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By B. D. Cullity

Gold and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,' this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low-temperature beta form will be considered in this paper. Experimental Procedure The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be prepared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsym-metrically in the camera in order to afford a basis for film-shrinkage corrections. A sample homogenized at 500°C gave the same diffraction pattern as a sample taken from the as-melted ingot. General Results The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 + 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the diffraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an LCaverage" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing sornewhat more and somewhat less than so at' pet gold, indicating a fixed composition for AuBe.

Jan 1, 1947

By B. D. Cullity

Gold and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,' this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low-temperature beta form will be considered in this paper. Experimental Procedure The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be prepared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsym-metrically in the camera in order to afford a basis for film-shrinkage corrections. A sample homogenized at 500°C gave the same diffraction pattern as a sample taken from the as-melted ingot. General Results The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 + 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the diffraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an LCaverage" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing sornewhat more and somewhat less than so at' pet gold, indicating a fixed composition for AuBe.

Jan 1, 1947

By John L. Ham, Robert M. Parke

The melting point of molybdenum is 2625° + 50°C. Heretofore the metal has been considered too refractory to be melted in commercial quantities; hence, it has been formed into rod, wire, and sheet by the methods of powder metallurgy, wherein the temperatures do not exceed 90 per cent of the melting temperature. The manipulation of liquid metals at temperatures of about 2000°C. and above presents some difficult problems in heat transfer, in purification, and in container materials. For metals melting at such high temperatures, it is generally regarded as expedient to circumvent the more common melting and casting process by resorting to powder metallurgy. This circumvention is not accomplished without some penalties, the more notable of which are the relatively high cost of the powder metallurgy method and particularly the size limitations of its product. In an effort to overcome the inherent disadvantages of the powder metallurgy method, especially in respect to the limit of size, a project was begun in 1943 at the Climax Molybdenum Co. laboratory to develop a method of melting and casting molybdenum capable of producing larger bodies of molybdenum than were then obtainable. Later, from Feb. I, 1944, to Aug. 31, 1945, the project was under the supervision of the National Research Committee, Division One. In peacetime, too, there are needs for molybdenurn, which make consideration of another process desirable; for example, large parts for heat engines generally, the omnipresent demand for metal of higher quality and lower cost, and the development of molybdenum-base alloys. This paper describes methods for melting and casting molybdenum, with details of the special process needed to make molybdenum castings ductile, and reports some of the properties of what may be regarded as a new, or at least modified, form of the metal. First Process for Melting and Casting Molybdenum The maintenance of a temperature greater than 2625°C. in a 'pace large enough to melt several pounds of molybdenum may involve the loss of heat at a Very considerable rate. For melting molybdenum, therefore, the source of heat must be of high potential and of fairly high power. Evidently, also, the source of heat must not impair the purity of the product. The electric arc operating in vacuum appeared to meet these requirements and was accordingly the first choice as a source of energy. A number of arc devices for melting molybdenum were examined, and several were tried. In the first experiment, a 20-kw., 60-cycle-per-second alternating-current arc was operated between two horizontal and opposed electrodes of molybdenum- In this arrangement the falling droplets of molybdenum solidified below the arc in an irregular mass. This experiment did not produce a useful casting, but the data obtained indicated that

Jan 1, 1947

By John L. Ham, Robert M. Parke

The melting point of molybdenum is 2625° + 50°C. Heretofore the metal has been considered too refractory to be melted in commercial quantities; hence, it has been formed into rod, wire, and sheet by the methods of powder metallurgy, wherein the temperatures do not exceed 90 per cent of the melting temperature. The manipulation of liquid metals at temperatures of about 2000°C. and above presents some difficult problems in heat transfer, in purification, and in container materials. For metals melting at such high temperatures, it is generally regarded as expedient to circumvent the more common melting and casting process by resorting to powder metallurgy. This circumvention is not accomplished without some penalties, the more notable of which are the relatively high cost of the powder metallurgy method and particularly the size limitations of its product. In an effort to overcome the inherent disadvantages of the powder metallurgy method, especially in respect to the limit of size, a project was begun in 1943 at the Climax Molybdenum Co. laboratory to develop a method of melting and casting molybdenum capable of producing larger bodies of molybdenum than were then obtainable. Later, from Feb. I, 1944, to Aug. 31, 1945, the project was under the supervision of the National Research Committee, Division One. In peacetime, too, there are needs for molybdenurn, which make consideration of another process desirable; for example, large parts for heat engines generally, the omnipresent demand for metal of higher quality and lower cost, and the development of molybdenum-base alloys. This paper describes methods for melting and casting molybdenum, with details of the special process needed to make molybdenum castings ductile, and reports some of the properties of what may be regarded as a new, or at least modified, form of the metal. First Process for Melting and Casting Molybdenum The maintenance of a temperature greater than 2625°C. in a 'pace large enough to melt several pounds of molybdenum may involve the loss of heat at a Very considerable rate. For melting molybdenum, therefore, the source of heat must be of high potential and of fairly high power. Evidently, also, the source of heat must not impair the purity of the product. The electric arc operating in vacuum appeared to meet these requirements and was accordingly the first choice as a source of energy. A number of arc devices for melting molybdenum were examined, and several were tried. In the first experiment, a 20-kw., 60-cycle-per-second alternating-current arc was operated between two horizontal and opposed electrodes of molybdenum- In this arrangement the falling droplets of molybdenum solidified below the arc in an irregular mass. This experiment did not produce a useful casting, but the data obtained indicated that

