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By Gerhard Derge

Metallurgists have used borax as a fluxing agent traditionally, but until recently elemental boron has played an insignificant role as an alloying element. Neither the metal nor its compounds have been regarded as important metallurgical materials and there is a surprising lack of knowledge concerning their metallurgical behavior. The new applications to steel-making of both boron and borates, which arose in part from wartime incentives and restrictions, have been seriously handicapped by this lack of data. For example, rasorite, a naturally occurring sodium borate, has been shown to be an effective substitute for aluminum as a ladle deoxi-dizer in rimming steels.' Likewise, the effectiveness of boron as an alloying agent has been demonstrated,2,3 giving deep hardening when used in restricted amounts. The exploitation of both of these uses has been retarded by the difficulty of attaining suitable metallurgical control. Recognizing that the most important information required was a knowledge of the equilibrium between boron and oxygen dissolved in liquid iron. Gurry4 calculated this relation from the best thermal data available. However, estimates of the entropy of melting of boron, the activity coefficient of boron in liquid iron and the activity coefficient of B2O3 in slag were involved, and experimental work on this problem was obviously desirable. The experiments to be described were planned to establish the boron-oxygen relations in liquid iron and to demonstrate at the same time the ferroborate slag compositions in equilibrium with various amounts of oxygen in liquid iron. Accordingly, slags containing varying proportions of iron and boron oxides were held in contact with molten iron, and samples of both slag and metal were analyzed. The limitations upon the accuracy of the data will be considered, but in a practical sense the oxygen levels that can be attained in iron by iron borate slags, and the amounts of boron in iron at these oxygen levels were established. Experimental Procedure No entirely suitable refractory was found for the mixtures of iron oxide and boron oxide used as slags. Crucibles of silica, magnesia, Ramix, beryllia, and zirconia were all tried unsuccessfully. The must satisfactory method discovered for handling them was the rotating-crucible technique, which creates a parabolic crucible of liquid iron.5,6 Even this was not entirely successful, for at steelmaking temperatures (1600°C.) the slags had such a low surface tension that they crept up to the refractory and slowly dissolved it. These difficulties made it impossible to maintain a constant slag composition for an unlimited period Of time. However, by using the rotating technique, short runs could be made in

Jan 1, 1947

By C. E. Sims

The carbon-oxygen reaction without doubt is the basic reaction in steelmaking. It is important on several counts: In the first place, carbon is the element that distinguishes steel from iron. It is the principal element controlling properties, and its control is of prime concern. Although the principal objective of the carbon-oxygen reaction is to oxidize excess carbon, the accompanying boil should not be underrated. The mechanical agitation, stirring, and mixing resulting from the boil are so useful in the distribution of heat and in promoting uniformity of composition in the bath that, were it not a natural accompaniment of the carbon-oxygen reaction, it is probable that something would have to be invented to replace it. The open-hearth operation, for example, with the bath heated from above by radiation, would be impracticable without the carbon boil. The electric-arc furnace is somewhat less dependent on it, but every melter knows how much easier it is to gain temperature with minimum damage to refractories during the boil than with a dead bath The motor action of the induced current of the induction furnace makes the carbon boil unnecessary but even there a severe oxidation has been found useful in giving greater freedom from porosity in certain steels. The quantitative aspects of the carbon-oxygen reaction have been given considerable attention by a large number of investigators, and the principles of physical chemistry have played an important part in these studies. Physical chemistry is the science of the mechanics and mathematics of chemical reactions. It is possible to study the mechanisms of reactions in a qualitative manner writhout reference to mathematics and thus obtain valuable concepts as to the manner in which the wheels go around. When it is desired to express quantitative relations in these reactions, however, resort to mathematics is not only convenient but necessary. Mathematics may also be regarded as the shorthand language of physical chemistry. A basic relation whose description requires numerous words may be expressed very simply by a mathematical formula or equation. A good example of this is the equilibrium constant for a chemical reaction. Expressed verbally, it is: When a chemical reaction has reached a condition of equilibrium, the Product of the concentration of the reacting substances on one side of the equation, divided by the product of the concentration of the reacting substances on the other side, gives a quotient that is a constant at constant temperature For the carbon-oxygen reaction C + O ^ CO this is expressed simply as % C X % O -%co where K (from the German Konstant) is the equilibrium constant for the reaction. Although mathematics is such a necessary and useful tool, it is also a potential pitfall. Mathematics in itself is an abstract science, which is not inhibited by consideration of mechanisms or materials.

