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By C. D. Dolman

SINCE the outbreak of the war we have discovered in the United States minerals of which there was no general knowledge, and which compared very favorably with anything that could be found in any foreign country. One of these was magnesite, or the carbonate of magnesium as it occurs in nature. This mineral crystallizes in the rhombohedral form, has a specific gravity of 3.00, molecular weight of 84 4, molecular volume of 28.1, and a hardness of 3.5 to 4.5.1 Had it not been for the development of the California deposits of this mineral and the discovery of immense new deposits in Stevens County, Wash., the production of steel during the war would have been more seriously handicapped than it was. Now, that the war is over, we face the possibility of competition' with the cheap Austro-Hungarian magnesite; and while that may not he so cheap as it was before the war, adequate protection should be given the producers in this country to insure the full development of our own resources. The consumption of magnesite in the United States in 1913, the year preceding the war, was 172,591 tons of calcined and 22,872 tons of crude magnesite. Less than 3 per cent. of this amount was produced at home. At the present time, practically all of the magnesite used in the United States is produced at home. Expensive plants have been constructed, extensive exploration work done, and production pushed to the utmost to supply the necessary requirements of the war. Thus a considerable industry has been built up within our borders. Some magnesite has been imported from Canada and Mexico, but the Canadian ore was of an inferior grade and could not be used satisfactorily. During the year 1918, production decreased in both the United States and Canada; the production in the United States was 225,000 tons in 1918 as against 315,000 in 1917, and in Canada 39,365 tons in 1918 as against 58,090 in 1917.

Jan 8, 1919

A. MALINOVSZKY,* Belleville, Ill. (written discussion?).-I have been very much interested in Mr. Dolman's paper. We all realize, I think, that this question of developing our home industries and support-ing the new industries which have developed during the great war is very important at present. Mr. Dolman has well shown the quantity and quality of the raw magnesite in the United States, and the commercial and industrial possibility of our home magnesite and I believe, with him, that our home industries should receive adequate protection. There are two reasons, however, for believing that this may be difficult. One reason is that much American capital is invested in the Austro-Hungarian magnesite industry. The raw magnesite can be quarried and prepared for the market in Austria with much cheaper labor expense than in the United States; large deposits which are very easy to quarry and good transportation facilities also contribute to the cheapness of production. The second reason is the old saying that the magnesite found in the United States is not of the same quality as the Austro-Hungarian mag-nesite; this I doubt. Even if the magnesite found here does not in a raw state equal the Austro-Hungarian, it can be synthetized so that the finished article will have the same properties as the Austro-Hun-garian finished magnesite refractory possesses. Thaw magnesite from Greece is not the same as the. Austro-Hungarian, but it has linen demon-strated that a good refractory can be made from the Greek product.

Jan 10, 1919

By J. D. Hanawalt, W. H. Gross

Magnesium has long been known as the lightest of our engineering metals. This metal, silvery white in color, has a specific gravity of only 1.74. Aluminum, the next lightest structural metal, is 1 ½ times heavier; zinc is 4 times heavier; iron and steel are 4 ½ times heavier; and copper and nickel are 5 times heavier. Magnesium does not occur in the free state but is very abundant in nature, constituting 2.5 pct of the earth's crust in the form of various ores. It is the third most abundant structural metal, being exceeded only by iron and aluminum. Magnesium is unique, however, in that in the form of magnesium chloride it also exists in the oceans. Sea water is the source most widely used for production in the United States but magnesium is also commercially produced from magnesite, dolomite, and other ores as well as from certain inland brines. The vast quantity of magnesium existing in the waters of the oceans can be visualized when it is realized that the removal of one hundred million tons per year (the approximate annual steel production in the United States) for a million years would reduce the magnesium content of sea water only from 0.13 to 0.12 pct, providing no more magnesium had washed into the sea in the meantime. Not only is magnesium potentially very abundant but it is in addition a very versatile metal and can be shaped and worked by practically all methods known to the art of metal working. It can be cast by sand, die, and the various permanent-mold methods;

Jan 1, 1953

By H. B. Pulsifer

ABOUT 15 varieties, or modifications, of the best magnesium available were prepared and subjected to etching tests, then examined for microstructure. Of the 30-odd etching reagents that were tried, nearly half, mostly ammonium salts, etched the metal satisfactorily. The surfacing and etching of magnesium is shown to be a very simple and quick operation. The density and hardness of magnesium were determined. The most interesting new observations relate to the finding of the hexagonal etch figures, the crystal laminations, and the fact that the metal is plastic, cold, when restrained or quickly deformed. Under slowly applied pressure cold metal deforms slightly, then shears to fracture without plastic flow. The chief structural features of magnesium are presented in two reduced photographs and 30 photomicrographs. MATERIALS TESTED There are only two sources in the United States from which new metal can be procured: the American Magnesium Corpn. and the Dow Chemical Co. No pronounced structural or property differences in the metals from these two companies were disclosed by the work of this investigation. The following materials were obtained from the manufacturers: 1. Massive crystals of distilled metal (American Magnesium Corpn.). 2. Rods of hot-extruded metal, ½ -in. squares and 5/8-in. rounds (American Magnesium Corpn.). 3. Sheet magnesium, 0.005-in. thick (American Magnesium Corpn.). 4. Cast stick metal, 1 3/8-in. dia. (Dow Chemical Co.). 5. Magnesium-aluminum alloy, hot-rolled plate, ½ in. thick (American Magnesium Corpn.). From these materials, were prepared: 6. Sections from a furnace-cooled ingot made from distilled crystal. 7. Cold-strained pieces from (6), (4) and (2). 8. Pieces cold-squeezed to fracture from (6), (4) and (2). 9. Hammer-struck pieces from (6), (4) and (2). 10. Steam-hammer struck pieces from (6), (4) and (2). 11. Sections from furnace-cooled ingot of the magnesium-aluminum alloy.

