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By F. H. Rhines, A. H. Grobe

The constitution of the indium-zinc alloy series has been investigated by Wilson and Peretti,1 who determined the liquidus and eutectic temperatures by the conven-tional method of cooling curves and the eutectic composition by analyzing eutectic exudations. Recent developments affecting the availability of indium and consequent increased interest in its applications make a more complete knowledge of the constitu- tion of its alloys desirable. As a part of a program far the reexamination of the constitution of indium alloys by precision methods, the indium-zinc phase diagram (Figs. I and 2) has been redetermined in its entirety. The eutectic temperature (I43. 5°C.) reported by Wilson and Peretti has been confirmed exactly, but their value of the zinc concentration at the eutectic, 4 per cent, was found to be high; the new value is 2.8 per cent of zinc. There is also a rather large difference between the forms of the liquidus curves of Wilson and Peretti and those found in the present studies. The solidus curves herein have been located for the first time and the limits of solid solubility have been tenta-

Jan 1, 1944

By A. H. Grobe, F. H. Rhines

The constitution of the indium-zinc alloy series has been investigated by Wilson and Peretti,1 who determined the liquidus and eutectic temperatures by the conven-tional method of cooling curves and the eutectic composition by analyzing eutectic exudations. Recent developments affecting the availability of indium and consequent increased interest in its applications make a more complete knowledge of the constitu- tion of its alloys desirable. As a part of a program far the reexamination of the constitution of indium alloys by precision methods, the indium-zinc phase diagram (Figs. I and 2) has been redetermined in its entirety. The eutectic temperature (I43. 5°C.) reported by Wilson and Peretti has been confirmed exactly, but their value of the zinc concentration at the eutectic, 4 per cent, was found to be high; the new value is 2.8 per cent of zinc. There is also a rather large difference between the forms of the liquidus curves of Wilson and Peretti and those found in the present studies. The solidus curves herein have been located for the first time and the limits of solid solubility have been tenta-

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. W. Hickman, E. A Gulbransen

The physical and chemical structure of the oxide films formed on metals and alloys is of interest in our understanding of their protective properties. According to Pilling and Bedworth,¹ if the specific volume of the oxide is equal to or greater than that of the metal, a compact or continuous structure results; if the volume of the oxide is less, a cellular or porous structure forms. With the cellular type of coating the surface layer of oxide offers no impedance to oxidation; at a given temperature the rate of oxidation is quite constant. On the other hand, the compact type of coating acts as an effective barrier to oxygen and the rate of oxidation will follow a parabolic law. The recent work of Gulbransen2 and of Leontis and Rhines3 on the oxidation of magnesium indicates that it is not necessary for the volume of the oxide to be greater than that of the metal in order that the oxidation may follow a parabolic rate law. One exception to the rule of Pilling and Bedworth¹ is noted by Scheil;4 namely, tungsten. At 500° and 700°C long-time oxidations indicate a linear rate law with time. However, Dunn's6 0xidation measurements from 700°to 1000°C indicate that a parabolic rate law is followed. The oxide is mainly yellow WO a with a thin layer of the blue oxide. Preliminary results on the oxidation of tungsten6 in the temperature range 400° to 500°C indicate that the oxidation does proceed according to a parabolic rate law. Irrespective of the actual rate law that tungsten may obey, it is of interest to compare the results obtained on the oxidation of tungsten in the thin film region with those found when the metal is scaling. A time-temperature study of the oxides formed on both molybdenum and tungsten may indicate whether there exist any peculiarities in the oxide structures of the thin film region compared with those of the scaling region of oxidation. In a recent paper the authors7 presented an investigation of the structures of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper. The results of these studies are presented in graphical form as existence diagrams of the oxides on a time-temperature scale. The existence diagrams of the oxides occurring on some of the metals are simple and show few chemical transitions, but there are many cases in which the physical state of the oxide surface changes as a function of time and temperature, as evidenced by the appearance or disappearance of orientation effects and sharpness of patterns. In general an increase in temperature results in an increase in

