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By W. Bradley, R. G. Hall

This paper will attempt to show how a metallurgical problem at one California quicksilver mine was solved, and how the solution was applied successfully at another mine. The pronouns "we" and "our," as used below, refer '0 the Bradley 'lining Co. of San Francisco. The term "concurrent firing" for the purpose of this paper can be defined as feeding and firing a a kiln at the same end—that is, of course, the upper end' This is as opposed to "countercurrent firing," the orthodox method, in which a kiln is fed at the upper and fired at the lower end. The terms "quicksilver" and "mercury" are used interchangeably. Early References The earliest work on nonferrous metallurgy, we believe, was The Pirotechnia of Vannocio Biringuccio,l its first edition having been printed in Italy in 1540. Quoting from its chapter entitled "Concerning Quicksilver and Its Ore": Quicksilver ... is one of the gods and has divine strength in itself, and also, to the annoyance of the alchemists, it is winged. Hence, when it sees that it is in gravest danger, it loosens itself from . . . every bond . . . and fies away into the heavens, escaping from the hands of those who crucify it. Almost laughing, it leaves all its adversaries mocked and scorned, with their phials and filters empty . . . How thorough a job, under certain conditions, it can do of mocking its adversaries and leaving their phials and filters empty, was found out four centuries later at the Sulphur Bank mine, on the east shore of Clear Lake, in Lake county, California, The other mine mentioned in the title is the Reed, in Yolo County, California, 35 miles by road southeast of Sulphur Bank, Reed and Sulphur Bank ranked respectively Nth and seventh in U. S. production in 1943. The earliest direct reference we can find to furnacing troubles at these mines was by Thomas Egleston in 1890.2 Speaking of Sulphur Bank, Egleston says: of there is more sulphur than cinnabar in the ore, which is a detriment to both . . . making the sulphur impure, and rendering the cinnabar difficult to work on account of the soot. In some of the early . . . furnaces the accumulation of soot from the excess of sulphur has been known to penetrate as far as the fan blower at the end of the . . . condensers, and completely prevent its revolution. In order to get rid of the inconvenience of this accumulation . . . , as well as to get a commercial value from the sulphur, it (the sulphur) is now separated by steam and sold. It is claimed that the sulphur alone pays all the expenses of ... the mine. The mine was first worked for sulphur, and the cinnabar it contained was considered to be an inconvenience, and was carefully picked out and thrown away, as its richness and value were not

Jan 1, 1949

By M. Cohen, R. T. Howard

It has long been realized among metallurgists that a fast, reliable method for the quantitative determination of the percentage of microconstituents in an alloy would be of great benefit in studies of equilibrium and transformation in the solid state. For example, Polushkinl has shown that the compositions of two coexisting phases in a binary system at a given temperature may be calculated very simply with the aid of two alloys lying in the two-phase field if the relative amounts of the two phases in each alloy can be determined. Recently, Grange and Stewart2 have traced the course of the austenite-martensite reaction in a series of commercial steels by making visual estimates of the percentage of martensite formed as a function of cooling temperature. The correlation of mechanical properties with structure, a subject of wide-spread current interest, is likewise dependent upon quantitative microanaly-sis. Yet, there are very few investigations described in the metallurgical literature, wherein methods of quantitative microscopy are employed. Usually, the relative amounts of the microconstituents are estimated in a qualitative or semiquantita-tive way. The authors were faced with this problem some time ago in studying the kinetics of austenite decomposition. Several aspects of this research could not be treated satisfactorily by other quantitative tools, such as specific volume,' magnetic,6 dila-tometric, electrical resistance7 or x-ray measurements.a It became necessary to find an impersonal quantitative method that could be applied to microstructures. Fortunately, it was noted that geologists and petrographers had coped with quantitative microscopy to a considerable degree in their attempts to evaluate the mineral contents of rocks. A number of excellent articles were found on this subject, and since they appear to be unknown generally to many metallurgists, the first part of the present paper is concerned with a review of the literature in some detail. With this survey as a background, the authors have adapted the so-called methods of point-counting and lineal analysis to metallography, as described in the second part of the paper. Austenite-martensite structures were selected for illustration not only because they are important in many ways, but because such fine intermixtures are notoriously difficult to estimate visually. Literature Survey Perhaps the earliest work on quantitative microscopic analysis goes back to Delesse9 (1848) who proved mathemati-

