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By W. M. Peirce

Commencing in 1922, each year a lecture has been presented to the Institute of Metals Division at this February meeting. The range of subjects has been very- broad. Some speakers have dealt with the most advanced work in the very heart of the science of physical metallurgy. Others have stimulated our imaginations by discussing the most recent progress in related fields of science. Others have told us of the latest art, which is at any moment of greater practical importance than the latest science, of metals. I feel that this broad precedent in the choice of subjects will justify my choosing to talk about some of the prosaic details of how, during the last generation, industry has effectively organized research to accelerate progress in our own and all other fields of science and related art. A number of years ago I visited one of this country's well-known research laboratories and had the pleasure of chatting for a few minutes with its equally well-known director. Being particularly interested at the time in the organization problems connected with industrial research, I broached that subject. My host stated in effect that he didn't believe in organized research. He was, of course, resorting to a rhetorical hyperbole. to pain: out the danger of overorganization which can so easily drift into regimentation and destroy individual initiative. Actually nearly all of us, much as we cherish our personal freedom of action, believe in organization because the history of progress in every field of human activity has been a history of men learning to work together, to cooperate, to create an efficient division of labor. We use organization to achieve this coordination. At the same time our form of organization must not stifle individual initiative or it will prove a deterrent rather than an aid to accomplishment. Research, too, must be organized for greatest achievement but especial skill and care are perhaps needed to avoid stifling the initiative of the individual workers. I have, of course, followed with keen interest and much benefit the vast amount . that has been said and written on this subject in the past twenty years but I still find new stimulation in discussions with my good friends working in this field. It is my hope that this discussion may serve a like purpose. It would be ungracious not to make due acknowledgment to the many able contributors to this particular phase of human progress, but their very number and the great volume of their writing makes it impossible to trace to any one individual a particular significant and valuable idea. I shall content myself therefore with this general acknowledgment and with acknowledgment of the specific debt that every research man owes to those who have so ably kept before the public, and in particular before industrial executives, the place of research in the modern scheme of things' Because of the legitimate publicity thus given to research, the day is past when any

Jan 1, 1944

By W. M. Peirce

Commencing in 1922, each year a lecture has been presented to the Institute of Metals Division at this February meeting. The range of subjects has been very- broad. Some speakers have dealt with the most advanced work in the very heart of the science of physical metallurgy. Others have stimulated our imaginations by discussing the most recent progress in related fields of science. Others have told us of the latest art, which is at any moment of greater practical importance than the latest science, of metals. I feel that this broad precedent in the choice of subjects will justify my choosing to talk about some of the prosaic details of how, during the last generation, industry has effectively organized research to accelerate progress in our own and all other fields of science and related art. A number of years ago I visited one of this country's well-known research laboratories and had the pleasure of chatting for a few minutes with its equally well-known director. Being particularly interested at the time in the organization problems connected with industrial research, I broached that subject. My host stated in effect that he didn't believe in organized research. He was, of course, resorting to a rhetorical hyperbole. to pain: out the danger of overorganization which can so easily drift into regimentation and destroy individual initiative. Actually nearly all of us, much as we cherish our personal freedom of action, believe in organization because the history of progress in every field of human activity has been a history of men learning to work together, to cooperate, to create an efficient division of labor. We use organization to achieve this coordination. At the same time our form of organization must not stifle individual initiative or it will prove a deterrent rather than an aid to accomplishment. Research, too, must be organized for greatest achievement but especial skill and care are perhaps needed to avoid stifling the initiative of the individual workers. I have, of course, followed with keen interest and much benefit the vast amount . that has been said and written on this subject in the past twenty years but I still find new stimulation in discussions with my good friends working in this field. It is my hope that this discussion may serve a like purpose. It would be ungracious not to make due acknowledgment to the many able contributors to this particular phase of human progress, but their very number and the great volume of their writing makes it impossible to trace to any one individual a particular significant and valuable idea. I shall content myself therefore with this general acknowledgment and with acknowledgment of the specific debt that every research man owes to those who have so ably kept before the public, and in particular before industrial executives, the place of research in the modern scheme of things' Because of the legitimate publicity thus given to research, the day is past when any

