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By E. G. De Coriolis

The development of huge production facilities and of new or improved processes for manufacturing magnesium from its raw sources has been an outstanding achievement of this war. Furthermore, at least one new method has reached a stage of pilot production that offers promise. Its potentialities seem to indicate that a reduction in cost and simplification or elimination of problems incident to the use of at least one of the present processes are quite within the realm of possibility. Although magnesium of very high purity (99.9 per cent and higher) is obtained, and the rate of recovery reasonable (60 to 70 per cent). the ferrosilicon reduction process is open to a serious objection, which at the time its use was proposed was thought to be sufficient to raise some doubts as to its success, at least on a high production basis. The temperature range at which the reaction is carried out—namely, 2100" to 2150°F.—is very close to the failure temperature of the material of which the retort is made. It is so close that for a time it was assumed it might make commercial use of the process an impossibility. However, at the time under discussion, the demand for magnesium was so great that it was felt by those who had to go ahead and produce this essential metal that the emergency warranted their taking a chance on this process. Subsequent developments have fully justified the soundness of their decision. Fortunately for the war effort, when the plants were put into operation it was discovered that although the retorts did collapse in rather short periods of time, as predicted, they could be blown back into operable shape by application of high-pressure air. This practical method of operation so relieved the situation that the problem disappeared. Nevertheless, if the process had not been successful, or the production of magnesium by the electrolytic process had not been able to keep pace with demands, our war program would have been seriously impaired. Fireless Cooker'' Process For this reason a program was set up and assigned for the development of a new method that had been suggested to the War Production Board in 1941. It is believed justifiable in terming the method "new" for several reasons: (I) while utilizing the same (ferrosilicon) process as the Pidgeon, hence involving similar reactions, the type of retort or furnace is essentially different, (2) the method of operation, reaction temperatures, etc., differ materially, and, most important of all, (3) the problems to be overcome in making the process successful were not and could not have been anticipated by anything previously known about the Pidgcon process. As will be shown later, the briquetting process, the condenser, the furnace lining

Jan 1, 1949

By T. E. Leontis, J. P. Murphy

During the last few years, the trend in the aircraft and automotive industries has been toward higher and higher operating engine temperatures. This has created considerable interest in the effect of temperature on the properties of alloys. In the magnesium field, it has been recognized for many years that the addition of cerium imparts high strength and good resistance to creep at elevated temperatures. Beck,' in his treatise on magnesium, has summarized the work of German investigators. This includes the unpublished data of Menking, showing the increase in strength and hardness of extruded alloys containing 2 to 20 per cent Ce at temperatures from 20' to 300°C. (68" to 57z°F.) and the results of Vosskiihler, who demonstrated the improved resistance to creep of alloys containing 6 per cent Ce plus 2 per cent Mn and 0.5 per cent Ce plus 2 per cent Mn at 150°C. (302°F.). Wellinger and Kei12 have also reported the creep properties of a forged magnesium-cerium-man-ganese alloy at 200' and 250°C. (392' and 482°F.). Haughton and Prytherch have determined the tensile properties of various forged magnesium alloys containing cerium, cerium plus manganese, cerium plus calcium, cerium plus nickel, cerium plus nickel plus manganese, and cerium plus cobalt plus manganese at temperatures up to 290°C. (554OF.). Magnesium-cerium alloys have been used in some commercial applications. It is reported that an alloy containing 3 per cent Ce plus 0.5 per cent Mn plus 0.5 per cent Ca is being used on a forged impeller in Great Britain. Two forged parts made from an alloy with a nominal composition of 5 per cent Ce and 2 per cent Mn have been found on the German BMW-8o1D aircraft engine. These two forgings consist of a supercharger impeller and a rear cam-follower guide. In this country, several types of pistons have been made experimentally in both the cast and the forged conditions from an alloy containing 6 per cent Ce plus 2 per cent Mn and in the cast condition from an alloy of magnesium plus 10 per cent Ce. The cast pistons have been tested in various types of internal-combustion engines, with promising results. This paper presents the results of an extensive investigation on the properties of various cerium-containing magnesium alloys in both the cast and the forged conditions. Data are presented to show the beneficial effects of increasing amounts of cerium on the mechanical properties of magnesium at at temperatures' The effects of heat-treatment on the properties of these alloys and the attendant changes in the microstructure are discussed. The alloys investigated most extensively are

