Search Documents

Jan 1, 1963

By J. K. Edgar

FOR a number of years the production and use of super-purity aluminum (better than 99.99 pct) has been steadily increasing. High-grade lots of such aluminum show certain outstanding characteristics not found in lower grades containing principally silicon, iron and copper as impurities. One such characteristic is the so-called "self annealing," that is, the recrystallization of the heavily cold worked metal at room temperature.' Interest therefore is aroused as to the effects of the impurities. It is well known that the amounts of silicon and copper which occur in aluminum of better than 99.95 pct are completely soluble, at least at elevated temperatures (above 200°C). Iron, on the other hand, is known to be fairly insoluble in solid aluminum. Thus, a knowledge of the limits of this solubility would be of considerable use in studying the characteristics of the high purity metal. All investigators have agreed that iron has very low solubility in solid aluminum. Rosenhain, Archbutt and Hanson2 reported traces of an aluminum-iron phase in the "purest samples of aluminum obtainable." Gwyer and Phillips3 reported that an iron constituent was visible under the microscope in metal containing ".0088 per cent iron." Roth1 found that in the solid state the solubility of iron in high purity aluminum was 0.01, 0.01, 0.017 and 0.022 pct at 225, 320, 500 and 600°C respectively. Dix5 working with alloys containing less than 0.03 pct impurities, concluded from microscopic and chemical analyses of eutectic areas that the eutectic composition was close to 1.7 pct iron. Dix placed the eutectic temperature at 655°C'. Archer and Fink,6 using high purity aluminum-iron alloys, found that the hypoeutectic liquidus intersects the eutectic horizontal at 1.7 pct. This is in fair agreement with the investigation of the aluminum-iron system by Gwyer and Phillips who placed the eutectic at 1.89 pct iron with a freezing point of 653° PREPARATION AND CHEMICAL ANALYSIS OF ALLOYS Electrolytically refined aluminum (99.991 pct aluminum) and a high purity aluminum-iron alloy (11.45 pct iron) were used in the preparation of the alloys for this investigation. To aid in controlling the iron content of the experimental alloys, an alloy of lower iron content was prepared first from these materials. The high purity aluminum was melted and heated to about 700°C in a plumbago crucible coated with alundum cement and the aluminum-iron alloy was then added. The alloy was thoroughly stirred, fluxed and skimmed and then chill-cast into notch bars. The analyses of the three materials are given in Table I. The alloys for the determination of the solid solubility of iron in aluminum were prepared by melting 600 g total of the aluminum plus the required quantity of the aluminum-iron alloy (No. 92531). These

Jan 1, 1948

By LEWIS F. THOMAS

MINING geologists and mining engineer, rarely give due thought to the geography of mining deposits. They realize, it is true that what may be ore in one place would be only worthless rock in another because f the in accessibility of a smelter r a market; and they may consider the lack of a supply of labor, or water, or power to carry on operations. But they do not think (of these things in terms of geography. Geography may be defined as the science of relationships between earth and man, so geographers are vitally interested in the how and why of mining as it is carried on at different place, having entirely different environment-. Such environments are geographic complexes or composites of natural and cultural elements, which are listed and briefly discussed in the following paragraphs.

