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By F. W. Glaser

Iron-silicon alloys have had a great influence, in many ways, in modern industry. Silicon steels have been used almost exclusively for the construction of electrical machinery, but have also become an important material for structures which benefit by the high tensile and yield strengths of this material. In elaborating on the early history of work done on iron-silicon alloys, Greiner, Marsh and Stoughton1 went back as far as 1808, and pointed to Berzelius as the first producer of ferrosilicon. During the last twenty years some very important contributions in the form of studies of the iron-silicon system, as well as of the physical properties of these alloys, have been published. In consideration of the brit-tleness and poor machinability of alloys containing more than 5-6 pct Si, commercial interests have stimulated the research done on iron-silicon alloys, but mainly in the range of 0 to 6 pct Si. Yensen2 has shown the influence of im- purities, such as carbon, sulphur and phosphorus on the magnetic properties of 2, 4, and 6 pct Si alloys. Corson3 extended his investigation of physical properties to approximately 32 pct Si, and attributed the brittleness of the high-silicon material to the particular constitutional features of the alloys. Though mentioned earlier in the literature, the effect of nitrogen on crystal growth and magnetic permeability of iron-silicon alloys has been demonstrated recently by Morrill4 and Rostoker,5 respectively. In all the above quoted investigations, except that of Rostoker,5 sand or chill casting processes were employed for the preparation of samples. A major advantage of the powder metallurgy process is that it does away with time-consuming machining in many applications. The powder metal industry is always interested in pro- ducing a finished product employing a material which has presented considerably greater difficulties in manufacture by other methods. Steinit26 described preparation and testing of various Fe-Si alloys which were produced by the powder metallurgy process for the manufacture of armatures for small electric motors or generators. While Steinitz investigated alloys up to 6 pct Si, Rostoker5 went as high as 9 pct Si. The author7 previously discussed the diffusion of iron-silicon compacts containing 6 and 10 pct silicon. It is the object of this paper to study the progress of diffusion occurring in iron-silicon alloys by electrical resistivity measurements. All samples were prepared by pressing and sintering of compacts. Iron, silicon, and Fe-Si powders of various mesh size and compositions were employed to obtain test samples. It was assumed that complete diffusion had been obtained when the electrical resistivity reached a constant value characteristic for that particular alloy. To this end, electrical resistance measurements were used to follow the progress of alloying under various conditions.

Jan 1, 1950

By James P. Sloss

MOST students that plan to enter the mining profession attempt to obtain some kind of practical experience before graduation. Six or seven years ago it was an easy matter for undergraduates to find employment during the summer vacation and return to school in the fall filled with enthusiasm to dig deeper into the theoretical field. However, during the past few years it has become extremely difficult for an inexperienced undergraduate to obtain even a menial job in mining. This was the situation which presented itself to the author and his partner, T. M. Patten several months before school closed in May, 1934. At that time, Mr. Patten's training consisted of two years study in Mining, and mine included three years' study in Mining Geology at the Missouri School of Mines and Metallurgy. With this technical training and no practical experience, we conceived the idea that custom assaying in some of the western mining districts should be a lucrative business. We thought that the renewed interest in prospecting for gold and the opening of new mines should provide more assay work, and believed that we might secure it if we were on the spot where the assaying was needed. We realized that it would be out of the question for us to obtain the necessary equipment with which to establish an assay office. Even if such an office were established we had a maximum of but three months during which to operate. So we determined to build some kind of inexpensive equipment that could be placed in an automobile, or trailer, and be moved from one camp to another. We then began to study the theoretical aspects of assaying and started experimental work with the equipment that we proposed to build.

