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By R. S. Dean

THE commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in MINING AND METALLURGY for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for "the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. PRACTICE AT BOULDER CITY The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: I. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By Max Y. Seaton

THE scope of this paper will be limited to finished materials that contain a large preponderance (around 80 per cent or more) of magnesium oxide. The large and commercially important production of refractory dolomite and modified dolomites is not discussed here, and the production of magnesium basic carbonate for use as a heat insulator is barely mentioned. The discussion is confined mainly to magnesias produced in comparatively great quantity by direct processing of naturally occurring raw materials and hence excludes secondary or highly purified products such as pharmaceutical products or U.S.P. light and heavy calcined magnesias of commerce. NOMENCLATURE The nomenclature of the magnesia products that will be discussed is somewhat confusing, in that it is customary in the trade to designate as "calcined magnesite" the materials that result from the calcining of magnesite to temperatures that remove the contained carbon dioxide. The finished product, therefore, is not magnesite at all but simply a more or less pure magnesium oxide or magnesia. Furthermore, partly for statistical and partly for commercial reasons, it has been customary, during recent years, to classify as "calcined magnesite" products that result from the heat-treatment of magnesium hydroxide precipitated from magnesium-containing brines; products that, obviously, have no relationship whatever to magnesite. In the listing of magnesia-containing materials, tonnages of which are regularly reported by the Bureau of Mines, reports ordinarily are made under two headings: "caustic calcined" magnesite, in which all of the varieties of products treated at relatively low temperatures are lumped; and "dead-burned" magnesite, in which are included both high-purity and low-purity, and particularly both high-iron and low-iron, materials that have been so heat-treated that the magnesium oxide occurs predominantly as crystalline periclase-materials used almost entirely for refractory purposes. In 1940 the apparent domestic consumption of "caustic calcined" magnesite was approximately 17,000 tons, about 95 per cent of which was produced in this country. The apparent consumption of "dead-burned" magnesite was approximately 172,000 tons, some 82 per cent of which was domestically produced. In both total quantity and percentage of material produced within the United States, these figures are record highs for many years past. UTILIZATION As indicated by these figures, the major tonnage outlet for magnesia is the refractories industry, in which magnesia is employed principally in three ways: (I) as dead-burned grain magnesite for the construction and maintenance of the hearths or bottoms of basic open-hearth furnaces; (2) in the form of refractory magnesite bricks and shapes; and (3) as a chemical

Jan 1, 1942

By Gordon G. Bentle, W. P. Fishel

GREINER, Marsh, and Stoughton1 have reviewed the literature in a monograph on the iron-silicon system. The lack of agreement among the various studies may be due to the difference in the purity of materials in some cases. The results of the X-ray method indicate only a general rather than a specific limit of the y loop. The iron-titanium system was investigated by Roe and Fishel,' whose results are used in determining the iron-silicon-titanium y loop. The literature indicates that no study has been made thus far of the iron-silicon-titanium system in the y loop region. Experimental Procedure The alloys were made from Armco iron, 99.86 pct Si, and 98.5 pct Ti. The titanium contains 1.07 pct Fe. The Armco iron contains 0.01 pct C, 0.005 pct Si, 0.02 pct Mn, 0.006 pct P, 0.01 pct S, and 0.04 pct Cu. A dilatation sample of Armco iron was prepared in the same manner as were the other samples. Several dilatation runs indicated that Ac3 begins at 905°C and ends at 910°C, which compares favorably with the study of Wells, Ackley, and Mehl' employing specially purified iron. All alloys were melted in an induction furnace in Alundum crucibles and were top poured into baked core sand molds. The ingots weighed about 600 g as cast. Dilatation samples of 4 in. by % in. diam were taken from the bottom end of the ingot, from which turnings for analysis were taken. Turnings from each end of two of the samples indicated that the alloys possessed uniform silicon content. A hole was drilled halfway through each end of a 4 in, dilatation sample. A chromel-alumel thermocouple was inserted in each hole and the surrounding metal peened in to hold the thermocouple in place. Fig. 1 represents the dilatation apparatus. The heating unit is an Alundum tube wound with resistance wire; the dilatation tube is a McDanel combustion tube; the push rod is zircon; the dial gage is graduated in 0.0001 in. and was vibrated to prevent sticking. A blank run over the temperature range of interest gave no significant dilatation. The thermocouples were attached to a multiple recording micromax which indicated the temperature at each end of the sample at 35 sec intervals. A Lindberg control unit governed the rate of heating of the furnace, and lowering or raising the