Jan 1, 1941

By W. M. Myers

Certain minerals possess inherent color and other properties that make them suitable for the pigmentation of paints, mortar, plaster, concrete, face brick, and other materials. Their production is one of the most ancient of mineral industries and their use by primitive man is well known. These natural pigments have some economic factors in their favor, particularly wide geographic distribution, low cost of production, ease of preparation, chemical stability, and permanence in use so that they continue to form the basis of a small but useful industry. When used in paints such pigments act as a filler and supply body and opacity in addition to color. Natural mineral pigments are prepared for the market by the comparatively simple operations of washing, grinding, blending, and calcining. Any one, or all of these processes may be applied to a single pigment. The development of synthetic pigments and the use of byproduct materials have introduced competition with the products of nature and are having a growing influence on the economic position of the mined minerals. Development of the Industry The industry developed to commercial stature in Pennsylvania largely because of the presence of beds of ocher extending from Easton in a southwesterly direction toward Reading, and a variety of small iron mines in the region. The mining of paint ores in the Lehigh Valley was active as early as 1850 and shortly after the Civil War the establishment of mills expanded production and led to the development of new products and eventually the manufacture of synthetic pigments. Pennsylvania continues to maintain it.s leadership as a producer of mineral colors. Production is recorded also in New Jersey, Illinois, Virginia, Ohio, and Georgia. Iron as a Pigment Iron in various compounds is the most important pigment in nature. The iron pigments are characterized by stability, light fastness, good covering power, high index of refraction, and economy in production. Ferrous compounds display a typical green coloration. This has not been employed as a commercial pigment to any great extent except incidentally in such greenstones as have been used in construction, or crushed and sized for application as a granule to roofing. Ferric oxides are characteristically red and form an important group of industrial pignents. Hydrated ferric oxides exhibit various shades of yellow and are present in such familiar pigments as ocher and sienna. The addition of small amounts of manganese oxide or carbon as organic matter to the yellows produces the brown umbers. Magnetite is one of the few black minerals that grinds to a black powder. The mineral pigments vary from earth colors of low intensity and great dilution of iron content to almost pure iron compounds with high tinting strength and correspondingly greater value. There has been some relationship between the mining of iron ores and the production of mineral pigments; although the production of colors is not carried on appreciably as a byproduct of iron mining. A number of mineral pigment producers, particularly in the eastern states, have operated mines which in the past were small producers of hematite, bog ore, or carbonate ore. The knowledge of the location of the deposit and its possibilities as a producer of pigment are due to its past history as a producer of metallic ore. Many iron compounds may be changed in color by calcination, the end product being Fe2O3, a stable red oxide. The yellow hydrated oxides may be changed to red. The gray carbonate, found in Carbon County, Pa., calcines to a fine red product. Ferrous sulphate (copperas) often available in tonnage as a byproduct of the steel industry, breaks down under heat or chemical action leaving a residual red oxide. Pigments produced by calcination or dissassociation of compounds possess the advantage of fine particle size and ease of grinding. Mineral Pigments MINERAL BLACKS Many black minerals grind to a light colored powder. This characteristic is familiar to the mineralogist as the white streak produced by a black

Jan 1, 1950

By T. J. Woodside

Prior to 1927 the lead blast furnace charge at El Paso consisted principally of direct-smelting carbonate ores, very low in zinc, and the resulting slag seldom carried more than 4.0 pct. With the exhaustion of the mines in Northern Mexico which supplied these ores, they were supplanted with a much smaller tonnage of sulphide concentrates containing appreciable amounts of zinc, and the zinc content of the slag rose to 10.0 pct. The Anaconda Company's slag fuming plant at East Helena, Montana, had then been in successful operation for several years, and it was immediately recognized that, while at that time the production of high zinc slag was small, if the grade held, a plant for the recovery of zinc from the accumulated slag might some day be practical. The grade not only held but became increasingly higher so that by 1946 suffcient slag had been accumulated to warrant the construction of a fuming plant regardless of future slag production from the blast furnaces, and with the removal of Government restrictions on construction at the end of the war the project was undertaken. The general design of the plant follows that at Bunker Hill, with waste heat boiler, unit coal pulverizers and even more extensive instrumentation and automatic control. The area around the lead blast furnaces is rather congested, being cut off from the nearest feasible site for the fuming plant by the copper plant, so that the most practical route for hot slag transfer is through the converter aisle. For this reason and also to make use of the existing converter cranes to serve the fuming furnace, an unused reverberatory at the north end of the converter building was dismantled and the fuming furnace and boiler located in its place. A flue at right angles to the furnace and boiler runs northward to the U-tube coolers and baghouse (Fig 1). From the bag-house a steel flue runs eastward to an existing and long unused 300 ft con- Crete stack. The coal handling system and de-leading plant lie north of the furnace and east of the cooling tubes and baghouse. The furnace is conventional, 8 X 21 X 33 ft high inside and completely water jacketed (Fig 2). There are 21