Jan 1, 1935

By W. Mostowitsh

I. Introductory LEAD sulphate occurs as anglesite, and is formed in every roasting of lead sulphides or sulpho-salts containing lead. In smelting in the blast furnace an ore containing natural or artificial lead sulphate, a large part of the sulphur present goes to the formation of the intermediary product matte which requires further treatment for the recovery of the values it contains. It is therefore of importance to study the behavior of lead sulphate at elevated temperatures, both without and with reducing agents, especially as the information available gives data which are more or less conflicting. II. Decomposition of Lead Sulphate by Heat The dissociation of PbSO4 into PbO and S03 or S02 and 0 has been discussed by many metallurgists. The following data are considered to be representative. Doeltz and Graumann1 found that PbSO4 was not affected by heat at 800° C.; that dissociation began at 900° C., and was rapid at 1,000° when the salt lost in 1 ½ hr. 14.3 per cent. of its weight, the dry salt containing 26.43 per cent. SO3. Hofman and Wanjukow2 summarize their work upon the dissociation of metallic sulphates with the statement that the decomposition of PbSO4 begins at 195° C., but progresses very slowly, with the formation of the basic salt 6PbO.5S03 at 705°; that this salt undergoes a transformation at 847°, begins to be decomposed at 888°, to sinter at 896°, and to fuse at 910°; rapid dissociation begins at 952°, and is accompanied by volatilization of PbO; retardations at 958° and 962° indicate an acceleration of decomposition which, however, is not complete. Proske3 found that PbSO4 gave off at 900° C. in 30 min. only 0.63 per cent. of its SO3, and that the loss increased with

Jan 5, 1916

By E. H. Erwin Gartner

The Rhenish lignite deposit in the Nordrhein-Westphalia province of the German Federal Republic covers an area on the left bank of the Rhine River of about 970 sq miles (Fig. 1). Here, in the Miocene era, some 20 million years ago a lignite seam was formed and later broken, through tectonic movements into several blocks, some thrown down into depths of over 1,500 ft. This deposit consists of a single seam, in places up to 300 ft thick, but averaging about 150 ft. In a few areas, it is split into as many as five seams, separated by barren strata. It contains about 60 billion tons (2000 lb/short ton) of lignite which, however, being relatively young geologically, has, because of approximately 60% moisture, 2 to 8% ash, and low sulfur, a net calorific value of 3,340 Btu. That calorific value increases, however, with rising thickness of the cap rock. About one-third of the yearly production of 90 to 100 million tons of raw lignites is converted into briquets. Raw lignite is pulverized and dried to about 18% water content and then pressed without binder into briquets under a pressure of about 14,000 psi. The briquets are being used primarily for residential heating; their sales, however, have been declining sharply since 1963. On the other hand, the volume of raw lignite used in steam power plants has been rising steadily and amounts at present (1968) to about two-thirds of the total production. Huge steam power plants, such as Frimmersdorf, shown in Fig. 2 (which, with an installed capacity of 2,600 MW [megawatt], represents the world's largest steam power plant) with a generating capacity of up to 300 MW per unit and a total installed capacity of over 6,000 MW, contribute about 26% of the total electric power production of the German Federal Republic.

