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By Moorrees C, Everson P

A detailed examination of carbonic acid leaching of crude iron-containing magnesia derived from Savage River magnesite shows that the rate and extent of magnesium and iron dissolution are affected by the slake time, leaching temperature, carbon dioxide pressure, pulp density and rate of agitation. In order to produce high-purity magnesia from the leachate by precipitation and calcination, the optimum leaching conditions, which are those that yield maximum magnesium and minimum iron dissolution, have to be a compromise in terms of the above parameters. For example, iron dissolution can be limited by leaching at an elevated temperature (-45°C), but because the maximum concentration of magnesium biearbonate decreases rapidly with an increase in temperature, it is necessary to use a low pulp density (-2 per cent solids) in order to achieve an acceptable degree of magnesium dissolution.Evidence is obtained that iron dissolution involves the formation of a soluble ferric bicarbonate complex that decomposes at elevated temperatures. The extent of iron dissolution is much higher than might be expected and it is probably because the original magnesite contains siderite in solid solution with the magnesite; on calcination, the hematite whieh is formed is in a very finely divided condition and hence more reactive.

Jan 1, 1983

By Dimitrios Fillippou

Magnesium hydroxide is used in a number of industrial applications, from the neutralisation of acid effluents to the production of pharmaceuticals. High-quality magnesium hydroxide powders can be produced by hydrating slow-reacting magnesia in dilute magnesium acetate solutions. The process of magnesia hydration shows many similarities with a typical hydrometallurgical leaching operation; however, its kinetics are crucial not only for process design and control, but also for the production of powders with a desirable particle morphology. This article shows the results of an experimental work whereby industrial heavily-burned magnesia powders were hydrated in 0.01 to 0.1 mol/L magnesium acetate solutions at temperatures ranging between 333 and 363 K. Examination of the magnesium hydroxide produced and the analysis of the kinetic data suggest that the hydration of heavily-burned magnesia in magnesium acetate solutions is a dissolution-precipitation process controlled by the dissolution of magnesia particles. The activation energy was estimated to be 60 kJ/mol, while the reaction order with respect to magnesium acetate concentration was found to be about one.

Jan 1, 1999

By G. M. Carrie

Introduction The subject of basic refractories is daily becoming of increased importance in metallurgical processes, and there is a constantly growing necessity for the development of better materials. This fact, together with the realization that Canada possesses one of the best sources of such refractories in the British Empire, if not in the world, made it appear? advisable that the subject be presented to the Empire Mining and Metallurgical Congress at the 1927 meeting. Having been in close touch with developments in the Canadian product during the past five years, G. M. Carrie was requested to prepare such a paper. The Canadian producers of magnesia refractories have succeeded in developing the product to a place where it has almost entirely displaced imported materials from the Canadian market. These developments were made possible by a close study of the methods of preparation of the material, and by an exceedingly careful control of the manufacturing process so as to obtain a thorough blending of the different constituents with the resultant uniformity of composition. This point is very important to the metallurgist, as un-uniform materials are a potent cause of difficulties in most manufacturing processes and the constant trend is towards their elimination. The temperature at which the Canadian material is burned ensures high specific gravity and thorough shrinkage. The grain size of the product is so controlled that the voids are only just sufficient to allow of proper bonding, thus making possible a dense, hard bottom affording high resistance to erosion and shock. Careful proportioning of the constituent elements absolutely prevents disintegration.

Jan 1, 1927

By M. L. Maniocha

Most magnesia, MgO, whether of natural or synthetic origin, is utilized in its dead burned or periclase form as refractory linings for the production of steel. Continued research in refractory science combined with good refractory maintenance and improvements in steel making practice have resulted in decreased use of magnesia. To make up for this loss of business producers of synthetic magnesia have started to manufacture a variety of magnesium based chemicals that are utilized in many diverse industries and applications.

