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By George A. Roberts

The development of an alloy system, high-speed steel, is used as an example of the progress of physical metallurgy. Tracing the history of men and their thoughts as they studied and invented and modified these materials, the story of high-speed steel since the 1890's is seen to be a long, slow, but steady progression of achievements. Today's multiplicity of high-speed steels are the result. Data are presented on quantitative metallography of carbides in high-speed steel with high vanadium content using the QTM instrument. Grindability as well as mechanical properties are related to the content of excess MC and M6C carbides in a series of high-speed steels and the newer matrix steels. These emphasize the present state of knowledge and show the current stages of thought that may affect the development in succeeding years. It is a great thrill for me, an ex-research metallurgist and ex-practicing metallurgical engineer, to speak to an audience currently engaged in both pursuits on the occasion of the 43rd Howe Memorial Lecture before the Iron and Steel Division of the AIME. I shall not review Henry Marion Howe's distinguished career, so adequately reviewed in Maxwell Gensamer's contribution in the 1965 AIME History of Metallurgy, except to point out that, while leading the life of an intellectual, he worked as a practicing research metallurgist and a practicing metallurgical engineer for significant periods of time and contributed greatly in both areas. For those of you who believe, as I do, that in the intellectual activity of metallurgy we are blessed with an intimate mixture of science and engineering (see Mehl's 1960 Howe Lecture), we might recall that Howe, while pursuing a life of writing and teaching in later years, served as the first Chairman of the Division of Engineering of the National Academy of Sciences. That metallurgists were called upon then to lead an engineering recognition movement is perhaps related to the strong part played by the AIME and its members in the recent establishment of a National Academy of Engineering and to the fact that a metallurgist is its head, 47 years after Howe served. I stress these engineering aspects for I wish to talk about a metallurgical engineering subject today. Alloy systems, physical metallurgy, and steel blended with an historical perspective and a report on new techniques to improve the old will, I trust, be of sufficient interest to bring these lectures back to the physical-metallurgy banner from which they have departed for 4 years. Those process metallurgists, open-hearth fiends, and physical chemists among you will just have to be patient. The development of an alloy system is the engineering application of scientific thought and fact. There are many interesting alloy systems, developed to a high degree of technology and sophistication over the past 40 to 70 years. These systems are bound together and related by a similar set of characteristics. For example, stainless steels are a system in which the members are related by a high chromium content which gives a corrosion-resistant characteristic. A subfamily in this system would be austenitic steels

Jan 1, 1967

By E. H. Jr. Dix

IN selecting the subject, "Acceleration of the Rate of Corrosion by High Constant Stresses," for the 1940 Institute of Metals Division Lec-ture, I have been influenced by its highly theoretical and speculative nature as well as by the great practical importance of the correct inter-pretation and appraisal of the engineering significance of the phenomenon. I lay no claim to originality in talking on this topic, since it has been the subject of discussion for over a quarter of a century. However, as our technical thinking advances, old phenomena take on new and more significant aspects. In our studies at the Aluminum Research Labora-tories, we have encountered many perplexing and seemingly contradictory results and have been fascinated by the problem of dovetailing all of the many pieces of information to make a complete picture. I hope that in the brief period of this lecture I may share with you some of the enjoy-ment we have had in attempting to meet this challenge to metallur-gical science. The emphasis generally has been placed on the spontaneous failure by cracking of a metal under the combined action of high stress and corrosion, hence the present-day use of the terms "stress corrosion" or "stress corrosion cracking." The older term "season cracking," applied more specifically to copper-base alloys, includes, by inference, the element of time. For the purpose of the discussion today I will use "stress corro-sion" to cover broadly the effect of stress in accelerating the rate of corrosion of metals. To stay within the limits of allotted time the dis-cussion will cover the effect of high static stresses rather than repeated or dynamic stresses, which would take us into the related field of corro-sion-fatigue. The subject is particularly appropriate for an Institute of Metals Division Lecture because much the same phenomenon has been observed in almost all metal systems. Thus, in addition to the season cracking of brass may also be mentioned the "caustic embrittlement" of steel boiler

Jan 1, 1940

By F. F. Claussen

The method of making silver ingots in use at this Mint being radically different from that employed at any other Mint of the United States or, so far as known to me, any Mint in the world, there may be some interest in a description of the apparatus used and a brief history of its distinguishing feature, viz., the rotary ingotmould, which, though not a recent improvement, is comparatively unknown. The furnaces used for silver-ingot-melting are four in number and have a capacity of some seventy thousand standard ounces of silver per day of eight hours. This output is increased, when the exigencies of the service demand it, to one hundred thousand ounces. They are built of fire-brick and elevated 21/2 feet from the floor of the melting-room, in order to have space to place iron boxes and to work, in case a crucible breaks in the furnace and its contents run into the ash-pit. The furnaces are circular in horizontal section, 2 $ feet in diameter and 29 feet high inside in the clear, and rest on castiron plates, with top-plates of the same, and sides encased in boileriron. The furnace-covers are also of cast-iron, dome-shaped, and are handled by means of a small crane and lever. The furnaces stand in sets of two, and one crane and one ingot-machine serves two furnaces. The crucibles used are made specially for this purpose of a mixture of black-lead and fire-clay; the size known as No. 200 will contain and safely melt, without danger of slopping over, from 8600 to nearly 10,000 ounces of standard silver; and this is the usual weight of the ingot-melt at this Mint, as against 1800 ounces at the Carson City mint and 2600 to 3000 ounces at Philadelphia and San Francisco. Each crucible will endure, on the average, ten melts. The crucible stands in the center of the furnace, on the bottom of an old one, cut down to a height of about three inches. The fuel used is coke. Experience has shown that, notwithstanding the higher first cost, Connellsville coke is cheaper than Alabama coke and much more suitable to the work. A small triangular black-