Jan 1, 1948

By C. E. Sims

The carbon-oxygen reaction without doubt is the basic reaction in steelmaking. It is important on several counts: In the first place, carbon is the element that distinguishes steel from iron. It is the principal element controlling properties, and its control is of prime concern. Although the principal objective of the carbon-oxygen reaction is to oxidize excess carbon, the accompanying boil should not be underrated. The mechanical agitation, stirring, and mixing resulting from the boil are so useful in the distribution of heat and in promoting uniformity of composition in the bath that, were it not a natural accompaniment of the carbon-oxygen reaction, it is probable that something would have to be invented to replace it. The open-hearth operation, for example, with the bath heated from above by radiation, would be impracticable without the carbon boil. The electric-arc furnace is somewhat less dependent on it, but every melter knows how much easier it is to gain temperature with minimum damage to refractories during the boil than with a dead bath The motor action of the induced current of the induction furnace makes the carbon boil unnecessary but even there a severe oxidation has been found useful in giving greater freedom from porosity in certain steels. The quantitative aspects of the carbon-oxygen reaction have been given considerable attention by a large number of investigators, and the principles of physical chemistry have played an important part in these studies. Physical chemistry is the science of the mechanics and mathematics of chemical reactions. It is possible to study the mechanisms of reactions in a qualitative manner writhout reference to mathematics and thus obtain valuable concepts as to the manner in which the wheels go around. When it is desired to express quantitative relations in these reactions, however, resort to mathematics is not only convenient but necessary. Mathematics may also be regarded as the shorthand language of physical chemistry. A basic relation whose description requires numerous words may be expressed very simply by a mathematical formula or equation. A good example of this is the equilibrium constant for a chemical reaction. Expressed verbally, it is: When a chemical reaction has reached a condition of equilibrium, the Product of the concentration of the reacting substances on one side of the equation, divided by the product of the concentration of the reacting substances on the other side, gives a quotient that is a constant at constant temperature For the carbon-oxygen reaction C + O ^ CO this is expressed simply as % C X % O -%co where K (from the German Konstant) is the equilibrium constant for the reaction. Although mathematics is such a necessary and useful tool, it is also a potential pitfall. Mathematics in itself is an abstract science, which is not inhibited by consideration of mechanisms or materials.

Jan 1, 1948

By B. M. Larsen

Jan 1, 1948

By B. M. Larsen

Jan 1, 1948

By Terkel Rosenqvist

Few subjects in iron metallurgy and steelmaking have caused so much discussion and have resulted in so many divergent and partly contradictory statements as the theory of the distribution of sulphur between molten iron and slag. An interesting survey of the different points of view is given by Grant and Chipman.1 Grant and Chipman themselves conclude in their paper that, at least in the open hearth and electric steel furnaces, the governing reaction is a simple distribution like: FeS steel ? FeS alas [Ia] and MnS steel ? MnS alas [Ib] They conclude that no significant reaction takes place according to the more classical scheme: FeS steel + CaO slag ? FeOslag + CaS slag [2a] This is the reaction which is regarded by most investigators as the primary sulphur reaction in the blast furnaces, where it is accompanied by the reaction with carbon: FeO slag + C ? Fe + CO [2b] The writer suggests an alternative to the reactions mentioned above. It is the opinion of the writer that the a priori assumption of defined molecular compounds being present in molten steel as well as in molten slag, has retarded rather than promoted a solution of the sulphur problem. As for the constituents of molten steel, it is taking too much for granted to mention the presence of FeS and MnS. If this infers that the melt contains diatomic molecules, the statement must be made that at least such molecules do not exist in the solid state at room temperature. Solid FeS crystallizes in the nickel-arsenide structure, and MnS (high temperature form) in the sodium-chloride structure. In these structures the sulphur is surrounded by six metal neighbors, and no molecular groups can be isolated. When sulphur is dissolved in molten steel, it is expected to maintain the same coordination number as in the solid state. We know that sulphur in steel has a certain chemical potential and a chemical activity which can be expressed by the reaction: S steel + H2 ? H2S where the activity A. is proportional to the ratio PH2S/Ph2. We know also that this activity is influenced by the presence of other constituents. For instance, there is reason to assume that carbon and silicon increase the sulphur activity and manganese decreases it. However, the exact relationship here is scarcely known, and further investigations are needed. Concerning the molten slags, if anything should be assumed a priori it would be that they are composed of ionic rather than molecular parts. There are indications of this in that solid silicates form ionic structures, and molten slags show high electric conductivity and can be electrolyzed.2 It has been claimed by Taylor and Chipman3 that their activity investigations