Jan 1, 1928

By Louis Ware

At the beginning of the present war, the United States faced the need to multiply its production of magnesium metal almost roo times within the shortest possible period. Urgently needed for construction of military aircraft, incendiary bombs, and other war uses, magnesium was at the top of the list of critical war materials. Up to that time only one Producer, employing Only One process and using One raw material in a single plant, represented this country's entire Production capacity. It was immediately desirable to plan a numher of plants located strategically over the Count'Y and to expand an industry more rapidly and to a greater extent than ever before had been attempted in so short a time. In '939 this American producer, the Dow Chemical .9 was making about 7 million Pounds of magnesium metal. It utilized as a raw material brine containing magnesium chloride, which was pumped from wells in Michigan. The logical ap-preach to certain increased production was to employ the same process on the same raw material in other sections of the United States. In Europe and other countries, different processes had been used and different raw materials were being utilized, but all of the skill and knowledge for production in this country was that of using the Dow type of cell and magnesium chloride as a raw material. The Government was testing other processes, but none then had been proved commercially feasible. Development OF New Process The International Minerals and Chemical Corporation had available a large quantity of magnesium ,chloride at Carls-bad, New Mexico, contained in the end liquor produced from its potash plant sillce the buildng of the plant in 1941 It was the only company mining commercially a magnesium ore and having anything like this quantity of magnesium chloride liquor. The magnesium ore, langbeinite, was being mined from the 800-ft. level for its content of potassium sulphate. This ore, a potassium magnesium sulphate, was reacted in a base exchange plant with potassium chloride to produce potassium sulphate, the discharge liquor having a high content of magnesium chloride. Three potash-producing companies are in the Carlsbad area, but only International has developed and is commercially producing the potash-magnesium ores. The lower, or No. 4, veil, in that area is potassium chloride ore, and is continuous through all the properties. The langbeinite, or No. 2, vein is minable at the International property, but occurs sparsely, if - at in other areas being mined in that vicinity. It is understood that most of the mag. nesium produced] by Germany comes from magnesium and magnesium-potassium ores obtained from potash mines. It was logical for International to pro-pose to make available this magnesium material and to offer its technical staff to design, construct and manage a magnesium plant for the account of the Government. The plan that finally was adopted by the

Jan 1, 1944

By R. G. Knickerbocker, R. R. Lloyd, W. T. Rawles

In July 1041, the Experiment Station of the Bureau of Mines at Boulder City, Nevada, began a study of methods of producing magnesium metal from magnesium oxide, with particular emphasis upon the direct use of magnesium oxide in a molten chloride electrolyte. The program was extended to include pilot-plant study of chemical methods for the preparation of pure magnesia from dolomites and magnesites. Preliminary work on the production of magnesia from dolomite was done with the cooperation of Kobert D. Pike and the Harbison-Walker Refractories Co. These investigatipns included a cooperative arrangement whereby the Bureau tested certain steps of the Harbison-Walker-Pike process. The process finally developed by the Bureau includes the precarbonation mixing step of the H.W.P. flowsheet prepared by Mr. Pike. Two magnesium-reduction plants using MgO as a source of magnesium were being constructed in the West, and they enormously stimulated interest in various dolomite deposits as possible sources of the magnesia needed by them. This paper describes one phase of this program—the operation of a pilot plant for producing cell-grade magnesia from dolomite from Sloan, Nevada. The process developed for this purpose is an adaptation of a well-known process first proposed by Clossonl and modified by others,2"1 involving the use of calcium chloride and carbon dioxide. It is based on the following chemical reactions: MgCl2 + Ca(OH)2 = CaCl2 + Mg(OH)2 [1] Mg(OH)4 + CaCU + CO2 = MgCl2 + CaCO, + H2O [2] The first reaction proceeds almost completely to the right because of the much greater solubility of calcium hydroxide as compared with magnesium hydroxide. Under equilibrium conditions, when only the four components shown in reaction I are involved, the ratio of magnesium to calcium in solution, according to solubility-product relationship, will be: This reaction is the basis of present commercial processes for recovering magnesium from sea water and dolomite. The second reaction is, in effect, a reversal of the first reaction produced by adding COz. This reaction also proceeds nearly to completion, the solubility relationship being: Ca where P indicates partial pressure of COz, in atmospheres.