Jan 1, 1888

By AIME AIME

TRADITIONALLY, the Annual New York Meetings of the A.I.M.E. cover four days, but the program is growing on each end as well as in the middle, and this year it lasted from 3 p. m., Sunday, Feb. 16, when the Education Division got under way, to 8:40 p. m., Friday the 21st, when a trainload of electrical inspectors, pro tern, got back fro111 the General Electric plant at Schenectady. The meeting has ceased to be a mere three- ring circus: on Wednesday afternoon eight sessions were being held simultaneously in the Engineering Societies Building, if one includes the Woman's Auxiliary, and according to frequent testimony one should include the W. A. as one of the most important units in Institute affairs.

Jan 1, 1936

By Walter G. Perkins

As this particular product holds a place by itself, it seems desirable to give a paper dealing especially with it as a corollary to my paper entitled " The Litharge Process of Assaying Copper-Bearing Ores and Products, and the Method of Calculating Charges."* The process is first to convert the metallic copper into matte by the addition of sulphur, allowing the two elements to combine at the bottom of the crucible when heat is applied. The

Jan 1, 1903

By H. D. Wilde

GREAT emphasis is being placed today on petroleum as a source of chemicals. Such prominence is well merited, for rapid strides have been made in developing processes for the conversion of petroleum into synthetic chemical products, which are now being made on a huge scale. These marvelous accomplishments have resulted in some highly optimistic predictions as to what can be expected in the future. Many of these forecasts are well justified, but some writers, especially those contributing to the Sunday supplements and the popular-cience type of publications, have let their imagination run wild and present a rather distorted picture of the possibilities in this field in the postwar period. Commercial manufacture of synthetic organic chemicals had its beginning in England with the establishment of a plant by Sir William Perkin in 1857 for the manufacture of "Aniline Purple" or "Mauve." The preceding year he had discovered in the laboratory how this dyestuff could be made from aniline, one of the many derivatives of coal tar, and he soon made commercial application of his discovery. Influenced largely by his success, organic chemists began research on production of a vast array of synthetic dyestuffs, medicinals, flavors, scents, and explosives. Rapid progress was made and by the turn of the century hundreds of these products were being manufactured. Most of these synthetic chemicals were derived from materials obtained as by-products in the conversion of coal into coke. These by-products are generally referred to as "aromatics" and are obtained by processing coal tar recovered in the coking process, so they are popularly known as "coal-tar chemicals." During the early years of this century, coal-tar chemistry was the wonder of the age, and rightfully so, since the products so made seemed limitless.

Jan 1, 1944

By Arthur B. Cummins

Diatomite is a siliceous rock of sedimentary origin, which may vary in degree of consolidation, but which consists mainly of the fossilized remains of diatoms. These are microscopic algae of the order Bacillaria. Diatomite is a unique form of silica, there being nothing else found in nature or produced by the manufacturing arts, that has its characteristic physical structure. There are numerous sediments which contain some diatom residues, admixed with a substantial amount of other materials-clay, carbonates or silica. While these are classified as diatomaceous silts, shales, or mudstones, they are not properly diatomite, a designation which is restricted to material of such qualities that it is suitable for commercial uses. The terms diatomaceous earth and kieselgur are synonymous with diatomite. The expressions infusorial earth and tripolite are obsolete. Diatomaceous silica is a definition best used to distinguish the basic component of diatomite, that is, the substance of the silica shell itself and is the major constituent of beneficiated diatomite or processed diatomaceous products. Some highly indurated materials, such as cherty shale, porcelanite, and opaline cherts which have resulted from diagenetic changes cannot be considered as diatomite although they may have been derived therefrom. On the other hand, diatomaceous oozes or loose sediments consisting mainly of diatom residues with or without much organic matter are source materials in process of becoming diatomite. Composition and Properties Pure diatomite is composed of opaline or hydrous silica, with small amounts of associated inorganic components-alumina, iron, alkaline earths, alkali metals, and minor constituents, all of which may occur in solid solution or as an essential part of the opal complex. Crude diatomite on the other hand may contain variable amounts of organic matter and soluble salts, and the usual contaminants of sedimentary formations-particles of rockforming minerals, sand, clay, or carbonates. As occurring in nature, diatomite contains an unusual amount of free water, which may vary from 10 to 60 pct or more. Diatomite, in the dry deposits which are characteristic of most of the important world deposits, occurs as a lightweight, comparatively light colored, "chalklike" material. The apparent density (dry basis) in situ varies from 20 to 40 lb per cu ft. The structure may be either massive or finely stratified. The earth is highly porous, usually soft and easily friable. It is nonreactive with acids and may be tentatively identified by the above characterizations. Confirmation is by microscopic examination which readily reveals the nature of the material. In deposits which contain organic matter the appearance of the material is totally different. The color may vary from light tan or gray to brown, greenish or nearly black. There is frequently difficulty in distinguishing it in the field from peatlike materials, but the difference is readily apparent after calcination. Powdered diatomite or diatomite products have an apparent density (loose weight) of 5 to 16 lb per cu ft, wet densities of 10 to 30 lb per cu ft, specific gravities 1.9 to 2.35, index of refraction 1.42 to 1.48. Diatomite is essentially micro-amorphous, but does show some tendency toward orientation in structure after a cristobalite pattern. Amorphous silica has been considered as a random association of cristobalite crystallites, the size of which are only slightly larger than a unit cell.20 The prop-