Jan 1, 1948

By M. Cohen, R. T. Howard

It has long been realized among metallurgists that a fast, reliable method for the quantitative determination of the percentage of microconstituents in an alloy would be of great benefit in studies of equilibrium and transformation in the solid state. For example, Polushkinl has shown that the compositions of two coexisting phases in a binary system at a given temperature may be calculated very simply with the aid of two alloys lying in the two-phase field if the relative amounts of the two phases in each alloy can be determined. Recently, Grange and Stewart2 have traced the course of the austenite-martensite reaction in a series of commercial steels by making visual estimates of the percentage of martensite formed as a function of cooling temperature. The correlation of mechanical properties with structure, a subject of wide-spread current interest, is likewise dependent upon quantitative microanaly-sis. Yet, there are very few investigations described in the metallurgical literature, wherein methods of quantitative microscopy are employed. Usually, the relative amounts of the microconstituents are estimated in a qualitative or semiquantita-tive way. The authors were faced with this problem some time ago in studying the kinetics of austenite decomposition. Several aspects of this research could not be treated satisfactorily by other quantitative tools, such as specific volume,' magnetic,6 dila-tometric, electrical resistance7 or x-ray measurements.a It became necessary to find an impersonal quantitative method that could be applied to microstructures. Fortunately, it was noted that geologists and petrographers had coped with quantitative microscopy to a considerable degree in their attempts to evaluate the mineral contents of rocks. A number of excellent articles were found on this subject, and since they appear to be unknown generally to many metallurgists, the first part of the present paper is concerned with a review of the literature in some detail. With this survey as a background, the authors have adapted the so-called methods of point-counting and lineal analysis to metallography, as described in the second part of the paper. Austenite-martensite structures were selected for illustration not only because they are important in many ways, but because such fine intermixtures are notoriously difficult to estimate visually. Literature Survey Perhaps the earliest work on quantitative microscopic analysis goes back to Delesse9 (1848) who proved mathemati-

Jan 1, 1948

By M. F. Hawkes

Austenite grain size has long been recognized by metallurgists as an important property of steels because of its influence on toughness, hardenability, ma-chinability and creep strength. Much research has been carried out on wrought steels to develop methods for disclosing austenite grain size, and to, provide knowledge of the grain-size characteristics of steels produced and heat-treated in various ways. Much less work in these fields has been done on steel castings; partly because, owing to the variable and complex microstruc-tures of cast steels, it is frequently very difficult to obtain results that are not questionable. The object of this investigation, therefore, was to establish, for a wide variety of carbon and alloy cast steels, suitable methods for disclosing austenite grain size and some knowledge of the grain-size variations to be expected. The steel foundryman is interested in austenite grain size at two different stages in the manufacture of his products; one is just after the steel is cast, and the other is after any reheating operation carried out above the critical temperature range. In both, it must always be kept in mind that the grain size being sought is actually a previous austenite grain size, and that the austenite no longer exists once the steel has cooled to room temperature. The prob-lem of the investigator is always to use evidence obtained from the structure at room temperature to deduce this previous austenite grain size, which was established the last time the steel existed at a temperature above the critical range. Since most steel castings today are at least annealed or normalized, the measurement of austenite grain size established by heat-treatment will he considered first. More than 50 commercially produced cast steels rcpresenting a wide variety of compositions and melting practices were used in the study. For each steel, grain-size determinations were made after each of three widely varying heat-treating schedules namely, one hour at I550'F, one hour at I700°F, and six hours at 1700 F. The list of steels and results obtained on them will be found in the appendix. (See page 530.) A discussion of the knowledge gained on the applicability of various test methods and on grain-size characteristics of cast steels in general follows. MEASUREMENT OF AUSTENITE GRAIN SIZE ESTABLISHED BY HEAT TREATMENT Methods Suitable foR Determining Austenite Grain Size after Heat-treatment at Ordinary Temperatures and Times It was desired, as one of the results of this investigation, to be able to recommend to steel foundries a method, or methods, of disclosing grain size best suited to accurate