Jan 1, 1944

By Andrew Mayer

Early in 1942 National Lead Co. was requested by the War Production Board to construct and operate a plant for the Government to produce magnesium by the ferrosilicon process which had been developed by Dr. E. M. Pidgeon in the laboratories of the Canadian National Research Council. A contract with the Defense PlantCorporation was concluded in May 1942 and Magnesium Reduction Co., a wholly owned subsidiary of National Lead Co., was formed to carry out this project. The capacity of the plant was rated at I0,000,000 lb. of magnesium per year, equivalent to an average production of about 14 tons per day. The Process The process, in brief, is as follows: The raw materials are dolomite and ferro-silicon, 75 per cent grade. The dolomite is calcined, the calcine and ferrosilicon are ground and mixed and the mixture is briquetted. The briquets are charged into tubular retorts of chrome-nickel steel set horizontally in a furnace with the open ends projecting outside the front wall. The retorts are then closed and evacuated. Magnesium is liberated according to then reaction 2(MgOl CaO) + Si = 2Mg + zCaO, Si% It is distilled from the charge and con- densed on a removable sleeve in the throat of the retort. Sodium and potassium, if present, are also liberated, distilled and condensed on a "sodium condenser" in the end of the retort. At the expiration of the distillation period the retorts are discharged and the cycle of operations is repeated. For the rated daily capacity of 14 tons of magnesium there are required approximately 170 tons of dolomite, equivalent to about 85 tons of calcine, and 16.5 tons of ferrosilicon. The retort residue, a bulky powder which at present is waste, amounts to about 87 tons. Choosing the Site The investigation to select the location of the plant was conducted by the Research Laboratories of National Lead Co. This work included geologic and economic surveys of a number of districts, examination of dolomite samples by chemical, spectrographic and petrographic methods and large-scale tests of dolomite from several of the more promising localities. in the last-named tests 2-ton samples were put through the ferrosilicon process in the pilot plant of the Canadian National Research Council, under the guidance of Dr. Pidgeon. The conclusions drawn from the investigation, in regard to the quality of dolomite to be used in the ferrosilicon process, were: First, the dolomite should contain not less than 21 per cent MgO and not more than 2 per cent acid-insoluble material. Second, the dolomite should

Jan 1, 1944

By T. W. Atkins

ATHOUGH the magnesium industry in this country is about thirty years old, not until American industry began to amaze the rest of the world and confound our enemies with the extent and variety of our war production did the industry begin to come into its own. At the outset of the war, only three companies were producing and fabricating magnesium in this country. Today, about sixty companies are producing, casting, forging, extruding, rolling, and stamping this lightweight champion of metals. Experience in alloying, processing. and fabricating the metal gained during the war years is now being translated into hundreds of civilian peacetime applications. In no sense should magnesium be considered as a substitute for other metals. It has come into popular favor because If many unique properties in addition to is being the lightest known structural metal. These attributes are toughness, igidity, corrosion-resistance, and the ease with which it can be machined and worked. Magnesium is the third most abundant element in nature. Sea water, magnesite,

Jan 1, 1946

By J. R. Coulter, F. O. Case, H. G. Satterthwaite, B. Harden

During the two years that the Henderson plant has been in operation, a number of technical improvements have been made by the staff of Basic Magnesium, Inc., the effects of which were realized subsequent to the writing of the paper by Major C. J. P. Ball (p. 28j, this volume). Pellet Mix The process as originally installed required the use of peat moss in the mixture going to the chlorinators. This had to be imported from Canada at a considerable cost, and, besides being expensive, constituted a serious fire hazard in the dry climate of Nevada. Experimentation looking toward its elimination had been going on for some time and was actively pushed as soon as operations commenced. It was found that a pellet mix containing no peat, which would chlorinate at a satisfactory rate, could be cast as a fluid slurry, which would set up into a hard mass having the desired porosity. For carrying out this operation, equipment similar to that used in the manufacture of phosphate fertilizer at Anaconda, Mont., was installed and proved eminently successful. The dry materials, with peat moss and raw concentrates entirely eliminated, are mixed with magnesium chloride solution in two Pratt phosphate mixers and the resultant slurry is poured onto two 48-in. slowly moving rubber conveyor belts. By the time the slurry has reached the head pulley, the material has set su4iciently to be broken and sized as desired. The discharge from the casting belts is fed to the four rotary kilns in the preparation plant, where it is dried and coked to the proper degree for subsequent chlorination. With the peatless feed the capacity of the kilns was found to be about double what it had been before, so that the four rotaries suffice for a 10-unit operation, thus making it unnecessary to operate the extruders and tunnel kilns. In addition to saving the cost of the peat, the new system can be operated with about 85 per cent less labor than was formerly required in the preparation plant. The new pellet production system has also made it feasible to install centralized crushing equipment with suitable conveyors and a loading station. Containers of 8000 lb. capacity were substituted for small cubicles of 1000 lb. capacity which formerly were used for charging the chlorinators, and trailer trucks were substituted for the small trains originally provided for transportation from the preparation plant to the chlorinators. These changes resulted in a considerable saving in handling and transportation charges. Handling Molten Metal The molten magnesium originally was ladled from the electrolytic cells into small gas-fired brick-lined cars standing between the cell rows. From these cars the metal nes ium. into ''cheeses'' weighing from 150 to 300 lb. After solidification the