Jan 1, 1944

By R. A. Stauffer

The chief ore of lithium is spodumene, a lithium-aluminum silicate containing up to 3 pct lithium. The preparation of lithium salts from spodumene is costly because of the low concentration of the metal and the difficulty of separating it from the other alkali metals present. Dr. Kroll's and Dr. Schlecten's recent paper1 has reviewed various methods proposed for preparation of lithium. It will be seen from this paper that the methods proposed to date have required one or another of the lithium salts as a raw material. The high cost of these salts has been the chief item of expense in the lithium metal produced. This situation has made it interesting to investigate the possibility of producing the metal directly from spodumene. When spodumene is calcined at 1000ºC in the presence of lime, lithium oxide is replaced in the ore as is evidenced by the fact that it may be leached from the reaction mixture with water.2 Free energy calculations suggested that lithium oxide might be reduced with aluminum or silicon and the lithium produced distilled from the reaction mixture by heating-to about 1000ºC in a vacuum. These facts taken together suggested that it might be possible to prepare lithium metal directly from spodumene by heating a mixture of the ore, lime, and a suitable reducing agent in vacuum and distilling off the lithium metal as formed. The Replacement of Li2O in Spodumene A series of experiments were undertaken to determine the ratio of lime to spodumene necessary to free substantially all the lithium oxide Present in the Ore. The spodumene used in these experiments was supplied by Foote Mineral Co. in the form of powder of about 200 mesh' Analysis of the spodumene was as follows: PCT SiO2......................... 62.7 Al2O3........................ 29.9 Li2o......................... 4.9 Na2O........................ 0.89 CaO......................... 0.75 MgO........................ 0.49 K2O......................... 0.44 Lime (cp —200 mesh) was added in various ratios to spodumene and thoroughly mixed in a ball mill. Two hundred gram samples of spodumene-lime mixtures were charged loosely in fireclay crucibles and held at 1000ºC in a gas-fired furnace for 5 hrs. The product in each case was ground to pass 140 mesh and then placed in a thimble in a soxhlet extractor. Extraction with water was carried on for 6 hrs. After this period the extract was reduced in volume by evaporation in order to precipitate dissolved lime and was then filtered and titrated with 1/4 normal hydrochloric acid. After correcting for residual calcium oxide in solution, the alkali present was calculated as lithium oxide. The results of these experiments are shown in Table I and Fig I. At lime-spodumene ratios less than 1.5, the products were invariably fused. At the ratio of 1.5 and above, the product was loosely sintered with little evidence of fusion. When the ratio of lime to spodumene was three, replacement of alkali oxides in the

Jan 1, 1949

By E. C. Houston

The presence in the Tennessee Valley of extensive deposits of olivine, a silicate of magnesium and iron that contains approximately 28 per cent magnesium, has been recognized since 1896 when Lewis8 published a survey of basic magnesium rocks of western North Carolina. A recent field survey by T.V.A.7 showed that more than two hundred million tons of high-grade olivine occurs above local drainage levels in western North Carolina and northern Georgia. Except for sporadic attempts to work the olivine for its nickel and chromium contents,10 the ore received little attention industrially until 1926 when Goldschmidt3 suggested its use in the manufacture of refractories. Only one instance is recorded of an attempt to utilize the ore commercially for its magnesium content;" in this case a process was used in which olivine was treated with sulphuric acid, the resultant mixture was leached with water, and the leach solution was purified and evaporated to form epsom salts, which was the end product. As a part of its program of contributing to the development of the natural resources of the region, the Tennessee Valley Authority became interested in the olivine deposits as a source of metallic magnesium because of their high magnesium content and proximity to hydroelectric power. Studies were undertaken to determine the feasibility of producing magnesium chloride by extraction of olivine. The experimental work was carried out successively at the T.V.A. Minerals Testing Laboratory, Norris, Tenn., at the Georgia State Engineering Station,* Atlanta, Ga., and at the T.V.A. laboratory at Wilson Dam, Ala. The present paper describes a process. developed through the pilot-plant stage, whereby magnesium chloride suitable for reduction to metallic magnesium can be prepared from olivine by extraction with hydrochloric acid and subsequent purification. Research on the magnesium-from-olivine process, originally intended for peacetime use, was given impetus by the shortage of magnesium that existed at the beginning of the current world war. By the time the process was sufficiently developed to justify a proposal for its inclusion in the war program, the shortage had been met by expansion and development of other processes. However, it is believed that the magnesium-from-olivine process may have advantages that will warrant consideration of its use after the war, when the economics of the various processes rather than production on a wartime scale will be the criterion for commercial production of magnesium. Description OF Process Metallic magnesium is produced electro-lytically by the Dow and the Elektron

Jan 1, 1949

By C. K. Stoddard, R. G. Knickerbocker, E. T. Leidigh, R. R. Lloyd, K. L. Mattingly