Jan 1, 1950

Discussion of the paper of O. P. Hood, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 94, October, 1914, pp. 2607 to 2611. R. V. Norris, Wilkes-Barre, Pa.-I have had a little experience with gasoline locomotives and I want to indorse very strongly Mr. Hood's point with regard to the danger of carbon monoxide poisoning. I think .the terrible danger is not fully realized. I was foolish enough some time ago, in investigating a gasoline locomotive, to attempt to walk out of the mine entry behind it, and for several days I felt very seriously the carbon monoxide effects. The use of gasoline locomotives ought to be confined to mine entries where there is a very large amount of air. One of the grave dangers is their great convenience and the temptation to run them into chambers for just a few moments to get a car or two. GEORGE S. RICE, Pittsburgh, Pa.-Apparently one of the great dangers is in the style of the gasoline engine. When my attention was. first directed to the type of gasoline locomotives which I saw in the foreign mines-France, Belgium, and Germany, I was most favorably impressed with them, and they have given no trouble on account of fumes, so far as I could learn. Large numbers of them were being used, but all were of small capacity, and of a kind in which the speed control is by a governor of the hit-or-miss type, the engine running continuously. Their power capacity was very low, if I remember correctly it was not over 4 or 5 h.p., but they were used under favorable conditions where the grades in the mines were slight, since the entries or tunnels bad a slight grade in favor of-the load, making about the same pull for the empties against the grade as for the load with the grade. I understand the hit-or-miss valve arrangement enables a setting that will give more perfect combustion than can be insured with the valve controlled by the operating man, as in the automobile type of valve and engine used in this country. Apparently the European type of locomotive does not have the capacity to permit use under the conditions existing in this country, where most of our entries or tunnels have variable grades and long heavy trips of mine cars are used.

Jan 4, 1915

By Ralph H. Sweetser

AT the end of 1943 the charcoal pig iron capacity of the United States was at the lowest point in over 1110 years, with only one strictly charcoal blast furnace in operation, and all others permanently out of blast except one in Tennessee d reported to he running on part charcoal and part coke. Such a decrease in production has taken place in spite of the O.P A.'s high-premium price on charcoal pig iron of +34 per ton f.o.b. furnace in Michigan. Depletion of the hardwood supply within fifty mlles or inure of the blast furnace is the reason why; the deplorable lack of reforesting is the cause.

Jan 1, 1944

By A.J. PHILLIPS, Wm. B. Price

ADMIRALTY nickel is a new corrosion-resisting and heat-resisting white metal alloy composed of 70 per cent. copper, 29 per cent. nickel and 1 per cent. tin. It has been given the trade name "Adnic." In 1924, Win. B. Price1 described this alloy and its successful use as a diaphragm metal. The physical properties of Adnic at ordinary and elevated temperatures were given in Mining & Metallury.2 A patent3 was granted on Adnic, April 28, 1925. Work was first started on this alloy during December, 1921. An investigation of the patent situation in this country and abroad, and also a search of the literature, did not reveal any work on the ternary diagram, copper-nickel-tin; and the only wrought copper-nickel-tin alloy found was that known as "Newloy," composed of copper, 64 per cent.; nickel, 35 per cent.; tin, 1 per cent. This was being manufactured and sold by Wm.. Gallimore & Sons, Ltd., Sheffield, England, for unplated spoon and fork stock, and first came to our attention in January, 1922. The preliminary work in connection with the development of Adnic was started by casting four, binary copper-nickel alloys of the compositions shown in Table 1. Various amounts of tin were added to each of these mixtures, to produce the series of ternary copper-nickel-tin alloys also given in Table 1. A 200-gm. sample of each of these was cast by melting in a clay graphite crucible and allowing the melt to slowly cool with the furnace. A longitudinal section from each of these castings was polished and etched for-examination. The castings were not homogeneous solid solutions, but showed the usual cored structure associated with cast alloys. However, from an examination of these sections we roughly determined

Jan 1, 1928

By G. K. Manning, A. R. Elsea, A. B. Westerman

A considerable number of high-tem-perature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. .4t the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in vitalliurn after various heat treatments. Howcver, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chro-mium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja and Guertler2 indicated that cobalt and chro-mium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to 85 pct chromium undergo a transformation at [zoo to 12 50 c More recently, Wever and Haschimoto,3 Wever andLange,4and Matsunaga5 carried Out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallogra~hic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Mat-SUnaRa. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these excep-tions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data arid the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitalhum by deter-mining the diagram for the cobalt-chro-mi~m system- Experimental Work For the convenience Of the reader, the diagram as determined by the present investigation is presented in Fig 3. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the melting point for pure chromium is the