Jan 1, 1944

By T. A. Dungan

The thermal processes for the production of metallic magnesium can be divided into two general classifications, the direct reduction of magnesia with carbon and the indirect reduction of compounds of magnesium by reducing agents that are themselves products of carbon reduction. The latter are so chosen as to cause reduction of magnesium compounds wherein only the magnesium is liberated in the vapor phase. Reducing agents used are: calcium carbide, silicon carbide, silicon, aluminum, various silicides or combinations of calcium, aluminum, silicon in iron. All of these are products of highly endothermic reactions and, with the exception of scrap aluminum, can be produced in an open, submerged arc furnace; that is, the arc is covered only by the charge itself. The more investment in energy required to prepare such a reducing agent, the less is the energy required in the subsequent step to reduce the magnesium compound to the metal. It is impossible, however, to avoid the laws of thermodynamics, no matter how much circumambulation is resorted to in the preparation of successively more powerful reducing agents. Since each such step carries forward its own inefficiencies, it appears evident that the ultimate status of such processes is dependent upon the development of by-products. The direct reduction of magnesium oxide by carbon has a decided appeal to both the scientist and the industrialist. The successful production of the carbo-thermic plant at Permanente is a significant fact in the substantiation of this concept. Like most developments, however, the history of carbon reduction of magnesia is not one of triumph after triumph, or immediate heady success to the investigators. It is understood that one of the early investigators conducted an experiment wherein he placed carbon and magnesia in one end of an evacuated tube and managed to heat this end to a temperature high enough that magnesia and carbon deposited at the other end of the tube. The charge, unreduced, appeared to have been completely transported from the hot to the cold end of the tube. This raised doubt for some time as to whether magnesia could be reduced at all with carbon. It was correctly suspected, however, that the magnesia was in fact reduced and the resultant magnesium vapor and carbon monoxide reacted upon one another upon reduction in temperature to reform the starting ingredients. Attempts were then made to dilute the two vapors by passing a considerable stream of hydrogen through an arc furnace charged with magnesia and carbon. Thus by dilution of the products it was' expected to obtain metallic magnesium. The results were positive and metallic magnesium was .0

Jan 1, 1944

By L. D. Fetterolf, G. T. Mahler, W. M. Peirce, R. K. Waring

Until recently, the only commercial method of producing magnesium has been fused salt electrolysis, despite a considerable amount of experimental work on the direct reduction of magnesium oxide. In this early work, a number of investigators demonstrated that magnesium oxide would react with any one of several reducing agents to produce magnesium vapor, but that the mixture of magnesium oxide and reducing agent must be heated to a high temperature even in a vacuum. In particular, it was demonstrated that silicon and aluminum are effective reducing agents and that when either of these is used the magnesium vapor can be condensed to massive metal. In spite of this knowledge, no successful commercial reduction process was developed, at least in this country, because of the operational difficulties imposed by the requirement of high temperature and vacuum and because of the high cost of the reducing agent. The outstanding experimental work done by Pidgeon, who carefully reviewed all of the known methods of making magnesium and then selected ferrosilicon reduction, overcame some of the operational difficulties. The process developed by Pidgeon comprises briquetting a mixture of calcined dolomite and reducing agent, preheating the briquets to about 600°C. in an externally heated alloy retort, reducing the MgO with silicon in an evacuated horizontal alloy retort heated externally to about II50 C., and condensing the magnesium vapor to a solid in a cold extension of the retort projecting beyond the front of the furnace. A major advantage of Pidgeon's process is that the retort is not cooled down between charges. Earlier investigators had used apparatus that necessitated cooling and reheating of the retort between charges. Early in January 1942, when the War Production Board was considering the Pidgeon process for quickly increasing the production of magnesium, The New Jersey Zinc Co. offered to have a research investigation of the process carried on, with the hope of assisting in its further development. This offer was accepted, and a two-retort pilot plant was built at Palmerton and put in operation on Jan. 29,1942. An intensive investigation of certain phases of the process was carried out in the ensuing four months. This investigation was completed in the last part of May 1942) and the pilot plant was then shut down. Subsequently, The New Jersey Zinc Co. was requested to have further development work done on the process, and a more extensive investigation was undertaken in August 1942 under contract with the War Production Board and under the supervision of the War Metallurgy Committee. This paper describes the ,phases of the investigation that are thought to be of sufficient general interest to merit publication.