During July 1941, a study was initiated at the Boulder City Experiment Station of the Bureau of Mines on proposed methods for the production of magnesium metal. The major emphasis was placed upon development of a process that required minimum reliance upon the sale or utilization of by-products to meet economic competition from processes already in operation. It was felt that only through the development of such a process could the nation's vast resources of dolomite and low-grade magnesite that are contiguous to large blocks of firm power be properly utilized. During the course of exploratory tests on electrolytic and electrothermic processes, it was noted that fused magnesium chloride would dissolve appreciable quantities of magnesium oxide in the presence of small amounts of boric oxide. The use of such a solution in an electrolytic cell employing a graphite anode and a steel cathode caused the deposition of magnesium at the cathode and the evolution of carbon oxides at the anode with minimal amounts of chlorine The original results were sufficiently encouraging to justify further investigation on an enlarged scale, since the process seemed to present advantages over other proposed processes.1,2 for the direct use of magnesium oxide in a fused chloride electrolyte. When work oil a larger scale was initiated it was found that the addition of boric oxide to the electrolyte resulted in dispersion of metal and constantly decreasing current efficiency. However, by this time solubility studies had shown that magnesium oxide was sufficiently soluble in magnesium chloride melts containing no boric oxide to effect the same anode reactions, and development work was continued. Over two years of development work have been carried out, and considerable work remains to be done. It is desired to emphasize the fact that many of the difficulties met require a long period of continuous operation before they become serious enough to affect operation of the cell. ACKNOWLEDGMENTS This paper is one of many reporting on various aspects of the Bureau of Mines' program initiated in August 1939 by passage of the Strategic Minerals Act the scope of which was greatly expanded by subsequent legislation. Some of these papers are published as war minerals reports. others as bulletins, technical papers, reports of investigations

Jan 1, 1949

By C. M. Shigley

The record of the largest magnesium plant in the country utilizing sea water as a primary raw material stands as another victory in the struggle for large-scale production of pure chemical elements from the oceans. Bromine was the first element to be economically and commercially recovered when, in 1933, a six million pound per year unit was built on the Atlantic Coast near Wilmington, North Carolina, by the Ethyl-Dow Chemical Co.' The bromine was reacted with ethylene to produce ethylene dibromide, a necessary associate of tetraethyl lead in ethyl antiknock fluid. Within eight years that plant was doubled and redoubled, and another large unit was put into operation at Freeport, Texas, taking bromine from the Gulf of Mexico. In 1940, in fortunate anticipation of the impending demand for magnesium and the limitations of the production from natural brines, the Dow Chemical Co. turned again to the sea, and designed and erected a plant at Freeport to produce 18,000,000 lb. of magnesium per year from sea water.2 In March 1941, two months after the new plant had been put into successful operation, construction of an 18,000,000-lb. Government-financed addition was started. Late in 1941, as a part of the $400,000,000 defense program intended to produce 600,000,000 to 700,000,000 lb. of magnesium per year, Dow was asked to build and operate for the Government a 72,000- ooo-lb. plant near its original plant at Freeport. Within a few days after the Japanese made their attack at Pearl Harbor, preparation of a site was started at Velasco, Texas, for the construction of the Texas plant of the Dow Magnesium Corporation—the largest known magnesium plant utilizing sea water as its raw matcrial. Less than six months after the first piling was driven, urgently needed magnesium was in steady production. Five months later, the plant had exceeded its rated capacity. It remained above rated production until the general magnesium curtailment was applied to Government-owned plants in September 1944. Credit for the construction and operation record of the Dow magnesium plant must be divided among the efforts of a very determined group of men, an extremely favorable location, and a simple process. It is with the two latter aspects of the plant that this article will deal. The site for the new enterprise was chosen near Velasco, Texas, on property bordering the Brazos River at a point approximately 6 miles inland from the original magnesium plant and 7 miles inland from the Freeport Harbor on the Gulf of Mexico. This location was far enough away from the operating units to reduce both interference from construction and the vulnerability of closely bunched manufacturing operations to the then feared air attack. Yet the distance inland was not too great for the economical construction of a barge canal from the harbor to serve both the transportation of raw

Jan 1, 1949

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 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 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 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 C. S. Barrett, C. T. Haller

Twinning in magnesium is known to occur profusely under certain conditions, and when it occurs in polycrystalline materials it brings about a partial or even a complete change in the preferred orientation. The amount of research on this subject, however, has not been in proportion to its importance as a mechanism of deformation and reorientation. Much of the research has been limited to twinning in single crystals. The present study1 concerns polycrystalline sheet, and is an investigation of the twinning produced by plastic deformation as a function of the following variables: 1. Direction and type of deformation. 2. Amount of deformation. 3. Speed of deformation. 4. Temperature of deformation 5. Composition and temper of the sheet. 6. Twins previously produced. 7. Twins previously produced, then annealed. By proper control of these variables it is shown that, on a laboratory scale, samples can be produced that are free from preferred orientations. The materials used were samples of commercial magnesium-alloy sheets with nominal compositions given in Table I. X-ray diffraction was used in most of this work to detect the twins and to estimate the amount of twinning. Since twinning on (102) planes causes a re-orientation of the crystal lattice by 86", it is very easy to study with X-ray diffraction patterns, particularly if one notices the diffraction ring from the basal plane— the 002 reflection. By properly directing the X-ray beam, it is possible to produce 002 reflections from twinned material at, say, the 6 and 12 o'clock positions on the 002 ring, with the untwinned material reflecting to 3 and 9 o'clock positions; and by judging the relative intensity of the arcs on the diffraction ring at these positions, it is possible to judge the amount of twinned material relative to the untwinned. This X-ray method of estimating the amount of twinning is generally superior to metallo-graphic observation, for it was found