Jan 1, 1949

By Terkel Rosenqvist

Few subjects in iron metallurgy and steelmaking have caused so much discussion and have resulted in so many divergent and partly contradictory statements as the theory of the distribution of sulphur between molten iron and slag. An interesting survey of the different points of view is given by Grant and Chipman.1 Grant and Chipman themselves conclude in their paper that, at least in the open hearth and electric steel furnaces, the governing reaction is a simple distribution like: FeS steel ? FeS alas [Ia] and MnS steel ? MnS alas [Ib] They conclude that no significant reaction takes place according to the more classical scheme: FeS steel + CaO slag ? FeOslag + CaS slag [2a] This is the reaction which is regarded by most investigators as the primary sulphur reaction in the blast furnaces, where it is accompanied by the reaction with carbon: FeO slag + C ? Fe + CO [2b] The writer suggests an alternative to the reactions mentioned above. It is the opinion of the writer that the a priori assumption of defined molecular compounds being present in molten steel as well as in molten slag, has retarded rather than promoted a solution of the sulphur problem. As for the constituents of molten steel, it is taking too much for granted to mention the presence of FeS and MnS. If this infers that the melt contains diatomic molecules, the statement must be made that at least such molecules do not exist in the solid state at room temperature. Solid FeS crystallizes in the nickel-arsenide structure, and MnS (high temperature form) in the sodium-chloride structure. In these structures the sulphur is surrounded by six metal neighbors, and no molecular groups can be isolated. When sulphur is dissolved in molten steel, it is expected to maintain the same coordination number as in the solid state. We know that sulphur in steel has a certain chemical potential and a chemical activity which can be expressed by the reaction: S steel + H2 ? H2S where the activity A. is proportional to the ratio PH2S/Ph2. We know also that this activity is influenced by the presence of other constituents. For instance, there is reason to assume that carbon and silicon increase the sulphur activity and manganese decreases it. However, the exact relationship here is scarcely known, and further investigations are needed. Concerning the molten slags, if anything should be assumed a priori it would be that they are composed of ionic rather than molecular parts. There are indications of this in that solid silicates form ionic structures, and molten slags show high electric conductivity and can be electrolyzed.2 It has been claimed by Taylor and Chipman3 that their activity investigations

Jan 1, 1949

By J. H. Hollomon, L. D. Jaffe, M. R. Norton

In the practical heat-treatment of steel the decomposition of austenite usually occurs during cooling rather than at constant temperature. Nevertheless, the course of this decomposition has generally been studied only isothermally. Isothermal studies are not only simpler experimentally, but have the great theoretical advantage that one of the variables, temperature, is constant. It is the purpose of this paper to outline the principles that govern the relations between isothermal and anisothermalt‡ decomposition of austenite, to present and systematize the available experimental information, and to indicate the gaps in the existing knowledge. Some of the experimental information is the result of new work.§ Most of it is derived from scattered data in the literature. Many of these data were obtained incidentally in the course of research on other subjects and their significance has not been pointed out and perhaps not understood. It is hoped that this paper will aid future planning of more extensive research on anisothermal decomposition. Method In order to study the relations between isothermal and anisothermal decomposition, it appears fruitful to view anisothermal decomposition as taking place at a series of constant temperatures1 (except for the martensite reaction, which does not occur isothermally to an appreciable extent). When the time the steel is at each temperature is finite, the over-all amount of the reaction is considered to be the sum of the amounts occurring at each of the successive temperatures. During continuous cooling or heating, the time the steel is at each temperature and the difference between successive temperatures can be considered to approach zero. The over-all amount of transformation will then be given by integration over the range of temperatures involved. This point of view is advantageous in that it considers anisothermal transformation to be a series of isothermal transformations. The problem thus becomes one of determining the effect of partial decomposition at any given temperature upon subsequent decomposition at another temperature. Single Anisothermal Reaction Consider a phase brought to a temperature at which it is unstable, held there until it has partially transformed, and then brought to another temperature at

Jan 1, 1947

By L. D. Jaffe, M. R. Norton, J. H. Hollomon

In the practical heat-treatment of steel the decomposition of austenite usually occurs during cooling rather than at constant temperature. Nevertheless, the course of this decomposition has generally been studied only isothermally. Isothermal studies are not only simpler experimentally, but have the great theoretical advantage that one of the variables, temperature, is constant. It is the purpose of this paper to outline the principles that govern the relations between isothermal and anisothermalt‡ decomposition of austenite, to present and systematize the available experimental information, and to indicate the gaps in the existing knowledge. Some of the experimental information is the result of new work.§ Most of it is derived from scattered data in the literature. Many of these data were obtained incidentally in the course of research on other subjects and their significance has not been pointed out and perhaps not understood. It is hoped that this paper will aid future planning of more extensive research on anisothermal decomposition. Method In order to study the relations between isothermal and anisothermal decomposition, it appears fruitful to view anisothermal decomposition as taking place at a series of constant temperatures1 (except for the martensite reaction, which does not occur isothermally to an appreciable extent). When the time the steel is at each temperature is finite, the over-all amount of the reaction is considered to be the sum of the amounts occurring at each of the successive temperatures. During continuous cooling or heating, the time the steel is at each temperature and the difference between successive temperatures can be considered to approach zero. The over-all amount of transformation will then be given by integration over the range of temperatures involved. This point of view is advantageous in that it considers anisothermal transformation to be a series of isothermal transformations. The problem thus becomes one of determining the effect of partial decomposition at any given temperature upon subsequent decomposition at another temperature. Single Anisothermal Reaction Consider a phase brought to a temperature at which it is unstable, held there until it has partially transformed, and then brought to another temperature at

