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By W. Crafts, J. L. Lamont

Studies of the effect of composition of steel on hardenability by Grossmann,' and as-quenched hardness by Field2 and by the authors, have made it possible to predict the results of quenching when the composition and cooling rate are known In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tem-pred properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq, in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as-quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content. Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after like heat-treatment, differ considerably in tensile strength. Procedure In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08 to 0'65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc' The accuracy of the method was finally checked on a variety of carbon, low-alloy and high-alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from 1/2 to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability speci-menS quenched from a normal temperature for austenitizatios were used to obtain a range of as-quenched Rockwell C

Jan 1, 1948

By A. S. Nowick, E. S. Machlin

One of the main criteria used to rate the heat-resisting properties of alloys is stress rupture.' During a stress-rupture test a tensile specimen is held under a constant load at a constant temperature until it fractures. The chief measurement made during this test is the time requird for rupture at the specific test stress and temperature. It was found empirically from a series of stress-rupture tests at a constant temperature that when the logarithm of the time for rupture is plotted against the logarithm of stress a straight line is obtained within experimental error This method of showing stress-rupture data has been adopted by many investigators and the NACA.' By interpolation and extrapolation from these plots, values of the stresses required to rupture the specimens (the rupture strengths) in 10, roo, and 1000 hr are obtained for specific temperatures. Alloys are then rated for a particular application on the basis of their rupture strengths at the rupture life that most nearly represents the application. Inasmuch as stress rupture is an important criterion in rating heat-resisting alloys, it would be advantageous to know the quantitative dependence of the time lor rupture on stress, temperature, composition, and structure. In order to obtain this information, an investigation was made at the NACA Cleveland laboratory during the spring of 1945. The theory of rate processes was used because it has been found to apply to certain processes such as chemical reactions, viscous flow, and creep that occur at a definite rate for given conditions. It was thought that stress rupture was such a process. An equation was derived that gives, for a given composition and structure, the dependence of the time for rupture on stress and temperature. The investigation is part of a general program to provide information that will lead ultimately to the development of better alloys in order that the efliciency and power output of gas turbines used in aircraft propulsion can be increased. Theory The theory of rate processes will first be discussed as a general theory. It will then be shown that if stress rupture of heat-resisting alloys can be treated as a rate process, certain equations must be satisfied. Later sections will then show that these equations are satisfied. General Theory of Rate Processes The theory of rate processes5 developed by Eyring and others has been applied to chemical reactions as well as to other processes such as viscosity of liquids and diffusion. In every case in which rate-process theory can be applied, there is a small subdivision, so that the macroscopic process is the net effect of all the small processes. This smallest subdivision is called the "unit process." For example, in a chemical reaction the unit process is

Jan 1, 1948

By A. S. Nowick, E. S. Machlin

One of the main criteria used to rate the heat-resisting properties of alloys is stress rupture.' During a stress-rupture test a tensile specimen is held under a constant load at a constant temperature until it fractures. The chief measurement made during this test is the time requird for rupture at the specific test stress and temperature. It was found empirically from a series of stress-rupture tests at a constant temperature that when the logarithm of the time for rupture is plotted against the logarithm of stress a straight line is obtained within experimental error This method of showing stress-rupture data has been adopted by many investigators and the NACA.' By interpolation and extrapolation from these plots, values of the stresses required to rupture the specimens (the rupture strengths) in 10, roo, and 1000 hr are obtained for specific temperatures. Alloys are then rated for a particular application on the basis of their rupture strengths at the rupture life that most nearly represents the application. Inasmuch as stress rupture is an important criterion in rating heat-resisting alloys, it would be advantageous to know the quantitative dependence of the time lor rupture on stress, temperature, composition, and structure. In order to obtain this information, an investigation was made at the NACA Cleveland laboratory during the spring of 1945. The theory of rate processes was used because it has been found to apply to certain processes such as chemical reactions, viscous flow, and creep that occur at a definite rate for given conditions. It was thought that stress rupture was such a process. An equation was derived that gives, for a given composition and structure, the dependence of the time for rupture on stress and temperature. The investigation is part of a general program to provide information that will lead ultimately to the development of better alloys in order that the efliciency and power output of gas turbines used in aircraft propulsion can be increased. Theory The theory of rate processes will first be discussed as a general theory. It will then be shown that if stress rupture of heat-resisting alloys can be treated as a rate process, certain equations must be satisfied. Later sections will then show that these equations are satisfied. General Theory of Rate Processes The theory of rate processes5 developed by Eyring and others has been applied to chemical reactions as well as to other processes such as viscosity of liquids and diffusion. In every case in which rate-process theory can be applied, there is a small subdivision, so that the macroscopic process is the net effect of all the small processes. This smallest subdivision is called the "unit process." For example, in a chemical reaction the unit process is