Jan 1, 1960

By A. A. Jr. Smith, J. S. Smart

Numerous investigations of the effects of the various impurities common to commercial coppers have been published, and the data have found wide use in industry. Naturally, emphasis has been placed on the oxygen-bearing coppers of the tough-pitch variety, but need is now evident for data covering the oxygen-free condition as well. Furthermore, relatively few of the important reactions between oxygen and the various impurities are well understood, and often the data at hand are not applicable to the low concentrations encountered in commercial coppers. This paper presents the changes in conductivity and softening temperature derived from individual additions of the group VIII triad, iron, cobalt and nickel, to high-purity copper, and constitutes a portion of the copper-research program being conducted at the Central Research Laboratory of the American Smelting and Refining Co. The method of preparation of high-purity copper and its alloys in either the oxygen-free or oxygen-bearing form has been described previous1y.l The purity of this material, and the methods developed to produce it, provide the means for direct investigation of the very low concentration range in which the various impurities generally exist in commercial coppers. The usual necessity for extrapolation to this range using the results obtained from higher concentrations, and the interfering effects of extraneous impurities, are thus simultaneously circumvented. Since previously published data have adequately presented the effects of higher concentrations of iron, cobalt and nickel, the present investigation has been confined to the composition range o to 0.05 per cent. All alloys were initially prepared in the form of oxygen-free continuous cast rod, the weighed alloying additions in suitable form being charged with the pure copper to the continuous casting crucible. The best of the available high-purity alloying materials were used, and spectrographic analyses confirmed the absence of interfering elements from the alloys formed. Each series was compounded in the direction of increasing concentration, starting with pure copper in a new crucible and finishing with the 0.05 per cent alloy. Composition was closely controlled by adding the alloying element in the form of a carefully compounded and analyzed master alloy rendered uniform by continuous casting. The accuracy of this method of synihesis was proved by chemical analysis of the more concentrated alloys, and, accordingly, there is every reason to credit the stated composition of the very dilute alloys in the range where chemical analysis becomes highly uncertain. Oxygen-free samples for measurements of conductivity and softening temperature Were obtained by drawing the continuous cast rod to wire of 0.08I-in. diameter. employing a number of intermediate anneals to refine the grain structure. The

Jan 1, 1942

By A. A. Jr. Smith, J. S. Smart

Numerous investigations of the effects of the various impurities common to commercial coppers have been published, and the data have found wide use in industry. Naturally, emphasis has been placed on the oxygen-bearing coppers of the tough-pitch variety, but need is now evident for data covering the oxygen-free condition as well. Furthermore, relatively few of the important reactions between oxygen and the various impurities are well understood, and often the data at hand are not applicable to the low concentrations encountered in commercial coppers. This paper presents the changes in conductivity and softening temperature derived from individual additions of the group VIII triad, iron, cobalt and nickel, to high-purity copper, and constitutes a portion of the copper-research program being conducted at the Central Research Laboratory of the American Smelting and Refining Co. The method of preparation of high-purity copper and its alloys in either the oxygen-free or oxygen-bearing form has been described previous1y.l The purity of this material, and the methods developed to produce it, provide the means for direct investigation of the very low concentration range in which the various impurities generally exist in commercial coppers. The usual necessity for extrapolation to this range using the results obtained from higher concentrations, and the interfering effects of extraneous impurities, are thus simultaneously circumvented. Since previously published data have adequately presented the effects of higher concentrations of iron, cobalt and nickel, the present investigation has been confined to the composition range o to 0.05 per cent. All alloys were initially prepared in the form of oxygen-free continuous cast rod, the weighed alloying additions in suitable form being charged with the pure copper to the continuous casting crucible. The best of the available high-purity alloying materials were used, and spectrographic analyses confirmed the absence of interfering elements from the alloys formed. Each series was compounded in the direction of increasing concentration, starting with pure copper in a new crucible and finishing with the 0.05 per cent alloy. Composition was closely controlled by adding the alloying element in the form of a carefully compounded and analyzed master alloy rendered uniform by continuous casting. The accuracy of this method of synihesis was proved by chemical analysis of the more concentrated alloys, and, accordingly, there is every reason to credit the stated composition of the very dilute alloys in the range where chemical analysis becomes highly uncertain. Oxygen-free samples for measurements of conductivity and softening temperature Were obtained by drawing the continuous cast rod to wire of 0.08I-in. diameter. employing a number of intermediate anneals to refine the grain structure. The