Jan 1, 1948

By M. F. Hawkes

Austenite grain size has long been recognized by metallurgists as an important property of steels because of its influence on toughness, hardenability, ma-chinability and creep strength. Much research has been carried out on wrought steels to develop methods for disclosing austenite grain size, and to, provide knowledge of the grain-size characteristics of steels produced and heat-treated in various ways. Much less work in these fields has been done on steel castings; partly because, owing to the variable and complex microstruc-tures of cast steels, it is frequently very difficult to obtain results that are not questionable. The object of this investigation, therefore, was to establish, for a wide variety of carbon and alloy cast steels, suitable methods for disclosing austenite grain size and some knowledge of the grain-size variations to be expected. The steel foundryman is interested in austenite grain size at two different stages in the manufacture of his products; one is just after the steel is cast, and the other is after any reheating operation carried out above the critical temperature range. In both, it must always be kept in mind that the grain size being sought is actually a previous austenite grain size, and that the austenite no longer exists once the steel has cooled to room temperature. The prob-lem of the investigator is always to use evidence obtained from the structure at room temperature to deduce this previous austenite grain size, which was established the last time the steel existed at a temperature above the critical range. Since most steel castings today are at least annealed or normalized, the measurement of austenite grain size established by heat-treatment will he considered first. More than 50 commercially produced cast steels rcpresenting a wide variety of compositions and melting practices were used in the study. For each steel, grain-size determinations were made after each of three widely varying heat-treating schedules namely, one hour at I550'F, one hour at I700°F, and six hours at 1700 F. The list of steels and results obtained on them will be found in the appendix. (See page 530.) A discussion of the knowledge gained on the applicability of various test methods and on grain-size characteristics of cast steels in general follows. MEASUREMENT OF AUSTENITE GRAIN SIZE ESTABLISHED BY HEAT TREATMENT Methods Suitable foR Determining Austenite Grain Size after Heat-treatment at Ordinary Temperatures and Times It was desired, as one of the results of this investigation, to be able to recommend to steel foundries a method, or methods, of disclosing grain size best suited to accurate

Jan 1, 1948

By M. F. Hawkes, R. F. Mehl

The rate of isothermal transformation of austenite to pearlite depends upon the rate of nucleation, N, and the rate of growth, G, of pearlite in austenite. Values of N are given in terms of the number of nuclei forming in unit time per unit grain boundary area of unreacted austenite; values of C are given in terms of the linear rate of radial growth. Variations in the isothermal rate with temperature result from variation of N and G with temperature. Depth of hardening of a steel depends fundamentally upon values of N and G; changes in carbon and alloy content effect changes in N and G and thus affect depth of hardening. Quantitative studies are available on N and G for the formation of pearlite in plain carbon eutectoid steels.3 Systematic studies in this field are necessary if the phenomena are to be well enough known to furnish a proper basis for full rationalization and for theory. Accordingly, the studies are continuing, both with respect to the effect of alloying elements upon the values of N and G in the formation of pearlite and to the values of N and G for the formation of ferrite in hypoeutectoid steels. The present paper is the first relating to the effect of alloying elements upon the values of N and G for pearlite. It offers special interest since cobalt is known to have an anomalous effect upon the rate of formation of pearlite, accelerating it, whereas all other elements retard it.4 It will be shown that cobalt increases both N and G for pearlite and that this effect is inherent in the Fe-Co-C system and not dependent upon factors relating to austenite heterogeneity nor upon any recognizable adventitious factor. Inasmuch as the rate of diffusion of carbon in austenite and the interlamellar spacing of pearlite are variables related to G and possibly to N (in a manner not yet certain), measurements of the effect of cobalt upon them are also reported here. In the course of the work, measurements were made on the effect of cobalt upon the marten-site temperature and these are given. COBALT AS AN ALLOYING ELEMENT IN STEEL Properties of Cobalt Cobalt resembles iron more closely than does any other chemical element. Its atomic number is 27, hence it is the element immediately following iron in the periodic system. The two differ in atomic structure only in the fact that cobalt contains seven electrons instead of six in the third, or transition, level of .the third shell. The next shell, which is the