Jan 1, 1997

By L. R. Duncan, W. H. McCracken

Magnesium is the eighth most abundant element in the earth's crust and the third most plentiful element in seawater. It is found in more than sixty minerals and in brines and seawater as a magnesium salt. One of the more important magnesium minerals is magnesium carbonate, MgCO3, with a theoretical maximum magnesia, MgO, content of 47.6%; this carbonate form represents the world's largest source of magnesia. The next most used sources for magnesia are magnesia-rich brines and seawater, where it occurs as magnesium sulfate and magnesium chloride. Other commercially important magnesium-bearing minerals are dolomite, CaMg(CO3)2, which serves the aggregate industry as well as the chemical industry; brucite, Mg(OH)2, which is used in the production of both caustic and sintered magnesia; olivine, ([MgFe]2-SiO2), which serves the refractory and heat storage industries; talc, (H2Mg3(SiO3)4), which serves several industries as a filler and as an ingredient in cosmetics; and serpentine, (H4Mg3SiO9). All these minerals are of commercial value because of the desirable characteristics given to them by magnesia and by its placement in the crystal structure. These minerals are the starting raw materials for a wide range of products. These include the production of magnesium metal, and several grades of magnesia used for the production of both sintered magnesia for refractory manufacture and lighter fired caustic magnesia, the latter is used in fluxes, fillers, insulation, cements, decolorants, fertilizers, chemicals, in the treatment of waste water including pH control, and in the removal of sulfur compounds from exhaust stacks. Magnesite is one of several major minerals possessing a dual character, i.e., non-metallic industrial mineral because of its principal end use as a calcined/dead burned raw material in non-metallic end products and magnesium metal. A large percentage of the magnesia used to produce magnesium metal comes from seawater1 brines. The total primary metal production worldwide is about 350 ktpy. This report reviews magnesite solely as an industrial non- metallic raw material. Magnesite for most refractory purposes must have a content of sintered magnesia above 85%, with a preference for those sources that have the potential for 90 to 98% magnesia values. Dolomite, used in large tonnages because of its physical properties in the construction industry, also has a use in the chemical and the refractory industry. In its calcined form, dolomite is used as a slag addition in the making of steel, and it is used in a high-purity calcine to precipitate magnesium hydroxide from brines or seawater. The precipitated magnesium hydroxide is intermediate for the production of deadburned clinker for refractories and the production of magnesium metal. In many cases the high-purity magnesium hydroxide obtained by precipitation with calcined dolomite, or in some cases limestone, has supplanted much of the world's production of magnesia from the natural mineral magnesite. This is especially true of the United States and in major industrialized areas of Europe and Japan. The best known of the minerals directly and widely exploited for its magnesia content is magnesite (MgCO3), one of the calcite group of rhombohedra1 carbonates, which includes calcite (CaCO3), siderite (Fe2CO3), and rhodocrosite (MnCO3), among others. The members of this group enter into a wide range of substitutional solid solutions when the positive ions have similar radii. The radii of magnesium and iron ions are within 6% of each other; hence magnesite and siderite form a complete series, of which the mineral breunnerite (ferroan magnesite) is a well known end member. The radii of calcium ion is 36% larger than that of magnesium ion and only limited substitution exists at each end of the MgC03-CaCO3 series. Dolomite is not a member of the calcite group, but it occurs when calcium and magnesium ions alternate in equal number in an ordered structure among carbonate ions. The result of this relationship is that calcite and dolomite are commonly found intermixed with magnesite. They occur, commonly, as identifiable crystal entities, which can be separated to a varying degree from the magnesite by benefication techniques. Magnesite, when pure, contains 47.8% MgO and 52.2% CO,. The pure mineral is found occasionally as transparent crystals resembling calcite. Magnesite principally contains variable amounts of the carbonates, oxides, and the silicates of iron, calcium, manganese, and aluminum. Although the genesis of natural magnesite deposits can be complex, it is distinguished in nature in two distinct physical forms, namely crystalline, (with a wide range of visible crystal sizes) and cryptocrystalline, sometimes referred to as amorphous, where the crystal size is not detectable to the eye and will range from 1 to 10 pm. The two types not only differ in crystal structure but in the sizes of the deposits and in modes of formations. The crystalline form has a Mohs hardness of 3.5 to 4.0. The color range is from white to black with shades of yellow, blue, red, or gray. The color is not a significant indicator of purity but in a given deposit an experienced person can often roughly grade the magnesite by observing color and crystallinity. Macrocrystalline deposits occur in relatively few, but generally large, deposits on the order of several million tons. The ore shows a marble-like crystal structure and belongs to the sedimentary or metasomatic groups of origin. The cryptocrystalline variety of magnesite frequently occurs in many small deposits, although there are exceptions. Cryptocrystalline magnesite is typically massive with no cleavage and is sometimes descriptively called bone magnesite. The fracture is usually conchoidal, with a hardness of 3.5 to 5.0. The color is mainly white, but it can have tints of yellow, orange, or buff. Accessory silaceous minerals such as serpentine, quartz, or chalcedony are usually present. Calcium minerals are normally absent or in low concentration, this contrasting with the macrocrystalline form where calcium minerals are almost invariably present and some- times in high concentration. The specific gravity of cryptocrystalline magnesite ranges between 2.90 and 3.00, whereas the value of pure crystalline magnesite is 3.02. In actuality, the normal specific