Jan 1, 1947

By Leonard D. Jaffe

In recent years, the advantages of tempered martensite as a microstructure for steel parts have been well established. For parts that must not fracture brittlely when loaded at high rates, at low temperatures, or under conditions of combined stress, tempered martensite is especially desirable. One of the factors that determine whether a steel part will have a martensitic structure after heat treatment is the hardenability of the steel. Despite the large amount of recent research, there are still many unsettled basic questions concerning hardenability and its relation to chemical composition, and, indeed, considerable disagreement among investigators in the field. Much of the uncertainty that beclouds the existing knowledge of hardenability arises from the fact that hardenability is still a wholly empirical concept, and has not been quantitatively related to the more fundamental knowledge of isothermal decomposition of austenite. Hardenability is, essentiaily, a measure of the time required for small percentages of austenite to decompose, during continuous cooling, to pearlite, bainite, proeutectoid ferrite, or proeutec-toid carbide. In the practical heat-treat- ment of steel, also, the decomposition of austenite is usually not isothermal but rather during cooling, or, in general, is not at a single constant temperature. Thus, both hardenability and practical heat treatment involve anisothermal decomposition of austenite. In a previous publication1 the author and his collaborators outlined the principles that govern the relations between isothermal and anisothermal decomposition of austenite, and reviewed the experimental information available in 1945. To avoid repetition, familiarity with that article (Paper I) will be assumed, and attention given primarily to work carried out or published since 1945. The method generally employed was explained in Paper I: anisothermal transformation is studied through investigation of the effect of holding austenite at one temperature upon its subsequent decomposition at another temperature. Both temperatures are below the stability range of the austenite. This paper is confined to studies in which only a small amount of transformation occurred at the first temperature. This is the only case of importance in practical heat treatment when an essentially martensitic structure is sought. Materials and Procedure It was necessary to use different steels for the studies involving proeutectoid ferrite and for those involving proeutectoid carbide, beeause the two constituents have not been found to form in the same steel. Several steels were tried and rejected

Jan 1, 1949

By Leonard D. Jaffe

In recent years, the advantages of tempered martensite as a microstructure for steel parts have been well established. For parts that must not fracture brittlely when loaded at high rates, at low temperatures, or under conditions of combined stress, tempered martensite is especially desirable. One of the factors that determine whether a steel part will have a martensitic structure after heat treatment is the hardenability of the steel. Despite the large amount of recent research, there are still many unsettled basic questions concerning hardenability and its relation to chemical composition, and, indeed, considerable disagreement among investigators in the field. Much of the uncertainty that beclouds the existing knowledge of hardenability arises from the fact that hardenability is still a wholly empirical concept, and has not been quantitatively related to the more fundamental knowledge of isothermal decomposition of austenite. Hardenability is, essentiaily, a measure of the time required for small percentages of austenite to decompose, during continuous cooling, to pearlite, bainite, proeutectoid ferrite, or proeutec-toid carbide. In the practical heat-treat- ment of steel, also, the decomposition of austenite is usually not isothermal but rather during cooling, or, in general, is not at a single constant temperature. Thus, both hardenability and practical heat treatment involve anisothermal decomposition of austenite. In a previous publication1 the author and his collaborators outlined the principles that govern the relations between isothermal and anisothermal decomposition of austenite, and reviewed the experimental information available in 1945. To avoid repetition, familiarity with that article (Paper I) will be assumed, and attention given primarily to work carried out or published since 1945. The method generally employed was explained in Paper I: anisothermal transformation is studied through investigation of the effect of holding austenite at one temperature upon its subsequent decomposition at another temperature. Both temperatures are below the stability range of the austenite. This paper is confined to studies in which only a small amount of transformation occurred at the first temperature. This is the only case of importance in practical heat treatment when an essentially martensitic structure is sought. Materials and Procedure It was necessary to use different steels for the studies involving proeutectoid ferrite and for those involving proeutectoid carbide, beeause the two constituents have not been found to form in the same steel. Several steels were tried and rejected