Jan 1, 1969

By J. A. Morgan

IN the art of roasting sulfides it is well known that the lower the temperature and the higher the pressure of SO, the larger will be the amount of sulfate present in the product. However, the mechanism of sulfate formation is not generally understood. The following experiment" demonstrates in a direct way that, in the roasting of Cu2S, the sulfate forms from the reaction of Cu2O, formed by the oxidation of Cu2s, with gaseous SO, (or SO3) and 0,. Thus, the sulfate does not form at the sulfide surface. The reaction at the sulfide surface is the same whether or not sulfate is formed. Using an indirect method, Ong, Fassell, and Wadsworth' infer that sulfate forms after oxidation, during the roasting of sphalerite, agreeing with the observations of this paper. The method presented here of demonstrating that sulfate forms after formation of Cu2O is to roast a sample of Cu2S and then to locate and identify the phases formed.' A solid cube of cuprous sulfide, made by melting Fisher reagent grade Cu2S powder and measuring about 1.5 cm on edge, was placed on a Nichrome wire grid suspended over the top of an Alundum combustion boat. The assembly was placed in a tube furnace at 600°C and oxygen gas, flowing at 0.60 liters per min, was passed around the specimen for 24 hr. The furnace tube diameter was 1.5 in. The partially roasted sample was removed from the furnace and impregnated with resin No. BR 0014, obtained from the Palmer Products Co., and the impregnated sample was then mounted in Lucite. A cross section was obtained by grinding and the surface was prepared by the following steps: 1) grinding—60 grit, 3M disk, dry; 2) preliminary polishing —60 through 600 grit, 3M disk, dry; 3) polishing— 8 µ diamond putty, silk cloth; and 4) final polishing —1evigated magnesia in isopropyl alcohol, Selvyt cloth. The color micrograph of the polished surface is shown in Fig. 1. The layers present in the micrograph are given along the side. The comwositions of the various layers were established by Debye-Scherrer patterns. From this evidence the following sequence of reactions which occur in the roasting of Cu2S is inferred: 1) The oxidation of Cu2S occurs with oxygen which has been transported through the oxide-sulfate layer by either gaseous or solid state diffu- sion. The products of this reaction at the Cu2S surface are Cu2O and SO,. 2) The SO, diffuses out through the pores in the Cu2O and finally reaches a position in the Cu2O where the oxygen pressure and the SO, pressure have values such that the thermodynamic conditions for the formation of CuSO4 are fulfilled. Then, the mixture of SO2, SO3, and oxygen reacts with the Cu2O to form CuSO1. 3) The CuSO, decomposes by the evolution of SO,, or SO, and O2, to form the basic sulfate. This is reasonable, since the SO, gradient will decrease toward the oxygen gas phase from the CuSO4 layer. 4) For this same reason the basic sulfate will decompose to form CuO. The above sequence of events is based on the assumption that diffusion through the oxide and sulfate layers, rather than the reaction at the sulfide-oxide interface, is rate-determining. This assumption is supported by the observation that these oxide and sulfate layers combined are almost nonperme-able to the flow of gases through them. Acknowledgments This research was supported by the U. S. Air Force, through the Office of Scientific Research of the Air Research and Development Command. The authors wish to acknowledge the helpful suggestions of Ralph Wells of the Applied Research and Developmeit Laboratory, U. S. Steel Corp. References E. A. Peretti: A New Method for Studying the Mechanism of Roasting Reactions. Discussions Faraday Soc. (1948) 4, p. 174. - J. N. Ong, Jr., M. E. Wadsworth, and W. M. Fassell. Jr.: Kinetic Study of the Oxidation of Sphalerite. Trans. AIME (1956) '206, pp. 257-263; Journal OF Metals (February 1956).

Jan 1, 1957

Jan 1, 1957

By J. F Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

By J. F. Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

By C. H. Mathewson

MY treatment of the subject of "Metals of the Future" is imaginative rather than statistical or scientific, because reliable information concerning useful concentrations in the form of ore deposits of by far the majority of the elements does not exist and the chemical, physical, and mechanical properties of the unfamiliar metals are recorded only in fragmentary and uncertain form or not at all.

Jan 1, 1944

By Stuart St. Clair

EARLY in 1936, when the American Petroleum Institute issued -J "American Petroleum Industry," which was a survey of the current position of the petroleum industry, and its future outlook, and the figures for petroleum requirements .for 1950 and 1960 were widely publicized by the several oil journals, the impression was given that the petroleum- industry must be nearing maturity and would by 1950 have passed the high' point of its obligations to business progress in the United States.`' Let -us look at the figures which might conduce, this thought. Referring to p. 32 of the report, the total indicated crude-oil requirements in 1940 are 1,099,000,000 bbl-; for 1950, the peak, 1,109,800,000 bbl.; for 1960 a decline to 1,071,020,000 bbl. This downward trend, then established, is probably expected to continue. And this in the face of a crude production in 1935 of 993,942,000 bbl., 38,858,000 bbl.

