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By Franz R. Dykstra, R. F. Tatnall

A ferroalloy is defined as: "An alloy of iron with some element other than carbon used as a vehicle for introducing such an element into the manufacture of steel. The element may alloy with the steel by solution or, as the carbide, -neutralize the harmful impurities, by combining with them and separating from the steel as flux or slag before solidification."a The most commonly used ferroalloys are: ferromanganese, ferrochrome, ferrosilicon, ferrovanadium, ferromolybdenum, ferronickel, ferrotungsten, ferrocolumbium, and ferrophosphorus. Concern here is with the sources and markets of the major metallic alloying elements. The discussion is further restricted to those - ferroalloy ores, the principal use of which is in the production of steel. Phosphorus, silicon, and tungsten, for example, are ferroalloys of some economic significance, but other uses dwarf their alloying applications. Thus, this discussion will deal with the ores of managanese, chromium, nickel, molybdenum, vanadium, and columbium. As shown in Table 14.1B.1 ferroalloys serve to- facilitate processing and impart to the finished steel such characteristics as tensile strength, ductility, low-temperature impact, hardenability, high-temperature strength, corrosion resistance, toughness, and abrasion resistance. In the steel-making process, ferroalloys may be added in the charge, in the molten bath near the end of the finishing period, in the ladle, or in the molds. Timing of the addition depends on the effect of the addition on the temperature of the molten metal, the formation and elimination of reaction products, and the protection of subsequent additions from oxidation. MANGANESE General Approximately 95% of the manganese ore sold is consumed by the steel industry, either as ferromanganese or as manganese metal. Manganese is the universal alloy, without which good steel cannot be made. It serves as a scavenger, removing phosphorus, sulfur and, to a degree, oxygen from the melt. As an alloying material it makes steel hard, tough, and resistant to wear. Approximately 6 kg of manganese is required for every ton of common steel produced by United States steelmaking practice. The remaining 5 % of the manganese ore consumed consists of special or so-called "chemical" ores, including high-grade pyrolusite ores, electrochemically reactive "battery ores," and a number of special varieties, as well as those otherwise regarded as "metallurgical ores."

Jan 1, 1976

By M. D. Ballain, V. C. Storhok, B. Pesic, J. C. Sever

Northwest Alloys, a wholly owned subsidiary of Alcoa, produces magnesium from dolomite by reduction with ferrosilicon and aluminum. This process produces alkaline by-products in quantities that allow their consideration for use as commercial by-products. Two such products are dicalcium silicate slag, Di-Cal, and magnesium oxide condensate, MgO. The alkaline properties of these materials offer acid neutralizing capability comparable to the traditionally used lime, therefore, warranting a study for their use in applications where the neutralization of acidic waters or process solutions is required, such as treatment of mine waters. In this ongoing study, three mine waters (Bunker HillMine, Berkeley Pit, and Blackbird Mine) were selected for treatment with Di-Cal and MgO. Lime was used as the background control. The solid precipitates were subsequently contacted with pure water at four different pH conditions for stability testing of prepared metal precipitates (expanded TCLP). It was found that neutralization with Di-Cal results in precipitates which are of equivalent to superior stability than those from lime treatment.

Jan 1, 1999

By Grafton M. Thrasher

Discussion of the paper of GRAFTON M. THRASHER, presented at the New York meeting, February, 1916, and printed in Bulletin No. 106, October, 1915, pp. 2129 to 2138. RICHARD MOLDENKE, Watchung, N. J.-Mr. Thrasher is to be commended for developing a very interesting comparison between high- and low-carbon and silicon malleable cast irons for an equal degree of chill. His deductions are unquestionably correct, though the application to daily practice is open to serious criticism, from the standpoint of the man who receives the castings, as will be shown later on. Running over some of the points which affect the tests in question: Mr. Thrasher admits that the temperature of pouring has a serious influence on the degree of chill shown in the test plugs he made. This is a well-known fact, and I would like to add that another serious trouble comes from oxidized iron when the heats have been unduly prolonged. Such metal always shows more chilling action for a given silicon and carbon content than normally melted iron. Indeed, the test piece quoted giving the extreme of the chill line (1.07 per cent. Si and 2.47 per cent. total carbon) was such a poor heat, a ferro-silicon addition never "doctoring" up the metal sufficiently to show normal good strength. In spite of these irregularities, which would simply change the curve slightly, I take it that Mr. Thrasher's results can be accepted as reliable enough to establish the relationship of silicon and total carbon as shown. When, however, the claim is made that silicon and carbon can be substituted for each other in mixture-making (a claim which may be perfectly correct metallurgically), a very important factor is forgotten, causing the purchaser of the castings much annoyance. This is the contraction (erroneously called shrinkage) of the castings. They will no longer be true to pattern. The lower the total carbon is allowed to drop, the greater the contraction, and increasing the silicon correspondingly will not correct this trouble. No wonder that recently, in revising the Standard Specifications for Malleable Castings it was necessary to increase the variation of castings from requirements considerably over what was formerly found sufficient. The habit of running up the proportion of silicon and escaping danger from grayness of the metal by copious steel additions was evidently too tempting to manufacturers, as their molding losses were thus kept down and a very soft malleable iron resulted. The customer, however, got serious variations in his work, which was not the case when the total carbon was kept between 3.25 and 2.75, and the silicon held as low as possible without undue cracking of the hard castings.