Jan 1, 1946

By J. P. Murphy, T. E. Leontis

During the last few years, the trend in the aircraft and automotive industries has been toward higher and higher operating engine temperatures. This has created considerable interest in the effect of temperature on the properties of alloys. In the magnesium field, it has been recognized for many years that the addition of cerium imparts high strength and good resistance to creep at elevated temperatures. Beck,' in his treatise on magnesium, has summarized the work of German investigators. This includes the unpublished data of Menking, showing the increase in strength and hardness of extruded alloys containing 2 to 20 per cent Ce at temperatures from 20' to 300°C. (68" to 57z°F.) and the results of Vosskiihler, who demonstrated the improved resistance to creep of alloys containing 6 per cent Ce plus 2 per cent Mn and 0.5 per cent Ce plus 2 per cent Mn at 150°C. (302°F.). Wellinger and Kei12 have also reported the creep properties of a forged magnesium-cerium-man-ganese alloy at 200' and 250°C. (392' and 482°F.). Haughton and Prytherch have determined the tensile properties of various forged magnesium alloys containing cerium, cerium plus manganese, cerium plus calcium, cerium plus nickel, cerium plus nickel plus manganese, and cerium plus cobalt plus manganese at temperatures up to 290°C. (554OF.). Magnesium-cerium alloys have been used in some commercial applications. It is reported that an alloy containing 3 per cent Ce plus 0.5 per cent Mn plus 0.5 per cent Ca is being used on a forged impeller in Great Britain. Two forged parts made from an alloy with a nominal composition of 5 per cent Ce and 2 per cent Mn have been found on the German BMW-8o1D aircraft engine. These two forgings consist of a supercharger impeller and a rear cam-follower guide. In this country, several types of pistons have been made experimentally in both the cast and the forged conditions from an alloy containing 6 per cent Ce plus 2 per cent Mn and in the cast condition from an alloy of magnesium plus 10 per cent Ce. The cast pistons have been tested in various types of internal-combustion engines, with promising results. This paper presents the results of an extensive investigation on the properties of various cerium-containing magnesium alloys in both the cast and the forged conditions. Data are presented to show the beneficial effects of increasing amounts of cerium on the mechanical properties of magnesium at at temperatures' The effects of heat-treatment on the properties of these alloys and the attendant changes in the microstructure are discussed. The alloys investigated most extensively are

Jan 1, 1946

By F. N. Rhines, T. E. Leonitis

The oxide scale that forms upon magnesium at elevated temperatures is non-protective in the sense that the rate of oxidation is constant and thus does not decrease with the growth of the scale as it does with other common metals. This generality was first stated by Pilling and Bedworth' and has been verified by Suzuki2 and by ScheiL3 Pilling and Bcdworth argued that the nonprotective characteristic could be predicted from the fact that magnesium oxide occupies less space than does the metal from which it springs, wherefore the scale is not expected to cover the metal so completely as to exclude all direct access to the atmosphere. Linear oxidation is thought by Scheil to be common to all cases where the reaction occurs at the oxide-metal interface. According to Suzuki," he product of high-temperature oxidation in the air is MgO contaminated with no more than traces of a nitride. When the metal is allowed to burn freely a fume composed of cubic crystals of Mg04 is given off. Delavaults observed that excrescences form upon liquid magnesium and alloys in thc course of oxidation. Beyond this it is known that the use of atmospheres containing small quantities of sulphur dioxide6 or carbon dioxide serve to retard the oxidation of solid magnesium and that beryllium' and calciums minimize the oxidation of molten magnesium exposed to the air. Many studies have been devoted to the nature and rates of "protective" oxidation, as exemplified by the cases of copper and iron, wherein the rate is characteristically parabolic. The theory of parabolic oxidation is well developed.~ Linear oxidation, on the other hand, has received but little attention and the theories proposed by Pilling and Bedworth and by Schcil have yet to withstand careful examination. There exists no comprehensive survey of the high-temperature oxidation of magnesium (or of any other metal that exhibits linear oxidation) over a broad range of temperature, under a variety of atmospheric conditions and covering a large group of alloys. It has been the purpose of the present investigation to provide such a survey, with the object of gaining a fuller understanding of linear oxidation, especially as applied to magnesium. Experimental Procedure and Results The experimental studies undertaken were of two kinds: (I) measurement of the rate of oxidation as influenced by the 6c

Jan 1, 1946

By T. E. Leonitis, F. N. Rhines

The oxide scale that forms upon magnesium at elevated temperatures is non-protective in the sense that the rate of oxidation is constant and thus does not decrease with the growth of the scale as it does with other common metals. This generality was first stated by Pilling and Bedworth' and has been verified by Suzuki2 and by ScheiL3 Pilling and Bcdworth argued that the nonprotective characteristic could be predicted from the fact that magnesium oxide occupies less space than does the metal from which it springs, wherefore the scale is not expected to cover the metal so completely as to exclude all direct access to the atmosphere. Linear oxidation is thought by Scheil to be common to all cases where the reaction occurs at the oxide-metal interface. According to Suzuki," he product of high-temperature oxidation in the air is MgO contaminated with no more than traces of a nitride. When the metal is allowed to burn freely a fume composed of cubic crystals of Mg04 is given off. Delavaults observed that excrescences form upon liquid magnesium and alloys in thc course of oxidation. Beyond this it is known that the use of atmospheres containing small quantities of sulphur dioxide6 or carbon dioxide serve to retard the oxidation of solid magnesium and that beryllium' and calciums minimize the oxidation of molten magnesium exposed to the air. Many studies have been devoted to the nature and rates of "protective" oxidation, as exemplified by the cases of copper and iron, wherein the rate is characteristically parabolic. The theory of parabolic oxidation is well developed.~ Linear oxidation, on the other hand, has received but little attention and the theories proposed by Pilling and Bedworth and by Schcil have yet to withstand careful examination. There exists no comprehensive survey of the high-temperature oxidation of magnesium (or of any other metal that exhibits linear oxidation) over a broad range of temperature, under a variety of atmospheric conditions and covering a large group of alloys. It has been the purpose of the present investigation to provide such a survey, with the object of gaining a fuller understanding of linear oxidation, especially as applied to magnesium. Experimental Procedure and Results The experimental studies undertaken were of two kinds: (I) measurement of the rate of oxidation as influenced by the 6c