Jan 1, 1949

By Wayne L. Worrell

Thermodynamic data for the stable carbides and oxides of chromium, molybdenum, and tungsten have been critically eualuuted and are used to determine the stable condensed phases at 1 atm total pressure in each metal-carbon-oxygen system. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures neces.see)*y to oblain these metals by corbolhermic redlrction under reduced pressures. USING recently reported data for the carbides and oxides of chromium, molybdenum, and tungsten, the stable phases in the Group VI metal-carbon-oxygen systems at specific temperatures and pressures can be determined. The thermodynamically stable regions in each metal-carbon-oxygen system can be completely pictured using a Pourbaix-Ellingham diagram in which the two coordinates are oxygen potential (-RT In Po2) and temperature. Worrell and chipman' have described and constructed such diagrams for the metal-carbon-oxygen systems of vanadium, columbium, and tantalum. Downing2 has used similar diagrams to provide a description of the reactions in submerged arc furnaces. One of the examples which he cited was the Cr-C-O system; however, an improved diagram is presented in this paper using recently obtained data for the carbides of chromium. Although some of the oxides and carbides of the Group VI metals exist over slight ranges of composition,3 all solid phases are represented as stoi-chiometric compounds in the subsequent diagrams. Any error introduced into the calculated equilibria by neglecting the compositional variation of these phases is less than the uncertainty in the thermodynamic data. In a Pourbaix-Ellingham diagram for a three-component system, the phase rule requires that at equilibrium four condensed phases specify a point, three condensed phases determine a line, and two condensed phases define an area. To obtain a well-defined area at high oxygen potentials and teniperatures, the initial carbon to oxygen mole ratio is specified to be more than sufficient to reduce the oxide but not enough to convert all the metal to carbide. Thus, the lowest regions in the subse- quent Pourbaix-Ellingham diagrams represent areas in which the metal and its carbide are the stable condensed phases. Cr-C-O SYSTEM A) Thermodynamic Data. To simplify the subsequent calculations, all thermodynamic data are presented in the form of linear Gibbs-energy-of-formation* equations which were derived for the temperature range 505° to 2000°K and are reasonably accurate over the entire temperature ranges of the diagrams. The thermodynamic data for the compounds occurring in the Cr-C-O system are summarized in Table I. Several volatile chromium oxides have been reported,4 but their influence is negligible in the Cr-C-O system. Thermodynamic data for CO and CO2 were taken from the compilation of Coughlin.5 The only solid chromium oxide sufficiently stable to exist below 1800°K in the Cr-C-O system is Cr2Os.11 The Gibbs-energy-of-formation equation for Cr2O3 was obtained by revising the data tabulated in Coughlin,5 using the heat of formation of ah' and the high-temperature thermal data for chromium.7 In 1953 Richardson8 re-evaluated the original work of Kelley and coworkers,9 who measured the thermodynamic properties of the chromium carbides. However, the high-temperature equilibrium results of Boericke9 yield values for ?G°f of Cr2O3 which are 2 kcal more positive than the accepted data. His results for the chromium carbides are based on the same questionable equilibria. Gleiser10 recently determined the Gibbs energy of formation of Cr3C2 and the equation in Table I was calculated from her data and the thermal data of Kelley and coworkers.9 Thermodynamic data for the Cr7C3 and Cr23C6 carbides were obtained by combining the Cr3C2 data

Jan 1, 1965

By G. K. Manning, A. R. Elsea, A. B. Westerman

INTRODUCTION A CONSIDERABLE number of high-temperature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. At the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in Vitallium after various heat treatments. However, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases- might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chromium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja1 and Guertler2 indicated that cobalt and chromium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to '85 pct chromium undergo a transformation at 1200 to 1250°C. More recently, Wever and Haschimoto,3 Wever and Lange,4 and Matsunaga5 carried out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallographic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Matsunaga. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these exceptions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data and the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitallium by determining the diagram for the cobalt-chromium system. EXPERIMENTAL WORK For the convenience of the reader, the diagram as determined by the present investigation is presented in Fig g. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the, melting point for pure chromium is the