Jan 1, 1947

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

The physical and chemical structure of the oxide films formed on metals and alloys is of interest in our understanding of their protective properties. According to Pilling and Bedworth,¹ if the specific volume of the oxide is equal to or greater than that of the metal, a compact or continuous structure results; if the volume of the oxide is less, a cellular or porous structure forms. With the cellular type of coating the surface layer of oxide offers no impedance to oxidation; at a given temperature the rate of oxidation is quite constant. On the other hand, the compact type of coating acts as an effective barrier to oxygen and the rate of oxidation will follow a parabolic law. The recent work of Gulbransen2 and of Leontis and Rhines3 on the oxidation of magnesium indicates that it is not necessary for the volume of the oxide to be greater than that of the metal in order that the oxidation may follow a parabolic rate law. One exception to the rule of Pilling and Bedworth¹ is noted by Scheil;4 namely, tungsten. At 500° and 700°C long-time oxidations indicate a linear rate law with time. However, Dunn's6 0xidation measurements from 700°to 1000°C indicate that a parabolic rate law is followed. The oxide is mainly yellow WO a with a thin layer of the blue oxide. Preliminary results on the oxidation of tungsten6 in the temperature range 400° to 500°C indicate that the oxidation does proceed according to a parabolic rate law. Irrespective of the actual rate law that tungsten may obey, it is of interest to compare the results obtained on the oxidation of tungsten in the thin film region with those found when the metal is scaling. A time-temperature study of the oxides formed on both molybdenum and tungsten may indicate whether there exist any peculiarities in the oxide structures of the thin film region compared with those of the scaling region of oxidation. In a recent paper the authors7 presented an investigation of the structures of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper. The results of these studies are presented in graphical form as existence diagrams of the oxides on a time-temperature scale. The existence diagrams of the oxides occurring on some of the metals are simple and show few chemical transitions, but there are many cases in which the physical state of the oxide surface changes as a function of time and temperature, as evidenced by the appearance or disappearance of orientation effects and sharpness of patterns. In general an increase in temperature results in an increase in

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

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

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

By Bruce W. Gonser, Robert I. Jaffee

Recent work by the authors1 established the constitutional diagram of the gold-germanium system. Of particular interest in the simple euctectiferous system was the eutectic alloy at 12 per cent Ge, which melted at the very low temperature of 356°C and had an unusually fine eutectic structure. It was of interest to investigate the effect of third components on the melting point, microstructure, and strength of this alloy, and in this work the effect of copper is discussed rather completely, with less complete data on the effects of silver, platinum, nickel, and zinc. No reference in the literature has been found on ternary systems with gold-germanium. Materials and Alloying -4s in the work on the binary system, gold-germanium, the germanium used in this investigation was the cyanide-reduced, 99.9 per cent product, produced by the Eagle-Picher Co. Fine gold sheet from Handy and Harmon, pure platinum sheet from the American Platinum Works, copper magnet wire from Anaconda, nickel wire assaying 99.6 per cent Ni. and electrolytic zinc were used for alloying. To make the alloys, charges of the pure metals were put in a graphite crucible and melted in an atmosphere of pure hydrogen. The temperature was brought up to about I050 C, and the metal allowed to freeze in the crucible. Except with alloys containing zinc, melting losses were consistently less than a few milligrams. When zinc was a component, weight losses up to half the weight of the zinc present were incurred, and the alloy compositions were calculated by assuming the entire weight loss to be that of zinc. In all other cases the composition of the alloys could safely be taken as that of the charge. The ingots, as solidified, were segregated, the heavier primary phases being at the bottom and sides of the ingots and the lighter primary phases at the top, but by sectioning the entire ingot vertically for microscopic examination, this factor could be evaluated. Ingots for microscopic examination weighed one gram, and those for thermal analysis weighed three grams. Thermal Analysis In this work, the eutectic line composition and thermal arrests were desired, and, after microscopic exploration had established the position of the eutectic line at a given percentage of the third component, a thermal analysis was run at that composition. The method of thermal analysis used in the work on the binary Au-Ge system,' a method particularly well suited for a small quantity of material, was used in this work. Clearly defined arrests were obtained, although with some alloys containing platinum