Jan 1, 1944

By C. J. P. Ball

Prior to 1939 the bulk of the magnesium metal produced outside of the united Stater was extracted directly from the ore and ifi the United States from magnesium chloride obtained as a by-product from the treatment of natural brines. A typical brine is one containing about 0.25 to 0.75 per cent bromine, 11 to 14 per cent sodium chloride, 9 to 11 per cent calcium chloride and 3 to 10 per cent magnesium chloride. The state of Nevada was known to possess large deposits of magnesite ore (MgCOs, the carbonate of magnesium), in Gabbs Valley, near Luning, approximately 350 miles north of Boulder Dam. Deposits mined in Europe were supplying magnesite giving 97 per cent MgCOs with about I per cent each of silica, lime and oxides of iron and aluminum. parts of the Luning de-posits Were almost equally rich, and the general average was of sufficiently high grade for production of magnesium. power to the amount of 200,000 kw. was available immediately from Boulder Dam, and water from Lake Mead, and it was this combination of available power, water, and ore that led to the initial proposal to erect a magnesium reduction plant in southern Nevada to reduce the magnesite ores from Gabbs. The extraction of magnesium metal from these magnesite deposits had been considered by the I. G. Farbenindustrie of Germany as far back as 1929. Mine and Oxide Plant The mine and oxide plant of Basic Magnesium Incorporated are perched upon the oride slope of the Paradise Range, at an altitude of 5000 ft., overlooking the 30 mile desert panorama of Gabbs Valley, Nevada. , Ore Occurrence The Gabbs magnesite ores occur in a thick series of flat, westerly dipping dolomites of Upper Triassic age. The mag-"esite bodies are exposed in steep canyon "areas encircling the north and east edges of a northerly projecting tongue of a roughly elliptical stock of granodiorite, which intrudes the dolomite. The magnesite mineralization is considered to be a a of calcium by magnesium through the agency of hydro-thermal solutions associated with the intrusion of the granodiorite. The ore bodies are of very irregular shape and distribution. Incomplete evidence points to deep pipelike replacement shapes that mushroom out erratically at various elevations. A wide latitude in the degree of magnesium replacement is reflected in a variance of quality from pure magnesite to magnesitic dolomite. The, ore is a massive crystalline mag-nesite. Though some differences in characteristics occur between ore bodies, in general the ore is a medium-grained carbonate varying in color from white, through all shades of gray, to black. Recrystallized dolomite, which encloses and occurs as

Jan 1, 1944

By C. E. Nelson

The purpose of this discussion is to outline briefly the practices commonly followed in this country for the melting and refining of magnesium and its alloys. The processes used for the various forms of primary magnesium, as far as there are differences in the physical shape or behavior, will be discussed. The refining of general fine scrap or secondary magnesium was presented in an earlier paper.1 Inasmuch as the use of fluxes is an essential part of all the melting and refining processes, the principal aim of this paper will be to deal with these in sufficient detail to point out their unique characteristics, in order to make their use more effective. Types oF Melting Practice All melting and refining processes for magnesium and its alloys require the use of fluxes. These fluxes have a magnesium chloride base and other halide salts or oxides are added to give a density or behavior exactly suited to the particular melting practice. The successful handling of magnesium depends upon the proper use of the correct fluxes. There are four general methods of melting, summarized in the following paragraphs and treated in more detail in the section on Melting and Refining. Open-pot Method The open-pot method makes use of No. 230 flux.2 The flux provides protection during melting and a molten pool of flux into which the solid magnesium melts. It is stirred through the molten metal bath and agglomerates oxide or similar foreign bodies; then on quiet standing separates away, leaving the refined metal ball floating in an encircling layer of molten flux. It forms only a thin fluid film over the surface of the molten metal, which may be ' parted for hand-ladling processes and tends to cover the metal again after the ladle is removed. A very light dusting of the pot surface with fresh flux immediately after the ladle is removed is usually desirable. The open-pot method is used generally in the following processes: (I) alloying and secondary smelting in the production of ingot, (2) in sand foundries for premelting and to a smaller extent for the production of small castings requiring hand ladling, (3) in permanent-mold founding for premelting and also direct ladling to castings, (4) for continuous methods of preparing metal in the production of billets or ingots from which wrought products are fabricated, (5) in general scrap recovery. Crucible Process The crucible process makes use of No. 310 flux, which has the property of being thinly fluid at the start, to provide protection and refining qualities, and then drying out or thickening after a time, leaving a protecting crust on the pot surface until the time of casting. At that time it can be readily skimmed off or held back, thus allowing the contents of the crucible to be poured out directly into castings without fear of flux contamination. This flux is not