Jan 1, 1948

By Edward Saibel

The object of this study is to investigate the effect of prior tensile strain on the fracture stress of a metal. This is done in a theoretical manner starting from the point of view developed by the author in his thermodynamic theory of the fracture of metals. The results are compared with experimental findings and a rational interpretation is given to work that shows the variation of fracture stress with prior tensile strain. Theory op Fracture In the thermodynamic theory of the fracture of metals developed earlier,' it was shown that a critical strain energy per unit volume exists. This is characteristic of the material and may be calculated from basic thermodynamic data. When the area under the flow curve reaches this characteristic value, fracture occurs. The general criterion for fracture is expressed in the form « ± u. = JLJW/V [r] where L, is the latent heat of melting of the unit volume, AV/V is the ratio of the change in volume of the unit volume to the original unit volume on passing from the solid to the liquid state, uo is an initial energy density, and J is a conversion factor, which changes energy from heat to mechanical units. As a first approximation, it will he assumed that the stress-strain curve is the straight line that extends from the point of maximum load onward, extrapolated back to the axis of zero strain, for example, line AC of Fig. I. If the point of intersection of the straight line with the axis of zero strain is represented by v., and the slope of the straight line is p, the analytic form of the flow curve is a = (To + pd [2] and the strain energy per unit volume evaluated from Jud6 becomes (u,6 + pa2/2). When this latter term reaches the critical value JLbVIV (designated hereafter by M), it is assumed that fracture occurs. This leads to the following expression for the fracture stress: a; = V«r.2 + iMp [3] The strain at fracture may be calculated from Eqs 2 and 3. It is assumed in this paper that the initial energy density is either zero or that it may be neglected. Furthermore, the complicated states of stress and of strain existing in the necked region of the tensile specimen after "necking" has occurred will also be neglected for the present, so that average conditions will be assumed to prevail. Flow and Fracture Curves LudwigZ attributed to materials two fundamental properties: (I) a resistance to flow and (2) a resistance to fracture. He reasoned that at each instant the

Jan 1, 1948

By Edward Saibel

The object of this study is to investigate the effect of prior tensile strain on the fracture stress of a metal. This is done in a theoretical manner starting from the point of view developed by the author in his thermodynamic theory of the fracture of metals. The results are compared with experimental findings and a rational interpretation is given to work that shows the variation of fracture stress with prior tensile strain. Theory op Fracture In the thermodynamic theory of the fracture of metals developed earlier,' it was shown that a critical strain energy per unit volume exists. This is characteristic of the material and may be calculated from basic thermodynamic data. When the area under the flow curve reaches this characteristic value, fracture occurs. The general criterion for fracture is expressed in the form « ± u. = JLJW/V [r] where L, is the latent heat of melting of the unit volume, AV/V is the ratio of the change in volume of the unit volume to the original unit volume on passing from the solid to the liquid state, uo is an initial energy density, and J is a conversion factor, which changes energy from heat to mechanical units. As a first approximation, it will he assumed that the stress-strain curve is the straight line that extends from the point of maximum load onward, extrapolated back to the axis of zero strain, for example, line AC of Fig. I. If the point of intersection of the straight line with the axis of zero strain is represented by v., and the slope of the straight line is p, the analytic form of the flow curve is a = (To + pd [2] and the strain energy per unit volume evaluated from Jud6 becomes (u,6 + pa2/2). When this latter term reaches the critical value JLbVIV (designated hereafter by M), it is assumed that fracture occurs. This leads to the following expression for the fracture stress: a; = V«r.2 + iMp [3] The strain at fracture may be calculated from Eqs 2 and 3. It is assumed in this paper that the initial energy density is either zero or that it may be neglected. Furthermore, the complicated states of stress and of strain existing in the necked region of the tensile specimen after "necking" has occurred will also be neglected for the present, so that average conditions will be assumed to prevail. Flow and Fracture Curves LudwigZ attributed to materials two fundamental properties: (I) a resistance to flow and (2) a resistance to fracture. He reasoned that at each instant the