Jan 1, 1946

By Robert I. Jaffee, Bruce W. Gonser

Recent work by the authors1 established the constitutional diagram of the gold-germanium system. Of particular interest in the simple euctectiferous system was the eutectic alloy at 12 per cent Ge, which melted at the very low temperature of 356°C and had an unusually fine eutectic structure. It was of interest to investigate the effect of third components on the melting point, microstructure, and strength of this alloy, and in this work the effect of copper is discussed rather completely, with less complete data on the effects of silver, platinum, nickel, and zinc. No reference in the literature has been found on ternary systems with gold-germanium. Materials and Alloying -4s in the work on the binary system, gold-germanium, the germanium used in this investigation was the cyanide-reduced, 99.9 per cent product, produced by the Eagle-Picher Co. Fine gold sheet from Handy and Harmon, pure platinum sheet from the American Platinum Works, copper magnet wire from Anaconda, nickel wire assaying 99.6 per cent Ni. and electrolytic zinc were used for alloying. To make the alloys, charges of the pure metals were put in a graphite crucible and melted in an atmosphere of pure hydrogen. The temperature was brought up to about I050 C, and the metal allowed to freeze in the crucible. Except with alloys containing zinc, melting losses were consistently less than a few milligrams. When zinc was a component, weight losses up to half the weight of the zinc present were incurred, and the alloy compositions were calculated by assuming the entire weight loss to be that of zinc. In all other cases the composition of the alloys could safely be taken as that of the charge. The ingots, as solidified, were segregated, the heavier primary phases being at the bottom and sides of the ingots and the lighter primary phases at the top, but by sectioning the entire ingot vertically for microscopic examination, this factor could be evaluated. Ingots for microscopic examination weighed one gram, and those for thermal analysis weighed three grams. Thermal Analysis In this work, the eutectic line composition and thermal arrests were desired, and, after microscopic exploration had established the position of the eutectic line at a given percentage of the third component, a thermal analysis was run at that composition. The method of thermal analysis used in the work on the binary Au-Ge system,' a method particularly well suited for a small quantity of material, was used in this work. Clearly defined arrests were obtained, although with some alloys containing platinum

Jan 1, 1946

By E. L. Anderson, J. R. Long, R. S. Dean, F. S. Wartman

Titanium has been estimated to comprise about 0.65 per cent of the earth's crust and ranks fourth in abundance among the metallic elements suitable for engineering uses. In spite of this, applications of titanium for structural purposes have not as yet been developed. Its commercial exploitation has been largely confined to the chemical industries and the production of paints and pigments; no doubt because of the difficulties that lie in the way of preparing the pure ductile metal. Published reports, however, indicate that ductile titanium can be prepared and possesses some unique properties. This, together with the occurrence in this country of several important titaniferous deposits, has led the Bureau of Mines to investigate processes for the production of metallic titanium, methods required for its fabrication, and the properties that may be produced in this interesting metal. Methods of Preparing Metallic Titanium Many early investigators claimed to have isolated metallic titanium; but in the light of present knowledge, it seems that they really had produced various mixtures of carbides and nitrides that have a metallic appearance but are brittle, hard, and unworkable. The first metallic titanium pure enough to be malleable when cold was produced by Hunter1 in the early part of the twentieth century. Kroll,~ van Arkel,~ and Fast,4 subsequently confirmed the facts that pure titanium is a. ductile metal and that small amounts of impurities were responsible for previous reports of brittleness. When heated, titanium reacts chemically with various gases, such as hydrogen, oxygen and nitrogen; if the volume of gas thus absorbed is too great, the metal becomes brittle and unworkable. The principal difficulty in making ductile titanium is prevention of such contamination, and the success of a given process may be judged by the completeness with which it solves this difficulty in a practical manner. Of the gases mentioned, hydrogen is the least objectionable, since its absorption by the metal is completely reversible and, although dimensional changes occur and absorption of hydrogen embrittles the metal, the gas may be removed readily by heating in a high vacuum for a short time. On the other hand, the absorption of oxygen or nitrogen results in the formation of permanent solid solutions of the oxide and nitride, which cannot be decomposed by the strongest reducing agentsz with sufticient completeness to restore the inherent ductility of the metal. Because of