Jan 5, 1916

By James Norman, O. C. Ralston, John Dasher

Most mineral products are used in the finely divided state, but some are sold in larger sizes. Coal, gravel, metallurgical fluorspar, phosphate rock, hematite, chro-mite, and other products are sold in sizes coarser than can be treated by many mineral-dressing methods. Gravity separation of coarser sizes by log washing and jigging is probably as ancient as any process now in use. The performance of jigs on a feed with sufficient difference in density of the minerals is excellent, but many families of minerals are too similar in density to be separated effectively by this method. The use of heavy suspensions of fine solids to separate coarse coal from bone and slate has been in use for some years. This separation by sink-and-float was limited until recently to light minerals. Development of galena and ferrosilicon as suspension media, by Minerals Beneficia-tion, Inc., at Mascot, Tenn., Pitcher, Okla., and Crosby, Minn., under patents granted during and since 1938, has permitted excellent results to be obtained on minerals of very similar densities up to 3.3. This process has been put In the hands of American Cyanamid Co. for exploitation, and further research now in progress may increase the density of suspension obtainable so that separations at a density of 4.0 may be practicable before this is published. The Huntington-Heberlein dense-medium process, developed in England, is also being commercialized in the United States by Sink and Float Corporation. Du Pont has developed a sink-and-float separation using halogenated hydrocarbons as parting liquids; at this writing, the method is used commercially only on coal but has been successful in the pilot plant on many other minerals using tetrabrom-ethane at densities up to 2.95. While these processes were being developed to extend the range of separation by difference in density to the coarser sizes, the Bureau of Mines was engaged in developing a process that will extend the range of separation by difference in wettability up to 2-in. size. War work has pushed aside its further development indefinitely. The results are published here with the hope that some use may be suggested that will justify post-war development, and so that readers that may be able to make immediate use of the scheme may have the information. Earlier Work It has been known since the time of Herodotus (B.C. 484(?)-425) that water-repellent particles will adhere to sticky surfaces. That early historian reports the recovery of gold from the mud of a lake

Jan 1, 1943

By James Norman, O. C. Ralston, John Dasher

MOST mineral products are used in the finely divided state, but some are sold in larger sizes. Coal, gravel, metallurgical fluorspar, phosphate rock, hematite, chromite, and other products are sold in sizes coarser than can be treated by many mineral-dressing methods. Gravity separation of coarser sizes by log washing and jigging is probably as ancient as any process now in use. The performance of jigs on a feed with sufficient difference in density of the minerals is excellent, but many families of minerals are too similar in density to be separated effectively by this method. The use of heavy suspensions of fine solids to separate coarse coal from bone and slate has been in use for some years. This separation by sink-and-float was limited until recently to light minerals. Development of galena and ferrosilicon as suspension media, by Minerals Beneficiation, Inc., at Mascot, Tenn., Pitcher, Okla., and Crosby, Minn., under patents granted during and since 1938, has permitted excellent results to be obtained on minerals of very similar densities up to 3.3. This process has been put in the hands of American Cyanamid Co. for exploitation, and further research now in progress may increase the density of suspension obtainable so that separations at a density of 4.0 may be practicable before this is published. The Huntington-Heberlein dense-medium process, developed in England, is also being commercialized in the United States by Sink and Float Corporation. Du Pont has developed a sink-and-float separation using halogenated hydrocarbons as parting liquids; at this writing, the method is used commercially only on coal but has been successful in the pilot plant on many other minerals using tetrabromethane at densities up to 2.95. While these processes were being developed to extend the range of separation by difference in density to the coarser sizes, the Bureau of Mines was engaged in developing a process that will extend the range of separation by difference in wettability up to 2-in. size. War work has pushed aside its further development indefinitely. The results are published here with the hope that some use may be suggested that will justify post-war development, and so that readers that may be able to make immediate use of the scheme may have the information. EARLIER WORK It has been known since the time of Herodotus (B.C. 484(?)-425) that water-repellent particles will adhere to sticky surfaces. That early historian reports the