Jan 1, 1948

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 Ivor Jenkins

Processes employing 'controlled at-mospheres in the heat-treatment of metals and alloys are now well established on an industrial scale, and the general principles involved and the advantages to be gained in the use of the technique have received considerable publicity over a period of years. During this time the greatest emphasis has been on the establishment of the process in industry, the main effort being devoted to development work on various types of atmospheres, their useful fields of application and the design of suitable heat-treatment furnaces in which they are to be used. The various types of controlled atmospheres are fairly well standardized, but there still remains a considerable field for the investigation of related problems, in connection with both the gas-generating equipment and the surface chemistry of the heat-treatment of metals, especially in complex controlled atmospheres. This paper describes certain investigations of this nature that were carried out in England up to 1939. The development of processes employing controlled atmospheres has been asso-ciated to a very large extent with the heat-treatment of steels, both because of the major importance of steel in industry and the many diverse and dificult prob-lems of surface chemistry involved when steels of such a wide range of composition are heated in the presence of active gases. Controlled atmospheres such as disso-ciated and burnt ammonia or charcoal gas are used in the heat-treatment of low-carbon and high-carbon steels, but from certain points of view a suitable atmosphere generated by the partial combustion of city gas is to be preferred. Both the ammonia derivatives are comparatively expensive, and even if the burnt ammonia is regenerated, thereby reducing operating costs, the capital expenditure of the gas plant may make it prohibitive for the smaller type of furnace installation. Charcoal-gas generators are not without their operating difficulties especially those associated with the quality of the charcoal, clinker formation and the removal of carbon dust from the generated gas. City gas has the advantage of being comparatively cheap and "on tap" in most if not all industrial centers. The use of raw city gas as a protective atmosphere in the heat-treatment of steels has been described,' but it presents certain difficulties because of its complex composition and its explosive nature when mixed with air. These factors, together with the tendency toward sooting at elevated temperatures, arising mainly from the hydrocarbon gases present, all militate against its use as a protective atmosphere in industrial furnaces. The following analysis, based on the analyses of city gas in different localities in Great Britain, indicates the wide limits existing

Jan 1, 1948

By Ivor Jenkins

Processes employing 'controlled at-mospheres in the heat-treatment of metals and alloys are now well established on an industrial scale, and the general principles involved and the advantages to be gained in the use of the technique have received considerable publicity over a period of years. During this time the greatest emphasis has been on the establishment of the process in industry, the main effort being devoted to development work on various types of atmospheres, their useful fields of application and the design of suitable heat-treatment furnaces in which they are to be used. The various types of controlled atmospheres are fairly well standardized, but there still remains a considerable field for the investigation of related problems, in connection with both the gas-generating equipment and the surface chemistry of the heat-treatment of metals, especially in complex controlled atmospheres. This paper describes certain investigations of this nature that were carried out in England up to 1939. The development of processes employing controlled atmospheres has been asso-ciated to a very large extent with the heat-treatment of steels, both because of the major importance of steel in industry and the many diverse and dificult prob-lems of surface chemistry involved when steels of such a wide range of composition are heated in the presence of active gases. Controlled atmospheres such as disso-ciated and burnt ammonia or charcoal gas are used in the heat-treatment of low-carbon and high-carbon steels, but from certain points of view a suitable atmosphere generated by the partial combustion of city gas is to be preferred. Both the ammonia derivatives are comparatively expensive, and even if the burnt ammonia is regenerated, thereby reducing operating costs, the capital expenditure of the gas plant may make it prohibitive for the smaller type of furnace installation. Charcoal-gas generators are not without their operating difficulties especially those associated with the quality of the charcoal, clinker formation and the removal of carbon dust from the generated gas. City gas has the advantage of being comparatively cheap and "on tap" in most if not all industrial centers. The use of raw city gas as a protective atmosphere in the heat-treatment of steels has been described,' but it presents certain difficulties because of its complex composition and its explosive nature when mixed with air. These factors, together with the tendency toward sooting at elevated temperatures, arising mainly from the hydrocarbon gases present, all militate against its use as a protective atmosphere in industrial furnaces. The following analysis, based on the analyses of city gas in different localities in Great Britain, indicates the wide limits existing