Jan 1, 1946

By J. R. Long, E. L. Anderson, R. S. Dean, F. S. Wartman

Titanium has been estimated to comprise about 0.65 per cent of the earth's crust and ranks fourth in abundance among the metallic elements suitable for engineering uses. In spite of this, applications of titanium for structural purposes have not as yet been developed. Its commercial exploitation has been largely confined to the chemical industries and the production of paints and pigments; no doubt because of the difficulties that lie in the way of preparing the pure ductile metal. Published reports, however, indicate that ductile titanium can be prepared and possesses some unique properties. This, together with the occurrence in this country of several important titaniferous deposits, has led the Bureau of Mines to investigate processes for the production of metallic titanium, methods required for its fabrication, and the properties that may be produced in this interesting metal. Methods of Preparing Metallic Titanium Many early investigators claimed to have isolated metallic titanium; but in the light of present knowledge, it seems that they really had produced various mixtures of carbides and nitrides that have a metallic appearance but are brittle, hard, and unworkable. The first metallic titanium pure enough to be malleable when cold was produced by Hunter1 in the early part of the twentieth century. Kroll,~ van Arkel,~ and Fast,4 subsequently confirmed the facts that pure titanium is a. ductile metal and that small amounts of impurities were responsible for previous reports of brittleness. When heated, titanium reacts chemically with various gases, such as hydrogen, oxygen and nitrogen; if the volume of gas thus absorbed is too great, the metal becomes brittle and unworkable. The principal difficulty in making ductile titanium is prevention of such contamination, and the success of a given process may be judged by the completeness with which it solves this difficulty in a practical manner. Of the gases mentioned, hydrogen is the least objectionable, since its absorption by the metal is completely reversible and, although dimensional changes occur and absorption of hydrogen embrittles the metal, the gas may be removed readily by heating in a high vacuum for a short time. On the other hand, the absorption of oxygen or nitrogen results in the formation of permanent solid solutions of the oxide and nitride, which cannot be decomposed by the strongest reducing agentsz with sufticient completeness to restore the inherent ductility of the metal. Because of

Jan 1, 1946

By F. R. Hensel

PuRe silver and silver-lead alloys have been studied as to their suitability for bearing~.' A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materia1s. t The silver-rich end of the diagram as reported in the literatureg-" was found to be sketchy and it was necessary to carry out corisiderable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. Test Materials In the beginning of the work, only fused alloys were investigated. Later, research Table i.—Composition of Fused Silver-thallium Alloys Tested for Antifriction Properties Percentage Alloy No. of Thallium 1533...................... 0.48 1534.................... 1.06 a31 HT................... 2.04 231....................... 2.10 232 HT................... 3.83 Balance 232....................... 4.07 Silver 233 HT................... 5.86 a33....................... 6.38 a34....................... 9.84 a34 HT................... 10.07 was carried out on electroplating methods and diffusion processes. In preparing the fused alloyst care was taken to exhaust the toxic fumes caused by the thaillium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in, diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr207, 8 C.C. H2S04, and IOO C.C. H20. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475OC. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not iesiilt iii complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1946

By F. R. Hensel

PuRe silver and silver-lead alloys have been studied as to their suitability for bearing~.' A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materia1s. t The silver-rich end of the diagram as reported in the literatureg-" was found to be sketchy and it was necessary to carry out corisiderable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. Test Materials In the beginning of the work, only fused alloys were investigated. Later, research Table i.—Composition of Fused Silver-thallium Alloys Tested for Antifriction Properties Percentage Alloy No. of Thallium 1533...................... 0.48 1534.................... 1.06 a31 HT................... 2.04 231....................... 2.10 232 HT................... 3.83 Balance 232....................... 4.07 Silver 233 HT................... 5.86 a33....................... 6.38 a34....................... 9.84 a34 HT................... 10.07 was carried out on electroplating methods and diffusion processes. In preparing the fused alloyst care was taken to exhaust the toxic fumes caused by the thaillium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in, diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr207, 8 C.C. H2S04, and IOO C.C. H20. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475OC. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not iesiilt iii complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1946