Jan 1, 1942

By Carl F. Floe, Hung Liang, Michael B. Bever

DATA on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Sims1 have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan,2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett6 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid - iron were reported in 1910-1911 by Sieverts and Krumbhaar8 and by Sieverts.9 They found that 100 grams of iron absorbs 28 C.C. of hydrogen at 1550°C. and one atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 c.c. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon

Jan 1, 1946

By James Norman, O. C. Ralston, John Dasher

Most mineral products are used in the finely divided state, but some are sold in larger sizes. Coal, gravel, metallurgical fluorspar, phosphate rock, hematite, chro-mite, and other products are sold in sizes coarser than can be treated by many mineral-dressing methods. Gravity separation of coarser sizes by log washing and jigging is probably as ancient as any process now in use. The performance of jigs on a feed with sufficient difference in density of the minerals is excellent, but many families of minerals are too similar in density to be separated effectively by this method. The use of heavy suspensions of fine solids to separate coarse coal from bone and slate has been in use for some years. This separation by sink-and-float was limited until recently to light minerals. Development of galena and ferrosilicon as suspension media, by Minerals Beneficia-tion, Inc., at Mascot, Tenn., Pitcher, Okla., and Crosby, Minn., under patents granted during and since 1938, has permitted excellent results to be obtained on minerals of very similar densities up to 3.3. This process has been put In the hands of American Cyanamid Co. for exploitation, and further research now in progress may increase the density of suspension obtainable so that separations at a density of 4.0 may be practicable before this is published. The Huntington-Heberlein dense-medium process, developed in England, is also being commercialized in the United States by Sink and Float Corporation. Du Pont has developed a sink-and-float separation using halogenated hydrocarbons as parting liquids; at this writing, the method is used commercially only on coal but has been successful in the pilot plant on many other minerals using tetrabrom-ethane at densities up to 2.95. While these processes were being developed to extend the range of separation by difference in density to the coarser sizes, the Bureau of Mines was engaged in developing a process that will extend the range of separation by difference in wettability up to 2-in. size. War work has pushed aside its further development indefinitely. The results are published here with the hope that some use may be suggested that will justify post-war development, and so that readers that may be able to make immediate use of the scheme may have the information. Earlier Work It has been known since the time of Herodotus (B.C. 484(?)-425) that water-repellent particles will adhere to sticky surfaces. That early historian reports the recovery of gold from the mud of a lake

Jan 1, 1943

By R. B. G. Yeo

The effects of alloy additions on the M, and A, temperatures of an Fe-22.5 pct Ni alloy have been determined. Increasing amounts of titanium, colum-bium, vanadium, and silicon raise and then lower M,while raising A, cmtinuously. Cobalt raises both M, and A,. Aluminum has little effect on Ms but raises A,. Chromium md nickel lower M, and A,. It is proposed that elements raise M, in accordance with their effect on the Ae3 temperature of iron until the lattice becomes stiffened against the shear transformation so that M, is then lowered. An anomaly, first pointed out by Zener,1 arises in steels when the addition of elements, such as molybdenum and tungsten, which raise the Ae3 temperature, also lower the M, temperature.2'3 During the development of a series of martensitic precipitation-hardening (maraging) steels, the effect of several elements on the transformation of austenite to martensite was studied. The results show that under suitable conditions several elements which raise Ae3 also raise the M, and A, temperatures. PREPARATION OF MATERIALS STUDIED A series of alloys was made in which cobalt, titanium, columbium, vanadium, silicon, aluminum, molybdenum, chromium, and nickel were added to an iron base containing 22.5 pct Ni. The compositions of the alloys prepared are given in Table I. The residual manganese contents of the heats were in the range of 0.030 to 0.35 pct, silicon 0.05 to 0.1 pct, carbon 0.0008 to 0.009 pct, and nitrogen from 0 to 0.004 uct. The allois were made as 50-lb induction heats starting with electro-iron and electro-nickel, melted in air to oxidize impurities. Additions of silico-manganese and ferro-silicon were made after which the power was turned off to allow the products of deoxidation to rise and be skimmed from the surface of the melt. The furnace chamber was pumped down to a pressure of 5 p and the charge was heated to 2900°F for the addition of other alloying elements. The heats were poured into five 10-lb ingots, making successive alloy additions to each. The ingots were soaked for 2 hr at 2300°F and hot-worked to 3/4-in.-diam bars. This stock was heated to 1500°F for 1