Jan 1, 1948

By A. Hultgren, B. Herrlander

The original aim of the present investigation was to study the mechanism of cracking on hot-deforming red-short steels. During the microscopical examination of hot-deformed soft steels attention was directed to various patterns of so-called veining in the ferrite, as related to variations in the deformation procedure and the heat-treatment of the steels. Later, a hot-short steel of higher carbon content was also studied. Historical Storey1 suggested in 1914 that veining developed during the gamma-alpha transformation from the growing together of several alpha nuclei within the same gamma grain. Rawdon and Berglund2 found that in soft steel, forged somewhat below A3, the ferrite showed profuse veining, while usually there was very little veining after forging at very high temperatures. They emphasized the similarity between the pattern of veining formed by deformation about 600°C and that of slip lines formed by deformation at room temperature. They also suggested a relation between the gamma-alpha transformation and veining. They became convinced from etching and from the slip-line pattern in cold-deformed material, that the orientation within any ferrite grain showing veining was uniform. In recrystallized alpha grains veining was absent. Veining did not appear materially to affect the properties of ferrite. Independent of veining, continuous networks, attributed to preexisting delta and gamma grain boundaries were sometimes found, the former only in cast steel. Those networks were usually connected with small inclusions. Ammermann and Kornfeld3 confirmed that recrystallized ferrite grains showed no veining. In soft steel annealed between A1 and A3 there was veining only in the ferrite grains formed during cooling. Electrolytic iron deformed at 880' was free from veining. Bannister and Jones' considered veining in ferrite to be a manifestation of microscopical and sub-microscopica~ inclusions. NorthCOtt,5,6 in studies on veining in steel and other metals and alloys, attributed veining to oxide inclusions. It could generally be removed by annealing in hydrogen, a suggestion earlier made by Rawdon and Berg1und. TrittOn (discussion in ref. 5) emphasized the importance of perfect polishing for bringing out veining by etching, and thought the veins or subboundaries were produced during the gamma-alpha transformation, when it was rapid, as a result of the volume change and contraction during cooling. Slight distortion would not allow projecting parts of a growing crystal to join up with atomic symmetry. Hanemann and co-workers showed that veining in ferrite consisted of ridges

Jan 1, 1948

By B. Herrlander, A. Hultgren

The original aim of the present investigation was to study the mechanism of cracking on hot-deforming red-short steels. During the microscopical examination of hot-deformed soft steels attention was directed to various patterns of so-called veining in the ferrite, as related to variations in the deformation procedure and the heat-treatment of the steels. Later, a hot-short steel of higher carbon content was also studied. Historical Storey1 suggested in 1914 that veining developed during the gamma-alpha transformation from the growing together of several alpha nuclei within the same gamma grain. Rawdon and Berglund2 found that in soft steel, forged somewhat below A3, the ferrite showed profuse veining, while usually there was very little veining after forging at very high temperatures. They emphasized the similarity between the pattern of veining formed by deformation about 600°C and that of slip lines formed by deformation at room temperature. They also suggested a relation between the gamma-alpha transformation and veining. They became convinced from etching and from the slip-line pattern in cold-deformed material, that the orientation within any ferrite grain showing veining was uniform. In recrystallized alpha grains veining was absent. Veining did not appear materially to affect the properties of ferrite. Independent of veining, continuous networks, attributed to preexisting delta and gamma grain boundaries were sometimes found, the former only in cast steel. Those networks were usually connected with small inclusions. Ammermann and Kornfeld3 confirmed that recrystallized ferrite grains showed no veining. In soft steel annealed between A1 and A3 there was veining only in the ferrite grains formed during cooling. Electrolytic iron deformed at 880' was free from veining. Bannister and Jones' considered veining in ferrite to be a manifestation of microscopical and sub-microscopica~ inclusions. NorthCOtt,5,6 in studies on veining in steel and other metals and alloys, attributed veining to oxide inclusions. It could generally be removed by annealing in hydrogen, a suggestion earlier made by Rawdon and Berg1und. TrittOn (discussion in ref. 5) emphasized the importance of perfect polishing for bringing out veining by etching, and thought the veins or subboundaries were produced during the gamma-alpha transformation, when it was rapid, as a result of the volume change and contraction during cooling. Slight distortion would not allow projecting parts of a growing crystal to join up with atomic symmetry. Hanemann and co-workers showed that veining in ferrite consisted of ridges