Jan 1, 1949

By R. A. Grange, H. M. Stewart

Man.; steel parts may crack if quenched directly into a bath near room temperature, but not if quenched at a temperature just above the range where martensite forms and then allowed to cool slowly to room temperature. This latter procedure, which is the basis for such modern hardening techniques as "martempering" and "isothermal quenching," may entail some sacrifice in depth of hardening but very little, if any, in intensity of hardening. In planning such treatments, it is necessary to know the upper limit of the martensite range, and often desirable to know the proportion of martensite that would form on cooling to any lower temperature; furthermore, the tendency of a particular steel to crack when quenched is unquestionably associated with the temperature range of martensite formation, and consequently knowledge of this range aids in selecting the optimum composition for a given application. Certain puzzling phenomena associated with the properties of quenched and tempered steel may be at least partly clarified as the manner in which martensite forms is more fully understood. Information on the temperature range of martensite formation, particularly with respect to how much martensite results from quenching to a given temperature, is lacking for most commercial types of carbon and low-alloy steel. These considerations led us to study martensite formation in 14 carbon and low-alloy steels. The resultant data may be directly used in the following ways: (I) for selecting the lowest quenching temperature at which no martensite will form; (2) for selecting the highest quenching temperature at which virtually all marten . site will form, thereby avoiding quenching to an unnecessarily lower temperature with attendant danger of cracking; and (3) in producing a mixture of tempered martensite and bainite, which in high-carbon steels has been found to possess somewhat better ductility than tempered martensite, yet does not require the full transformation time necessary for a completely bainitic (austempered) structure. PART I. OBSERVATIONS OF MARTENSITE FORMATION IN FOURTEEN CARBON AND LOW-ALLOY STEELS Transformation of austenite to pearlite or bainite can be conveniently studied by observing the change that occurs over a period of time at constant temperature; such studies are the basis of the isothermal transformation diagram (S-curve). This isothermal technique is not applicable to martensite formation, which occurs within a time interval too small to measure, at least by any ordinary means. For all practical purposes, therefore, martensite may be regarded as forming only during cooling and not during a period of time at constant temperature. As austenite is cooled below

Jan 1, 1947

By H. M. Stewart, R. A. Grange

Man.; steel parts may crack if quenched directly into a bath near room temperature, but not if quenched at a temperature just above the range where martensite forms and then allowed to cool slowly to room temperature. This latter procedure, which is the basis for such modern hardening techniques as "martempering" and "isothermal quenching," may entail some sacrifice in depth of hardening but very little, if any, in intensity of hardening. In planning such treatments, it is necessary to know the upper limit of the martensite range, and often desirable to know the proportion of martensite that would form on cooling to any lower temperature; furthermore, the tendency of a particular steel to crack when quenched is unquestionably associated with the temperature range of martensite formation, and consequently knowledge of this range aids in selecting the optimum composition for a given application. Certain puzzling phenomena associated with the properties of quenched and tempered steel may be at least partly clarified as the manner in which martensite forms is more fully understood. Information on the temperature range of martensite formation, particularly with respect to how much martensite results from quenching to a given temperature, is lacking for most commercial types of carbon and low-alloy steel. These considerations led us to study martensite formation in 14 carbon and low-alloy steels. The resultant data may be directly used in the following ways: (I) for selecting the lowest quenching temperature at which no martensite will form; (2) for selecting the highest quenching temperature at which virtually all marten . site will form, thereby avoiding quenching to an unnecessarily lower temperature with attendant danger of cracking; and (3) in producing a mixture of tempered martensite and bainite, which in high-carbon steels has been found to possess somewhat better ductility than tempered martensite, yet does not require the full transformation time necessary for a completely bainitic (austempered) structure. PART I. OBSERVATIONS OF MARTENSITE FORMATION IN FOURTEEN CARBON AND LOW-ALLOY STEELS Transformation of austenite to pearlite or bainite can be conveniently studied by observing the change that occurs over a period of time at constant temperature; such studies are the basis of the isothermal transformation diagram (S-curve). This isothermal technique is not applicable to martensite formation, which occurs within a time interval too small to measure, at least by any ordinary means. For all practical purposes, therefore, martensite may be regarded as forming only during cooling and not during a period of time at constant temperature. As austenite is cooled below