Jan 1, 1942

OPEN-HEARTH refractories are not merely an accessory to the furnace. They themselves ore the furnace, to all intents and purposes. The steel work of the main structure is merely a frame which helps to support the refractories; and the regenerators, a necessary part of the furnace system, consist almost entirely of refractories with very little supporting structure. Not only do refractories constitute the essential part of the furnace, but they also carry the liquid steel all the way to the point where it begins to solidify. On leaving the furnace the liquid passes through a refractory runner into a refractory-lined ladle, then through a refractory nozzle closed by a refractory stopper on the end of a refractory- protected rod. The liquid is sometimes sent through an additional refractory-lined tun-dish, a supplementary ladle, or a refractory runner for bottom pouring, until it finally enters the iron mold in which it solidifies. Even in the mold, refractory materials are sometimes used to provide a non-conducting "hot top." These materials, from ladle to hot top inclusive, are often referred to as the "pouring-pit refractories." CAUSES OF FAILURE Compared with the equipment used in most industrial processes the open-hearth furnace has a relatively short life. The most important quality of an open-hearth refractory, therefore, is its rate of failure. The discussion here of the individual refractory materials will therefore keep uppermost the question "Why, how, and where does it fail?" The principal causes of failure of open-hearth refractories are, in their order of importance: 1. Reaction with iron oxides. 2. Reaction with slag. 3. Flow and failure under load. 4. Melting. 5. Spallimg. 6. Mechanical breakage. Reaction with Iron Oxides and Slag. This is by far the most important cause of failure. Liquid iron oxide comes very near to being the

Jan 1, 1944

By Strathmore R. B. Cooke, Iwao Iwasaki, C. S. Chang

The effects of aeration on an aqueous suspension of pyrrhotite were studied and their results correlated with flotation tests using xanthates as collectors. The effects of copper activation and of pH variation were determined and possible mechanisms postulated. PYRRHOTITE has long been considered a gangue mineral to be eliminated as tailing in the treatment of various sulphide ores. However, in recent years the world-wide lack of sulphur resources has called attention to this mineral as a potential source of both sulphur and iron. Its importance as an economic mineral, however, has not been particularly emphasized. For this reason very little is known about its response to flotation, except that it can be depressed easily in alkaline circuit, by long aeration,1,2 addition of oxidizing agents,3 or by starch.' The object of this work was to study the floatabil-ity of pyrrhotite. This includes the effect of oxidation by aeration, of copper activation, and of change in pH. Preparation of the Pyrrhotite Sample: It was desirable that the highest grade of pyrrhotite obtainable be used for this experiment, since the presence of other minerals could affect the surface properties.5 However, no pyrrhotite was available as crystals, and massive deposits of hydrothermal origin commonly contain considerable amounts of chalcopyrite. Pyrrhotite concentrate was, therefore, prepared from a sulphide deposit occurring near Aitkin, Minn. The deposit is of pyrometamorphic nature consistirlg mainly of pyrrhotite and pyrite with graphite, silicates, and carbonates as gangue. The ore, already crushed through 3 mesh when received, was screened at 65 mesh and the undersize discarded. The oversize was crushed through rolls, and then stage-ground dry in an Abbe porcelain mill, the —65 mesh portion being screened out after every 15 min of grinding until all the material passed through this size. The ground product was then concentrated with a drum-type dry magnetic separator. The rougher concentrate was cleaned twice and then demagnetized. The final product was split in a Jones splitter and stored in air-tight bottles. Microscopic examination of the concentrate showed that it was relatively clean and free of pyrite, locked particles, and gangue. By means of the krypton gas adsorption method," the specific surface was determined to be 3000 cm2 per g. The chemical and screen analyses of the final concentrate are given in Tables I and II respectively. It is a well-recognized fact that the oxidation of some sulphide ores during stockpiling, grinding, and conditioning affects their flotation behavior. The problem of oxidation may become serious in the case of pyrrhotite, since this is known to be more easily oxidized than many other sulphides. To ascertain the extent of oxidation, an experiment was carried out by aerating an aqueous suspension of pyrrhotite with air, oxygen, and nitrogen as follows. A 300-g sample of pyrrhotite in 2700 ml of water was agitated and simultaneously aerated in a Fager-gren-type laboratory flotation machine. A Precision wet test meter was connected to the air inlet valve, the flow rate of the gas being kept constant at 0.3 cu ft per min throughout the experiment. Samples of approximately 30 ml each were taken from the cell at 0, 4, 10, 20, 35, 60, and 90 min. After the pH was taken, each sample was filtered and the filtrate was analyzed for total iron and sulphur. The iron was determined colorimetrically by the thioglycolate method using a green filter.' The filtrate was oxidized with bromine to convert all of the soluble sulphur compounds into sulphate and this was determined with a Parr turbidimeter." When aeration tests were made in alkaline circuit, calcium hydroxide or sodium hydroxide was added at regular intervals to maintain a constant pH. A similar procedure was followed in an experiment to determine the abstraction of copper. ion by pyrrhotite. In this case various quantities of cupric chloride were added. The filtrate from each sample taken was analyzed for copper, total iron, and sulphur. The carbamate method with a green filter was used for the copper analysis,' since this method could tolerate a considerable amount of iron in the solution. A pneumatic cell, made from a 350-ml fritted glass Buechner funnel, was used for this experiment. The detail of the assemblage has been described elsewhere." In the present work a stainless steel baffle was inserted in the cell. This baffle overcame the tendency for the coarse pyrrhotite particles to be swirled around the wall of the cell and thus fail to collect in the froth. A 50-g sample of pyrrhotite was added to the cell which contained 260 ml of water. When pretreat-ment of the sample was desired, reagents, such as activator and pH regulator, were then added and the pulp was conditioned for a specified conditioning time. Prior to the addition of the collector approximately 15 ml of the solution were removed for pH measurement and for iron and sulphur analyses. Copper when used as activator was also determined. Collector and frother were then added and the pulp was conditioned for an additional 2 min. Air was admitted to the cell and the froth removed. The separation required from 4 to 6 min, depending on the characteristics of the froth. The float and non-float products were filtered, dried, weighed, and assayed for iron.