Jan 1, 1944

By W. A. Alexander, L. M. Pidgeon

Metallic magnesium and similar meta!s near the top of the electromotive series have been commercially produced by the electrolysis of a suitable molten salt. Despite the success of electrolysis, sufficient inherent objections exist to justify the search for a direct reduction method. Such a method would widen the choice of raw materials, relax the rigid electrolytic requirements of raw-material purity, and, by obviating direct current, over simplicity of plant equipment. This paper describes the pilot-plant development of one such method, which has subsequently formed the basis of operation of six commercial plants-—one in Canada and five in the United States. Unlike aluminum, magnesium is volatile at relatively low temperatures. This physical property, which produces its greater inflammability, also offers possibilities of direct reduction that are not available with aluminum. In the basic reaction MgO + X = XO + Mg if X is nonvolatile, the reaction may be forced to the right at high temperatures by the evolution of magnesium vapor, despite the large negative value of the heat of reaction which is almost bound to follow the use of any available commercial reducing agent. The cheapest X, of course, is carbon, but this notable advantage is modified by the production of a volatile oxide CO, so that both Mg and CO are evolved simultaneously. Elaborate devices are required to shock-cool the equilibrium mixture in order to prevent back reaction. At best, a pyrophoric powder is produced, requiring redistillation to provide marketable metal. The practical development of this process, is due to F. Hansgirg, and his methods have recently been given a trial on a grand scale in the plant at Permanente, California, and smaller plants were previously built in Austria, England and Japan. A second class of reducing agents is available, those which produce nonvolatile oxides. When XO and X are relatively nonvolatile, magnesium is the only volatile member of the system. It may be evolved in a simple distillation step and condensed without the formation of powder. Two basic requirements must bc fulfilled in order that such a reaction may proceed: I. The reducing agent when heated to a reasonable temperature in presence of MgO must cause the production of an appreciable equilibrium vapor pressure of magnesium. This magnesium must be removed continuously. z. A supply of heat must be maintained. In order to fulfill the first requirement, operations must be conducted in vacuo or in a stream of Hz. Owing to its greater efficacy and relative safety, vacuum has been employed in the work to be described. The choice of a suitable reducing agent formed the subject of an extensive series

Jan 1, 1944

By W. B. Humes

The use of high vacuum on a large industrial scale in the ferrosilicon process for the production of magnesium marks the coming of age of an important new metallurgical technique. The economical production of reactive metals, such as magnesium, which combine with all the well-known furnace atmospheres, has until recently been successfully carried out only by electrolytic methods. It is now apparent that, through the use of high vacuum, the distillation or sublimation of many metals can be done industrially at much lower temperatures, and hence in much simpler equipment, than heretofore has been thought possible. At the beginning of the present emergency, when the ferrosilicon process of producing magnesium was brought to the fore, little was generally known about vacuum engineering, practices, and techniques. In a comparatively short time, the available equipment has been adapted, new equipment designed and built, and a fund of know-how evolved to make possible the production of thousands of pounds of magnesium per day at pressures less than 1/ r0,000 of an atmosphere. Pilot-plant operations have been consistently maintained at pressures even as low 2s one micron (0.001 mm.). These low pressures, which previously were regarded as prohibitively costly or impossible to attain, have been demonstrated as economically feasible on an industrial scale. Necessity for Vacuum The main function of vacuum in the ferrosilicon process, and hence in most vacuum smelting processes, is to lower the temperature at which the metal may be distilled or sublimed from the reduction mixture. A secondary function is to protect the distilled metal from attack by the furnace atmosphere and to permit the formation of a dense condensate. In the ferrosilicon process, magnesium is formed by the reaction between dolomite and ferrosilicon: 2(Mg0-Ca0) -\- HFeSU / t=> aMg + MFe + (CaO)2-SiO2 The metal is distilled from the pelleted charge at a free air pressure of about 0.100 mm. of mercury (100 microns). This low pressure is not needed for the reaction, but rather serves to protect the metal vapor from the oxygen or nitrogen of the atmosphere and permits the formation of a condensate free of pyrophoric material. The reaction proceeds at air pressures as high as several millimeters of mercury, and evidence has been offered to show that the actual equilibrium pressure of magnesium at operating temperatures of 2I50°F. is somewhat higher. Experimentation indicates that the yield begins to decrease at pressures above 500 microns. While no real operating data are yet available on the relationship between