Jan 1, 1947

By E. V. Potter, H. C. Lukens

In general, during all electrowinning processes, large volumes of gas are liberated at the cathodes of the electrolytic cells. Most of this gas escapes from the electrolyte, but much of it may be absorbed or entrapped in the metal being plated. In many cases, this is not objectionable, but since it is liberated when the metal is heated, it is a potential source of trouble where the metal has to be heated or melted. Since this gas is principally hydrogen, in escaping from a melt it may cause minor explosions and scattering of the molten metal, while in other cases it has been reported to make the metal rise in the molds when cast. Therefore such metals would be more generally useful if all or most of the gas were removed before they were used. In an earlier investigation1 the gas content of electrolytic manganese was determined and methods found for removing most of it without detrimentally affecting the properties of the metal. In this paper results of a similar investigation on electrolytic chromium are presented. Apparatus The apparatus used in these investigations is essentially the same as that used in the manganese work1 and is shown in Fig I. It consists of sample chamber A, vacuum or pressure gauge B, volume gauge C, vacuum pump D, hydrogen container E, auxiliary gas chamber F, and furnace G. The pressure in the system is measured by the mercury manometer B. Changes in gas volume are measured by volume gauge C which is essentially another mercury manometer in which the volume of the mercury column is large and can be varied by raising or lowering the well H. In this apparatus the tube had a volume of 100 cc for a 60 cm length. Larger changes in gas volume can be accommodated by auxiliary containers attached to the system at F. The sample is heated by furnace G, the temperature of which is regulated within 5°C by an automatic controller. The only change in the apparatus was the sample container which was made smaller because of the chromium metal's containing more gas than the manganese metal and a smaller sample was used. Method The measurements were made as follows: The complete system when cold was evacuated and refilled with H2 until all the air was removed. It was then refilled with H2 to the desired pressure, as indicated on manometer B. The temperature was then raised to the desired value and as gas was either liberated from or absorbed by the sample, the height of well H was changed to alter the volume of the system so as to keep the pressure constant. In determining rates of liberation of gas, volume readings were taken at convenient tirne intervals depending on the rapidity with which the gas was liberated. In determining total volumes, the specimen was held at constant temperature and pressure until

Jan 1, 1949

By M. T. Martinson, I. W. Nicholson, C. J. Chindgren, F. P. Williams, L. C. Bauerle, S. F. Ravitz

The vanadiferous shales of southeastern Idaho and southwestern Wyoming constitute the largest known reserve of vanadium in the United States.' These deposits have never been exploited except for the relatively small amounts of vanadium recovered by the Anaconda Copper Mining Co. in the treatment of phosphate rock from southeastern Idaho. The maior domestic source of vanadium has been the sandstone ores of southeastern Utah and southwestern Colorado. Early in World War 11, it appeared that these ores could not meet the greatly increased demand for vanadium, so the investigation described in this report was undertaken to develop processes for the recovery of vanadium from the Idaho-Wyoming deposits. The utilization of these deposits became unnecessary, however, because of greatly expanded production from the Utah-Colorado sandstone ores and the continued availability of vanadium from other sources, chiefly Peru. The major use of vanadium is as an alloying agent in the manufacture of high-quality steels. Vanadium constructional steels usually contain 0.05 to 0.20 pct vanadium, which refines the grain and increases the strength, elastic limit, and resistance to shock and fatigue. Vanadium tool steels not used in high-speed work contain 0.10 to 0.60 pct whereas high-speed tool steels contain 1.0 to 4.0 pct. Vanadium compounds are used as catalysts (principally for the oxidation of SO2 to sulphuric acid and of naphthalene to phthalic acid) and in the paint, chemical, ceramic, dye, and printing industries. The selection of the particular ore deposit to be exploited would involve consideration of many factors besides the metallurgical results that might be obtained. Chief among these would be the reserves of ore available, the grade of the ore, and the mining costs. As very little was known about any of these factors, it was necessary to investigate methods of treatment of all the ores under consideration, working with samples obtained in the course of the exploration work, even though they were not positively representative of the whole deposit from which they were taken. Because of wartime conditions prevailing when this investigation was started, first consideration was given to processes that could be put into operation most quickly and would involve minimum use of strategic materials, even though these processes might not be the most economical.

Jan 1, 1949

By B. M. Harra, F. G. McCutcheon, O&apos

Until about 1930, the universal practice of horizontal-retort zinc smelters in the United States, as far as the writers are aware, was to operate the retort furnaces on a 24-hr cycle; that is, the retorts were charged in the early morning of one day, and in the early morning of the following day the residues were cleaned out, the retorts recharged, and a new cycle started. During the business depression of the early thirties, zinc production fell off to the extent that zinc smelters had idle retort capacity. Rather than continue to run some of the retort furnaces on a 24-hr cycle and shut down the remainder, a few companies decided to try out a longer cycle. Although the output of zinc per retort per day is lower, the longer cycle permits a larger charge per retort and improved zinc recovery. Advantages of the longer cycle were soon evident, and the practice spread rapidly. Various lengths of cycle were used, typical examples being 28-hr, 32-hr, 36-hr, and 48-hr. The 48-hr cycle fits in best with the standard routine of smelter practice that was built up on the basis of the 24-hr cycle; that is, the retort furnace "maneuver" always comes at the same time of day, and can be performed in the cool hours of the early morning. Under some conditions, particularly in some of the older plants, where the retorts are smaller than in newer plants, a 48-hr cycle is longer than necessary, and some intermediate length of cycle may theoretically be most economical. Use of an intermediate cycle, however, means that the maneuver comes at different times on consecutive days, and that sometimes it comes during the hottest part of the day. The work on the retort furnaces is extremely hot and arduous at best, and it is much worse, of course, if it is done during the heat of a summer day. When labor was plentiful and tractable, many plants were able to operate on cycles of intermediate length, but the workmen did not like the working hours. Under present labor conditions, it is hardly practicable to operate with a cycle of intermediate length, so the choice has narrowed down to the alternatives of 24-hr or 48-hr cycles. In any discussion of economics, too comprehensive generalization is not warranted, because local conditions affecting economics vary greatly. The best economic practice at one plant at any given time may be uneconomical at another plant, or even at the same plant at another time. To determine the length of cycle that is the better practice at a given plant at a given time requires a weighing of the advantages and disadvantages of each cycle, taking into consideration all the local conditions. some of the factors that must be considered in making the comparison are discussed briefly in the following paragraphs.