Jan 1, 1936

By E. Miller, K. L. Komarek

Equatiorzs have been derived which related maximum solid solubilities in semicondcting compounds having retvograde solidus curves with 1iqllidus data. Liquidus curves in Lke Pb-Te, Pb-Se, ard PB-S systetris have been defermined by thertrzal aralyses. Fvotrz expevimental maximum solibilities ia CdTe, PbTe, uxd PbS vetvograde tetrperatures hale beep1 calculated. TIze resllts support the concept that under certaiz conditiots pronounced itjlections in the liquidis curves arc indzcatiz:e of retropade solidus curves and that the tenlperatltre of the lmaximum solid solubility will be close to the temperature of the point of inflection in the liquidus curve. The maximum solid solihility within a gvoup of homologous cottrpoods SeetlLs to increase with increasing flatness ol the liquidus curvres. The phenomenon of retrograde solubility in metals, i.e., maximum solubility in a solid terminal phase in equilibrium with a liquid phase, has been theoretically predicted by Van aar' in his calculations of hypothetical binary phase diagrams. It was not until 1926, however, that retrograde solubility was experimentally verified in the Zn-Cd system.' Since then many sys- tems with retrograde solubility have been found, so that at present approximately fifty binary diagrams with a retrograde solidus curve are known.3 Meijering4 has critically appraised the accumulated data and has presented calculations which alloy predictions as to whether or not a solidus line will be retrograde. Interest in retrograde solubility increased when it was found that the solidus curves of germanium and silicon alloyed with a great many doping elements are retrrade. The problem was treated thermody-namically by odkinson,% d all available data on solid solutions in germanium and silicon were summarized by Trumbore.7 Although it is to be expected that intermetallic compounds will also exhibit retrograde solubility, experimental evidence is much more limited. Until now retrograde solidus curves have been reported for the compounds de,' be, Ps:" ne," SnSe," and SnS.13 All these compounds are semiconductors, and the solidus curves were usually obtained by determining the carrier concentration at room temperature of samples equilibrated at elevated temperatures and then quenched. It has been hown,'' however, that it is not always possible to quench in the equilibrium compositions from above a certain temperature. Theoretical discussions have either explicitly excluded intermetallic compounds4 or not treated them with respect to retrograde slubilit.j In the following a thermodynamic treatment of retrograde solu-

Jan 1, 1967

By Samuel B. Christy

At the last meeting of the Institute, several contributions were made to the subject of miners' aid funds. Such matters will always form important factors in the administration of large industrial enterprises. From the frequently remote and isolated position of mining properties, it is a subject that often forces itself upon the attention of the mining engineer. Local conditions are usually so variable that no single method can be found equally well adapted to all localities. At the same time, a study of different types is often suggestive and valuable, and it is with this in view that these notes are presented. The Miners' Fund of New Almaden is a remarkably successful example of what may be done for miners by a wise and at the same time firm management, by simply directing their own efforts and without incurring any great expense to the stockholders,—a practical consideration not without importance in most cases. The quicksilver mines of New Almaden are situated at a distance

Jan 1, 1885

By E. A. Anderson

In 1918 the American Society for Testing Materials held a symposium2 on what was then known as season cracking. The sessions included six papers, all on brass. During the ensuing 26 yr., many new workers have come into the field and several other metals have been found subject to failure by stress-corrosion cracking when the right combination of stress and environment is achieved. It is not surprising, therefore, that the present symposium has brought forth 29 papers covering alloys of seven important metals. The phenomenon of stress-corrosion cracking is not necessarily confined to these seven metals. Dix3 has stated, "Indeed, it is probable that ingenious investigators can find solutions which will stress-corrosion crack any known metal or alloy." Mears, Brown, and Dix4 have indicated that stress- corrosion cracking failures are not necessarily limited to metals but may include the plastics. It is to be expected that the increase in the number of metals known to crack in service and the general emphasis on such failures at a symposium such as this will alarm many to whom the subject is un- familiar. Such alarm is not justified by the record. It is true that stress-corrosion

Jan 1, 1945

By W. J. Taylor

Nature has furnished us with fuel in three forms, solid, liquid, and gaseous; solid, the most common; liquid, containing the greatest energy; gaseous, the most convenient for use. The tendency of the day is to the conversion of solid and liquid fuel into the gaseous form. There is magic in the word gas to many men who through ignorance or indifference imagine that by mere conversion into gas an immense quantity of energy can he added to fuel of other forms, forgetful of the law of nature, that. the conversion of any substance from one form to another involves a loss of effective energy, and therefore that if in certain cases more duty can be obtained out of the gas resulting from a given amount of coal than the coal itself will supply when used direct, the cause lies solely in the more efficient utilization of the fuel in its gaseous state. Nevertheless, new processes for making gas are constantly crowded upon our notice with claims of less cost for manufacture and delivery than natural gas, and often of far more energy for the product than is contained in the coal or oil from which it is made. I was recently asked to examine a new process of this kind. From an analysis shown me the calorific energy of the gas approximated 375 heat-units per cubic foot; on ascertaining the quantity of gas claimed to be made from a given amount of solid and liquid fuel, it appeared, that for every 325 heat-units contained in the latter 900 heat-units were alleged to he delivered into the gas, or nearly three times as much energy as the original fuel really held. The extravagant claim of some oil-gas advocates is still frequently heard, that by vaporizing oil with steam and then passing the mixture through a coil of hot iron pipe, an oil-water-gas containing 26,600 heat-units is formed from 1 pound of oil carrying originally 21,000 heat-units, while the only energy expended on the gas has been by the introduction of a -little steam and a little extraneous heat. Theoretically, 1 pound of oil converted into water-gas carries 26,600