Jan 1, 1946

By R. S. Busk, R. F. Marande

The magnesium-aluminum-zinc 'system contains most of the magnesium-base alloys used commercially, although in practice the ternary alloys are usually modified by the addition of a small amount of manganese. Table I contains the magnesium-base commercial sand-casting alloys most widely used throughout the world, together with their typical tensile properties. These alloys may be regarded as a single family of varying aluminum and zinc content, disregarding manganese. A concise means of presenting data for them is by means of iso-property lines plotted on triangular coordinate paper. Constitutional, casting, and mechanical properties are presented in this manner. The data are given with the obiect of providing reference material, and to aid in the choice of a commercial alloy to serve a particular purpose. Detailed, critical analysis of the commercial alloys has been covered in a previous paper.' All alloys reported were made in rj-lb. melts, superheated to r700°F. for 15 min., cooled to r400°F. and poured in sand molds. The test bars produced had a 1/2-in. reduced section and were about 6 in. long. Except for the data represented in Figs. I and 3 the alloys used were of commercial purity and contained 0.1 to 0.2 per cent Mn in addition to the aluminum and zinc. Constitutional Data Under the heading of Constitutional Data are included all known data on con-

Jan 1, 1946

By R. F. Marande, R. S. Busk

The magnesium-aluminum-zinc 'system contains most of the magnesium-base alloys used commercially, although in practice the ternary alloys are usually modified by the addition of a small amount of manganese. Table I contains the magnesium-base commercial sand-casting alloys most widely used throughout the world, together with their typical tensile properties. These alloys may be regarded as a single family of varying aluminum and zinc content, disregarding manganese. A concise means of presenting data for them is by means of iso-property lines plotted on triangular coordinate paper. Constitutional, casting, and mechanical properties are presented in this manner. The data are given with the obiect of providing reference material, and to aid in the choice of a commercial alloy to serve a particular purpose. Detailed, critical analysis of the commercial alloys has been covered in a previous paper.' All alloys reported were made in rj-lb. melts, superheated to r700°F. for 15 min., cooled to r400°F. and poured in sand molds. The test bars produced had a 1/2-in. reduced section and were about 6 in. long. Except for the data represented in Figs. I and 3 the alloys used were of commercial purity and contained 0.1 to 0.2 per cent Mn in addition to the aluminum and zinc. Constitutional Data Under the heading of Constitutional Data are included all known data on con-

Jan 1, 1946

By N. Tiner

The mechanical properties of magnesium-alloy castings are greatly improved by grain refinement, and at present considerable attention is being paid to methods of obtaining fine-grained castings. One method of achieving this end is the use of proper melting and superheating techniques. These have been employed com-rnercially to a great extent, but no comprehensive study of the subject appears to have been published at present. Numerous investigations found in the literature include some reference to superheating techniques,1"4 and Achenbach, Nippcr and Piwowarsky,% ased principally on thermal analysis, ascribe the grain-refilling action of superheating to the influence of solid foreign particles or dissolved gases present in the melt upon the course of crystallization. The primary purpose of this paper is to present the principal facts concerning the cffect of superheating on grain size of magilesium alloys. .ittempts are also made to explain the experimental results in terms of a general hypothesis. The investigations are limited chiefly to common commercial casting alloys. In order to carry on this work, it was necessary to determine the factors influencing grain size and to develop a proper technique for the preparation of samples. Thc preliminary tests made by the author indicated that the grain size of magnesium alloys resulting from the solidification of a melt is determined by alloy composition, presence of impurities, rate of cooling during solidification, thermal history of the melt and to some extent the structure of the charge used. The rate of cooling is in turn dependent upon the mass of the melt, pouring temperature, and dimensions, properties and temperature of the mold into which the melt is poured. The final grain size of the alloys is still further modified by heat-treatment subsequent to casting. It is not within the scope of the present paper to discuss all of these factors, and it would suffice to note here that when equal amounts of magnesium alloys are prepared from the same alloying materials, melted in graphite crucibles under the same thermal conditions, then cast into graphite molds at a constant temperature, the resultant solids have the same grain size. By maintaining all other factors constant, it is thus possible to vary thermal conditions of a melt and to examine the grain size of resultant castings. Preparation of Samples and Grain-size TestiNg The alloys investigated in this paper were taken from ingots made by Permanente the Or or prepared by the author with pure carbothermic magnesium and necessary alloying elements. Melting was carried out under a flux in a graphite crucible heated uniformly by an