Jan 1, 1948

By M. F. Hawkes, R. F. Mehl

The rate of isothermal transformation of austenite to pearlite depends upon the rate of nucleation, N, and the rate of growth, G, of pearlite in austenite. Values of N are given in terms of the number of nuclei forming in unit time per unit grain boundary area of unreacted austenite; values of C are given in terms of the linear rate of radial growth. Variations in the isothermal rate with temperature result from variation of N and G with temperature. Depth of hardening of a steel depends fundamentally upon values of N and G; changes in carbon and alloy content effect changes in N and G and thus affect depth of hardening. Quantitative studies are available on N and G for the formation of pearlite in plain carbon eutectoid steels.3 Systematic studies in this field are necessary if the phenomena are to be well enough known to furnish a proper basis for full rationalization and for theory. Accordingly, the studies are continuing, both with respect to the effect of alloying elements upon the values of N and G in the formation of pearlite and to the values of N and G for the formation of ferrite in hypoeutectoid steels. The present paper is the first relating to the effect of alloying elements upon the values of N and G for pearlite. It offers special interest since cobalt is known to have an anomalous effect upon the rate of formation of pearlite, accelerating it, whereas all other elements retard it.4 It will be shown that cobalt increases both N and G for pearlite and that this effect is inherent in the Fe-Co-C system and not dependent upon factors relating to austenite heterogeneity nor upon any recognizable adventitious factor. Inasmuch as the rate of diffusion of carbon in austenite and the interlamellar spacing of pearlite are variables related to G and possibly to N (in a manner not yet certain), measurements of the effect of cobalt upon them are also reported here. In the course of the work, measurements were made on the effect of cobalt upon the marten-site temperature and these are given. COBALT AS AN ALLOYING ELEMENT IN STEEL Properties of Cobalt Cobalt resembles iron more closely than does any other chemical element. Its atomic number is 27, hence it is the element immediately following iron in the periodic system. The two differ in atomic structure only in the fact that cobalt contains seven electrons instead of six in the third, or transition, level of .the third shell. The next shell, which is the

Jan 1, 1948

By K. A. Grange, W. S. Holt, E. T. Tkac

Quantitative knowledge of the time clement involved in austenite transformation in a particular steel provides a sound basis for understanding and planning heat-treatment. Such knowledge is conveniently obtained by measurement of austenite transformation as it occurs at each of a series of temperature levels. The results of these measurements usually are summarized in the form of the now familiar isothermal transformation diagram (I-T diagram, TTT diagram, or S-curve). Although a considerable number of such diagrams already have appeared in the literature, there remain many compositions of commercial importance for which no I-T diagram is available. The diagram for many such steels may be predicted from published data with sufficient accuracy for most practical purposes, but for others no satisfactory prediction can be made because the effect on austenite transformation of one or more of the important alloying elements present is not well enough known. Such a steel is Nitralloy, Type 13s-Modified, which, containing about 1.25 per cent aluminum, differs from any whose I-T diagram has been published. This paper presents results of a study of the isothermal transformation behavior of a sample from a commercial heat of this aluminum-chromium-molybdenum steel, together with pertinent supplementary data including the equilibrium transformation temperatures (Aeaand Ae,), the temperature range of martensite formation, and the end-quench harden-ability. These data are directly applicable to the hcat-treatment of this type of steel and are of interest in revealing some of the fundamental effects of aluminum as an alloying element in steel. Material All specimens were prepared from a 1 1/4 i-in. diam bar forged from a 5 by 5-in. billet from a commercial heat made in an electric arc furnace. The composition of the bar was; C, 0.41 per cent: AIn, 0.57: P, 0.016: S, 0.005: Si, 0.24: Ni, 0.17: Cr, I.j7: Mo, 0.36: All 1.26. The forged bar was normalized from r750°F (95s°C) and then tempered for one hour at rzoo°F (650°C), this tempering treatment having been given to facilitate the machining of specimens. Equilibrium Transformation Temperatures In hypoeutectoid steel the minimum temperature at which austenite is completely stable, Aep, and the maximum temperature at which austenite is completely unstable, Ael, are of great significance in heat-treatment. Since these temperatures are dependent upon com-