Jan 1, 1948

By H. Siebel, N. A. D. Parlee

MIZIKAR, Grace, and parlee' studied rates of absorption of oxygen in stagnant liquid silver in a new type of open-ended gas-liquid metal diffusion cell, where the capillary diameters used were 1.5, 2, and 3 mm. They reported that the rates appeared to be controlled by the rate of diffusion of oxygen atoms in liquid silver and they used their data to arrive at the following equation as a reasonably good representation of the diffusivity (D) of oxygen in liquid silver: D = (14.7)10-4 exp (-7100 ± 3200)/RT cm2/sec Since this type of diffusion cell offers a promising method of measuring diffusivities of gas atoms in liquid metals, the senior author of this note and his students are carrying on a critical examination of the method, and are attempting to improve and extend the technique. The research reported briefly here was designed to examine more carefully the earlier conclusion1 that the absorption rate is diffusion-controlled, and to find out whether the diameter of the cell could be greatly increased and thus extend the method to systems where gas solubilities and diffusion rates are much smaller than in the case of oxygen in silver. For the purpose of these experiments, the open-ended capillary cell used by Mizikar, Grace, and Parlee was replaced by a small cylindrical crucible (1 to 1.7 cm in diam) containing pure silver (to a depth of 1.3 to 3 cm) resting in the bottom of a closed-ended vertical quartz tube, with an evacuated quartz filler tube just above the crucible to reduce dead volume. The method of measuring the rate of absorption was otherwise very similar to that of Mizikar, Grace, and Parlee and all the same precautions were taken. A much smaller and shorter tube furnace was used for heating, but simi- lar precautions about temperature gradients were observed. This technique was nothing more than the application of a Sieverts apparatus to the measurement of rates of absorption in small crucibles of stagnant liquid silver. In each run the volume of gas absorbed (V) was plotted against the square root of time (vt) and apparent diffusivities were calculated from the slope of the line, as described by Mizikar, Grace, and parlee.' Care was taken to use only the data obtained during the early part of the total absorption period while the cell functioned as one of infinite depth. The results at 1000°C are summarized in Table I and Fig. 1. The following conclusions may be drawn: 1) Diffusion cells up to 1.7 cm in diam yield, within experimental error, the same values for the diffusivity of oxygen (D) as the capillary cells of 1.5, 2, and 3 mm in diam employed by Mizikar, Grace, and Parlee. Cell diameters as large as 1.7 cm are probably not desirable for the most precise work. Intermediate sizes, perhaps 0.5 cm, will be most practical. 2) All absorptions measured were consistent with a model where the rate is controlled by the diffusion of gas atoms in the metal. The fact that runs at absorption pressures ranging from 0.1 to 1 atm (at any one temperature) give

Jan 1, 1965

By John Tyssowski

IN 1925, Harry Howard Stout, then metallurgist for Phelps Dodge Corporation, while investigating the cleaning of cathode copper by various gases at elevated temper-atures below the melting point of the metal, observed in the laboratory that particles of pure copper heated in a closed tube filled with hydrogen seemingly "stuck together." By further investigation he found that there was actual crystal growth across the boundaries of the particles of pure metal; in other words, there was a complete new crystal realignment and growth throughout the newly formed copper mass. It was coalescence, not adhesion; the several parti-cles had become one unit. From this dis-covery has been developed the coalescence process, whereby copper of cathode purity is squirted out in semifabricated form from an extrusion press, by the appli-cation of about 3000 tons pressure on a 10-in. piston. Stout decided that cathode copper pro-duced by electrolytic deposition was the logical source of the pure copper required for the coalescence process, but as there was no way of reducing the ordinary tough commercial cathodes to the small particles required he was confronted by a serious problem at the outset. Under his direction, this problem was solved by William H. Osborn and Harry Howard Stout, Jr. They developed the process and technique for producing cathode copper in brittle, friable

Jan 1, 1940

By A. J. Phillips, C. G. Grant, Wm. B. Price

ADMIRALTY nickel is a new corrosion-resisting and heat-resisting white metal alloy composed of 70 per cent. copper, 29 per cent. nickel and 1 per cent. tin. It has been given the trade name "Adnic." In 1924, Wm. B. Price1 described this alloy and its successful use as a diaphragm metal. The physical properties of Adnic at ordinary and elevated temperatures were given in Mining & Metallury.2 A patent3 was granted on Adnic, April 28, 1925. Work was first started on this alloy during December, 1921. An investigation of the patent situation in this country and abroad, and also a search of the literature, did not reveal any work on the ternary diagram, copper-nickel-tin; and the only wrought copper-nickel-tin alloy found was that known as "Newloy," composed of copper, 64 per cent.; nickel, 35 per cent.; tin, 1 per cent. This was being manufactured and sold by Wm. Gallimore & Sons, Ltd., Sheffield, England, for unplated spoon and fork stock, and first came to our attention in January, 1922. The preliminary work in connection with the development of Adnic was started by casting four binary copper-nickel alloys of the compositions shown in Table 1. Various amounts of tin were added to each of these mixtures, to produce the series of ternary copper-nickel-tin alloys also given in Table 1. A 200-gm. sample of each of these was cast by melting in a clay graphite crucible and allowing the melt to slowly cool with the furnace. A longitudinal section from each of these castings was polished and etched for examination. The castings were not homogeneous solid solutions, but showed the usual cored structure associated with cast alloys. However, from an examination of these sections we roughly determined