Jan 1, 1963

By A. W. Schlechten, W. J. Kroll

As this paper is written, the only method for the commercial production of lithium metal is by the fusion electrolysis of LiCl-KCl mixtures, as first proposed by Guntz.2 The details of the industrial process have not been made public but Osborg8 stated that an efficiency of more than go pct is obtained with a lithium metal recovery above 95 pct and that the metal is 99.5 pct pure. Pletenev9 gave a power consumption of 66 kw-hr per kilogram of lithium metal produced with a salt consumption of 9 kg of LiCl and 0.4 kg of KCI. Pletenev's figures indicate a somewhat lower recovery than that given by Osborg. In a recent report on German lithium plants, Motock7 gives figures that are also less favorable than those reported by Osborg. At the German plants the lithium recovery in electrolysis was only 83.4 pct, with a power consumption of too kw-hr per kilogram of lithium. The metal averaged only 97 pct pure, with sodium and potassium as the chief impurities. The presence of SO2, SO3, Si02, Ba, Ca, and appreciable amounts of Na and Fe2O3 were especially disturbing in the electrolysis, and it was necessary to run the cell for some time to eliminate most of these impurities and condition the bath. It may be noted here that most of these impurities do not interfere with a thermal reduction process. These facts show that the present method of producing lithium is fairly efficient and would suggest that other methods could not compete. However, fusion electrolysis has certain drawbacks, such as the necessity of supplying costly, low-voltage direct current and of collecting and processing the anodic chlorine if it is not to be wasted. An even greater disadvantage is that lithium chloride must be used for an electrolyte. It is one of the most expensive salts of lithium, since it cannot be produced in anhydrous form by precipitation from aqueous solution, as is done with LiF or Li2CO3. The reduction of lithium by a vacuum process similar to the ferrosilicon method for the production of magnesium would have certain advantages. Small units, such as Pidgeon retorts, would give flexibility of production to meet demand, and a small plant would require moderate capital outlay. There is a possibility of using idle Government-owned magnesium plants for such purposes. The raw materials needed for vacuum thermal reduction would not have to be extremely pure, especially with respect to the iron and calcium content. This paper describes a series of experiments to determine the effectiveness of various agents for the reduction of lithium compounds. The investigation is part of a program of vacuum metallurgy con-

Jan 1, 1947

By F. W. Glaser

Iron-silicon alloys have had a great influence, in many ways, in modern industry. Silicon steels have been used almost exclusively for the construction of electrical machinery, but have also become an important material for structures which benefit by the high tensile and yield strengths of this material. In elaborating on the early history of work done on iron-silicon alloys, Greiner, Marsh and Stoughton1 went back as far as 1808, and pointed to Berzelius as the first producer of ferrosilicon. During the last twenty years some very important contributions in the form of studies of the iron-silicon system, as well as of the physical properties of these alloys, have been published. In consideration of the brit-tleness and poor machinability of alloys containing more than 5-6 pct Si, commercial interests have stimulated the research done on iron-silicon alloys, but mainly in the range of 0 to 6 pct Si. Yensen2 has shown the influence of im- purities, such as carbon, sulphur and phosphorus on the magnetic properties of 2, 4, and 6 pct Si alloys. Corson3 extended his investigation of physical properties to approximately 32 pct Si, and attributed the brittleness of the high-silicon material to the particular constitutional features of the alloys. Though mentioned earlier in the literature, the effect of nitrogen on crystal growth and magnetic permeability of iron-silicon alloys has been demonstrated recently by Morrill4 and Rostoker,5 respectively. In all the above quoted investigations, except that of Rostoker,5 sand or chill casting processes were employed for the preparation of samples. A major advantage of the powder metallurgy process is that it does away with time-consuming machining in many applications. The powder metal industry is always interested in pro- ducing a finished product employing a material which has presented considerably greater difficulties in manufacture by other methods. Steinit26 described preparation and testing of various Fe-Si alloys which were produced by the powder metallurgy process for the manufacture of armatures for small electric motors or generators. While Steinitz investigated alloys up to 6 pct Si, Rostoker5 went as high as 9 pct Si. The author7 previously discussed the diffusion of iron-silicon compacts containing 6 and 10 pct silicon. It is the object of this paper to study the progress of diffusion occurring in iron-silicon alloys by electrical resistivity measurements. All samples were prepared by pressing and sintering of compacts. Iron, silicon, and Fe-Si powders of various mesh size and compositions were employed to obtain test samples. It was assumed that complete diffusion had been obtained when the electrical resistivity reached a constant value characteristic for that particular alloy. To this end, electrical resistance measurements were used to follow the progress of alloying under various conditions.