Jan 1, 1946

By N. Tiner

The mechanical properties of magnesium-alloy castings are greatly improved by grain refinement, and at present considerable attention is being paid to methods of obtaining fine-grained castings. One method of achieving this end is the use of proper melting and superheating techniques. These have been employed com-rnercially to a great extent, but no comprehensive study of the subject appears to have been published at present. Numerous investigations found in the literature include some reference to superheating techniques,1"4 and Achenbach, Nippcr and Piwowarsky,% ased principally on thermal analysis, ascribe the grain-refilling action of superheating to the influence of solid foreign particles or dissolved gases present in the melt upon the course of crystallization. The primary purpose of this paper is to present the principal facts concerning the cffect of superheating on grain size of magilesium alloys. .ittempts are also made to explain the experimental results in terms of a general hypothesis. The investigations are limited chiefly to common commercial casting alloys. In order to carry on this work, it was necessary to determine the factors influencing grain size and to develop a proper technique for the preparation of samples. Thc preliminary tests made by the author indicated that the grain size of magnesium alloys resulting from the solidification of a melt is determined by alloy composition, presence of impurities, rate of cooling during solidification, thermal history of the melt and to some extent the structure of the charge used. The rate of cooling is in turn dependent upon the mass of the melt, pouring temperature, and dimensions, properties and temperature of the mold into which the melt is poured. The final grain size of the alloys is still further modified by heat-treatment subsequent to casting. It is not within the scope of the present paper to discuss all of these factors, and it would suffice to note here that when equal amounts of magnesium alloys are prepared from the same alloying materials, melted in graphite crucibles under the same thermal conditions, then cast into graphite molds at a constant temperature, the resultant solids have the same grain size. By maintaining all other factors constant, it is thus possible to vary thermal conditions of a melt and to examine the grain size of resultant castings. Preparation of Samples and Grain-size TestiNg The alloys investigated in this paper were taken from ingots made by Permanente the Or or prepared by the author with pure carbothermic magnesium and necessary alloying elements. Melting was carried out under a flux in a graphite crucible heated uniformly by an

Jan 1, 1946

By Jay R. Burns

TWO magnesium sand-casting alloys are commonly favored in the United States. These are referred to as H and C alloys (Dow Chemical Co.) or 4Mz65 and AM260 alloys (American Magnesium Corporation). Both are of an aluminum-zinc-manganese type. H alloy contains 6 per cent aluminum and 3 per cent zinc and is characterized by relatively good toughness. C alloy contains 9 per cent aluminum and 2 per cent zinc and is employed where high yield strength and pressure tightness are required. Examination of magnesium castings poured in Europe and England,'J however, demonstrates that H and C alloys are replaced by .%8 and AZ~I, respectively. That is, A8 reprcsents a magnesiurn alloy having superior toughness while A291 is suitable for high yield strength and pressure-tight applications. The basic difference between the .Ameri-can and European alloys is that the foreign alloys employ a somewhat higher aluminum content and less zinc than is found in H and C alloys. The mechanical properties of the alloys, when divided into high and low-aluminum groups, are quite similar, as determined from separately cast foundry-control type test bars ,In this paper the decrease of mechanical properties caused by any given amount of microporosity is measured for H, C, A8, and AZ~I alloys. The relative susceptibility of each of the four alloys to microporosity is also determined. Typical mechanical properties and nominal chemical analyses are reported in Table I. The apparent similarities between the two alloys in each group have led to considerable discussion as to the relative merits of each of the compositions.2 Popular points for comparison between the alloys have been the relative susceptibility of each of the four alloys to microporosity6 and the effect of this microporosity on their mechanical properties. It is primarily intended, in this paper, to show the

Jan 1, 1946

By Jay R. Burns

TWO magnesium sand-casting alloys are commonly favored in the United States. These are referred to as H and C alloys (Dow Chemical Co.) or 4Mz65 and AM260 alloys (American Magnesium Corporation). Both are of an aluminum-zinc-manganese type. H alloy contains 6 per cent aluminum and 3 per cent zinc and is characterized by relatively good toughness. C alloy contains 9 per cent aluminum and 2 per cent zinc and is employed where high yield strength and pressure tightness are required. Examination of magnesium castings poured in Europe and England,'J however, demonstrates that H and C alloys are replaced by .%8 and AZ~I, respectively. That is, A8 reprcsents a magnesiurn alloy having superior toughness while A291 is suitable for high yield strength and pressure-tight applications. The basic difference between the .Ameri-can and European alloys is that the foreign alloys employ a somewhat higher aluminum content and less zinc than is found in H and C alloys. The mechanical properties of the alloys, when divided into high and low-aluminum groups, are quite similar, as determined from separately cast foundry-control type test bars ,In this paper the decrease of mechanical properties caused by any given amount of microporosity is measured for H, C, A8, and AZ~I alloys. The relative susceptibility of each of the four alloys to microporosity is also determined. Typical mechanical properties and nominal chemical analyses are reported in Table I. The apparent similarities between the two alloys in each group have led to considerable discussion as to the relative merits of each of the compositions.2 Popular points for comparison between the alloys have been the relative susceptibility of each of the four alloys to microporosity6 and the effect of this microporosity on their mechanical properties. It is primarily intended, in this paper, to show the