Jan 1, 1947

By C. S. Barrett, C. T. Haller

Twinning in magnesium is known to occur profusely under certain conditions, and when it occurs in polycrystalline materials it brings about a partial or even a complete change in the preferred orientation. The amount of research on this subject, however, has not been in proportion to its importance as a mechanism of deformation and reorientation. Much of the research has been limited to twinning in single crystals. The present study1 concerns polycrystalline sheet, and is an investigation of the twinning produced by plastic deformation as a function of the following variables: 1. Direction and type of deformation. 2. Amount of deformation. 3. Speed of deformation. 4. Temperature of deformation 5. Composition and temper of the sheet. 6. Twins previously produced. 7. Twins previously produced, then annealed. By proper control of these variables it is shown that, on a laboratory scale, samples can be produced that are free from preferred orientations. The materials used were samples of commercial magnesium-alloy sheets with nominal compositions given in Table I. X-ray diffraction was used in most of this work to detect the twins and to estimate the amount of twinning. Since twinning on (102) planes causes a re-orientation of the crystal lattice by 86", it is very easy to study with X-ray diffraction patterns, particularly if one notices the diffraction ring from the basal plane— the 002 reflection. By properly directing the X-ray beam, it is possible to produce 002 reflections from twinned material at, say, the 6 and 12 o'clock positions on the 002 ring, with the untwinned material reflecting to 3 and 9 o'clock positions; and by judging the relative intensity of the arcs on the diffraction ring at these positions, it is possible to judge the amount of twinned material relative to the untwinned. This X-ray method of estimating the amount of twinning is generally superior to metallo-graphic observation, for it was found

Jan 1, 1947

By A. E. Back, W. Wyman, K. E. Tame, S. F. Ravitz

In 1940, when it appeared that the United States soon might be cut off from foreign sources of high-grade manganese ore, the Bureau of Mines began an extensive series of investigations on the production of ferro-grade products from low-grade domestic ores by ore-dressing, pyrometal-lurgical, and hydrometallurgical methods. Among the hydrometallurgical processes for oxide ores investigated was a sulphur dioxide process in which the manganese was recovered from solution by precipitation with lime;' this process is essentially as follows: The ground ore is suspended in water and leached with SO2 gas to extract the manganese as manganese sulphate. Calcium chloride is then added to the slurry to precipitate calcium sulphate and form manganous chloride solution, and the resultant slurry is filtered to remove the calcium sulphate together with the insoluble portion of the ore. Calcium hydroxide is added to the filtrate and the mixture is agitated with air to precipitate hydrated oxides of manganese and regenerate calcium chloride. The precipitate is calcined, and the calcium chloride is recycled. To determine manganese extraction, reagent consumption, grade of product, and similar data for this process, a labora- tory investigation was started. Two minor modifications in the process were soon made: (I) the ore was suspended in calcium chloride solution instead of in water in order to extract the manganese and precipitate the calcium sulphate in one step, and (2) the agitation with air after the addition of slaked lime to the filtrate was omitted because manganese hydroxide is readily precipitated without air agitation and can be nodulized or sintered to a satisfactory product. When the process was carried through a series of cyclic tests, it was noted that the concentration of dithionate ion (which is one of the products of oxidation of SO2 by MnO2) in the cycled solution gradually increased; at the same time the chloride content of the solution gradually decreased, owing to soluble losses in the leach residue and in the precipitate. After a number of cycles, the calcium chloride became virtually completely replaced by calcium dithionate, the quantity of dithionate ion formed during the leach being more than enough to make up for the losses of dithionate in filtering. The calcium chloride process thus developed into a calcium dithionate process. Since the latter eliminated the need for make-up calcium chloride, and the dithionate solutions appeared much less corrosive than the chloride solutions, work on the calcium chloride process was dropped in favor of the calcium dithionate process. Acknowledgments The dithionate process was developed by the Bureau of Mines as part of a

Jan 1, 1949

By J. L. Lamont, W. Crafts

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