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

The volume of hydrogen released from electrolytic manganese at various temperatures and pressures was determined in a previous investigation1 as part of a study to determine the most practical procedure for removing the hydrogen from electrolytic manganese metal. No attempt was made to determine the absolute volume of gas in the metal at any temperature and pressure; the volume of gas released showed only the variation in solubility with temperature and pressure. The results were very similar to those obtained by Sieverts and Moritz.² Both sets of data show a minimum solubility between 500' and 700°C., but they differ in certain respects; on cooling from 500°C., our results showed an increase in solubility of about 7 C.C. as compared with an increase of 34 C.C. per 100 grams shown by Sieverts. Furthermore, the transition temperatures, as indicated by sharp breaks in the solubility curves, did not agree well with Sieverts' data. This information was of secondary importance in the earlier investigations, and the solubility at low temperatures and the transition temperatures were subject to considerable error. Therefore, a subsequent investigation, reported in this paper, was made to measure the absolute solubility at temperatures from room temperature through the melting point and make more accurate observations of the transition temperatures. Apparatus and Method The apparatus and method were essentially the same as those described in the previous work,' as shown in Fig. I. At high temperatures, the small tube containing the thermocouple in the sample container A frequently broke off, so for some of this work the thermocouple was placed outside the sample container and protected by a quartz tube of about the same wall thickness as the sample container. No significant difference was found in the transition temperatures obtained in the two ways. The automatic temperature controller was used in these tests in the regions where there was little change in solubility with temperature. In the neighborhood of the transition points a continuously variable autotransformer was used instead of the automatic controller, and the power input to the furnace was adjusted so that the temperature increased or decreased at a very slow, uniform rate through the transition range. This procedure was followed because the temperature oscillations produced by the controller were too great compared with the transition range, and the transi- . tion points determined under such conditions were less accurate. Absolute Solubility Procedure ad Results The absolute solubility of hydrogen in manganese could be determined most

Jan 1, 1947

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

The volume of hydrogen released from electrolytic manganese at various temperatures and pressures was determined in a previous investigation1 as part of a study to determine the most practical procedure for removing the hydrogen from electrolytic manganese metal. No attempt was made to determine the absolute volume of gas in the metal at any temperature and pressure; the volume of gas released showed only the variation in solubility with temperature and pressure. The results were very similar to those obtained by Sieverts and Moritz.² Both sets of data show a minimum solubility between 500' and 700°C., but they differ in certain respects; on cooling from 500°C., our results showed an increase in solubility of about 7 C.C. as compared with an increase of 34 C.C. per 100 grams shown by Sieverts. Furthermore, the transition temperatures, as indicated by sharp breaks in the solubility curves, did not agree well with Sieverts' data. This information was of secondary importance in the earlier investigations, and the solubility at low temperatures and the transition temperatures were subject to considerable error. Therefore, a subsequent investigation, reported in this paper, was made to measure the absolute solubility at temperatures from room temperature through the melting point and make more accurate observations of the transition temperatures. Apparatus and Method The apparatus and method were essentially the same as those described in the previous work,' as shown in Fig. I. At high temperatures, the small tube containing the thermocouple in the sample container A frequently broke off, so for some of this work the thermocouple was placed outside the sample container and protected by a quartz tube of about the same wall thickness as the sample container. No significant difference was found in the transition temperatures obtained in the two ways. The automatic temperature controller was used in these tests in the regions where there was little change in solubility with temperature. In the neighborhood of the transition points a continuously variable autotransformer was used instead of the automatic controller, and the power input to the furnace was adjusted so that the temperature increased or decreased at a very slow, uniform rate through the transition range. This procedure was followed because the temperature oscillations produced by the controller were too great compared with the transition range, and the transi- . tion points determined under such conditions were less accurate. Absolute Solubility Procedure ad Results The absolute solubility of hydrogen in manganese could be determined most

Jan 1, 1947