Jan 1, 1949

By W. W. Schmittroth, A. Y. Bethune

The commercial analysis of Special High-Grade zinc usually involves the determination of lead, iron, copper and cadmium as impurities in the base metal. Over the past 20 years, as the result of metallurgical improvements in the art of producing Special High-Grade zinc metal there has taken place a gradual exclusion of almost all extraneous elements, and the few that do remain in the final product have been virtually reduced to the vanishing point. Thousands of tons of zinc are now commercially produced annually and made available to the trade, in which impurities are present only in the order of 0.0010 per cent or less and the sum total of all impurities does not exceed 0.0025 per cent. To such zinc the term "super-purity" might well be applied without undue exaggeration. The techniques used for production control and final analysis of Special High-Grade zinc by means of emission spectra in the laboratories of the electrolytic zinc plant of the Sullivan Mining Co. are based on the premise that self-electrodes are to be preferred over all other forms for the examination of the zinc in question. Furthermore, after a survey of the literature and considerable experimental work,' it was decided that the spectrographic method of internal control, the principle of which was first announced by Gerlach,2 using a modification of the high-voltage alternating-current arc source introduced by Duffendack and Thompson,3 with the calibration of each photographic plate as recommended by Wolfe,4 would yield the most accurate and reproducible results. Self-electrodes were chosen in order to make use of one of the unique advantages inherent in spectrographic analysis; namely, the rapid and almost effortless detection of elements other than those being quantified by the analyst; or conversely, the proof that the zinc is free from such impurities if no spectral line of the suspected element appears. This fact was verified for certain elements, and will be discussed later. Carbon electrodes impregnated or packed with zinc salts chemically prepared from the zinc to be assayed were avoided for a number of reasons. First, the chemical manipulation was another time-consuming step, which increased the chances for contamination. Second, none of the common zinc salts, such as the chloride, nitrate or sulphate, yielded reproducible results under our conditions, nor did the spectral line of the impurity appear as readily in the low concentrations as when using zinc metal. Third, no commercial carbon, except the very expensive, was pure enough to use with this grade of zinc and the continued time, effort and expense incurred in the purification of carbon were not desirable. The use of special High-Grade zinc self-electrodes introduces certain complications with regard to obtaining satisfactory excitation conditions, because it seems necessary to raise the temperature

Jan 1, 1949

By H. L. Gilbert, C. T. Anderson, W. J. Kroll

In a previous paper,' the use of a split graphite tube resistor as a heater element for high-temperature furnaces has been described. The principal advantages of this type of construction are: I. The quadruple resistance or voltage compared with the top-bottom clamp resistor furnace. 2. Free expansion of the resistor. 3. The ease of protection from oxidation by air. 4. The firmness by which it may be held in the compact split clamp. This construction appeared to be well adapted for the fusion of high melting metals which require fusion in a vacuum. Zirconium metal had previously been melted at the Albany Laboratory of the Bureau of Mines in a vacuum arc furnace on a water-cooled plate, using a movable tungsten top electrode.% When larger furnace capacities were desired, this type of construction proved to have its limitations as the largest tungsten rods available were about 7/8 in. in diameter. The supply of direct current of high amperage for producing the desired arc characteristics was also not available. Considerable difficulty was also found in compensating the atmospheric pressure on the flcxible tubing of the movable electrodc, at the same time keeping its movement sufficiently free to enable the striking of an arc on any part of the metal briquet. Among the various materials used for the electrodes in conducting experiments in the vacuum arc furnace was graphite. It was found that zirconium fused in a graphite cup with a carbon arc was contaminated to only 0.2 pct carbon. It was therefore decsed to melt zirconium directly in graphite crucibles. A high-frequency furnace was first used in the attempt to melt the zirconium in graphite crucibles. The high-frequency heating coil was placed outside a silica tube which was evacuated by means of an oil diffusion pump backed up by a mechanical pump. The graphite crucible was thoroughly degassed at 19oo"C before use. Considerable difficulty was experienced in operating at such temperatures in vacuo because, as shown by Zintl,3 carbon vapor formed and reacted with silica accortling to the reaction: SiO² + C = SiO + CO. The silicon monoxide which is volatile at these high temperatures reacted with the zirconium, thereby contaminating it with silicon and oxygen. The presence of carbon monoxide was detected by means of a gas discharge tube placed in the vacuum system as indicated by the pale blue glow of the tube as soon as carbon vapor started to react with the hot silica. The reaction between the carbon vapor and hot silica was avoided by the use of split cylindrical molybdenum shields which were inserted between the graphite crucible