Jan 1, 1947

By E. A. Nesbitt

The important permanent-magnet alloys 15 years ago contained carbon and depended upon it for their permanent-magnet properties. In recent years great advances have been made in a number of new alloys substantially free of carbon. These include Remalloy,' an alloy of iron, cobalt, and molybdenum, the various iron-nickel-aluminum alloys of the Mishima2 type, and the more recent Alnico V3 in which the best properties are developed by heat-treating in a magnetic field. The Mishima and the Alnico types of alloys are very brittle and after casting must be ground to size. This article describes a permanent-magnet material4 that can be machined as cast, and when handled with some care can be rolled to thin sheet and drawn to fine wire. Optimum magnetic properties are developed by a simple heat-treatment, and at this time the ductility of the alloy disappears. If the cast alloy is heat-treated without cold-working the mag netic energy product is about 1.0 X 106. This material is called Vicalloy I (pronounced vicalloy, V for vanadium, I for iron, and C for cobalt). When the alloy is first hot-worked and then considerably reduced in area by cold-swaging, drawing or grooved rolling, it is found that after heat-treatment the magnetic energy product measured in the direction of previous extension can be increased to 2.0 to 3.5 X 106. These higher values have been obtained only after reductions in area of 75 to 95 per cent, and since the material hardens considerably during working, the reduction ordinarily can be accomplished only in fine wires, although larger sizes can be reduced by the use of powerful machinery. When the material has been cold-worked in such a manner as to improve its energy product substantially, it is called Vicalloy 11. Commercial use of Vicalloy has been made in the recording of speech. Tape 0.002 by 0.050 in. has been found superior in quality to all others tried, and is now used in the Western Electric Mirrorphone 5 In a variety of forms Vicalloy I or I1 is useful in many laboratory instruments, and in experiments in which the sizes and shapes required cannot be obtained with the other more brittle permanent-magnet materials. In 1936, during a study of other age-hardening magnetic systems, it occurred to the author that some of the iron-cobalt-vanadium alloys might be suitable for permanent magnets. The proportions of iron, cobalt, and vanadium were varied and a range of alloys of particular interest was found, as shown by the indicated area in Fig. I. The limits of this range of composition are 30 to 52 per cent iron, 36 to 62 per cent cobalt, and 4 to 16 per cent vanadium. The compositions indicated by points outside this area were also tested. Preparation and Properties OF Vicalloy I The alloys were usually cast in graphite molds into bars 3/4 in. in diameter and

Jan 1, 1946

By E. A. Nesbitt

The important permanent-magnet alloys 15 years ago contained carbon and depended upon it for their permanent-magnet properties. In recent years great advances have been made in a number of new alloys substantially free of carbon. These include Remalloy,' an alloy of iron, cobalt, and molybdenum, the various iron-nickel-aluminum alloys of the Mishima2 type, and the more recent Alnico V3 in which the best properties are developed by heat-treating in a magnetic field. The Mishima and the Alnico types of alloys are very brittle and after casting must be ground to size. This article describes a permanent-magnet material4 that can be machined as cast, and when handled with some care can be rolled to thin sheet and drawn to fine wire. Optimum magnetic properties are developed by a simple heat-treatment, and at this time the ductility of the alloy disappears. If the cast alloy is heat-treated without cold-working the mag netic energy product is about 1.0 X 106. This material is called Vicalloy I (pronounced vicalloy, V for vanadium, I for iron, and C for cobalt). When the alloy is first hot-worked and then considerably reduced in area by cold-swaging, drawing or grooved rolling, it is found that after heat-treatment the magnetic energy product measured in the direction of previous extension can be increased to 2.0 to 3.5 X 106. These higher values have been obtained only after reductions in area of 75 to 95 per cent, and since the material hardens considerably during working, the reduction ordinarily can be accomplished only in fine wires, although larger sizes can be reduced by the use of powerful machinery. When the material has been cold-worked in such a manner as to improve its energy product substantially, it is called Vicalloy 11. Commercial use of Vicalloy has been made in the recording of speech. Tape 0.002 by 0.050 in. has been found superior in quality to all others tried, and is now used in the Western Electric Mirrorphone 5 In a variety of forms Vicalloy I or I1 is useful in many laboratory instruments, and in experiments in which the sizes and shapes required cannot be obtained with the other more brittle permanent-magnet materials. In 1936, during a study of other age-hardening magnetic systems, it occurred to the author that some of the iron-cobalt-vanadium alloys might be suitable for permanent magnets. The proportions of iron, cobalt, and vanadium were varied and a range of alloys of particular interest was found, as shown by the indicated area in Fig. I. The limits of this range of composition are 30 to 52 per cent iron, 36 to 62 per cent cobalt, and 4 to 16 per cent vanadium. The compositions indicated by points outside this area were also tested. Preparation and Properties OF Vicalloy I The alloys were usually cast in graphite molds into bars 3/4 in. in diameter and