Jan 1, 1994

By Oscar M. Wicken

The mineral magnesite (MgCO3) if pure would consist of 47.7 pct MgO and 52.3 pct CO2. It is one of the calcite group of rhombohedral carbonates which includes calcite (CaCO3), siderite (FeCO3), rhodocrosite (MnCO3), and smithsonite (ZnCO3) among others. The members of this group enter into a wide range of substitutional solid solutions, whose range is still imperfectly known.* MgCO3 and FeCO3 appear to form a complete series of which breunnerite (ferroan magnesite) is a well known variety. Because of the considerable difference in size of the Ca and Mg ions, there is only a limited range in substitution in the MgCO3-CaCO3 series. (Dolomite, not strictly a member of the calcite group, may be regarded as an ordered structure developed when Ca: Mg is approximately 1:1.) The practical consequence of these relationships is that the lime carbonates (calcite and dolomite) are commonly present in magnesite deposits chiefly as mechanical mixtures. Magnesite may be either crystalline or "amorphous" (cryptocrystalline). The crystalline form has a hardness of 3.5 to 4.0. The color may range from white to black through shades of yellow, blue, red or gray. It is rarely found pure but generally contains variable amounts of iron, lime, and silicate minerals. Color cannot be used as an index of purity except under specific local conditions in a single quarry. In a given quarry an experienced man may be able roughly to grade magnesite by intuitively assessing such features as crystallinity and color. Crystalline magnesite occurs in larger deposits, but the cryptocrystalline variety is more common. The latter is fine-grained and compact and shows no cleavage; often it is descriptively called "bone magnesite." The fracture is usually conchoidal, and hardness is 3.5 to 5.0. It is normally white, but sometimes it is light yellow to orange or buff because of included impurities. In addition to lime and iron, which may be present in small amounts, silica may be present as inclusions of serpentine, quartz, chalcedony, or other minerals. In general, commercial deposits of "amorphous" magnesite have lesser amounts of accessory minerals than does crystalline magnesite. The specific gravity of "amorphous" magnesite is 2.90 to 3.0. Pure, crystalline magnesite has a specific gravity of 3.02, but iron carbonate, commonly present, raises the specific gravity to somewhat higher values. Magnesite dissociates, when sufficiently heated, into magnesia (MgO) and carbon dioxide. Either simultaneously or upon further heating the magnesia develops a crystalline structure identical with that of the natural mineral, periclase, which occurs sparingly in nature but not normally in workable deposits. Brucite is another magnesium mineral capable of being directly reduced to magnesia by heat alone. Brucite (Mg(OH)2) has been mined for the production of various grades of magnesia. It theoretically contains 69.1 pct MgO and 30.9 pct H2O. It may be white, but is generally blue or green with a gray cast. It has a translucent appearance. The mineral is soft (hardness, 2.5), and has a specific gravity of about 2.4. Nomenclature of Products The word "magnesite" literally refers to the natural mineral, but common usage has applied it plus a prefatory word to two other

Jan 1, 1960

By Kilmar Mine

The Kilmar dolomitic magnesite deposit~ in sourhwesr Quebec lie in Grenville Province sedimentary rocks that strike north and dip steeply west. The sediments comprise quartzitic, carbonate and argillaceous members. The middle or carbonate member hosts the magnesite and, like the two other members, has been intensely mewmorphosed. Magnesite occurs as lenticular shaped zones of altered limestone and is mixed with 5 to 30% dolomite crystals. Diopside, serpentine and mica are common accessory minerals. Magnesite appears to have formed from merasomarism of all or part of the carbonate member due to intrusion of hot magnesia-rich solutions. Magnesite is mined from a 490 m vertical shaf1 and is milled and burned into clinkers, which then are shipped 10 pyroprocessing industries around the world.