Jan 1, 1949

By J. L. Tokich, A. R. Troiano

Since 1921, when Hull1 discovered that cobalt can exist in the face-centered cubic and hexagonal close-packed modifications, the transitions that occur in cobalt have been extensively studied. It is generally agreed that on heating the hexagonal lattice changes to the cubic structure at ternperatures ranging from 400° to 500°C although considerable doubt exists as to the exact temperature. Data concerning the temperature of the transformation on cooling are much less concordant and their interpretation has not been satisfactory. The study is further complicated by the fact that many investigators have reported the existence of a high temperature allo-tropic change in the range 850 to 1020°C, at which the cubic lattice reverts to the hexagonal modification. The transition on cooling, which has been reported as Occurring at various temperatures from approximately 400 to 100°C, is of particular interest. Troiano and Greninger2 have recently suggested and considered the possibility Of allotropic transformations occurring in pure metals by a shear-type, diffusionless (martensite) transformation. The case of cobalt was specifically discussed and certain observations of previous investigators evaluated in terms Of this type of Of Table 1 briefly outlines the methods and results Of previous investigators Of the transformation temperatures of cobalt. Materials and Methods The major portion of this investigatioll was performed with cobalt sheet containing a total of 0.2 pet impurities with carbon present to the extent of o,I pct. After melting in an induction furnace under an atmosphere of hydrogen, the carbon con. tent analyzed 0.03 pct. Some observations were repeated with hydrogen reduced cobalt compresses analyzing 99.9 pet pure. No significant variations in results were observed employing the as-received sheet, the remelted stock, or the cobalt compresses. Filings for X ray diffraction analysis were sealed in evacuated glass ampoules. Pyrex glass tubing was used for temperatures below (600°C and for higher temperatures clear fused quartz was satisfactory. After appropriate heat treatment at various ternperatures, the specimen ampoules were furnace cooled, air cooled or quenched by crushing under distilled water. This allowed a range of cooling velocities from less than one degree C per set to greater than 1,0oo°C per sec. X ray diffraction patterns were taken with a Debye camera and filtered characteristic cobalt K-alpha radiation. The of of the existing phases was roughly approximated by visual examina-

Jan 1, 1949

By David Turnbull

In most reactions involving solids the transformation kinetics may be represented by the combination of two processes —those of nucleation and of growth. For example, Mehl and his coiq-orker in their studies on the transformation of austenite to pearlite in steels have been able to describe the kinetics in terms of the rates of nucleation and of growth. By micrographic examination of their specimens they determined the nucleation rate (rate of appearance of pearlite colonies) as a function of time, of percent transformation, and of temperature. They observed that after an incubation period in which no nuclei are observed, the number of nuclei appearing per unit time per unit of untransformed grain boundary area, increases at an increasng rate with time. When recrystallization rates have been interpreted in terms of rates of nucleation and growth and the rate of nucleation determined, an incubation period followed by an increasing rate of nucleation has also been reported. Among the studies in which this phenomenon has been observed are those of Kornfeld and coworkers3 on cold-drawn aluminum wire, of Anderson and Mehl4 n the recrystallization of aluminum sheet, and of Stanlcy and Meh15 on the recrystallization of silicon ferrite sheet. The existence of an incubation period during which no nuclei are observed does not appear to have been reconciled with the generally accepted Volmer-Becker theory of nucleation in condensed systems. This theory ostensibly requires the rate of appearance of nuclei to be independent of time. Volmer-Becker Theory In order to form a stable nuclcus of a new phase B in a mother phase A, the molecules or atoms of the mother phase must surmount a free energy barrier whose height is determined by the volume free energy change accompanying the transformation and the energy of the surface separating the two phases. The free energy difference between nuclei of various sizes and the molecules or atoms of the mother phase is plotted schematically in Fig I as a function of the radius of the nucleus r. This free energy difference is plotted for two values of the change of free energy per atom, (Jb — ja) accompanying the transformation when the volumes of the two phases are infinite. One of these values of (Jb—Ja) corresponds to a temperature above the temperature To at which the phascs A and B are in equilibrium, and the other to a temperature below To. In order for a nucleus of phase B to be stable at a temperature T² < TO, its radius must be equal to or greater than the critical value r* for which the free energy of formatioil of the nucleus is a maximum, the of phase B having radii equal to or less than r* will be called embryos hfehl and Jetter," in discussing the kinetics of nucleation in solid systems, suppose that embryos of critical size are formed

Jan 1, 1949