Jan 1, 1946

By G. Derge, Lo Ching Chang

The chemical and physical propertties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use. These processes are carried out at high temperatures and involve such complex chemical systems that funda-mental scientific knowledge of the Properties and behavior of these slags is inadequate. Various hypotheses have been Proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenckl and the recent Papers of Chipman and co-authors. Another proposal is that these compounds dissociate by com-plete6 or partial ionization, the evidence for which has been reviewed by Martin and Derge.? whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: 1. Studies of solidified 51% samples by X ray diffraction, petrography, and similar methods that can be used at room temperature. The correlation of this information with the high-temperature properties of the molten slag is uncertain. 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature. However, even these data present problems of interpretation because they require a complete knowledge of the metal phase. 3. Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret. Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information. The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems cao-sio2 and cao-120,-SiO2 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1948

By G. Derge

The chemical and physical propertties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use. These processes are carried out at high temperatures and involve such complex chemical systems that funda-mental scientific knowledge of the Properties and behavior of these slags is inadequate. Various hypotheses have been Proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenckl and the recent Papers of Chipman and co-authors. Another proposal is that these compounds dissociate by com-plete6 or partial ionization, the evidence for which has been reviewed by Martin and Derge.? whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: 1. Studies of solidified 51% samples by X ray diffraction, petrography, and similar methods that can be used at room temperature. The correlation of this information with the high-temperature properties of the molten slag is uncertain. 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature. However, even these data present problems of interpretation because they require a complete knowledge of the metal phase. 3. Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret. Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information. The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems cao-sio2 and cao-120,-SiO2 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1948

By G. W. King, A. Bogrow, L. F. Marek

The purpose of this paper is to present the data and some interpretation of the results of a laboratory study of the reduction of iron ore and the deposition of carbon from the reducing gas mixtures in such reductions. One major object of the study was to determine the effect of gas pressures on these chemical processes. Effort was made to approximate the conditions of temperature, gas composition, linear and mass gas velocities, pressure range, and extent of reduction prevailing in commercial blast furnaces. The results show that the reduction of Fe203 proceeds by two steps, largely consecutive under the conditions used herein: reduction of Fe203 to FeO, and reduction of FeO to Fe. Unless the gas has a CO!CO, ratio greater than 2.1 only the first step occurs under these conditions (850°C) but the following generalizations apply to either step or to the combination. The rate of reduction of relatively fine ore particles .at any time is proportional to the mass rate of supply of CO (provided some of it is thermodynamically available): the rate therefore is proportional to the linear velocity at constant pressure, or to the pressure at constant linear velocity. Thus, the rate of reduction may be increased without increase in linear velocity of the reducing gas by increasing the mass velocity of the gas and increasing the pressure correspondingly to avoid any increase in the linear velocity. The rate "constants"—i.e., the efficiency of conversion of the "available" CO supplied— is not actually constant but decreases as the reduction proceeds, and is a function only of the state of the ore; i.e., of the amount of reduction already accomplished and hence of the amount of CO passed. The particle size of ore used in nearly all the experiments was relatively small (8 to 14-mesh). The rate of reduction in run 16 with 3 to 8-mesh ore particles is within experimental error the same as with the finer ore. Although this would indicate an absence of effect due to particle size in this range of ore particles, it is desirable to have more data on other ore sizes and on ore of different densities before arriving at any generalizations on this point. Although it is possible to extend the analysis of these results to consideration of the more detailed kinetics and mechanism of iron oxide reduction, such extension is beyond the scope of the present paper. From the experiments on carbon deposition, it was evident that if carbon deposition is increased at all by the application of pressures up to 10 psi ga., such increase appears to be less than the experimental and analytical error. It appears safe to conclude that at top pressures on the order