Jan 1, 1984

By Leroy Palmer

ALL the domestic. production of magnesite during 1925 came from two states, California and Washington. Of a total of 120,660 tons of crude ore, 64,600 tons, or 54 per cent., were produced in California.1 Of .this quantity California produced about 99 per cent. of the caustic calcined, but only 10 per cent. of the dead-burned. The largest producer was C. S. Maltby, of San Francisco, who operated the Red Mountain mine, in Santa Clara County, and the Sampson mine, in San Benito County, under lease. These two mines have been studied by the author, and offer interesting comparisons as to mining and treatment methods and final products. GEOLOGY The general geology of the magnesite deposits of California has been described by Hess,2 Bain3 and others,4 and although a detailed discussion is not necessary here, a brief summary will assist in understanding mining conditions. California magnesite, when comparatively pure, is usually a white, fine-grained rock, with a conchoidal fracture, occurring in veins and lense-like masses in serpentine. The veins vary considerably in width, and usually occur in a series of more or less parallel veins intersected by other series or systems of veins, probably following original or secondary fissures in the enclosing serpentine. The most generally accepted theory of origin is that the magnesite was formed by the action of surface waters charged with C02 percolating downward through fissures and changing the magnesium silicates of the serpentine into magnesium carbonate.

Jan 1, 1927

By A. T. GRIFFIS, R. J. GRIFFIS

A large magnesite-talc body is locared in Delora Township, 11 km sourh-southeasr of Timmins, Onrario. The deposit occurs in part of an Archean greensrone belt dominated by volcanic and sedimenrary rocks and large bodies of ultramafic intrusions. The magnesite-talc zane is abour 1800 m long, has a maximum width of 300 m and has been drilled ro 120 m below surface. Chemical analyses of rhe main carbonate zane average 20 ro 28% soluble MgO (magnesia), 5 ro 6% rota/ iron oxide and less rhan 0.1 % CaO (lime). Mineralogically, the zane consists of approximately 54% magnesite, 28% rate, /5% quartz and 3% hematire. Perrographic srudies suggest that rhe various assemblages of magnesite, rate, quartz and serpentine were derived from a parenr serpenrinire (after dunire). An early carbonitization stage, which produced a high-magnesite, low-talc assemblage, preceded a farer decarbonitizarion stage, which formed rhe main magnesite-talc assemblage. Despite a favourably low calcium oxide content of rhe magnesite-talc rock, considerable iron in the magnesire /at rice has limited the quality of the beneficiared product: rhe besr flotation concentrate to dare yields 92 to 94% dead-burned MgO. Experimen- I L t r i i c:~:.•-4- -------- ? -_;> ,•----1---- ta/ work continues on finding a process whereby high-purity magnesia can be produced on a commercial scale.

Jan 1, 1984

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

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 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 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 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

Quay Magnesium Limited (QMG) listed on the Australian Stock Exchange in late September 2004 having raised approximately A$30 million with the object of designing, constructing, commissioning and operating a 15 000 tpa magnesium alloy production facility in Nanjing, China. Site construction commenced in February 2005, with installation of all major components completed by the end of October 2005. Hot commissioning was simultaneously commenced with the final stages of installation, leading to the first stage of continuous ingot casting by mid November 2005. Since that time, ramp-up to the name plate capacity has been undertaken. This presentation highlights some of the more significant technical and logistical hurdles that have had to be overcome in order to meet the high quality product specifications required by a range of QMG customers.

Jan 1, 2006

By John Canterford

Quay Magnesium Limited (QMG) listed on the Australian Stock Exchange in late September 2004 having raised approximately A$30 million with the object of designing, constructing, commissioning and operating a 15,000 t/a magnesium alloy production facility in Nanjing, China, Site construction commenced in February 2005 with installation of all major components completed by the end of October 2005, Hot commissioning was simultaneously commenced with the final stages of installation, leading to the first stage of continuous ingot casting by mid November 2005, Since that time ramp-up to the name plate capacity has been undertaken, This presentation highlights some of the more significant technical and logistical hurdles that have had to be overcome in order to meet the high quality product specifications required by a range of QMG customers.

Jan 1, 2006

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