isothermal analysis it is necessary to compute the work performed by the interaction of the applied stress and the transformation strains. In the case of hydrostatic pressure this interaction has been treated by two different methods. In either case the applied pressure is assumed to remain constant during the transformation. In one treatment the applied pressure is assumed to interact directly with the dilatational strain associated with the formation of an individual martensite plate.3'4 This local strain has been measured at atmospheric pressure in iron-nickel alloys by Machlin and Cohen.6 In the above treatment this local strain is assumed invariant with temperature and pressure changes. In the other treatment the applied pressure is assumed to interact with the gross volume change of the transformation.7,8 The usefulness of this latter treatment has been demonstrated by Kaufman, Leyenaar, and Harvey7 who calculated the effects of pressure upon the martensite and austenite start temperatures of Fe-10 at. pct Ni and Fe-25 at. pct Ni alloys. Excellent agreement was obtained between their calculations and their experimental data on an Fe-9.5 at. pct Ni alloy. However, this treatment suffers from the fact that the data required to calculate the volume change of the transformation (i.e., the initial specific volumes, the thermal expansion and compressibility data for both the austenitic and martensitic phases) is, in general, not available for any material except pure iron. Thus the calculations of Kaufman et al.7 were necessarily performed by assuming that the volume change of the martensitic transformation in the iron-nickel alloys was that same volume change occurring during the a-? transformation in pure iron. While this approximation may suffice for very dilute alloys it is likely to be inaccurate in high nickel alloys. We have performed measurements of the effect of hydrostatic pressure to 20 kbar on the A, temperature of an Fe-28.4 at. pct Ni-0.5 at. pct C alloy. The composition is similar to the alloy used by Pate1 and Cohen3 to determine the effect of pressure upon the M, temperature. The present measurements permit calculation of the interaction between the applied pressure and the transformation strain. Additionally, measurements have been made which allow precise determination of the gross volume change of the transformation. The data allow direct comparison between the alternate hypotheses of the interaction between the applied pressure and a dilatational transformation strain characterized by either the formation

Jan 1, 1970

By G. M. Crosby

Seven mines with important production records in the Coeur d'Alene lie adjacent to the Gem stocks —the Frisco (Gem), Hercules, Interstate, Rex (Sixteen to One), Success (Granite), Sunset, and Tamarack. Old records are incomplete, but available data given in Table I show these mines have produced 10.550,721 tons of ore containing more than 50 million oz of silver, more than 1.5 billion lb of lead, and about 1 billion lb of zinc (approximately 1.25 million tons of lead and zinc combined). Average ore grade is 4.8 oz of silver per ton, 7.2 pct Pb, and 4.6 pct Zn. This impressive production represents about 12 pct of the District's yield. At present metal prices, with modern beneficiation, the gross value would be more than $400 million. THE GEM STOCKS The Gem stocks, considered to be outliers of the Idaho batholith of Late Cretaceous age, are located in the northern half of the Mullan quadrangle, and extend from the town of Gem, Idaho, along a strike of N30°E for a distance of approximately five miles. They occur as two major masses of monzonitic rocks commonly referred to as the North stock, which covers an area of 1.1 sq miles, and the South stock, which covers 2.6 sq miles. The areal pattern is roughly club-shaped, the North stock representing the handle and the South stock the head of the club. Two and a half miles west and five miles northeast are two groups of smaller stocks, isolated from the main masses but of the same general rock type. This discussion is limited for the most part to the North and South stocks. At the north end, where the intrusion is about 3200 ft wide, the walls are about parallel and dip very steeply west. At the south end, where the mass is about 7000 ft wide at surface, the walls dip away from each other at moderately steep angles. An aeromagnetic survey' detects and outlines with surprising accuracy the two main stocks. as illustrated on the magnetic contour map (Fig. 2). Of particular interest is the location and shape of the magnetic anomaly representing the South stock. The anomaly is centered over the south end of the outcrop, and a westerly extension joins it with a smaller anomaly over the Dago Peak stocks. The latter anomaly, likewise, is located over the south end of the isolated stocks. This pattern suggests the intrusion has greater extent at depth to the south and west. Though correlation between the Dago Peak stocks and the larger masses is suggested, the controversial aspects of the Dobson Pass fault, which separates the two areas, casts doubt on a correlation. Topographically the monzonite stocks are ignored by the drainage pattern indicating these rocks, and the invaded rocks of the Lower Belt Series react similarly to erosion. The drainage patterns of Nine Mile and Canyon creeks cut indiscriminately across the monzonite-Belt contact, resulting in both valleys and ridges in the southern end of the intrusion. Nine Mile Creek traverses diagonally the entire five-mile length of the stocks. The monzonite rocks of the intrusion are referred to locally as granite, but granite is rare and the rocks comprise a wide variety of types. Their characteristics, described in detail by F. L. Ransome and F. C. Calkins,' are summarized by P. J. Shenon.' The principal rock type is coarse-grained, light gray, porphoritic monzonite containing black crystals of hornblende. Pyroxene, epidote, and titanite

Jan 1, 1960

By W. R. Ingalls

In reviewing the history of the metallurgy of zinc, I shall pass hastily over what is only of antiquarian interest. That has been excellently treated by Dr. Bernhard Neumann in "Die Metalle" (1904) and has been described briefly in my "Production and Properties of Zinc" (1902), in my "Lead and Zinc in the United States " (1908), and in other metallurgical works of more or less the same date. In this present monograph, I have it in mind to confine myself mainly to technical practice, especially to that of the last 75 years, prior to which period advance was slow and of no great moment. The ancients made brass by the cementation process, i.e., embedding copper in a mixture of calamine and carbon and heating, whereby zinc oxide was reduced and zinc was vaporized and combined with the copper. Zinc was isolated by some of the alchemists, who named it and knew something of its properties, but made no use of it. Long before then, however, zinc was produced in India. Later it was produced in southern China. Possibly the Chinese obtained their knowledge from India. The Chinese in remote places still produce small quantities of zinc. I have seen photographs of their furnaces; or pots, for they hardly deserve the dignity of being called furnaces. I imagine that they are the same that were used centuries ago, for I cannot conceive of anything more primitive. Anyway, it is certain that the idea of a commercial production of zinc in Europe was imported from the Orient, where the metal was known in commerce as Speauter and Spiauter, whence speltrum and finally our term spelter. Tutanego and Tuteneague are other old names. Dr. Isaac Lawson went to China about 1730, expressly to discover the method of its production. What connection there was between Isaac Lawson and John Champion we do not know, but the latter obtained in 1739 a patent for a process of distillation downward and at some time between 1740 and 1743 erected a works at Bristol and actually began the manufacture of spelter. A production of 200 tons per annum is mentioned. In about the year 1766, Rishop Watson visited the Champion works and saw the process in operation, which previously had been

Jan 1, 1937