Jan 1, 1890

By P. H. Metzger, D. W. Fuerstenau

The activation of sphalerite was found to occur at a much lower rate with Pb++ then with Cut++ or Ag+. To prevent activation with Pb++, the ratio [m in solution must approximate 103. An example is given illustrating how this condition is met in practice through the addition of zinc sulfate and soda ash. In selective lead-zinc flotation, the mill operator, especially the one who is concentrating a partially oxidized ore, often must add zinc sulfate and/or soda ash for effective depression of the sphalerite. In the present paper the authors show how this practice prevents the activation of sphalerite in the presence of Pb++. A number of years ago Gaudin (1) postulated that Zn++ might control the activation of sphalerite with Pb++ through competitive adsorption. However, recent experimentation has shown the activation of sphalerite with Ag+ and Cut++ to be a chemical reaction in which silver or copper ions replace zinc in the sphalerite lattice through the formation of a more insoluble sul-fide (2,3,4) Thus, if activation with Pb++ is similar to that with Ag+ or Cu t+, zinc salts should control the activation of sphalerite not through competitive adsorption but because the ratio of [zn++/Pb++] in solution regulates the extent of the chemical exchange between Zn++ and Pb++ in the solid phase. The objective of this investigation has been to study the kinetics and equilibrium conditions for the uptake of Pb++ by sphalerite and to investigate the prevention of lead activation with zinc salts. BASIC PRINCIPLES Sphalerite activation has been shown to be a replacement reaction wherein a less soluble compound is formed at the expense of the more soluble zinc sul-fide (2,3,4) For example, if sphalerite is placed in an aqueous silver nitrate solution, ZnS gives to the solution more S= than can exist together with Ag+, and hence the following reaction takes place: ZnS + 2 Ag+? Ag2 S + Zn ++; k = [zn ++]/[Ag ++]2 = 10 26 (1) Therefore, ZnS will dissolve in the presence of Ag+ and activation of sphalerite with Ag+ will proceed after monolayer coverage by solid state diffusion until equilibrium conditions are reached in the system (2, 4) Because of the large difference in the solubility of ZnS and Ag2S, zinc salts cannot affect the reaction unless a complexing agent, such as cyanide ions, is present to complex Ag+ more tightly than Zn++ . By complexing Ag+ and Zn++ in solution, the uptake of Ag+ by sphalerite can be regulated by controlling the ratio m. . Experimentally (2) it was found that the activation of sphalerite by Ag+ could be prevented through the addition of NaCN if this ratio reached a value of approximately 10 26. The mechanism of sphalerite activation with copper salts is given by the following reactions: ZnS + Cu ++ ? CuS + Zn + + ; (2) k = [Zn++]/[Cu++] = 10 11 ZnS + Cu + ? Cu2S+ Zn++; (3) Experimentally Mao (3) found that the activation of sphalerite with Cu++ or Cu + was prevented if the ratios expressed in Equations 2 and 3 were approximately l09 and l022, respectively, with cyanide ions as the deactivator. Although zinc salts do not affect the activation of sphalerite with silver or copper ions in the absence of a complexing agent, activation with lead ions theoretically can be controlled by the addition of zinc salts because of the relatively small differences between the solubility of ZnS and PbS (5). Equilibrium

Jan 1, 1961

By R. J. Colony

MINING geology does not lend itself - very readily to a review embracing "improvements in methods," as perhaps do shop practices or laboratory procedures. The "methods" used in mining geology are simply the application of geology to mining; winning the ore, the handling of material, mechanical appliances, all belong strictly to mining proper, and have no place in a review of geology as applied to mining. A comprehensive review would necessarily cover a .very broad field, which could be subdivided into many -parts. Only a few of these can be discussed here. .Those that have been suggested to the chairman indude :