Jan 1, 1948

By W. S. Holt, K. A. Grange, E. T. Tkac

Quantitative knowledge of the time clement involved in austenite transformation in a particular steel provides a sound basis for understanding and planning heat-treatment. Such knowledge is conveniently obtained by measurement of austenite transformation as it occurs at each of a series of temperature levels. The results of these measurements usually are summarized in the form of the now familiar isothermal transformation diagram (I-T diagram, TTT diagram, or S-curve). Although a considerable number of such diagrams already have appeared in the literature, there remain many compositions of commercial importance for which no I-T diagram is available. The diagram for many such steels may be predicted from published data with sufficient accuracy for most practical purposes, but for others no satisfactory prediction can be made because the effect on austenite transformation of one or more of the important alloying elements present is not well enough known. Such a steel is Nitralloy, Type 13s-Modified, which, containing about 1.25 per cent aluminum, differs from any whose I-T diagram has been published. This paper presents results of a study of the isothermal transformation behavior of a sample from a commercial heat of this aluminum-chromium-molybdenum steel, together with pertinent supplementary data including the equilibrium transformation temperatures (Aeaand Ae,), the temperature range of martensite formation, and the end-quench harden-ability. These data are directly applicable to the hcat-treatment of this type of steel and are of interest in revealing some of the fundamental effects of aluminum as an alloying element in steel. Material All specimens were prepared from a 1 1/4 i-in. diam bar forged from a 5 by 5-in. billet from a commercial heat made in an electric arc furnace. The composition of the bar was; C, 0.41 per cent: AIn, 0.57: P, 0.016: S, 0.005: Si, 0.24: Ni, 0.17: Cr, I.j7: Mo, 0.36: All 1.26. The forged bar was normalized from r750°F (95s°C) and then tempered for one hour at rzoo°F (650°C), this tempering treatment having been given to facilitate the machining of specimens. Equilibrium Transformation Temperatures In hypoeutectoid steel the minimum temperature at which austenite is completely stable, Aep, and the maximum temperature at which austenite is completely unstable, Ael, are of great significance in heat-treatment. Since these temperatures are dependent upon com-

Jan 1, 1948

By E. A. Anderson, P. W. Ramsey, E. J. Boyle

Only a few zinc-rich alloys are in commercial use today, and these depend largely upon solid solution effects for their desirable properties. Typical examples are rolled alloys containing about 1 Per cent of copper, with Or without additions of elements such as magnesium, and die-casting alloys containing about 4 Per cent of aluminum with small amounts of magnesium and sometimes copper." A number of elements are capable of forming alloys with zinc, Which do not enter into solid solution except in limited degree. The Present Paper considers One such system, zinc-titanium, in which alloys having potentially useful properties in the rolled form were found. Zinc-titanium System The zinc-rich portion of the zinc-titanium diagram, as determined by standard methods in this laboratory,3 is shown in Fig. I. The portion of the diagram of significance in the present work extends from 0 to about 0.5 per cent titanium. Gebhardt4 places the eutectic at 0.45 per cent, but the evidence in favor 01 the composition given in Fig. I is considerable. The solid solubility of titanium in zinc is very low indeed and possibly places these alloys in a somewhat different category from the commercial alloys previously mentioned. Alloy Preparation All of the alloys used in this work were prepared with titanium metal of 98.9 per cent purity. In most cases high-purity zinc (99.99 per cent) was used but sufficient work was done later to show that zinc of about high-grade composition would yield approximately equal results. Best practice in alloy manufacture seemed to be to prepare a zinc-titanium hardener by adding about 4 per cent of titanium metal to molten zinc and holding under a boric acid cover, with frequent stirrings, at 750°C, until the titanium had dissolved. The desired titanium content could readily be obtained in the final alloy by adding the calculated amount 01 this hardener. The alloys proved to be quite stable in composition, unless overheated, and, with reasonable temperature control, required no cover or flux to prevent loss of titanium content by oxidatioll, Hot-rollig Tests Three alloys containing, by analysis, 0.05, 0.12, and 0.23 per cent titanium were selected for preliminary study. Slab cross sections a a marked grain refinement* (Fig. 2) in the two alloys of highest titanium content. Cast unalloyed zinc has a columnar grain structure similar to that shown for the alloy of lowest titanium content but without the scatter of small equiaxed grains at the center.