Jan 1, 1955

By Max Kraut

UNTIL VERY RECENTLY the flotation process has not found much application in the treatment of gold ores. No appreciable improvement has been made lately in the technology of this application; but the possibilities of flotation have been more fully appreciated. Excellent results were obtained long ago, but few operators paid much attention to them. For instance, in 1915 extensive experiments were carried out by Mr. Beauchamp and Minerals Separation on ores from the Dutch-Sweeney mine near Jimtown, Calif. The ore contained gold-bearing pyrite and laboratory tests indicated a 10c. tailing on a $6 head. In 1918 a 300-ton flotation mill using Minerals Separation machines was built based on the results obtained. However, when the mill began full-scale operation, mill heads did not come up to expectation, being only $4; also the-tonnage was considerably less than had been expected. Flotation mill tailing assayed 15c., indicating a recovery of over 96 per cent, so that excellent metallurgical results were obtained. The operation was a success but the patient died.

Jan 1, 1932

By Richard B. Reese, George R. St. Pierre, Robert A. Rapp

The vapor pressures of pure iron and pure chromium have been measured using a Knudsen cell coupled with a mass spectrometer. The experimental results agree well with some previously reported data; heats of sublimation and vaporization have been calculated. From vapor pressure rr~easurernents, the activities of iron and chromium in their binary alloys have been determined for NcY = 0.10 to 0.65 over a 1400" to 1700~ temperature range. The activity of chromium in the liquid alloys was found to exhibit positive deviation from ideal behavior when referred to solid chromium as the standard state; however, for the activity of chromium referred to nonequilibrium undercooled liquid chromium as standard state, the activity behavior is almost ideal. ALTHOUGH the Fe-Cr system is important as the basic system of alloy steels, the thermodynamic properties of this system have not been thoroughly investigated at elevated temperatures. In view of the potential practical applications of such data as well as their contribution to alloy theory, further study of the Fe-Cr system was undertaken. In addition, further development of experimental techniques for equilibrium measurements at high temperature is required. The present research involved an application of the Knudsen effusion method in conjunction with a time-of-flight mass spectrometer. Belton and ~ruehan' have measured the activities in Fe-Ni and Fe-Co alloys by a similar method. Speiser, Johnston, and lackbburn' have determined the vapor pressure of pure solid chromium between 1283" and 1561°K by a Langmuir free evaporation technique. The vapor pressure of chromium was described by the expression: over the temperature range 1283" to 1561°K. McCabe, Hudson, and paxton3 have measured the vapor pressures of pure iron and pure chromium by the Knudsen cell technique around 1500°K. The vapor pressure and heat of sublimation at O°K, AH,", for pure chromium agreed within experimental error with the measurements of Speiser et al. at 1200°C. Kubaschewski and HeYmer~ determined the vapor pressure of pure solid chromium in the temperature range 1170" to 1400°C by the Knudsen effusion technique combined with a radioactive tracer analysis of crS1. Their results agreed with the work of previous investigators. Edwards, Johnston, and Ditmars5 have measured the vapor pressure of pure solid iron by the Langmuir technique between 1356" and 1519°K. The vapor pressure of solid iron in the temperature range studied was given by: The data of McCabe, Hudson, and paxton3 on the vapor pressure of pure iron around 1500°K by the Knudsen effusion technique were in good agreement with those obtained by Edwards et a~.~ Hultgren, Orr, Anderson, and Kelley give the selected values for the AH: of pure iron and pure chromium as 98,990 *200 and 94,340 * 500 cal per mole, respectively. These values are the average values determined in the several investigations by different methods. The Fe-Cr phase diagram7 is shown in Fig. 1. Previous determinations of activities in this system have been carried out by several investigators, but most of the work has been done on solid alloys. Using a Knudsen effusion method with cr5', Kubaschewski and Heymer4 reported that the Fe-Cr system exhibits positive deviation from the ideal behavior for compositions ranging from NCr = 0.0398 to 0.699 at 1170"