Jan 1, 1950

By Bever M. B., Floe Carl F., Hung Liang

Data on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Simsl have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett5 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid iron were reported in 1910-191 1 sieverts and Krumbhaar8 and by sieverts.9 They found that 100 grams of iron absorbs 28 c.c. of hydrogen at 1550°C and One atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 C.C. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon are not available. Martin1' investigated

Jan 1, 1947

By R. F. Evans, J. M. Avert

Much has been written of the glamour of magnesium from sea water, the Aladdin-like creation of a huge magnesium plant in the Nevada desert using cheap hydroelectric power from Boulder Dam; the marvels of the Hansgirg process for the electrothermal reduction of magnesium oxide by carbon, and the ferrosilicon process for producing magnesium from dolomite. This is the story of the production of magnesium by the electrolytic process, using steam-electric power supplied by a public utility, in a plant at Painesville, Ohio, 30 miles east of Cleveland on the shore of Lake Erie. The story is not without interest, since it involves several unique developments that provide the answer to a question frequently asked: How is it possible to produce magnesium metal economically at such a location as Painesville, Ohio? Basically, the answer lies in making use of facilities already in existence for the production of soda ash, which makes it possible to manufacture magnesium chloride, the principal raw material, cheaply enough to offset the high cost of electric power. To this is coupled the successful conversion of by-product chlorine into a product required for the war program. The source of magnesium for this opera- tion is the enormous surface deposit of high-grade dolomite in the region south of Toledo, within reasonable freight haul of Painesville. This same geological stratum underlies the Painesville plant, but unfortunately at a depth of about 3000 ft.— apparently too great a depth to permit underground mining to compete with the delivered cost of rock from surface quarries in other areas. The cost of dolomite obviously is an important factor, since the rock contains only some 12 per cent magnesium (20 per cent MgO) so that one dollar on the cost of stone means more than $8 in terms of its magnesium content, and more than that in terms of recoverable magnesium metal. Production of Magnesia from Dolomite In the summer of 1941, the Diamond Alkali Co. was well along with construction of a plant intended for the commercial production of refractory and other grades of magnesia from dolomite. The process to be used was designed to make maximum economic advantage of existing plant and operations by tying the production of magnesia in with the manufacture of soda ash in such a way as to make use of the lime [CaO)., value of calcined dolomite. The process finally adopted after a lengthy research and development program has much in common with the old Clerc-Nihoul process, but includes certain innovations found to be necessary or advantageous. Essentially, the process is based upon the following series of reactions:

Jan 1, 1949

By Bever M. B., Floe Carl F., Hung Liang

Data on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Simsl have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett5 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid iron were reported in 1910-191 1 sieverts and Krumbhaar8 and by sieverts.9 They found that 100 grams of iron absorbs 28 c.c. of hydrogen at 1550°C and One atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 C.C. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon are not available. Martin1' investigated

Jan 1, 1947

By Emil Gathmann

(San Francisco Meeting, September, 1915) THROUGH wide experience at numerous mills in the United States I have found that there is a decided difference of opinion among the producers of steel as to what constitutes commercially sound steel. Some metallurgists insist upon having, for certain grades of steel, a so-called "open steel," -i.e., one which contains numerous blowholes of varying sizes, and consequently but little volume of true pipe, although a central intermittent shrinkage cavity often extends well down into the ingot: Such blowholes and pipe are expected to weld up during rolling or forging, because their surfaces are not oxidized. Even if this be admitted, included slag particles and a high degree of segregation are bound to be present in the product of such ingots. Blowholes are the result of an oxidized heat, and all heats, unless made or finished in the electric furnace, are oxidized more or less. Subsequent deoxidation, or rather degasification, either in the ladle or in the mold, or in both, is necessary to reduce or prevent blowholes. As is well known, a greater yield of billets or sheets is secured from the ingot by allowing the formation of blowholes, but this is undoubtedly obtained at the expense of the quality of the product. Decided segregation of carbon, phosphorus, and sulphur, as well as small included slag particles, undoubtedly exists throughout the greater portion of all so-called open steel, and cannot be removed by cropping. The first requisite for sound, homogeneous steel ingots and blooms is therefore, in my opinion, so to treat the steel in the furnace, ladle, and mold that "piping" steel is produced. The line of demarcation between harmful and so-called "harmless" blowholes is practically impossible to define. Is it not, therefore, the better and safer practice to use means for the elimination of blowholes and correspondingly reduce the segregation and allow the formation of a well-defined shrinkage cavity or pipe .at the upper end of the ingot? With the relatively cheap deoxidizers available at the present time, e.g., ferro-silicon, aluminum and titanium,