Jan 1, 1948

By L. F. Marek, G. W. King, A. Bogrow

The purpose of this paper is to present the data and some interpretation of the results of a laboratory study of the reduction of iron ore and the deposition of carbon from the reducing gas mixtures in such reductions. One major object of the study was to determine the effect of gas pressures on these chemical processes. Effort was made to approximate the conditions of temperature, gas composition, linear and mass gas velocities, pressure range, and extent of reduction prevailing in commercial blast furnaces. The results show that the reduction of Fe203 proceeds by two steps, largely consecutive under the conditions used herein: reduction of Fe203 to FeO, and reduction of FeO to Fe. Unless the gas has a CO!CO, ratio greater than 2.1 only the first step occurs under these conditions (850°C) but the following generalizations apply to either step or to the combination. The rate of reduction of relatively fine ore particles .at any time is proportional to the mass rate of supply of CO (provided some of it is thermodynamically available): the rate therefore is proportional to the linear velocity at constant pressure, or to the pressure at constant linear velocity. Thus, the rate of reduction may be increased without increase in linear velocity of the reducing gas by increasing the mass velocity of the gas and increasing the pressure correspondingly to avoid any increase in the linear velocity. The rate "constants"—i.e., the efficiency of conversion of the "available" CO supplied— is not actually constant but decreases as the reduction proceeds, and is a function only of the state of the ore; i.e., of the amount of reduction already accomplished and hence of the amount of CO passed. The particle size of ore used in nearly all the experiments was relatively small (8 to 14-mesh). The rate of reduction in run 16 with 3 to 8-mesh ore particles is within experimental error the same as with the finer ore. Although this would indicate an absence of effect due to particle size in this range of ore particles, it is desirable to have more data on other ore sizes and on ore of different densities before arriving at any generalizations on this point. Although it is possible to extend the analysis of these results to consideration of the more detailed kinetics and mechanism of iron oxide reduction, such extension is beyond the scope of the present paper. From the experiments on carbon deposition, it was evident that if carbon deposition is increased at all by the application of pressures up to 10 psi ga., such increase appears to be less than the experimental and analytical error. It appears safe to conclude that at top pressures on the order

Jan 1, 1948

By R. P. Fischer

A large production of vanadium during the war helped Germany to meet her critical requirements for the ferroalloy metals. Vanadium was needed not only in the ordinary high-speed too1 steels, but in other as a substitute for chromium, nickel, and molybdenum, which were scarce. Lacking a source of vanadium ore, however, the vanadium was obtained as a by-product of the steel industry—va-nadium-bearing pig iron smelted from iron ores containing about o. I per cellt V was blown in converters to yield vanadium-rich slag, from which vanadium was recovered by chemical treatment. The production capacity obtained was said to be about 6,500,000 lb. of vanadium a Year. Although the general Processes of Preparing vanadium-rich slags as well as the recovery methods described herein are known, some of the details presented may be of interest to both the American steel industry and the vanadium producers. No adequate data on the cost of the vanadium produced in Germany are known, but it seems likely that the cost exceeds the commonly quoted domestic price of about $1.10 per pound of contained VzOa. Information on the German vanadium production was obtained by a team of geologists from the Geological Survey* United States Department of the Interior, during investigations in May and June 1945 of the German utilization of low-grade raw materials. These investigations were sponsored by the Chief of Engineers, War Department. It is a pleasure to acknowledge the aid obtained from Messrs. H. C. Smith and J. D. Dickerson, investigators assigned to the Army Ordnance section of C.I.O.S., and Mr. C. F. Park, Jr., of the Geological Survey team. The data on vanadium recovery from iron ores were obtained from the Kaiser Wilhelm Institut fiir Eisenforschung, the Hermann Goring steel plant at Watenstedt, and from notes made by other investigators at other German steel plants. Preparation of Vanadium-rich Slags Most German iron ores contain only about 0.1 per cent vanadium, or even less, but some of the scandinavian iron ores available to the German iron industry in the past contain a little more than 0.1 per cent. In general German practice of vanadium recovery, nearly all of the vanadium in the ore goes into the pig iron, which is blown in the Thomas converter, yielding a slag containing about I per cent V. This slag is remelted, the vanadium again going with the iron, which is again blown in a converter, yielding a slag that averages about 10 per cent V. This slag is treated at special chemical plants, by the process of a sodadizing roast, water leach, and acid precipitation of vanadium oxide. The Herman Goring steel plant at Watenstedt used the low-grade Salzgitter iron ores, the average composition of which is shown in Table I, column I. The acid and basic iron produced in the blast furnaces contained about 0.3 per cent V. A Thomas