Jan 1, 1969

By C. W. Mueller, P. H. Robinson

A technique was developed for depositing single -crystal films of silicon on single-crystal sapphire substrates via the pyrolytic decomposition of SiH4/H2 mixtures. Electron diffraction and X-ray Laue reflection examinations of these films revealed single-crystal patterns. These films were characterized by measuring conductivity type, thickness, resistivity, and Hall mobility. Chemical etching, dislocation staining, and electron-microscopy examination have indicated the presence of low-angle grain boundaries and microtwinning in the silicon films. The role of the sapphire substrate with respect to its quality, orientation, surface finish, and thermal and chemical treatment was investigated. Hall mobility as a function of sapphire orientation was measured. A mobility equal to 88 pct of bulk silicon mobility was attained. Insulated-gate field-effect transistors which have a transconductance of 4000 pmho at 6 ma were fabricated using these films. THE technology of the fabrication of microelectronic circuits with active and passive components directly on a single wafer of semiconductor material has attained a high degree of perfection during the last few years. One inherent difficulty with the single-wafer approach has been undesirable coupling between components arising from the common base material. Several techniques have been developed for minimizing this coupling and obtaining good electrical isolation between components; however, these result in extra capacitance being added to the circuit. The extraneous capacitance of the connecting leads, resistors, and capacitors degrade circuit performance and limit the high-frequency operation of these circuits. Recently there has been considerable interestl-3 in the deposition of silicon films upon insulating substrates. The use of silicon as the semiconductor allows the subsequent utilization of the large amount of technology which has been developed for silicon for the fabrication of good active components. A sapphire substrate supplies an excellent insulating material which at the same time gives a thermal-conductivity improvement of an order of magnitude over glass-type substrates. This paper will describe the results obtained for the deposition of single-crystal silicon layers upon single-crystal sapphire substrates as well as the characterization of these films. I) APPARATUS The 'system used for the growth of silicon films on sapphire substrates by means of the pyrolysis of SiH4/H2 mixtures is shown in Fig. 1. The all-quartz reaction chamber is water-cooled and includes a quartz optical-flat window for use in conjunction with a 5 kw, 2.5 Mc per sec constant-temperature controlled rf generator. The temperature sensor for the rf generator is a thermopile which is focused through the quartz optical flat onto the susceptor surface. With this system the rf generator will hold the temperature of the susceptor to about +0.3°C at 1200°C. The susceptor is supported on a quartz sled inclined to the gas flow to increase the uniformity of the deposition. The water jacket surrounding the reaction chamber is used to keep the quartz wall temperature low enough to limit the decomposition of the silane to the rf-heated susceptor which contains the sapphire substrates. This eliminates the reaction of silicon with the hot quartz to form SiO which deposits out on the apparatus walls, thus obscuring vision, and interferes with the optical measurements of the temperature as well as with the growth process itself. Provision is also made for "n"- and 'p"-type doping by using mixtures of either phosphine or diborane in hydrogen which are added to the silane during the growth process. The hydrogen used is the purest commercially available tank hydrogen further purified by use of a palladium diffuser. The susceptors which were used include 1) spectro-scopically pure graphite, 2) high-purity molybdenum, 3) high-resistivity silicon using a low-resistivity insert to facilitate coupling to the rf generator, 4) silicon carbide-coated graphite. The latter two susceptor materials produced silicon films on sapphire substrates with more reproducible resistivities. Prior to silicon deposition all connecting lines as well as the reaction chamber are thoroughly flushed with argon and then hydrogen. After the hydrogen flow is set, the growth temperature is adjusted to 11009 to 1150°C, and when thermal equilibrium is reached the silane flow is started. The flow rate of the hydrogen must be fast enough so that turbulent flow occurs in the size of reaction tube used, otherwise a streaked nonuniform silicon deposit occurs. After the deposition

Jan 1, 1967

By N. M. Levine

WHETHER the United States and its allies can W meet the challenge of a war brought by the Communists will depend largely on who wins the battle of steel production. At the present stage of the world situation, the United States and the other members of the Western family of nations have the lead on iron curtain countries. But we have no sure way of knowing what is happening at Magnetogorsk and other Russian iron and steel producing centers. We must also face the possibility that we may have to meet the challenge alone. The fortunes of war and world politics can strip us of friends and co-fighters quickly. The destruction of Hiroshima and Nagasaki are indicative of what the world can expect if war-madness ever grasps the earth again. Our domestic supply of high grade open-pit and underground iron ore is dwindling because of the drain of three wars and higher than ever civilian consumption. The production of iron ore and its eventual use in blast furnaces are the critical problems of an armed democracy today. The world crisis has led to efforts towards beneficiation for increasing ore supplies. The huge reserves represented by the magnetic taconites at the eastern end of the Mesabi, once in production, should provide us with a substantial portion of our native ore for many years. The estimated 10 to 20 million tons of concentrates annually can be increased in an emergency. If we had a certainty of peace for the next 50 to 100 years, the situation would be a stable, hopeful one, aided by importations of high grade ore from sources such as Canada and Venezuela. The hard truth is that we have little surety of peace tomorrow morning. Let us assume 'the U. S. could build sufficient processing plants for increasing production of magnetic taconites under the pressure of national emergency. We must also recognize the power of atomic warfare to contaminate an area as large as the Eastern Mesabi. Thus, it becomes imperative to seek some means of protecting our ability to produce the steel we may one day need to survive. The nonmagnetic taconites, completely dwarfing the magnetic taconites areawise as well as tonnage-wise, might provide us with this insurance. Present indications are that they will be considerably more expensive to treat, but in a desperate situation we might be very grateful for ores yielding 40 to 50 pct Fe recoveries at grades of 53 to 58 pct Fe carrying low phosphorus. The University of Wisconsin, because of the difficult iron ore situation in the state, has been working on the nonmagnetic taconite problem for the past three years in the hope of making a contribution toward its eventual solution. In Wisconsin, the Western Gogebic Range has been the state's most effective iron producing area. Today however, only two mines are in operation, both underground and approaching depths of more than 3000 ft. The range, however, does have a large supply of nonmagnetic taconites and presents a promising field for study. While the Gogebic offers one large source of nonmagnetic taconites, Michigan and Minnesota have even greater supplies of such material. Alabama, the northeastern states and the West all have low grade iron ore sources which might be utilized under extreme conditions. The Gogebic Range located in northeastern Wisconsin and northwestern Michigan has a total length of about 70 miles, about 45 of which are in Wisconsin. The iron formation averages 500 to 600 ft in width, dips 70' to the north and strikes at approximately N 63° E. The formation is sedimentary and consists of six distinct members characterized by alternating divisions of ferruginous chert and ferruginous slate. The footwall is generally quartzitic and the hanging wall of a sideritic slatey character. The iron minerals are mainly hematites with some magnetites, goethites, limonites and small amounts of siderite. In the area studied, very small amounts of iron silicates were observed. The magnetites occurred mostly in the Anvil-Pabst and Pence members, mixed with hematites and representing roughly about 10 to 20 pct of the total iron in the formation, thereby characterizing it as nonmagnetic. The gangue is of various forms of silica such as chert, opal and flint. Complete liberation of iron and gangue minerals is rare. There is always some iron present in the chert ranging from jasper-like solutions to fairly coarse iron oxide specks. Likewise, one always finds finely dispersed silica within the iron minerals. In late 1943 the Bureau of Mines carried out a trenching and sampling program in the two mile stretch between Iron Belt and Pence in Iron County, Wis. Preliminary work was based on samples from one of the four trenches cut by the Bureau of Mines. More detailed work following the preliminary analysis was then undertaken on samples composited from all the trenches, thereby giving a wider and more representative coverage of the area. A study of the