Jan 8, 1915

By R. V. Riley

IN the metallographic examination of the alloys of iron and silicon, several investigators1-' have reported on the occurrence of an unusual type of etched structure, particularly in the alloys of higher silicon content. This, the so-called "barley shell" structure, has been observed with iron-silicon alloys over a wide range of silicon content, and under certain circumstances it can be seen upon the micro-sections of pure iron. The barley shell structure may be demonstrated most easily with iron-silicon alloys in the range 8 to 20 pct Si after etching in a hydrofluoric acid base etchant. Two etchants which produce the structure are: Corson's reagent, which is 2 parts hydrofluoric acid, 1 part nitric acid, and 2 parts glycerol; and picric acid reagent, which is 1 part hydrofluoric acid and 1 part saturated solution of picric acid in alcohol. Both when freshly prepared and used for etching commercial silicon-iron alloys containing 14 to 16 pct Si, invariably produce the barley shell structure shown in Fig. la. It is now well known that the barley shell structure is a pseudomorph and the true structure of an alloy of this composition consists of a single phase of silico-ferrite together with graphite as shown in Fig. lb. Lower silicon alloys and even pure electrolytic iron may also be etched in the above reagents to give the barley shell provided the etchant has been either: 1—Stored in contact with glass or silica, or 2—used previously for etching an iron containing silicon. Pure iron etched in perfectly pure hydrofluoric acid base etchants free from silicon contamination gives a normal structure free from the barley shells. Therefore, although the hydrofluoric acid in the reagent primarily is responsible for the barley shells, silicon, or its compounds, also must be present, either in the etching reagent or in the specimen. It was of considerable interest to the author to read the paper by Wachtell,? in which the barley shell etch was deliberately used for the identification of the boundaries of high and low silicon areas in diffusion experiments made upon laminate bars of compacted and sintered pure iron and ferrosili-con powders. This method of utilizing the barley shell etch is novel and in the hands of the investigator gave a useful differentiation between the high and low silicon areas in those specimens. For the reasons already given, however, the technique is not to be regarded as of universal application. Misleading results might be obtained, for example, if two or more specimens were etched in the same etchant. Fresh pure reagents only must be used each time. Provided this is done and the investigators are well aware of the limitations of the method, then the barley shell pseudomorph can be made of limited use in distinguishing between higher and lower silicon areas in a microspecimen of a ferrous material. The greatest of care must be exercised in the interpretation of the results which may be regarded as qualitative only and may, in fact, not be specific to silicon alloys.

Jan 1, 1952

By H. Conrad Meyer

The wizardry of nucleonics has added new and greater dimensions to the almost inseparable "twins"-zirconium and hafnium. So close is their relationship that neither element is found free of the other in any presently known mineral. Although zirconium in the form of its oxide was discovered in 1789 by Klaproth, the metal in an impure, nonductile form was not isolated until 1824 by Berzelius. About 100 years later -1925-van Arkel and deBoer developed and patented a technique for the deposition in vacuo of crystalline, coherent, highly ductile metal of extreme purity on an electrically heated filament through the dissociation of gaseous zirconium tetraiodide. Within the past five years both zirconium and hafnium have been dramatized by the press and in popular science magazines. This has led to the false assumption that practically all of the world consumption of zirconium ores is used in the production of the metals. Recent statistics on the subject show that not over 15 pct of the zirconium ore consumed in 1958 went to ferrosilicon zirconium and zirconium metal. The rest was consumed in refractories, foundry sand and facings and ceramics. The importance of zirconium as a component in compact, relatively lightweight nuclear energy units, such as those now used in the submarine Nautilus,6 is well established. A rival of zirconium metal as a casing for atomic fuels is a newly developed ceramic body. It is claimed to be cheaper than zirconium-to withstand higher temperatures-and to be more resistant to corrosion. Whether such ceramic casings have the required low thermal neutron absorption cross section, high strength and easy formability of zirconium is yet to be demonstrated. Hafnium, because of its low order of abundance and its close chemical relationship to zirconium, was not definitely recognized as a new element until around 1923, despite prior claims. A study of the X-ray spectra of zirconium led to its identification. The circumstances leading to the discovery of hafnium were much less fortuitous than those surrounding zirconium. The more precise tools of arc and X-ray spectrometry lent themselves admirably to the search for elements to fill certain gaps in the periodic table. [ ] Pure, ductile hafnium-a metal similar in appearance to stainless steel-has a specific gravity of 13.3 (zirconium 6.52) and a melting point of 2,200°C. In other respects it closely resembles zirconium except in one important respect which gives it a preeminent position in nuclear energy development, namely, a high thermal-neutron absorption cross section. This explains the necessity of hafnium-free zirconium in atomic piles. The ability of hafnium to capture thermal neutrons makes it an excellent "moderator" of "governor" when used as control rods in nuclear reactors (Table 1).