Jan 1, 1946

By Louis A. Carapella, William E. Shaw

Magnesium and its alloys have long been characterized as possessing limited capacity for mechanical forming at atmospheric temperatures prior to rupturing despite their outstanding performances in this respect at elevated temperatures. Responsible for this behavior are the fundamental facts that these hexagonal-type metals have comparatively few slip elements at low temperatures for any extensive deformation and that, at high temperatures, additional slip elements become operative, thus enhancing greater plasticity under strain. The transitionai point has been set at 2 25°C by Schmidl for single crystals, and at 250°C by Morel1 and Hanawalt² for extruded magnesium metal. In a recent X-ray investigation on poly-crystalline magnesium-alloy sheets, Barrett and Haller3 have revealed that, below the transitional tempelature, the initial plastic deformation proceeds mostly by a twinning action; that, above such a temperature, the action is mostly by slip. The deep-drawing performance of the magnesium + 1.5 pct alloy sheet† over a wide range of temperatures has been investigated by Weber and Vanden Berg,' and their results are presented in Fig I. It should be noted from this work that a maximum drawability of about 25 pct at room temperature has been obtained on this alloy under the conventional deep-drawing operations. For the same alloy, it is now possible to augment the cold drawability to about 40 pct by a process to be disclosed. Hitherto, this value has been obtained only by deep-drawing the alloy at around 230°C. That greater plastic flow is attainable at atmospheric temperatures on magnesium under certain deformational techniques was discovered by the authors6 in their analyses of plastic-deformational behaviors of pure magnesium. This fact is best illustrated in Fig 2 from the Har-greaves analysis6 performed by the authors under two different modes of loading. For direct test, a separate unstrained specimen was used for each load duration, whereas for the integrated test the same specimen was employed for all the five intermittent loadings so that the load duration was made additive throughout the investigation. The higher plastic flow-rate at room temperature, as designated by the Har-greaves constant S, was obtained by the integrated or intermittent loading procedure. The authors6 in further tests showed that, under such a procedure greater plastic flow was also realized with a progressive increase in deformatione 1 loads. These findings have been applicd

Jan 1, 1947

By William E. Shaw, Louis A. Carapella

Magnesium and its alloys have long been characterized as possessing limited capacity for mechanical forming at atmospheric temperatures prior to rupturing despite their outstanding performances in this respect at elevated temperatures. Responsible for this behavior are the fundamental facts that these hexagonal-type metals have comparatively few slip elements at low temperatures for any extensive deformation and that, at high temperatures, additional slip elements become operative, thus enhancing greater plasticity under strain. The transitionai point has been set at 2 25°C by Schmidl for single crystals, and at 250°C by Morel1 and Hanawalt² for extruded magnesium metal. In a recent X-ray investigation on poly-crystalline magnesium-alloy sheets, Barrett and Haller3 have revealed that, below the transitional tempelature, the initial plastic deformation proceeds mostly by a twinning action; that, above such a temperature, the action is mostly by slip. The deep-drawing performance of the magnesium + 1.5 pct alloy sheet† over a wide range of temperatures has been investigated by Weber and Vanden Berg,' and their results are presented in Fig I. It should be noted from this work that a maximum drawability of about 25 pct at room temperature has been obtained on this alloy under the conventional deep-drawing operations. For the same alloy, it is now possible to augment the cold drawability to about 40 pct by a process to be disclosed. Hitherto, this value has been obtained only by deep-drawing the alloy at around 230°C. That greater plastic flow is attainable at atmospheric temperatures on magnesium under certain deformational techniques was discovered by the authors6 in their analyses of plastic-deformational behaviors of pure magnesium. This fact is best illustrated in Fig 2 from the Har-greaves analysis6 performed by the authors under two different modes of loading. For direct test, a separate unstrained specimen was used for each load duration, whereas for the integrated test the same specimen was employed for all the five intermittent loadings so that the load duration was made additive throughout the investigation. The higher plastic flow-rate at room temperature, as designated by the Har-greaves constant S, was obtained by the integrated or intermittent loading procedure. The authors6 in further tests showed that, under such a procedure greater plastic flow was also realized with a progressive increase in deformatione 1 loads. These findings have been applicd