Jan 1, 1928

By T. O. Massalski, J. D. Ayers

A massive transformation, 0 —am, takes place in a number of copper-based systems where the ß phase field at high temperatures extends to compositions that are slightly less solute-rich than the limits of the a phase field that exists at lower temperatures. Consequently a solid-state transformation becomes possible that does not involve a change of composition. Within this narrow range of composition the massive am phase can be usually produced in two ways: by a fast quench from the ß phase through the a phase field, or by pulse heating into the a phase field of an undecomposed ß phase retained at room temperature by a prior quench. In the Cu-Ga system the occurrence of a massive am phase has been also observed in alloys whose composition falls outside the equilibrium a phase field1 but not in the Cu-Zn system.2 We have recently observed the occurrence of the ß — am transformation also in two silver-based systems, Ag-Zn and Ag-Cd. The a and 0 phase fields in these systems again slightly "overlap" in a narrow composition range. In the Ag-Zn system this range falls between 36.7 and 40.2 at. pct Zn, and in the Ag-Cd system between approximately 41 and 42.5 at. pct Cd. Alloys were prepared from high-purity materials and cast in quartz tubes under inert atmosphere. No significant change of composition occurred during casting. After homogenizing in the 0 phase field, small pieces of each alloy were reheated at the homogenizing temperatures for a few minutes and quenched into various media. There were examined metallographic-ally after removal of surface layers that may have suffered from contamination or from the loss of the solute element. In the Ag-Zn system extensive areas of the am phase (identified by selective etching, observation of the slip trace variants, and occurrence of twinning) were observed in a comparatively low-zinc alloy (37.8 at. pct Zn) for all quenching media employed: iced

Jan 1, 1969

By T. S. Washburn

Deoxidation is one of the most complex metallurgical operations in the basic open-hearth process. The necessity for deoxidation arises from the fact that the refining operations that precede it require the oxidation of the steel bath. when the refining is completed and the desired composition of the bath has been obtained with respect to the elements subject to control by 'oxidation. there is usually an excess of oxygen present in the bath from the standpoint of the amount desired in the finished steel. The objectives of deoxidation are to control the amount and type of oxides and, although not directly ilnp1it.d by the term or always considered as a Part of the process, to control the amounts of gases such as hydrogen or nitrogen that will be present in the finished steel. There are other aspects to be consideretl in connection with deoxidizing procedures. In addition to the primary objectives of oxide and gas control. the composition of the steel is affected by the elements introduced during the deoxidizing process. Factors in furnace operations are likewise involved, such as slag composition, temperature control. arid heat time. .ill of these should be considered in establishing the most satisfactory deoxidizing procedure for each grade of steel. The purpose of this paper is to outline the objectives of deoxidation as related to steel characteristics, and to summarize the factors in furnace practice and the economic aspects to be considered in connection with deoxidation procedures. Objectives of Deoxidation The primary objectives of deoxidation are the formation and elimination of oxides. The amount of oxygen present in the bath prior to deoxidation is an important factor, since it is the basis of any deoxidation procedure. The oxygen content of the bath is primarily a function of the carbon content, although it is affected also by the temperature, the oxidation of the slag, and transient conditions within the furnace. The relation of oxygen to carbon in the bath is shown in Table I. Table I shows that under actual operating conditions, the amount of oxygen present in the bath is higher than the theoretical amount. This relation would be expected, since the bath is in a state of metastablc equilibrium during the period that the carbon is being eliminated. The most important feature demonstrated by this table, however, is the rapid increase