Jan 1, 1948

By R. P. Fischer

A large production of vanadium during the war helped Germany to meet her critical requirements for the ferroalloy metals. Vanadium was needed not only in the ordinary high-speed too1 steels, but in other as a substitute for chromium, nickel, and molybdenum, which were scarce. Lacking a source of vanadium ore, however, the vanadium was obtained as a by-product of the steel industry—va-nadium-bearing pig iron smelted from iron ores containing about o. I per cellt V was blown in converters to yield vanadium-rich slag, from which vanadium was recovered by chemical treatment. The production capacity obtained was said to be about 6,500,000 lb. of vanadium a Year. Although the general Processes of Preparing vanadium-rich slags as well as the recovery methods described herein are known, some of the details presented may be of interest to both the American steel industry and the vanadium producers. No adequate data on the cost of the vanadium produced in Germany are known, but it seems likely that the cost exceeds the commonly quoted domestic price of about $1.10 per pound of contained VzOa. Information on the German vanadium production was obtained by a team of geologists from the Geological Survey* United States Department of the Interior, during investigations in May and June 1945 of the German utilization of low-grade raw materials. These investigations were sponsored by the Chief of Engineers, War Department. It is a pleasure to acknowledge the aid obtained from Messrs. H. C. Smith and J. D. Dickerson, investigators assigned to the Army Ordnance section of C.I.O.S., and Mr. C. F. Park, Jr., of the Geological Survey team. The data on vanadium recovery from iron ores were obtained from the Kaiser Wilhelm Institut fiir Eisenforschung, the Hermann Goring steel plant at Watenstedt, and from notes made by other investigators at other German steel plants. Preparation of Vanadium-rich Slags Most German iron ores contain only about 0.1 per cent vanadium, or even less, but some of the scandinavian iron ores available to the German iron industry in the past contain a little more than 0.1 per cent. In general German practice of vanadium recovery, nearly all of the vanadium in the ore goes into the pig iron, which is blown in the Thomas converter, yielding a slag containing about I per cent V. This slag is remelted, the vanadium again going with the iron, which is again blown in a converter, yielding a slag that averages about 10 per cent V. This slag is treated at special chemical plants, by the process of a sodadizing roast, water leach, and acid precipitation of vanadium oxide. The Herman Goring steel plant at Watenstedt used the low-grade Salzgitter iron ores, the average composition of which is shown in Table I, column I. The acid and basic iron produced in the blast furnaces contained about 0.3 per cent V. A Thomas

Jan 1, 1948

By E. P. Shoub, J. P. Riott, R. C. Buehl

Pilot-plant tests have demonstrated that it is possible to produce low-sulphur sponge iron (0.03 to 0.0; per cent sulphur) as a continuous process in an internally fired rotary kiln from iron ore or mill scale; a solid carbonaceous reducing agent; and dolomite to control the sulphur content. The proportion of dolomite employed is small, so that it does not add materially to the cost of the sponge iron. The entire operation is carried out at temperatures well below the melting point of iron, so that the product is discharged in granular form. Compared with other methods for the production of sponge iron, the rotary-kiln method has the advantage of simplicity and low cost of equipment and, in addition, requires little labor for the operation of the process. The pilot-plant equipment used for this work was sufficiently large to demonstrate that the production of low-sulphur sponge iron in rotary kilns is feasible and that the costs are not excessive for applications in which sponge iron has distinct advantages over competing materials. This report constitutes a part of a program by the Bureau of Mines under a special Congressional appropriation for studying gaseous and solid fuel reduction of iron ores. Numerous articles on various phases of these investigations have appeared in Bureau of Mines publications or technical journals. Other articles are being prepared and will be published in the near future. The present program, which is under the supervision of Dr. R. S. Dean, Assistant Director of the Bureau of Mines, was initiated in 1942. However, a considerable portion of the work was a continuation of previous research performed by the Bureau. Previous investigators1-4 utilizing the rotary kiln for the production of sponge iron did not develop a suitable method for controlling the sulphur content. A review of the literature shows that the sulphur content in the product usually exceeded 0.1 per cent unless reducing agents with very low sulphur contents were employed. This high sulphur value made the product generally undesirable for use as melting stock in electric or open-hearth furnaces. The production of sponge iron in an internally fired rotary kiln has been described in detail in Bureau of Mines Bullelin 2702; consequently, this article will be confined mostly to new features of the process—that is, means for controlling the sulphur content of the sponge iron. Suitable raw materials include iron ores or mill scale; coal or coke for reducing them, and sized dolomite ( — poi-100-mesh) as the sulphur-controlling agent. A mixture of the raw materials in granular form is fed into the elevated end of the kiln, which is fired axially from the lower or discharge end. In the reducing zone, which is approximately one third the length of the kiln measured from the dis-