Jan 1, 1947

By J. T. Lapsley, I. I. Cornet, A. E. Flanigan, R. Hultgren, J. E. Dorn

With the greatly expanding use of magnesium during the war, it appeared necessary to the War Metallurgy Committee that procedures of heat treating common magnesium casting alloys be investigated systematically. Accordingly, the National Defense Research Committee of the Office of Scientific Research and Development placed a research contract with the University of California, supervised by the War Metallurgy Committee. Research on the solution heat treatment and aging of magnesium alloy AZg2, (formerly ASTM No. 17; also known as Dowmetal C or AM26o) which was done under "Restricted" Project NRC-2I, in 1942-1943, and reported in detail in a final report to the OSRD on September 3, 1943, is the basis of this paper, which has been released for publication by the OSRD. American experience with magnesium alloys prior to World War II was limited, although some of these alloys had been in commercial use since 1909. Requirements of the aircraft industry for light alloys made it imperative to understand and utilize the advantageous strength-weight properties of magnesium castings. Magnesium casting alloys are commonly solution heat- treated to increase their ultimate tensile strength and ductility; this treatment may be followed by an age hardening at elevated temperatures, which raises the tensile yield strength but diminishes the ductility. In the present investigation, AZp was studied to determine the effects on properties of various solution heat treatment and aging schedules. The principles of heat treatment of magnesium alloys are the same as for other non-ferrous alloys. The alloy studied, AZp, has a nominal composition of 9 pct aluminum, 2 pct zinc, and minor constituents. Fig I shows, by the projection of isothermal sections on the concentration plane, the solubility surface1 of the ternary magnesium-rich solid solutions as determined by X ray 'analysis. From this figure it may be seen that above approximately 375°C (707OF), AZp alloy is a single phase alloy at equilibrium; below this temperature the equilibrium condition is a two phase alloy. The beta constituent which precipitates from the solid solution exerts a hardening effect. Because the zinc concentration is only 2 pct, ancl because of its solubility relations, AZqz resembles a binary alloy of magnesium with aluminum. The solubility curve1 of Fig 2 shows how rapidly the solubility of the beta phase decreases with decreasing temperatures. Unlike many aluminum alloys, magnesium alloys do not age harden at room temperatures; precipitation hardening of AZ² alloy is performed at about 177°C (350°F). At this temperature about 3 pct aluminum

Jan 1, 1949

By R. S. Busk, E. G. Bobalek

The relation between gases and metals has been a subject of increasingly active investigation during the past years, principally devoted to the study of metal-hydrogen systems. It has been found that hydrogen is soluble in most molten metals to an appreciable extent and somewhat soluble in most solid metals.l,2 In every known case there is a sudden decrease in solubility at the melting point. Thus a freezing mass of metal containing hydrogen in excess of the solid solubility must in some way expel that excess during the freezing process. This leads to internal blowholes, and such effects as pinhole porosity. Gas trapped in metal that is to be fabricated by a working process such as extrusion or rolling may be the cause of blisters. For some cases, notably in copper and iron alloys, the presence of hydrogen can lead to extreme embrittle-ment of the metal. The aluminum-casting industry has long recognized the importance of hydrogen in its techniques. Excess gas in molten aluminum alloys often leads to the formation of "pinhole porosity" in the solid casting.= To prevent this hydrogen pickup it is necessary to avoid overheating the melt and to protect it from such sources of hydrogen as water. In spite of all precautions, it is sometimes necessary to extract hydrogen from the melt just before pouring by bubbling with a gas such as chlorine or nitrogen. Reccntly it has been found that somewhat similar effects are possible with magnesium alloys, in that the presence of hydrogen can induce or aggravate micro-p~rosity.4-6 This paper is primarily concerned with a presentation of some facts concerning the solubility of hydrogen in magnesium and its alloys, with some discussion of the significance of these facts in a practical sense. In any study of gas-metal systems it is important to bear in mind a clear distinction between adsorption on surfaces and absorption within the lattice.' Considerable attention has been directed toward determining whether hydrogen is truly soluble in any solid metal, or whether the gas extracted from a sample was present at surfaces (external and internal) only.7 Most present day evidence supports the idea of true solution in addition to adsorption. A second important factor when dealing with gas solubility is the dependence of such solubility on external pressure. For diatomic gases such as H², solubility in both liquid and solid metals apparently is proportional to the square root of the pressure, indicating a breakdown to a monatomic gas before diffusion into the lattice.= For true equilibrium values of solubility, therefore, the pressure at the the surface must be constant and, preferably, known. Very little has been published concerning the hydrogen-magnesium system. Winterhager has presented the most