Jan 1, 1960

By Wilber Stout

In Ohio, the annual output of coke made from native coals has averaged not more than 70,000 tons, or about enough to run a 200-ton blast furnace. Raw coal locally mined from the Sharon, or No. 1, bed was used for iron smelting in Mahoning furnace at Lowellville, Mahoning Co., as early as 1846. This practice was continued in the Youngstown district until the coal became scarce and the Connellsville coke more popular. At present, the Sharon bed contributes a part of the fuel for the production of ferrosilicon iron at Jackson, Jackson CO. About one-third native coal and two-thirds soft coal are used. In this state, coke, on a commercial basis, was first made in Jefferson County probably about 1861 or 1862. The coals used were the Steuben-ville Shaft, or Lower Freeport, and the Strip Vein or Middle Kittanning. The practice, however, was discontinued before 1880 because of the competition of superior foreign cokes. Beehive ovens, later built at Leetonia, Columbiana Co., were operated for only a few years; the coal used at this place is the Lower Kittanning or No. 5. In a desultory way, slack from the Pittsburgh coal has been coked at a few places in eastern Ohio, and attempts, either for experimental or for commercial purposes, have been made in other parts of the state. Small quantities of coke were made from the Upper Freeport coal at Salineville, Columbiana Co., and near Nelsonville, Hocking Co.; the results were poor. Tests were made of the Middle Kittanning coal near Zanesville, Muskingum Co., at Moxahala Furnace, Perry Co., and at Washington Furnace, Lawrence Co.; the cokes were all high in sulfur and ash. Attempts were made to coke the Clarion coal at Vinton Furnace, Vinton Co.; a small battery of molding ovens and a pile of high-sulfur coke yet remain to tell the story. The Pittsburgh coal was coked on a commercial scale at Utley and at Lathrop, Athens Co., but the operations were not successful and were soon abandoned. These failures and indifferent successes are not to be attributed to a lack of demand for a first-class coke, as Ohio has held a commanding place for many years in iron smelting; nor to a deficiency of coals, as the state has a vast reserve of such material. They are to be ascribed to the inferior quality of the native products offered to the trade. The cokes

Jan 1, 1920

By Merete Tangstad, Eli Ringdalen

"In Norway ferrosilicon/silicon and ferromanganese production are strong with world markets of 4 % / 9 % and 4 %, respectively. Research and development in the academia mirrors the national interest; hence, there has been extensive academic research in these areas. There are some vital drivers and premises for a successful cooperation between the academia and industry with the main driver being a win-win situation for both. For industry,the potential advantages include cost-, competence- or environmental- benefits; for academia, the important drivers are building of competence and equipment, educating more students at higher levels, and increased possibilities to publish. In Norway, the benefits of cooperation between industry and academia are basic knowledge regarding thermodynamic and kinetic data, as well as reaction mechanisms within core processes. In recent years, such research interests have focused on the depletion of raw materials as well as environmental issues.IntroductionIn 1989, the Norwegian Ferroalloy Producers Research Association (FFF) was funded on the belief that a common research association would benefit the industry by making it easier to perform basic research as well as paving the ground for better recruitment to the industry. The funding partners in Norway were the FeSi/Si and FeMn producers. Today, the producers are Elkem, Finnfjord, Fesil, Wacker, Eramet and Vale. The main research partners working with FFF are SINTEF (Materials and Chemistry) and the Department of Material Science and Engineering at the Norwegian University of Science and Technology (NTNU). With more than 1700 employees, SINTEF is the largest independent research organization in Norway and NTNU is the largest technical university. Together, the two organizations provide an exceptionally strong materials technology research environment, and especially so for pyrometallurgical research."