Jan 1, 1948

By R. C. Buehl, J. P. Riott, E. P. Shoub

Pilot-plant tests have demonstrated that it is possible to produce low-sulphur sponge iron (0.03 to 0.0; per cent sulphur) as a continuous process in an internally fired rotary kiln from iron ore or mill scale; a solid carbonaceous reducing agent; and dolomite to control the sulphur content. The proportion of dolomite employed is small, so that it does not add materially to the cost of the sponge iron. The entire operation is carried out at temperatures well below the melting point of iron, so that the product is discharged in granular form. Compared with other methods for the production of sponge iron, the rotary-kiln method has the advantage of simplicity and low cost of equipment and, in addition, requires little labor for the operation of the process. The pilot-plant equipment used for this work was sufficiently large to demonstrate that the production of low-sulphur sponge iron in rotary kilns is feasible and that the costs are not excessive for applications in which sponge iron has distinct advantages over competing materials. This report constitutes a part of a program by the Bureau of Mines under a special Congressional appropriation for studying gaseous and solid fuel reduction of iron ores. Numerous articles on various phases of these investigations have appeared in Bureau of Mines publications or technical journals. Other articles are being prepared and will be published in the near future. The present program, which is under the supervision of Dr. R. S. Dean, Assistant Director of the Bureau of Mines, was initiated in 1942. However, a considerable portion of the work was a continuation of previous research performed by the Bureau. Previous investigators1-4 utilizing the rotary kiln for the production of sponge iron did not develop a suitable method for controlling the sulphur content. A review of the literature shows that the sulphur content in the product usually exceeded 0.1 per cent unless reducing agents with very low sulphur contents were employed. This high sulphur value made the product generally undesirable for use as melting stock in electric or open-hearth furnaces. The production of sponge iron in an internally fired rotary kiln has been described in detail in Bureau of Mines Bullelin 2702; consequently, this article will be confined mostly to new features of the process—that is, means for controlling the sulphur content of the sponge iron. Suitable raw materials include iron ores or mill scale; coal or coke for reducing them, and sized dolomite ( — poi-100-mesh) as the sulphur-controlling agent. A mixture of the raw materials in granular form is fed into the elevated end of the kiln, which is fired axially from the lower or discharge end. In the reducing zone, which is approximately one third the length of the kiln measured from the dis-

Jan 1, 1948

By R. B. Snow

This paper describes a technique of polishing and etching specimens of open-hearth furnace slags or hearth aggregates for identification of the crystalline constituents —lime (CaO), tricalcium silicate (3CaO.SiO2), dicalcium silicate (2CaO.-SiO2), rnonticellite (CaO.MgO.SiO2), or forsterile (2MgO.SiO2), with especial em-phasis on the mineral merwinite (3CaO.-MgO.2SiO2). With proper standardization, this identification does not require the use of the petrographic microscope. The composition of basic open-hearth slags and furnace bottoms falls, almost without exception, within systems containing CaO, MgO, 'IFeO,,, MnO and SiOz, in which the number of basic molecules so greatly exceeds the orthosilicate ratio (two molecules of base to one of silica) that free basic oxides, and combinations between them such as alumi-nates or ferrites, are present in cooled specimens. Orthosilicates of (CaO + NgO) are the most common in such specimens, since in nearly all cases, except premelt slags, the molecular ratio of (CaO + MgO) to SiO, is more than 2 to I. When sufficient lime is available it combines with the silica to form dicalcium silicate (2Ca0.Si02), which contains little, if any, IvfgO, FeO or MnO in solid solution whereas the latter oxides combine to form the oxide solid solution known as periclase. If the lime present is insufficient to form dicalcium silicate (2Ca0.Si02) it combines with Mgo to form either merwillite or moIlticellite (SiOz); these minerals take little if any FeO or MnO into solid solution and the remaining MgO, FeO and hInO combine as periclase. This generalization seems to be valid for basic slags and furnace bottoms, since minerals such as Ca0.MnOSi02 and CaO.FeO.SiOz are found only in slags in which the lime-silica ratio is less than 2 and are not observed in 'pecimens from furnace bottoms. The identification of crystalline constituents in such materials, especially of fine crystals in the groundmass, is difficult under the petrographic microscope. They are often masked by their neighbors because of their small size in relation to the thickness of the thin section and because of the presence of Opaque Or colored constituents. The indices of refraction and the optical sign of the mineral are sometimes difficult to determine because of the small size or because Of twinning or of inclusions within the crystal. Moreover, the positive identification of merwinite (3Ca0.Mg0.2Si02) from its optical properties is usually difficult in the presence of dicalcium silicate (zCaO.SiO2). CaO, MgO, jCa0.Si02 and 2Ca0.SiOz in open-hearth 'lags have been identified for a number of years in the U.S. Steel Corporation Laboratory by the usual