Jan 1, 1947

By R. S. Busk, E. G. Bobalek

The relation between gases and metals has been a subject of increasingly active investigation during the past years, principally devoted to the study of metal-hydrogen systems. It has been found that hydrogen is soluble in most molten metals to an appreciable extent and somewhat soluble in most solid metals.l,2 In every known case there is a sudden decrease in solubility at the melting point. Thus a freezing mass of metal containing hydrogen in excess of the solid solubility must in some way expel that excess during the freezing process. This leads to internal blowholes, and such effects as pinhole porosity. Gas trapped in metal that is to be fabricated by a working process such as extrusion or rolling may be the cause of blisters. For some cases, notably in copper and iron alloys, the presence of hydrogen can lead to extreme embrittle-ment of the metal. The aluminum-casting industry has long recognized the importance of hydrogen in its techniques. Excess gas in molten aluminum alloys often leads to the formation of "pinhole porosity" in the solid casting.= To prevent this hydrogen pickup it is necessary to avoid overheating the melt and to protect it from such sources of hydrogen as water. In spite of all precautions, it is sometimes necessary to extract hydrogen from the melt just before pouring by bubbling with a gas such as chlorine or nitrogen. Reccntly it has been found that somewhat similar effects are possible with magnesium alloys, in that the presence of hydrogen can induce or aggravate micro-p~rosity.4-6 This paper is primarily concerned with a presentation of some facts concerning the solubility of hydrogen in magnesium and its alloys, with some discussion of the significance of these facts in a practical sense. In any study of gas-metal systems it is important to bear in mind a clear distinction between adsorption on surfaces and absorption within the lattice.' Considerable attention has been directed toward determining whether hydrogen is truly soluble in any solid metal, or whether the gas extracted from a sample was present at surfaces (external and internal) only.7 Most present day evidence supports the idea of true solution in addition to adsorption. A second important factor when dealing with gas solubility is the dependence of such solubility on external pressure. For diatomic gases such as H², solubility in both liquid and solid metals apparently is proportional to the square root of the pressure, indicating a breakdown to a monatomic gas before diffusion into the lattice.= For true equilibrium values of solubility, therefore, the pressure at the the surface must be constant and, preferably, known. Very little has been published concerning the hydrogen-magnesium system. Winterhager has presented the most

Jan 1, 1947

By C. S. Barrett, O. R. Trautz

Previous investigations have shown that lithium is body-centered cubic from near its melting point to the temperature of liquid air.1,2,3 Nevertheless there was an incentive to search again for a transformation at low temperatures: C. Zener4.5 has remarked that the low value of the elastic modulus (C11 — Cl2)/z of body-centered cubic metals and alloys implies a rapid increase in free energy with decreasing temperature, which would favor the occurrence of a transformation; also the shear movement to which this modulus applies is one that can transform a body-centered cubic structure into a slightly distorted face-centered cubic structure. It was confirmed that lithium does not transform spontaneously at liquid nitrogen temperature, but it was found that a transformation can be induced at this temperature by cold working the metal,6 and at slightly lower temperatures a different transformation occurs spontaneously. Transformations were also found in solid solutions of magnesium in lithium. The Nature of the Transformations Before presenting a detailed treatment of the technique used and the specific data obtained, it would be well to give a brief survey of the general characteristics of the transformations. A new crystal structure begins to form spontaneously in a specimen when it is cooled below a critical temperature. In lithium the structure appears to be close-packed hexagonal; in theLi-Mg alloys most of the diffraction lines (but not all) are near those for hexagonal lithium. The transformation proceeds as the temperature is lowered and soon stops if the temperature is held constant or raised. The course of the transformation on cooling is indicated by the curve at the lower left of Fig -I. This curve is drawn in stepped fashion because the transformation goes by discrete steps with audible clicks. Because of the similarity to the decomposition of austenite into martensite in steels, it seems appropriate to designate the beginning of the spontaneous transformation on cooling as the Ms point. On heating to room temperature after the low temperature treatment only the usual BCC structure is found. On heating, the low temperature modification begins to disappear at a temperature which will be designated as Ac. The transformation on heating is halted when the rise in temperature is halted. The temperature must be raised 40 to 50°C above Ac before the reversion is complete—an interval which is sensitive to the rate of heating and to the time of holding at temperatures above Ac. This behavior on heating thus has similarities also to the formation of martensite in the cooling of steels.

Jan 1, 1949

By D. W. Mitchell

While pure magnesium does not corrode rapidly the presence of even very small quantities of certain other metals accelerates corrosion remarkably. Because magnesium is such an electropositive metal (E° = +2.34 volts)' the presence of substances that permit galvanic activity is extremely undesirable. It is stated that as little as 0.017 pct of iron in magnesium causes a marked increase in the corrosion rate.2 Magnesium and its alloys are commonly melted in iron or steel pots; consequently the commercial metal has the opportunity to pick up iron if it has that tendency. Quantitative data on the solubility of iron in magnesium are of practical as well as of academic interest. Some magnesium alloy castings tend to have large grain size unless suitable treatment is given to the liquid metal just prior to casting. One method of grain refinement consists of "superheating" the metal just prior to casting. "Superhcating" is heating to a temperature 100 to 200°C above the casting temperature and holding for a short period of time. Superheated metal has a much finer grain than unsuperheated metal. A satisfactory explanation of this phenomenon has not been forthcoming. One hypothesis attributes the grain refinement in the superheated metal to precipitation of some phase that is mis-cible at the temperature of superheat but not miscible just below the casting temperature and which is thought to provide nucleating centers for crystallization. This phase, if the foregoing hypothesis is correct, would probably be a metal or an intermetal-lic compound. Of the metals likely to be found in magnesium alloys, iron is one of the most likely candidates for the role of grain refiner for iron occurs in small quantities in all commercial magnesium and magnesium alloys. A. Beck³ states that magnesium, in either the liquid or the solid state, cannot dissolve iron and that iron exists as a finely divided suspension which does not settle out because of its extreme fineness. Beck also presents a micrograph showing a large iron dendrite in magnesium but does not comment on the crystallization of iron from a solution supposed to contain none. It is doubtful that dendrite formation from suspended iron -would be possible. This suspension theory is the basis of patents4 covering the removal of iron from magnesium by allowing the iron particles to act as nuclei for the formation of primary magnesium crystals which can be separated by segregation. Also covered by patents is the removal of iron by the addition of another metal to form an intermetallic compound with the iron which, because of its increased particle size, is able to settle out of the molten metal. Here, too, quantitative information on the extent of iron solubility in liquid magnesium is of more than theoretical interest. M. Hansen,5 in his critical collection of the data on binary alloys, states that iron is not soluble in liquid magnesium. W. R. D. Jones% ho studied the physical properties of low iron magnesium alloys observed a 57°