Jan 1, 1944

By P. W. Ramsey, E. J. Boyle, E. A. Anderson

Only a few zinc-rich alloys are in commercial use today, and these depend largely upon solid solution effects for their desirable properties. Typical examples are rolled alloys containing about 1 Per cent of copper, with Or without additions of elements such as magnesium, and die-casting alloys containing about 4 Per cent of aluminum with small amounts of magnesium and sometimes copper." A number of elements are capable of forming alloys with zinc, Which do not enter into solid solution except in limited degree. The Present Paper considers One such system, zinc-titanium, in which alloys having potentially useful properties in the rolled form were found. Zinc-titanium System The zinc-rich portion of the zinc-titanium diagram, as determined by standard methods in this laboratory,3 is shown in Fig. I. The portion of the diagram of significance in the present work extends from 0 to about 0.5 per cent titanium. Gebhardt4 places the eutectic at 0.45 per cent, but the evidence in favor 01 the composition given in Fig. I is considerable. The solid solubility of titanium in zinc is very low indeed and possibly places these alloys in a somewhat different category from the commercial alloys previously mentioned. Alloy Preparation All of the alloys used in this work were prepared with titanium metal of 98.9 per cent purity. In most cases high-purity zinc (99.99 per cent) was used but sufficient work was done later to show that zinc of about high-grade composition would yield approximately equal results. Best practice in alloy manufacture seemed to be to prepare a zinc-titanium hardener by adding about 4 per cent of titanium metal to molten zinc and holding under a boric acid cover, with frequent stirrings, at 750°C, until the titanium had dissolved. The desired titanium content could readily be obtained in the final alloy by adding the calculated amount 01 this hardener. The alloys proved to be quite stable in composition, unless overheated, and, with reasonable temperature control, required no cover or flux to prevent loss of titanium content by oxidatioll, Hot-rollig Tests Three alloys containing, by analysis, 0.05, 0.12, and 0.23 per cent titanium were selected for preliminary study. Slab cross sections a a marked grain refinement* (Fig. 2) in the two alloys of highest titanium content. Cast unalloyed zinc has a columnar grain structure similar to that shown for the alloy of lowest titanium content but without the scatter of small equiaxed grains at the center.

Jan 1, 1944

By R. S. Dean

The commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in Mining and Metallurgy for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for " the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. Practice at BouldeR City The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: 1. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By R. S. Dean

The commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in Mining and Metallurgy for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for " the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. Practice at BouldeR City The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: 1. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By G. P. Gladis, R. H. Atkinson

Palladium has been used for jewelry for many years, particularly in conjunction with gold. This use increased in amount during the war, as palladium and gold were only moderately used for war purposes while demands for platinum and some of the other members of the platinum group were so great that their use in jewelry was prohibited. Palladium hardened with a small percentage of ruthenium has the necessary technical properties and appearance for good jewelry, and it is sufficiently rare to be desirable for luxury items—at least I00 times as rare as gold. Although both visual and spectro-photometric examination demonstrated that the color of Palladium was almost the same as that of platinum, a few jewelers found the surface of palladium, even after some polishing, rather dark in areas that had been repeatedly heated during the soldering necessary to assemble certain types of handmade ornaments. This phenomenon is not to be confused with the thin, bluish oxide film that can be produced by heating in air over the range 400' to 800°C., as that film is easily reduced by dipping in warm 5 per cent formic acid or in warm methanol. It was suspected that the difficulty arose from heating in atmospheres that were alternately oxidizing and reducing, as Wise and Vines1 had found that this opened the grain boundaries of palladium and palladium-silver alloys in the same manner as in pure silver, as reported by Martin and Parker.2 This damage is caused by the reaction between oxygen in solid solution in the metal, acquired when heated under oxidizing conditions, and hydrogen diffusing in from subsequent heating under reducing conditions; the steam cannot diffuse out and therefore builds up sufficient pressure to disrupt the metal near the surface. Copper and various other metals can be damaged similarly, but platinum is nearly immune; therefore the problem was new to the platinum jeweler. Sulphur in the fuel gas also can cause trouble but did not appear to be dominant in the present instance. Metallographic examination of both pure palladium and ruthenium-palladium showed that the usual torch using oxygen and city gas as normally operated did in fact cause the surface and subsurface damage that had been observed, and also disclosed that a reducing flame caused more damage than an oxidizing flame and was very damaging even in the absence of any intentional swing in atmosphere from oxidizing to reducing (Fig. 7); besides the surface damage, there was serious loss of ductility. A full explanation of the mechanism of attack is not evident at the moment, but may be allied to the attack that occurs on heating catalytically active metals in nonequilibrium atmospheres.