Jan 1, 2012

By H. E. Dunn, C. M. Cosman, J. H. Brennan

Up to the beginning of World War I, the American ferro-alloy industry was in its infancy and largely dependent on Europe. During that War, capacity was over expanded. Later recovery and commercial and scientific development have resulted in an industry which in 1957 produced 1.8 million tons of ferro-alloys. THE ferro-alloy industry is today an important element of the industrial structure of the United States. Its output is valued at almost half a billion dollars annually and its products are basic not only to National defense but also to the peacetime standard of living. This has not always been so. The ferro-alloy industry from late in the last century has grown from small beginnings, nurtured by the demand for stronger, tougher materials; by the search for steels capable of absorbing severe impact loads and resisting corrosive media and high temperatures; and also by the need for electrical and electronic specialties. Conversely, the ferro-alloy industry has grown because it developed improved steels and alloys by extensive research, and because it was able to show to steel makers the advantages accruing from the more extensive and the more economical use of alloying elements. The industry has grown in scope from producing a few grades of ferro-alloys of the more common metals-manganese, chromium, vanadium, silicon, titanium, tungsten, and molybdenum-until there are today some 150 compositions of ferro-alloys available to the steel maker, including such elements as columbium, zirconium, and boron. In 1912 the industry produced 360,000 tons of alloys valued at about $12,000,000, while 1957 production figures show an output of 1.8 million tons worth $440,000,000. In the United States, the history of an industry is largely the history of the companies making up this industry; hence, this paper will briefly trace the development of the most important ferro-alloy-producing companies. Quite varied have been the reasons that caused the different companies to move into the ferro-alloy field; the Willson Aluminum Co., seeking methods of producing aluminum, succeeded with the production of calcium carbide, and their developing electric furnace skills led them to the production of ferro-silicon and ferrochromium alloys. Willson was the predecessor of the Electro Metallurgical Co. of Union Carbide. Two Pittsburgh undertakers, interested in vanadium as an alloying agent for steel, set about to find a mine and, ranging as far as Peru, fathered American Vanadium Co., the predecessor of Vanadium Corp. of America Experiments of the

Jan 1, 1961

By R. F. Evans, J. M. Avery

MUCH has been written of the glamour of magnesium from sea water, the Aladdin-like creation of a huge magnesium plant in the Nevada desert using cheap hydroelectric power from Boulder Dam; the marvels of the Hansgirg process for the electrothermal reduction of magnesium oxide by carbon, and the ferrosilicon process for producing magnesium from dolomite. This is the story of the production of -magnesium by the electrolytic process, using steam-electric power supplied by a public utility, in a plant at Painesville, Ohio, 30 miles east of Cleveland on the shore 'of Lake Erie. The story is not without interest, since it involves several unique developments that provide the answer to a question frequently asked: How is it possible to produce magnesium metal economically at such a location as Painesville, Ohio? Basically, the answer lies in making use of facilities already in existence for the production of soda ash, which makes it possible to manufacture magnesium chloride, the principal raw material, cheaply enough to offset the high cost of electric power. To this is coupled the successful conversion of by-product chlorine into a product required for the war program. The source of magnesium for this operation is the enormous surface deposit of high-grade dolomite in the region south of Toledo, within reasonable freight haul of Painesville. This same geological stratum underlies the Painesville plant, but unfortunately at a depth of about 3000 ft. apparently too great a depth to permit underground mining to compete with the delivered cost of rock from surface quarries in other areas. The cost of dolomite obviously is an important factor, since the rock contains only some 12 per cent magnesium (20 per cent MgO) so that one dollar on the cost of stone means more than $8 in terms of its magnesium content, and more than that in terms of recoverable magnesium metal. PRODUCTION OF MAGNESIA FROM DOLOMITE In the summer of 1941, the Diamond Alkali Co. was well along with construction of a plant intended for the commercial production of refractory and other grades of magnesia from dolomite. The process to be used was designed to make maximum economic advantage of existing plant and operations by tying the production of magnesia in with the manufacture of soda ash in such a way as to make use of the lime (CaO) value of calcined dolomite. The process finally adopted after a lengthy research and development program has much in common with the old Clerc-Nihoul process, but includes certain innovations found to be necessary or

Jan 1, 1945