Jan 1, 1945

By M. van Swaay, C. E. Birchenall

A. S. lBrling (Johnson, Matthey & Co. Ltd., Laboratories)— Because of its initial emphasis upon the production of membranes by powder metallurgy and by normal casting and rolling techniques, this paper is of considerable interest to those concerned with the design and application of industrial diffusion units. As the subsequent performances of the three grades of palladium were not compared in detail, it can perhaps be concluded that specific permeabilities were very similar. A short table in which the absolute diffusion rates obtained by the Authors with their three grades of palladium were compared with those of other investigators18-25 would, however, have been of particular value in view of the very variable results obtained with this membrane material. The Authors state early in the paper that the permeability of the thoriated samples decreased in much the same way as that of the nonthoriated samples. Later, they emphasize that sintered palladium without thoria was very susceptible to poisoning and did not respond as well as the other materials to the decontamination treatment. These results, which suggest that sintered membranes are less effective than those produced by normal methods, have considerable industrial implications, and amplified experimental details would be very welcome. The results of the Authors differ in one important respect from those of other investigators. Thus, no "bleeding" was required to maintain a constant rate of diffusion, although Davis, Darling, and De Rosset found this to be necessary. Davisz3 found that "bleeding" was necessary even when the hydrogen had already been purified by diffusion through a palladium tube, and it would be of value to know the purity of the gas stream emerging from the purification train shown on Fig. 1 of the Authors' paper. The Authors show that diffusion rates varied according to the square root of the pressure difference providing that the palladium membrane was not contaminated in any way. This finding is in agreement with the results of those workers2,18,19,23,24 who diffused their hydrogen through the membrane into a partly or completely evacuated system.Those workers who did not find this square-root law dependence did not have a partial vacuum on the downstream-side of the membrane.'' The difference between the two experimental con- ditions appears to be significant, as the absolute diffusion rates per sq cm of diffusion area are lower when the square-root law dependence is not observed. While the effect could be attributable to poisoning of the membrane it is conceivable that a positive pressure on the downstream side of the membrane might influence the mechanism of diffusion. In view of the capricious behavior of palladium, factors of this type, which are likely to influence its industrial significance, should be carefully considered. M. van Swaay and C. E. Birchenall (authors' 9-eply) — Our Eq. 191 may be compared with several others for hydrogen diffusion in palladium: D = 5.95 x exp (-5770/1)' D = 3.55 x 10"3 exp (-5550/)' D = 4.3 x 10"3 exp (-5620/1')' Other values are given in the literature, but in many cases surface poisoning may have affected the results. No analysis was performed on the hydrogen gas stream after purification. It should be noted that the presence of liquid nitrogen traps near the heated membranes may have set up convection currents and provided the equivalent of "bleeding." The question of whether a partial vacuum existed on the downstream side of the membrane is not clear. Does it imply that there is something unique about the permeability measured near one atmosphere pressure? We do not believe that there is. When square root pressure dependence is not observed, diffusion rates are not measured. Is "absolute diffusion rate per sq. cm. of diffusion area" equivalent to permeability? The terminology is new to us. In any case we doubt very much that pressures of the order of several atmospheres can affect the mechanism of diffusion.

Jan 1, 1962

By B. S. Norris, Charles R. Austin

IN a recent paper the authors1 discussed the reactions to tempering of hypereutectoid steels quenched from 1000° C., as revealed by studies on changes in hardness, electrical resistivity, coercive force and metallographic characteristics. The data, which related specifically to tempering temperatures of 550°, 650° and 710° C., for varying periods up to 125 hr., permitted the following important conclusions: 1. The rate of softening of the steels at the temperatures examined differed markedly although the steels were of "similar" general chemical composition. 2. The temperature of maximum softening spread over a range from about 650° C. to the eutectoid inversion. 3. The divergence in behavior was ascribed, at least in part, to a profound difference in tendency to graphitization on annealing at subeutectoid temperatures. 4. The node of spheroidization of the cementite, as revealed by metallographic studies, also varied considerably in the different steels. The purpose of the present investigation is to pursue further the study of the difference in behavior of the steels on tempering over a wider range of temperature. To this end the following features have received particular attention: 1. Comparison of temperatures of maximum softening of the various steels when the quenched samples were tempered for 5 hr. and for 75 hr. followed by furnace cooling and by quenching in water. 2. Determination of the effect of quenching temperature, prior to tempering, on the rate of softening. Quenching temperatures of 1000° and 850° C. were used in the investigations. 3. Examination of the microstructures obtained with the various heat-treatments employed.

Jan 1, 1938

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

By Kraig W. Grubaugh, Lee W. Saperstein

Rapid growth rate of surface mining for coal has caused many states to increase the rigor and complexity of their surface mining codes. The promulgation of federal surface mining standards may cause those states containing federal land to amend their codes also. Presented is an up-to-date review of these codes with tabular summaries that divide the codes into operative functions. These summaries will be of use to new operators, multiple-state operators, and state officials. Suggestions are made for industrial efforts to present workable and acceptable amendments to these codes.

Jan 1, 1978