Jan 1, 1944

By C. H. Mahoney, A. L. Tarr, P. E. Le Grand

Magnesium, it is now generally realized, differs in some important aspects from most other structural metals, not excepting even its close neighbors, the aluminum-base alloys. This is particularly true with respect to the effects of elevated temperatures on the two light metals when in the molten state. Aluminum, 0' the one hand, should not be raised above its melting point any higher than is absolutely necessary if one is to avoid danger of gas absorption and a tendency toward grain growth in the resultant casting.' Magnesium alloys, in sharp contrast, actually benefit by being heated to temperatures considerably above their melting point, It is a commonly accepted practice to establish the desired fine grain in the industrial magnesium alloys of the aluminum-hearing group by raising the temperature of the melt after the refining treatment to some 250°C (482°F.) above the melting range. To recall briefly the typical practice for magnesium alloys, the molten metal is refined by fluxing at about 730°C. (I350°F.), and after the melt has been covered with a suitable flux, the temperature is raised to between 870°C. (I600°F.) and 930°C. (1700°F.). It is then cooled as quickly as possible to the casting temperature. This superheating, as it is called, results in a fine-grained cast metal structure which has superior mechanical properties, enhanced amenability to 'solution heat-treatment, and better machinability than cast metal that has not been superheated. The minimum temperature of superheating varies to some extent with the composition of the alloys to be treated and usually increases with the percentage of magnesium in alloys containing the same constituent metals.' It should be noted that the grain-refining effect of superheating is markedly apparent only in connection with the alloys containing aluminum as an alloying Constituent—the binary alloy containing 1.5 per cent manganese, for example, is not refined in grain to any noticeable extent by a superheating effort. While the phenomenon of superheating is well known in the magnesium industry, the mechanism of the process has remained a mystery During the superheating cycle something occurs that forces a fine grain upon the solidifying metal. The process has been controlled in an empirical manner, and occasionally, especially on large-scale melts, and for no apparent cause, no grain refinement is obtained from a superheating treatment. Only a few papers of importance have been published on the subject. Of these, one of the most helpful is the paper by Achenbach, Nipper and Piwowarski,3 which gives considerable data concerning the effect of superheating on various properties such as fluidity, shrinkage and hot crack

Jan 1, 1945

By H. E. Elliott, R. S. Busk, A. T. Peters

One of the problems of the fabricator of metals and alloys is the propensity of some composition rarnges toward abnoermal grain growth during certain stages of fabrication. In this respect magnesium alloys are no exception among alloys. Fortunately, convenient foundry control methods have been developed by which the abnormal grain growth possible in certain magnesium-alloy castings can be suppressed. An unusual characteristic of magnesium alloys, however, is that castings of some composition ranges are subject to local grain growth during heat-treatment without the necessity of intentional mechanical stressing of the part prior to heat-treatment. This effect occurs only under certain critical casting conditions, and only in certain alloys of greater than about 8.5 per cent aluminum content, such as C alloy (Mg, 9 per cent A1, 2 Per cent Zn, 0.2 Per cent Mn) and G alloy (Mg, 10 per cent Al, 0.2 per cent Mn). The first observation of this phenomenon in cast magnesium alloys occasioned much surprise, since it is not observed in other meta1s- Jeffries and Archer1 have stated that "the grain size of cast metals, provided they have not been plastically deformed, cannot be changed by heating below the melting point." The study of the conditions leading to abnormal grain growth in cast magnesium alloys, and of the mechanism of this phenomenon, has led to some very interesting observations. Perhaps the most significant of these was the observation that stresses originating from cooling contraction in magnesium-alloy castings are the only stresses necessary, under certain conditions, to cause local recrystallization and subsequent grain growth in the casting during heat-treatment. Before recent developments, this phenomenon of abnormal local grain growth Was a definite problem in the production foundry on C alloy sand castings. Illustrated (Fig. I) is a picture of a casting scrapped because of this defect. A mottled effect is produced in coarse-grained areas by suitable etching solutions. The properties of metal in the affected area are much impaired by such grain coarsening. Ultimate tensile strengths of half the normal value have been measured in metal of this nature. In this paper are described the techniques that have been developed by The DOW Chemical Co. for studying, and in large measure solving, this production problem. Also discussed are studies of the mechanism by which excessive grain coarsening occurs, and the fundamental conditions that produce this effect. The abnormal grain growth discussed in this paper will be referred to as "germinasium since this term has been definedl as any process leading to an abnormally coarse grain size. This paper deals only with abnormal local grain growth that may occur during the solution heat-treatment of certain magnesium-alloy castings, as dis-

Jan 1, 1945

By Ralph Hultgren, Bernard York, David W. Mitchell

It is a well-known fact that magnesium-alloy castings are apt to be coarse grained if the melt is not superheated several hundred degrees above the melting point before casting. (The casting temperature varies according to the shape of the mold. A typical casting temperature is perhaps 1400°F.) British practice is to heat to 900°C. (1650°F.) for 15 min., cool rapidly to casting temperature, and cast.' In Germany superheating is carried out at 850' to 900°C. (1560° to I650°F.) depending on the amount of scrap used. It is stated that further refinement will be obtained by prolonging the period of superheating or by increasing the superheat temperature to 950°C. (I740°F.).2 In the United States superheating is carried out at 1600' to 1700°F. (871' to 927°C.), perhaps even higher in some places. It is stated that superheating effects are found as low as 1500°F. (816°C.), but several hours are required.3 These commercial treatments lead to grain sizes in sand castings that may vary from 4 to 8 grains per sq. mm.! in heavy sections and from 60 to IOO in 1/2-in. sections to perhaps 380 in thin sections. It is also generally known that the refining effect of superheating is lost if the melt is held for some time at lower temperatures before casting. Aside from these very qualitative statements, there is little to be found in the literature as to the effect of temperature and time of superheat on the final grain size. Because of the uncertainty of these factors, the Office of Production Research and Development of the War Production Board placed a research contract with the University of California, supervised by the War Metallurgy Committee. This research, which was done under the "Restricted" Project NRC-550, is the basis of this paper, which has been released for publication by the O.P.R.D. The material studied was an alloy prepared from carbothermic magnesium. The temperatures required for grain refinement proved to be widely different from those used in practice, as described in the statements in the first paragraph. This difference is attributed to the fact that the magnesium in the specimens was of carbothermic origin instead of the electrolytic magnesium in common use. Materials and Methods The magnesium alloy studied was one of the most popular sand-casting alloys, with a nominal composition of 9 Per cent aluminum, 2 per cent zinc, and 0.1 per cent (minimum) manganese and the balance magnesium. This is designated