Jan 1, 1948

By F. E. Harris

It has been said that carbon is "ubiquitous" with reference to iron alloys. Certainly at temperatures where carbon and iron form the solid solution, austenite, it may be readily added to, or removed from, steel surfaces. Differences in concentration potential are the sole requirements for carbon flow. To measure the rate of carbon flow, a proportionality factor, D, is arbitrarily expressed in units of (length)2 X (time)-'. If the term used for carbon concentration is weight Pet C, as is customary, then a factor must be found, changing this term to One of weight Per unit volume when the diffusion coeficient, D, is used in flow formulae. The determination of D values for carbon is complicated since D varies with the concentration itself. The Matano method has often been employed for systems involving a variant D. This method expresses all evaluation of unsteady flow whereby D is given a relationship with the numerical value of C-x slopes. The author contends that this solution is incorrect, except when D is invariant. The primary purpose of this paper is to support this contention. Here diffusion is controlled under two conditions of flow. The first part deals with the steady state; the second part considers unsteady flow under definite restrictions. Beginning with the fundamental concept, the development is continued until equations for C-x curves are obtained. The solution is then subjected to experimental data. It is realized that a great amount of reliable data is required for a rigorous proof. KO such research is claimed. Instead an attempt is made to set forth the physical significance of the diffusion mechanism, and particularly to express the factors which influence the flow of carbon in austenite. Of equal significance is the implication that gaseous media may be employed with reasonable accuracy in making these determinations. The Steady State Diffusion of Carbon in Au~tenite The fundamental experiment defining diffusion in solid metals may be readily performed for carbon in gamma iron.' For this experiment a thin plate of medium carbon steel is chosen. The surfaces of this plate may be taken as two parallel planes which may be considered infinite for points well in the Center of the planes. These two planes are held at different concentrations of carbon at a constant temperature. This temperature, 1700°F for example, is one where the single phase: carbon in solution with gamma iron, exists. When these conditions are held for a sufficient time the concentration of carbon of the different points of the solid ment down towards its steady state value. At points well removed from the ends, the concentration will remain the Same along planes parallel to the surfaces of the plate.

Jan 1, 1948

By F. E. Harris

It has been said that carbon is "ubiquitous" with reference to iron alloys. Certainly at temperatures where carbon and iron form the solid solution, austenite, it may be readily added to, or removed from, steel surfaces. Differences in concentration potential are the sole requirements for carbon flow. To measure the rate of carbon flow, a proportionality factor, D, is arbitrarily expressed in units of (length)2 X (time)-'. If the term used for carbon concentration is weight Pet C, as is customary, then a factor must be found, changing this term to One of weight Per unit volume when the diffusion coeficient, D, is used in flow formulae. The determination of D values for carbon is complicated since D varies with the concentration itself. The Matano method has often been employed for systems involving a variant D. This method expresses all evaluation of unsteady flow whereby D is given a relationship with the numerical value of C-x slopes. The author contends that this solution is incorrect, except when D is invariant. The primary purpose of this paper is to support this contention. Here diffusion is controlled under two conditions of flow. The first part deals with the steady state; the second part considers unsteady flow under definite restrictions. Beginning with the fundamental concept, the development is continued until equations for C-x curves are obtained. The solution is then subjected to experimental data. It is realized that a great amount of reliable data is required for a rigorous proof. KO such research is claimed. Instead an attempt is made to set forth the physical significance of the diffusion mechanism, and particularly to express the factors which influence the flow of carbon in austenite. Of equal significance is the implication that gaseous media may be employed with reasonable accuracy in making these determinations. The Steady State Diffusion of Carbon in Au~tenite The fundamental experiment defining diffusion in solid metals may be readily performed for carbon in gamma iron.' For this experiment a thin plate of medium carbon steel is chosen. The surfaces of this plate may be taken as two parallel planes which may be considered infinite for points well in the Center of the planes. These two planes are held at different concentrations of carbon at a constant temperature. This temperature, 1700°F for example, is one where the single phase: carbon in solution with gamma iron, exists. When these conditions are held for a sufficient time the concentration of carbon of the different points of the solid ment down towards its steady state value. At points well removed from the ends, the concentration will remain the Same along planes parallel to the surfaces of the plate.