Jan 1, 1952

By Frank Fahrenwald

I. INTRODUCTORY METALLURGICAL research has discovered many an alloy possessing properties not combined in any single metal, and progress still consists chiefly in the investigation and utilization of alloys. In the case of iron, the demands of automobiles, high-speed machines and high-duty engines have led to the production of special iron alloys which will meet any reasonable specifications in that field. In like manner, the bronzes, brasses and other alloys of copper have been brought to remarkable perfection, and for nearly every industrial purpose some alloy has been found more suitable than the pure metal. Less complete success has attended the attempt to find substitutes for gold, platinum, and the other precious metals. Indeed, it is not likely that a material can be produced which will possess all the properties of any one of them; yet it is reasonable to hope that, for any given use, the properties required may, be found in some less expensive material. Thus, in incandescent electric lamps, the wire passing through the thick glass neck of the bulb was, until recently, almost universally made of platinum, for the single reason that no other known material, suitable as a conductor, had the same coefficient of expansion as glass. But a comparatively recent investigation of the iron-nickel series' has shown that alloys of those metals may be produced, the coefficient of expansion of which can be accurately controlled between that of iron or nickel and zero. Thus, in that particular industry, a substitute for platinum has been found. According to statistical reports, not only considerable quantities of gold and iridium, but also more than one-third of the annual supply of platinum, are used (and, in the nature of the case, irrevocably lost) by dentists. Platinum is thus employed in several forms. As a thin foil, it serves various purposes for which its high melting point, pliability, chemical resistance, and other properties-including the ease with which

Jan 1, 1916

By Morton Macartney

FOR many years the developers or owners of worthy mining ventures in need of financing have found it almost impossible to obtain such financing under the conditions existing in most other lines of business. High rates of interest and unfair participation in profits have robbed the developers of much of their holdings, and have resulted in over-capitalization and many other like evils. When the general financial condition of the country is bad, this difficulty increases to a point where many operations must cease and hen are thrown out of employment. In 1.934 this situation had developed to such a point that Congress attempted to aid the mining industry. It first authorized the RFC to make loans to recognized and established corporations, individuals, and partnerships engaged in the business of mining, milling, or smelting of ores in June, 1934, limiting such authority to loans adequately secured, the security to consist of mineral acreage. The requirements of the law were stringent and of the 252 requests for loans received up to June 1, 1935, 35 were authorized.

Jan 1, 1936

By P. Niessen, W. C. Winegard, C. J. Beingessner

DURING the last 10 years, several grain-growth studies have been made using zone-refined metals with controlled amounts of solute to elucidate the interaction of solute with moving boundaries. In all these studies, it was more or less implicitly assumed that the alloys used were, after recrystallization and grain growth, homogeneous within the grains with respect to solute and lattice defects. This note deals with observations made on microstructures originating from solidification of dilute alloys and from grain growth. Briefly, the experimental procedure used in these studies was the following: zone-refined cadmium and master alloys were melted and cast in Pyrex under vacuum to produce bars 14 mm in diam and about 150 mm long. These bars were cut into 8-mm-thick slices which were mechanically and chemically polished. The specimens were then deformed 30 pct in compression and given a 1-week anneal at 260°C in argon. After this anneal, a second deformation produced completely recrystallized samples 4 mm thick. The time-temperature controlled anneals were carried out in a bath of silicone oil. After the grain-growth anneal, the specimens were polished in Gil-man's' solution (33 g CrOs, 6 g NazSO, in 100 ml of water). Several etches were used depending on the alloy investigated, but mostly a mixture of concentrated HC1 and HNOj (98:2 vol) was employed. In all the alloys examined, the ease with which substructures could be revealed depended strongly on the crystallographic orientation of the surfaces of the grains. However, very frequently the microstructures to be discussed here etched up over broad areas comprising several grains. Fig. 1 is a micrograph of a Cd-0.05 at. pct Mg alloy annealed for 100 sec at 270°C. Different substructures are seen in this photograph. A denotes the now existing grain boundaries. The well-defined lines and points marked B are the remains of a solidification substructure. The lines are boundaries between cell colonies, and the points are nodes located on regular two-dimensional cells. This cellular structure has the same appearance as that found by weinberg2 for rapidly quenched Zn-Au alloys. The "ghost boundaries", marked C, are very similar in appearance to a grain boundary array in a polycrystalline sample. Repeated polishing and etching showed that all the substructures observed were three-dimensional. To date, the ghost boundaries have been clearly observed in all samples containing 0.005, 0.01, 0.05, and 1 at. pct Mg, and in samples containing 0.01 at. pct Zn. Attempts to outline these ghost boundaries in cadmium alloys containing 0.01 at. pct Ag and Au were only partially successful. In these alloys, parallel lines, having a resemblance to the ghost boundaries in the Cd-Mg and Cd-Zn alloys, were observed, but it was not possible to obtain complete arrays of ghost boundaries which extended over several grains. It is possible that a different etch than that presently employed would reveal the ghost boundaries in the Cd-Au and Cd-Ag alloys as clearly as in the Cd-Zn and Cd-Mg alloys. A close examination of the ghost structure showed that it consisted of linear etch-pit arrays, Fig. 2. The ghost boundaries were resolvable even in grains which showed over-all faceting due to the etching, as seen in the corner of Fig. 2. The general appearance of the ghost structure suggests that it originated during grain growth. This is supported by the observation that the mesh width in the ghost-boundary array generally increased with increasing final grain size. To test whether the ghost structure was formed during the long homogenizing anneal or during the grain-growth anneal, some as-cast samples were deformed and given a grain-growth anneal. This anneal was terminated by air cooling or