Jan 1, 1945

By Ralph Hultgren, David W. Mitchell

Magnesium alloys usually are superheated before casting in order to ensure fineness of grain. Superheat temperatures in common use range from 1600" to r 7o0°F.; the casting temperature, which depends upon the mold shape, is usually 200° to 300°F. lower. The process of superhcating requires considerable time and seriously shortens the life of the iron pots used. Recently it has been reported1 that if acetylene, carbon dioxide or natural gas is bubbled through molten electrolytic A.S.T.M. No. 4 alloy at 1400°F. for 5 min., grain refinement equivalent to that of superheating will take place. Addition of certain solids such as graphite or aluminum carbide accomplishes the same results? As will be shown in this paper, it is possible to achieve grain refinement in magnesium casting alloys at low temperatures by mechanical stirring of the molten metal for a short time. This process was developed in the course of research work, supervised by the War Metallurgy Committee under the "Restricted' project NRC-550, for the Office of Production Research and Development of the War Production Board. This paper, based on that work, has been released for publication by the O.P.R.D. Materials and Methods The alloys studied were the most common American sand-casting alloys designated as No. 4 and No. 17 by the American Society for Testing Materials. The magnesiun used in these alloys was of both carbothermic3 and electrolytic' origin. Chemical analyses supplied by the producers are shown in Table I. Each heat consisted of approximately 5 lb. of alloy melted in a Tercod crucible. It was refined by fluxing with Permanente No. 7* refining flux at 1300° to 1350°F. After cooling to 1200° to 1250°F., portions of approximately one pound each, were ladled into iron crucibles contained in an electric furnace at about 1250°F. The molten metal was covered with Permanente No. 21 † covering flux and then heated to the temperature to be investigated. Normally each of the four portions was given a different treatment. In a typical case one portion was stirred vigorously for 5 min., acetylene gas was passed through a second portion for 5 min., a third portion was superheated to 1600°F. for 15 min., then . cooled to casting temperature, and the fourth was held for 5 min. at the temperature of stirring or gassing without other treatment. Each portion was then cast into one-inch diameter cylinders in three "nonturbulent" molds of identical shape. One mold was made of cast iron and the other two of baked sand. The cast-iron mold and one of the baked sand molds were heated to 360°F., the other baked sand mold was at room temperature. The freezing times in these molds were

Jan 1, 1945

By C. W. Phillips, R. S. Busk

With most cast metals the grain size may vary within wide limits, depending upon the conditions at the moment of freezing. These conditions are subject to control in magnesium-base alloys, by proper melting and superheating techniques, enabling production of quite uniform and fine-grained castings, almost independent of section thickness. However, such variations of grain size as do exist, in common with all metals, are reflected in corresponding changes in mechanical properties. It is the intent of this paper to present data giving the relationship between grain size and mechanical properties. Data are also included on the combined effects of grain size and micro-porosity. In addition, a short discussion of factors influencing the grain size of sand castings is included. Measurement OF Grain Size By grain size is meant the statistical distribution of volumes occupied by the individual crystallites in a metal section. Since this is almost always impossible of direct measurement, several methods of estimating and expressing the size have been evolved. Most exact methods make use of the microscope. This involves study of a single plane cut at random through the metal. What is seen in the microscopc are polygons, each the cross section of a grain. The diameters or areas of these polygons are then measured and the grain size is expressed as an average diameter, number of grains per unit area, average area per grain, or, rarely, average volume per grain. Rutherford, Abom, and Bain3 have discussed extensively the errors involved when using a plane section to estimate volume. They clearly point out that the tendency is to underestimate the true grain size because of the nature of the measurcment. The A.S.T.M. recommends that measurement be made by comparison with a standard chart, by means of Jeffries' planimetric method4 or Heyn's intercept method. The Society recommends that the notation be in terms of the number of grains per unit area (as is the grain-size number used for steel) or as an average diameter, expressed in inches or millimeters (as for copper and brass). The method of measurement used for this study was comparison with a standard chart, which has been described by P. F. George.5 The chart was constructed by photographing at Ioo diameters a uniform specimen with an average grain diameter of 0.003 in. The average diameter of this specimen was determined by numerous measurements, using both the Jeffries and Heyn methods. The other grain sizes were then obtained by appropriate enlargemcnt of the master sample. Careful comparison of the chart method with other methods on identical samples indicates that though the differences be-

Jan 1, 1945