Jan 1, 1948

By Gerald Edmunds

The liquidus line on the phase diagram for temperature versus composition of a binary alloy system, representing the boundary between the homogeneous melt and the heterogeneous melt plus solid, besides showing the minimum casting temperature, is useful in determining eutectic compositions and the presence of phase changes such as peritectic transformations and intermetallic compound formation. The liquidus often is determined by the cooling curves of thermal analysis, but supercooling frequently occurs, so that the temperature values are low. An alternative method, the one employed here, consists of determining the composition of samples of the melts from heterogeneous alloys that are at equilibrium. With meticulous attention to fundamentals, this method is capable of yielding values limited in precision only by the temperature control and measurement and analyses. Apparatus By starting, on the one hand, with a supersaturated solution and allowing the excess solute to precipitate, and on the other hand with an undersaturated solution and allowing more of the solute to be dissolved, both processes being carried out at the same temperature, equilibrium may be said to have been approached from both directions; that is, from above and from below. If the analyses show the solutions to contain the same fraction of solute when equilibrium has been approached from above and from below, one is assured that equilibrium has been reached in both determinations. In order to carry out such determinations, it is necessary to have equipment for obtaining and maintaining the proper temperatures; for holding the melt, measuring its temperature, and stirring, sampling and analyzing it. The present work required temperatures from 420° to 900°C. The equipment consisted of: A furnace, which was a vertical alundum tube, 13/4-in. diameter inside and 18 in. long, wound with Nichrome resistance wire, surrounded by a 3-in. i.d. alundum tube wound for 5 in. of length near each end, for compensation of end losses. This muffle was contained in an iron shell with Transite end plates, the intervening space being packed with Sil-O-Cel. The outside dimensions of the furnace were 12 in. in diameter by 181/2 in. in height. Heating current was supplied by three independent variable-voltage transformers (Variac), one connected to each end compensator winding and manually controlled, and one connected to the main winding through a series resistance of 5 ohms. This resistance was short-circuited for

Jan 1, 1944

By Gerald Edmunds

The liquidus line on the phase diagram for temperature versus composition of a binary alloy system, representing the boundary between the homogeneous melt and the heterogeneous melt plus solid, besides showing the minimum casting temperature, is useful in determining eutectic compositions and the presence of phase changes such as peritectic transformations and intermetallic compound formation. The liquidus often is determined by the cooling curves of thermal analysis, but supercooling frequently occurs, so that the temperature values are low. An alternative method, the one employed here, consists of determining the composition of samples of the melts from heterogeneous alloys that are at equilibrium. With meticulous attention to fundamentals, this method is capable of yielding values limited in precision only by the temperature control and measurement and analyses. Apparatus By starting, on the one hand, with a supersaturated solution and allowing the excess solute to precipitate, and on the other hand with an undersaturated solution and allowing more of the solute to be dissolved, both processes being carried out at the same temperature, equilibrium may be said to have been approached from both directions; that is, from above and from below. If the analyses show the solutions to contain the same fraction of solute when equilibrium has been approached from above and from below, one is assured that equilibrium has been reached in both determinations. In order to carry out such determinations, it is necessary to have equipment for obtaining and maintaining the proper temperatures; for holding the melt, measuring its temperature, and stirring, sampling and analyzing it. The present work required temperatures from 420° to 900°C. The equipment consisted of: A furnace, which was a vertical alundum tube, 13/4-in. diameter inside and 18 in. long, wound with Nichrome resistance wire, surrounded by a 3-in. i.d. alundum tube wound for 5 in. of length near each end, for compensation of end losses. This muffle was contained in an iron shell with Transite end plates, the intervening space being packed with Sil-O-Cel. The outside dimensions of the furnace were 12 in. in diameter by 181/2 in. in height. Heating current was supplied by three independent variable-voltage transformers (Variac), one connected to each end compensator winding and manually controlled, and one connected to the main winding through a series resistance of 5 ohms. This resistance was short-circuited for

Jan 1, 1944

By F. Keller, J. D. Edwards

The anodic treatment of aluminum presents problems of scientific as well as of commercial interest.l-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non-adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By F. Keller, J. D. Edwards

The anodic treatment of aluminum presents problems of scientific as well as of commercial interest.l-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non-adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

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

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