Jan 1, 1946

By G. P. Gladis, R. H. Atkinson

Palladium has been used for jewelry for many years, particularly in conjunction with gold. This use increased in amount during the war, as palladium and gold were only moderately used for war purposes while demands for platinum and some of the other members of the platinum group were so great that their use in jewelry was prohibited. Palladium hardened with a small percentage of ruthenium has the necessary technical properties and appearance for good jewelry, and it is sufficiently rare to be desirable for luxury items—at least I00 times as rare as gold. Although both visual and spectro-photometric examination demonstrated that the color of Palladium was almost the same as that of platinum, a few jewelers found the surface of palladium, even after some polishing, rather dark in areas that had been repeatedly heated during the soldering necessary to assemble certain types of handmade ornaments. This phenomenon is not to be confused with the thin, bluish oxide film that can be produced by heating in air over the range 400' to 800°C., as that film is easily reduced by dipping in warm 5 per cent formic acid or in warm methanol. It was suspected that the difficulty arose from heating in atmospheres that were alternately oxidizing and reducing, as Wise and Vines1 had found that this opened the grain boundaries of palladium and palladium-silver alloys in the same manner as in pure silver, as reported by Martin and Parker.2 This damage is caused by the reaction between oxygen in solid solution in the metal, acquired when heated under oxidizing conditions, and hydrogen diffusing in from subsequent heating under reducing conditions; the steam cannot diffuse out and therefore builds up sufficient pressure to disrupt the metal near the surface. Copper and various other metals can be damaged similarly, but platinum is nearly immune; therefore the problem was new to the platinum jeweler. Sulphur in the fuel gas also can cause trouble but did not appear to be dominant in the present instance. Metallographic examination of both pure palladium and ruthenium-palladium showed that the usual torch using oxygen and city gas as normally operated did in fact cause the surface and subsurface damage that had been observed, and also disclosed that a reducing flame caused more damage than an oxidizing flame and was very damaging even in the absence of any intentional swing in atmosphere from oxidizing to reducing (Fig. 7); besides the surface damage, there was serious loss of ductility. A full explanation of the mechanism of attack is not evident at the moment, but may be allied to the attack that occurs on heating catalytically active metals in nonequilibrium atmospheres.

Jan 1, 1946

By J. W. Hickman, E. A. Gulbransen

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By J. W. Hickman, E. A. Gulbransen

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By J. R. Long, R. S. Dean, F. S. Wartman, E. T. Hayes

The production of titanium in I5-lb. lots and with a purity sufficient to be consolidated into ductile metal, as described in a previous paper,' has provided adequate material for a study of the physical properties of titanium and a more thorough examination of its working qualities. Data on the physical properties reported in that paper were obtained on metal fabricated by a fixed procedure, standardized for the purpose of control of the reduction, and are representative only of material fabricated under those conditions. There are many possible variables in the working schedule, which will have significant effects on the properties of the finished material; and since the previous working methods were not necessarily the best, an investigation of the fabrication of titanium by other methods was undertaken. In this work the consolidation of the powder by pressing and sintering was conducted essentially as outlined in the report cited' and all efforts were centered on fabrication methods for those powders and the proper- ties produced by them. Hardness, density, microstructure, and tensile properties were determined at various stages in the working and annealing; and resistivity measurements were made on a few bars and drawn wire. Consolidation of the PowdeR The screen analysis of the available titanium powder is given in Table I. No attempt was made to alter the size distribution from that noted because this powder, although coarse by normal powder-metallurgy standards, produced acceptable compacts suitable for the present work. Because of their large specific surface, finer powders are more contaminated by oxygen and produce harder compacts, which are difficult to work. The powder as produced is soft, compresses in a normal fashion, and exhibits very little tendency to adhere to the die surfaces. Unlike aluminum and magnesium powders, it can be readily pressed without the use of die lubricants. When compacted at 50 tons per

Jan 1, 1946