Jan 1, 1949

By J. P. Doan, G. Ansel

The important literature concerning zirconium in magnesium-base alloys is predominantly contained in patent references. Sauerwald, Eisenreich, and Holubl-4 discovered the profound grain-refining influence of small amounts of zirconium on cast magnesium and the attendant increases in strength and ductility. They extended their work to reveal that limited amounts of certain other elements, including zinc, could be added for further improvement in strength and hardness. British Patent 5111375 relates to the parent discoveries of Sauerwald, Eisenreich, and Holub. All of these references deal primarily with casting characteristics and properties in the cast state. Minor mention is made of desirable tensile strength, ductility, and toughness of wrought Mg-Zr alloys* modified by one or more additional elements. No extensive reference in the literature5. has been found to the particular characteristics of wrought blg-Zn-Zr alloys, with which the present paper is concerned. The work to be discussed represents essentially an extrusion study of the blg-Zn-Zr alloys and indicates that this system is highly interesting in the wrought state both academically and commercially. Accordingly, an important aim of this paper is to describe the hot-workability, tension and compression properties, metallography, and toughness of these alloys. Compositional variations are limited to the ranges 0 to 7 per cent Zn and 0 to I per cent Zr. Experimental Procedure Alloying and Casting Alloying ingredients were cell magnesium, commercial zinc (intermediate grade), and a chloride salt containing approximately 50 per cent ZrCl² and 50 per cent alkali chlorides. This salt is produced by Titanium Alloy Manufacturing Company. Melting, alloying, and pouring procedure essentially followed the crucible process as described by Nelson.6 The magnesium was melted using Dow No. 310 flux, and the temperature raised to 1350° to 1400°F for the alloying operations. After alloying of the zinc, the zirconium containing salt was added in small portions with vigorous stirring. This is an adaptation of the method described in British Patent 533264.7 The alloying efficiency of zirconium was approximately 30 per cent. During the alloying of zirconium, fluorspar was added in amount required as a flux-inspissating agent. Next the melt was refined with Dow No. 310 flux and held quietly for 15 min. Finally billets were cast in a book-type permanent mold

Jan 1, 1947

By G. Ansel, J. P. Doan

The important literature concerning zirconium in magnesium-base alloys is predominantly contained in patent references. Sauerwald, Eisenreich, and Holubl-4 discovered the profound grain-refining influence of small amounts of zirconium on cast magnesium and the attendant increases in strength and ductility. They extended their work to reveal that limited amounts of certain other elements, including zinc, could be added for further improvement in strength and hardness. British Patent 5111375 relates to the parent discoveries of Sauerwald, Eisenreich, and Holub. All of these references deal primarily with casting characteristics and properties in the cast state. Minor mention is made of desirable tensile strength, ductility, and toughness of wrought Mg-Zr alloys* modified by one or more additional elements. No extensive reference in the literature5. has been found to the particular characteristics of wrought blg-Zn-Zr alloys, with which the present paper is concerned. The work to be discussed represents essentially an extrusion study of the blg-Zn-Zr alloys and indicates that this system is highly interesting in the wrought state both academically and commercially. Accordingly, an important aim of this paper is to describe the hot-workability, tension and compression properties, metallography, and toughness of these alloys. Compositional variations are limited to the ranges 0 to 7 per cent Zn and 0 to I per cent Zr. Experimental Procedure Alloying and Casting Alloying ingredients were cell magnesium, commercial zinc (intermediate grade), and a chloride salt containing approximately 50 per cent ZrCl² and 50 per cent alkali chlorides. This salt is produced by Titanium Alloy Manufacturing Company. Melting, alloying, and pouring procedure essentially followed the crucible process as described by Nelson.6 The magnesium was melted using Dow No. 310 flux, and the temperature raised to 1350° to 1400°F for the alloying operations. After alloying of the zinc, the zirconium containing salt was added in small portions with vigorous stirring. This is an adaptation of the method described in British Patent 533264.7 The alloying efficiency of zirconium was approximately 30 per cent. During the alloying of zirconium, fluorspar was added in amount required as a flux-inspissating agent. Next the melt was refined with Dow No. 310 flux and held quietly for 15 min. Finally billets were cast in a book-type permanent mold

Jan 1, 1947