Jan 1, 1948

By R. B. Snow

This paper describes a technique of polishing and etching specimens of open-hearth furnace slags or hearth aggregates for identification of the crystalline constituents —lime (CaO), tricalcium silicate (3CaO.SiO2), dicalcium silicate (2CaO.-SiO2), rnonticellite (CaO.MgO.SiO2), or forsterile (2MgO.SiO2), with especial em-phasis on the mineral merwinite (3CaO.-MgO.2SiO2). With proper standardization, this identification does not require the use of the petrographic microscope. The composition of basic open-hearth slags and furnace bottoms falls, almost without exception, within systems containing CaO, MgO, 'IFeO,,, MnO and SiOz, in which the number of basic molecules so greatly exceeds the orthosilicate ratio (two molecules of base to one of silica) that free basic oxides, and combinations between them such as alumi-nates or ferrites, are present in cooled specimens. Orthosilicates of (CaO + NgO) are the most common in such specimens, since in nearly all cases, except premelt slags, the molecular ratio of (CaO + MgO) to SiO, is more than 2 to I. When sufficient lime is available it combines with the silica to form dicalcium silicate (2Ca0.Si02), which contains little, if any, IvfgO, FeO or MnO in solid solution whereas the latter oxides combine to form the oxide solid solution known as periclase. If the lime present is insufficient to form dicalcium silicate (2Ca0.Si02) it combines with Mgo to form either merwillite or moIlticellite (SiOz); these minerals take little if any FeO or MnO into solid solution and the remaining MgO, FeO and hInO combine as periclase. This generalization seems to be valid for basic slags and furnace bottoms, since minerals such as Ca0.MnOSi02 and CaO.FeO.SiOz are found only in slags in which the lime-silica ratio is less than 2 and are not observed in 'pecimens from furnace bottoms. The identification of crystalline constituents in such materials, especially of fine crystals in the groundmass, is difficult under the petrographic microscope. They are often masked by their neighbors because of their small size in relation to the thickness of the thin section and because of the presence of Opaque Or colored constituents. The indices of refraction and the optical sign of the mineral are sometimes difficult to determine because of the small size or because Of twinning or of inclusions within the crystal. Moreover, the positive identification of merwinite (3Ca0.Mg0.2Si02) from its optical properties is usually difficult in the presence of dicalcium silicate (zCaO.SiO2). CaO, MgO, jCa0.Si02 and 2Ca0.SiOz in open-hearth 'lags have been identified for a number of years in the U.S. Steel Corporation Laboratory by the usual

Jan 1, 1948

By J. R. Lewis

During the past few years there has been considerable interest in the sizing and the preparation of the iron ore fed into blast furnaces. Furnacemen know that proper sizing of ore tends to increase the efficiency of the furnace. It has been shown by Joseph1 and his associates that there is a direct relationship between the porosity of an ore particle and the time required for its reduction in the blast furnace. This relationship may be stated as follows: All other factors remainig constant, the time for reduction of a given sample of ore is inversely propor-tiofid to its porosity. As a consequence, large pieces of very porous ore, say 3 or 4 in. in cross section, will be completely reduced by the time they reach the hot zone just above the tuyeres, while large pieces of dense, nonporous ore may reach the hot zone with their centers unreduced. This means that for the latter complete reduction will be accomplished by the so-called "direct method;" i,e., where carbon reacts directly with the ore. Some recent work by philbrook2 seems to contradict this rule. He found that of two unlike ores he studied, the one with the lower porosity reduced more readily. He explained his results as "possibly due to an apparently greater tendency of the rA, ore (lower porosity) to crack during preliminary dehydration and during reduction." This brings his results in line with the rule stated above. It is not the author's intention to enter into a discussion of the merits of "direct" versus "indirect" reduction. It is enough to Say that, in general, indirect reduction is desirable. For the greatest efficiency, Gruner's theorem3 requires that all reduction in the blast furnace be indirect. Joseph seems to believe this also, because in his recent article on Some Comparisons between Iron Ore, Sinter and Nodules as Blast Furnace Feed4 he concludes that: "In genera', the carbon in blastfurnace coke is used most efficiently when the largest amount of the carbon charged reaches the tuyeres." However, P. V. hlartin,3 in an excellent paper, has shown that some direct reduction may actually increase the efficiency of the furnace; that is, increase its rate of production while maintaining maximum fuel economy. For nonporous ores there is more opportunity to have an excess of direct reduction unless the factors that make for indirect reduction are favored; for instance; the Proper sizing of the Ore particles' Another factor that has an important bearing on the reduction rate, as it is affected by particle size, is the flow of heat into the particle. The ore particle

Jan 1, 1948

By J. R. Lewis

During the past few years there has been considerable interest in the sizing and the preparation of the iron ore fed into blast furnaces. Furnacemen know that proper sizing of ore tends to increase the efficiency of the furnace. It has been shown by Joseph1 and his associates that there is a direct relationship between the porosity of an ore particle and the time required for its reduction in the blast furnace. This relationship may be stated as follows: All other factors remainig constant, the time for reduction of a given sample of ore is inversely propor-tiofid to its porosity. As a consequence, large pieces of very porous ore, say 3 or 4 in. in cross section, will be completely reduced by the time they reach the hot zone just above the tuyeres, while large pieces of dense, nonporous ore may reach the hot zone with their centers unreduced. This means that for the latter complete reduction will be accomplished by the so-called "direct method;" i,e., where carbon reacts directly with the ore. Some recent work by philbrook2 seems to contradict this rule. He found that of two unlike ores he studied, the one with the lower porosity reduced more readily. He explained his results as "possibly due to an apparently greater tendency of the rA, ore (lower porosity) to crack during preliminary dehydration and during reduction." This brings his results in line with the rule stated above. It is not the author's intention to enter into a discussion of the merits of "direct" versus "indirect" reduction. It is enough to Say that, in general, indirect reduction is desirable. For the greatest efficiency, Gruner's theorem3 requires that all reduction in the blast furnace be indirect. Joseph seems to believe this also, because in his recent article on Some Comparisons between Iron Ore, Sinter and Nodules as Blast Furnace Feed4 he concludes that: "In genera', the carbon in blastfurnace coke is used most efficiently when the largest amount of the carbon charged reaches the tuyeres." However, P. V. hlartin,3 in an excellent paper, has shown that some direct reduction may actually increase the efficiency of the furnace; that is, increase its rate of production while maintaining maximum fuel economy. For nonporous ores there is more opportunity to have an excess of direct reduction unless the factors that make for indirect reduction are favored; for instance; the Proper sizing of the Ore particles' Another factor that has an important bearing on the reduction rate, as it is affected by particle size, is the flow of heat into the particle. The ore particle