Jan 1, 1967

By T. T. Read

TWO papers on health and safety were given Thursday afternoon when a joint session of the Health and Safety Committee and the Mining Methods Committee was held. T. T. Read presided and the first paper, on ventilation at Climax, was presented by the author, L. H. Glanville. In the subsequent discussion by Cloyd M. Smith, P. B. Bucky, B. F. Tillson, D. F. Haley, J. L. G. Weysser, and others a number of interesting points not covered by the paper, which appears in full in the January Mining Technology, were brought out. Ventilation troubles in mines so often hinge on the air being too hot and damp that it was interesting to hear of one where it is frequently too cold and too dry.

Jan 1, 1943

By T. G. Nilan

Steels containing 0.4 and 0.8 pet C have been transformed isothermally at pressures up to 34 kbuv. Decomposilion mechanisms are so intimately related to phase equilibvia that, as the equilibria shift under high pressure, the microstruclures of the decomposition producls change, maintaining at pressure the same correspondence between a given phase equilibrium and a given microstructure as a1 1 atm. A bainitic unicvo-structure occurs in these steels at high pressure that IS observed only at 1 aim abole 1.4 pct C. This strrrcl111,e 1s ruliorzalized in terms of the effect of pressure on the transformation to lower bainite. The pressuve depetlderlce of the kinetics of pearlile formation is descrihed by an absolute rule theory amalysis. The activation volume for the transformation is 7 cu cm per mlole, which is indicative of a phase-interface transformation-rate cotntrol mechanism. This fortmulation, when expressed in terms of known solule effects on the energelics of tvansformation, gives promise of explaining the effects of alloying elemenls on hnrden-abilily, particularly that of 'coball. KINETIC processes in solids are functions of the primary thermodynamic variables of state: composition, temperature, and pressure. Until the development of high-pressure techniques' that permitted the generation of sustained high pressure at high temperatures, metallurgical studies of such reactions were largely limited to isobaric conditions at atmospheric pressure. The data so obtained, and theoretical deductions based on these data, were necessarily incomplete For the particular case of austenite decomposition, a knowledge of the phenomenology of the reaction in terms of all the state variables should lead to a clarification of the process. This deeper understanding should facilitate a decision between conflicting theories that have been proposed to rationalize these phe- nomena. An analysis, derived from an understanding of the transformation mechanisms, may aid in the optimization of alloy steel development. The first studies of the effect of pressure on transformations in steel were made by Kulin et al. in 1952.' In a study of the influence of applied stress on mar-tensite formation in a 30 pct Ni steel, they found that the martensite start (M,) was depressed 8°C per kbar* by hydrostatic pressure. Jellinghaus and Friedewold3 were apparently the first to investigate the effect of pressure on isothermal transformations above the Ms. They found that the bainite transformation rate in a 1.2 pct C, 3.8 pct Mn steel was reduced by a factor of 3 by a hydrostatic pressure of 4 kbar. In both of these investigations,2,3 the M, of the steels studied was below room temperature. Austenitizing and quenching were done at atmospheric pressure, followed by the decomposition of the metastable austenite under pressure. The maximum temperature at pressure in the bainite study3 was 350°C. Until the advent of the present high-pressure devices, it was not possible to conduct isobaric high-pressure heat treatments from austenitizing through isothermal decomposition and quenching. The exploitation of high pressure as a variable in metallurgical studies was greatly advanced by the apparatus and techniques developed by Hall4 and co-workers. Utilizing these techniques, Radcliffe et a1.5 and Hilliard6 etermined the pressure dependence of phase equilibria in the Fe-C system. Hilliard and cahn7 examined the pearlite transformation rate in an AISI 1080 steel and also in a high-purity 0.92 C Fe-C alloy at 1 atm and at 34 kbar and found a 700-fold reduction in rate at pressure in the 1080 steel but only a fivefold reduction in the high-purity alloy. In agreement with the shift of phase equilibria under pressure, the microstructures were hypereutectoid at 34 kbar pressure, whereas they are eutectoid at 1 atm. Determination of the effect of pressure on carbon diffu-

Jan 1, 1968