Jan 1, 1930

By W. G. Lidman, H. J. Hamjian

' I HE fabrication of many materials from powders involves a sintering process. A mass of powder will sinter because of the excess free energy over the same mass in the densified state caused by the higher total surface area of the powder. An understanding of the kinetics and mechanism of sintering should assist in improving the properties of such materials. The present investigation conducted at the NACA Lewis laboratory deals with the sintering of chromium carbide. Dry sintering (sintering at a temperature below the melting point) was divided into two stages by Shaler:' the first stage, during which the particles preserve much of their original shape and the voids are interconnected, and the second stage, during which densification occurs and the pores are isolated. The mechanism of forming interfaces between particles, or welding together of particles, has been investigated by Kuczynski2 and may be described by any one or a combination of the following mechanisms: viscous flow, evaporation and condensation, volume diffusion, or surface diffusion. The mechanism by which pores are closed or eliminated (densification) during sintering, is of interest. Grain growth observed during sintering may be attributed to the variation in the surface energies of individual grains, causing some grains to grow at the expense of others. Grain boundary migration occurs presumably by a diffusion process, therefore the rate of grain growth would be expected to increase exponentially with increasing time and temperature. Thus, for practical sintering times of less than 1 hr, a certain minimum temperature may exist at which major structural and property changes will occur. Densification and kinetics of grain growth during sintering under pressure of chromium carbide were investigated to provide additional information which will aid in describing more accurately the sintering process and the mechanisms involved. This material was selected for this study because of the current interest in high strength, oxidation resistant refractory materials, such as carbides, which are sintered to produce solid, dense materials from powders. Sintering under pressure is a process where the heat and pressure are applied to the compact simultaneously, specimens for this work were prepared by sintering under pressure at different temperatures and for various time periods. Experimental Procedure Preparation of Specimens: Chemical analysis of the commercial chromium carbide used in this investigation was as follows: Cr 86.19 pct, C 12.14 pct, and Fe 0.2 pct. X-ray diffraction powder patterns gave characteristic diffraction lines of Cr3C2 crystal structure. Powder particle size was determined microscopically and the average initial particle size was 6 microns with 85 pct between 2 and 10 microns. Specimens sintered under pressure were formed in graphite dies3 heated by induction. Sintering temperatures were measured with an optical pyrometer by sighting into a 3/8-in. hole drilled 1 in. deep at the midsection of the graphite die. A load of approximately 1 ton per sq in. was applied to the powder. The die assembly was heated in 20 min to the highest temperature (2500°F') at which no increase in grain size could be observed, and less than 2.5 min were required to heat from this temperature to the maximum temperature (3000°F). Sintering temperatures and times for the specimens of this investigation are indicated in Table I. Analysis of Specimens: Specimens polished with diamond abrasives were etched to reveal the grain boundaries with a 1:1 mixture of 20 pct potassium hydroxide and 20 pct potassium ferricyanide heated to 160°F. Representative areas of each sample were photographed at 1000 diameters. The largest diameters of all well-defined grains were measured, but only the measurements of 15 of the largest grains were averaged in order to determine an index of grain size on the assumption that they were among the first to begin growth. Densities were determined from differential weighing of the samples in air and water. The reported density values are considered correct within ±0.01 g per milliliter. Results and Discussion Metal compacts have exhibited grain growth when sintered at temperatures about two-thirds of the absolute temperature of their melting point.' Grain growth also occurs during the sintering of chromium carbide and is illustrated by the micrographs shown in Fig. 1. These micrographs were prepared from specimens sintered for 90 min at temperatures ranging from 1371°C (2500°F) to 1648°C (3000°F). Average grain size and density measurements of specimens investigated are presented in Table I. The relationship between grain size and sintering tem-

Jan 1, 1954

By John Chipman, Theodore B. Winkler

IN order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chipman,3 dealt with the simplest possible slag system that would resemble those found in the basic open hearth-the slag system consisting of CaO-MgO-SiO2-FeO. (Taylor's rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemistry of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, Si02, FeO, Fe203, P205, MnO, A1203 and CaF2, but not all of the slag samples contained all of these components at one time. REVIEW OF LITERATURE Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Brings4' von Samson-Himmelstjerna,5 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution ratios