Jan 1, 1948

By Helmut Thielsch

MeTallographic specimens whose surfaces are to be investigated are too thick to allow either light or electrons to pass through them for microexamination by transmission. This difficulty is overcome with optical microscopes by illuminating the surface through the objective lens. For electron microscopes best results are obtained by preparing thin replicas of the surface of the specimen, placing them in the microscope and passing the electron beam through them. Since electron microscopes represent a rather recent invention, they have found little application as compared with optical microscopes. This is true because, aside from the cost of new equipment and development of new techniques, some of the older replica methods necessitated the destruction of the surface from which a thin transparent replica was obtained. In other processes in which the surface is preserved, either too tedious a procedure is required, unsuited to "mass-production" requirements of industrial laboratories, or replicas of insufficient contrast and sharpness are produced. In general, investigations with the electron microscope involve five steps: (I) polishing the surface of the metal specimen, (2) proper etching of the surface, (3) preparing the suitable replica from the surface, (4) examination and phorography in electron microscope and (5) interpretation. Preparation of Metal Surfaces Usual metallographic polishing is generclly satisfactory. It is important though that the final polish be applied very carefully, since otherwise evidence of a small amount of deformation might show up even on relatively deeply etched surfaces. A high-power microscope should be used to determine the suitability of the polish and etch. This, of course, is not different from optical examinations, but in these, if a deep etch is used, the problem is less serious. It is frequently difficult to detect with optical microscopes poor polishing aside fiom superficial scratches before etching. Figs. I and 2 show micrographs of "well" and "poorly" polished nickel etched by immersing the sample for 20 min. in a solution containing 8 grams cupric sulphate in 40 C.C. of concentrated HCl and 40 C.C. of Hz0 (Marble's reagent). The sample shown in Fig. I was polished in its final stages for 5 min. on a carborundum wheel followed by ro min. on a rouge wheel, whereas the sample shown in Fig. 2 was polished only I min. on the rouge wheel. Generally, this procedure does not guarantee that the surface of the specimen will be either undistorted or deformed. It was applied here merely to show the effects Of good and poor polishing. To the experienced investigator, plastic deformation is

Jan 1, 1946

By Helmut Thielsch

MeTallographic specimens whose surfaces are to be investigated are too thick to allow either light or electrons to pass through them for microexamination by transmission. This difficulty is overcome with optical microscopes by illuminating the surface through the objective lens. For electron microscopes best results are obtained by preparing thin replicas of the surface of the specimen, placing them in the microscope and passing the electron beam through them. Since electron microscopes represent a rather recent invention, they have found little application as compared with optical microscopes. This is true because, aside from the cost of new equipment and development of new techniques, some of the older replica methods necessitated the destruction of the surface from which a thin transparent replica was obtained. In other processes in which the surface is preserved, either too tedious a procedure is required, unsuited to "mass-production" requirements of industrial laboratories, or replicas of insufficient contrast and sharpness are produced. In general, investigations with the electron microscope involve five steps: (I) polishing the surface of the metal specimen, (2) proper etching of the surface, (3) preparing the suitable replica from the surface, (4) examination and phorography in electron microscope and (5) interpretation. Preparation of Metal Surfaces Usual metallographic polishing is generclly satisfactory. It is important though that the final polish be applied very carefully, since otherwise evidence of a small amount of deformation might show up even on relatively deeply etched surfaces. A high-power microscope should be used to determine the suitability of the polish and etch. This, of course, is not different from optical examinations, but in these, if a deep etch is used, the problem is less serious. It is frequently difficult to detect with optical microscopes poor polishing aside fiom superficial scratches before etching. Figs. I and 2 show micrographs of "well" and "poorly" polished nickel etched by immersing the sample for 20 min. in a solution containing 8 grams cupric sulphate in 40 C.C. of concentrated HCl and 40 C.C. of Hz0 (Marble's reagent). The sample shown in Fig. I was polished in its final stages for 5 min. on a carborundum wheel followed by ro min. on a rouge wheel, whereas the sample shown in Fig. 2 was polished only I min. on the rouge wheel. Generally, this procedure does not guarantee that the surface of the specimen will be either undistorted or deformed. It was applied here merely to show the effects Of good and poor polishing. To the experienced investigator, plastic deformation is

Jan 1, 1946