Jan 1, 1946

By P. A. Beck

ACCORDING to a recent hypothesis of Sully,' xY. binary CT phases are characterized by 1.7 bonding 3d electrons per atom, which completely fill the first Brillouin zone. This hypothesis appears to imply that there are no empty 3d orbitals in the u phase, and that, correspondingly, this phase must be dia-magnetic, or at most weakly paramagnetic. On the other hand, Bowen and Hoar' reported that a u phase extracted electrolytically from an alloy steel became ferromagnetic when cooled to about —113°C. In view of the fundamental interest of the problem from the point of view of the electron structure of the u phase, it seemed worthwhile to study the magnetic properties of massive u phase specimens of various known compositions. Sigma specimens of the following compositions were tested: 1—40 atomic pct Fe, 40 atomic pct Cr, and 20 atomic pct Mo 2—35 atomic pct Fe, 35 atomic pct Cr, and 30 atomic pct Mo 3—48.7 atomic pct Fe, 50.2 atomic pct Cr, and 1.1 atomic pct W 4—40.7 atomic pct Co and 59.3 atomic pct Cr All specimens were found to be strongly paramagnetic at room temperature, particularly alloy No. 1. At liquid nitrogen temperature, alloy No. 1 be- came ferromagnetic; the other u alloys remained paramagnetic. Even though apparently not all u alloys become ferromagnetic at liquid nitrogen temperature, in view of their strong paramagnetism it is probable that the electron structure proposed by Sully is not correct. Similar qualitative studies were made with the p, P, and 8 phases." A p phase specimen of 57.2 atomic pct Co and 42.8 atomic pct Mo; a P specimen of 19.9 atomic pct Cr, 37.8 atomic pct Ni, and 42.3 atomic pct Mo; and a 8 specimen of 50.4 atomic pct Ni and 49.6 atomic pct Mo were tested at room temperature, and all were found to be paramagnetic, although considerably weaker than the u phase specimens described above. A test at liquid nitrogen temperature gave similar results for all specimens; none became ferromagnetic. Thanks are due to D. K. Das for preparing several of the alloys and to Pol Duwez of California Institute of Technology for kindly loaning four specimens of cr alloys. References 1 A. H. Sully: The Sigma Phase in Binary Alloys of the Transition Elements. Journal Inst. Metals (1951) 80, p. 173. - K. W. J. Bowen and T. P. Hoar: Low Temperature Ferromagnetism of Sigma Phase in an Alloy Steel. Research (1950) 3, p. 484. 3 S. Rideout, W. D. Manly, E. L. Kamen, B. S. Lement, and P. A. Beck: Intermediate Phases in Ternary Alloy Systems of Transition Elements. Trans. AIME (1951) 191, p. 872; Journal of Metals (October 1951).

Jan 1, 1953

By John Hall

SOME months ago one of the authors was asked to write a paper on the heat treatment of steel castings that would be more comprehensive than other matter lie had published; this is an attempt to present in condensed form the results of experimental work and actual practice carried out for the most part in 1907, 1908; and 1909. It is not a laboratory research and the work done was carried out for the express purpose of putting in practice the processes discovered as fast as possible. Most of the tests are the result of commercial practice and not of bars annealed in our laboratory; most of the micrographs were made for our own records and not for publication. Certain of the micrographs, therefore, are not as clear as we may wish but they were good enough for our purpose at the time they were made. The tests and micrographs are selected from several thousands in our files. All of these micrographs are magnified 60 diameters. These experiments were conducted almost entirely on steel made in a 3-ton bottom-blown converter, and most of the steel illustrated analyzes about 0.05 in phosphorus and sulfur. Unfortunately, a certain number of specimens are shown of which we do not have the complete analysis, but in most cases in which the phosphorus and sulfur vary much from the figure just given that fact is noted. For purposes of comparison, we have included a certain number of micrographs and tests of steel made in the electric furnace, some of which were from specimens made in other shops and some in our own shop, and some tests of acid open-hearth and tropenas steel.

Jan 9, 1919