Jan 1, 1957

By Albert Sauveur

Some writers believe that when austenite transforms completely into pearlite on slow cooling through the thermal critical range, such transformation does not imply the formation of any of the so-called transition constituents: martensite, troostite and sorbite. Might it not be claimed with as much justification that when water freezes it does so suddenly, solid ice being obtained without passing through the intermediate stages of ice and water? Obviously, regardless of the speed of solidification, this would be erroneous. Before reaching the completed solid condition, this must of necessity pass through an unbroken series of stages when the system consists of mixtures of water and of ice, the former decreasing and the latter increasing in amount. Are not these "transitionV stages in the freezing of water similar to the transition stages occurring in the transformation of austenite into pearlite? To clarify, let us consider in Fig. 1 the mechanism of the transformation of eutectoid steel from its austenitic to its pearlitic condition as it cools slowly through its thermal critical range. It is generally admitted that this transformation is the result of two distinct phenomena: (1) the allotropic change of gamma iron into alpha iron and (2) the crystallizing out of solution of the carbide Fe3C. Whether this crystallizing of Fe3C implies also its formation is immaterial for our purpose. In other words, whether it is the carbon in atomic dispersion which is present in gamma iron or molecules of Fe3C has no bearing upon the matter to be discussed. The transformation of gamma iron into alpha iron cannot take place suddenly. It must of necessity be progressive, regardless of the speed with which it may take place. At A, for instance, there would be present AB gamma iron and BC alpha iron. The distance MN does not refer to falling temperature, but to the passage of time. It may be assumed that the transformation takes place at a constant temperature (the Ar321 point). In a similar way, the crystallization of Fe3C out of the austenite solid solution must be progressive as depicted between M and N. At A there would be present AB gamma iron, BC alpha iron, CD carbon dissolved in gamma and in alpha iron and DE Fe3C. This condition may be described according to individual preference as martensite or troostite. To sum up, can the metal pass from condition

Jan 1, 1931

By Paul Averitt

The U. S. Geological Survey has been actively engaged in work on coal for more than 50 years. During this long period we have released more than 300 publications containing information about coal and coal reserves, including details on the thickness, distribution, and quality of coal, and the structure and stratigraphy of the coal-bearing rocks. We have also cooperated with state surveys on many similar publications. For many areas these reports are the only reliable published data on our resources of coal. During the last several years we have substantially increased our activities above the wartime low. We now have field work in progress, or reports in preparation, on 13 detailed mapping projects distributed as follows: 1. Pennsylvania anthracite field 2. Casselman Basin, Md. 3. Leslie County, Ky. 4. Deep River field, N. C. 5. Coosa field, Ala. 6. Powder River field, Mont. 7. Spotted Horse field, Wyo. 8. Yampa field, Colo. 9. Paonia field, Colo. 10. Trinidad field, Colo. 11. Durango field, Colo. 12. Chaco River area, N. M. 13. Lewis and Thurston County fields, Wash. For two of these areas; the Paonia field, Colo., and the Coosa field, Ala., we have published recently preliminary reports, and final reports are in preparation. In addition, we are nearing completion of a coal reserve study of Montana, and are beginning similar studies in several other states, as part of a program of revising our estimate of national coal resources on the basis of presently available data. Factors Involved in Making Estimates Our responsibilities include detailed field mapping to secure information on areas of outcrop of coal beds, their range in thickness, nature of roof rock, amount of overburden, correlation of the beds, stratigraphy and structure of the coal-bearing rocks, and the preparation of coal reserve figures based on these data. The computation and estimation of resources of coal in the ground, like that of resources of other mineral commodities, involves consideration of many additional purely geological factors that can be appraised best through such regional studies. Regional variations in the thickness and texture of rocks overlying and underlying coal beds, for example, give evidence as to the probable position of the edges of the basin of coal deposition, or may aid in the delineation of sand-filled channels that sometimes cut out coal beds. It is apparent that the detailed field studies, in which data are gathered, are the basis for coal reserve studies, and in our present program these two phases of work are being carried on together. Previous Coal Reserve Estimates For many years we have been aware

Jan 1, 1950

By M. R. Tek, F. H. Poettmann, M. L. Grove

The general problem of single-phase natural gas flow through porous media has been considered both by mathematical analysis and field experiments. Theoretical studies on the fluid dynamics of natural gas wells resulted in derivations of expressions which permit a ber-ter understanding of the flow mechanism for conditions under which Darcy's law is no longer valid. In applying these results to natural gas production and testing technology, special emphasis war placed on the study of low permeability, slowly stabilizing formations. These applications resulted in a method of predicting the performance coefficients of tight natural gas wells. The calculation of the performance coefficient requires the determination of the "test-index", pkh/µ, the drain- age radius, R, and the effective wellbore radius, rw. Methods for estimating these parameters from field data were also developed. Field data from 15 wells were collected and analyzed. The measured values of the performance coefficients were compared with the predicted values. This statistical evaluation gave a bias of 7.14 per cent and a standard deviation of 11.6 per cent. INTRODUCTION The performance of a natural gas well is determined by the physical properties of the reservoir rock, the extent and the geometry of the drainage area, the properties of the flowing fluid, and the conditions of pressure distribution within the drainage matrix. The relation between the quantity of gas delivered and the pressure drop within the reservoir is characteristic of the behavior of each well and is often referred to as the back-pressure behavior of the well. It is well established that for normal, single-phase gas wells the relationship between the gas delivery rates and the bottom-hole pressure take, in general, the form, Q = c(P3 8 -P2 1)n. ,.......(1) where C is the performance coefficient, and n is the exponent corresponding to the slope of the straight-line relationship between Q and (P2 s, — P2 l) plotted on logarithmic coordinates. The determination of a well's performance by the back-pressure behavior not only permits the production engineers to analyze many operating problems, but also provides necessary information useful and essential to predict the future development of the field.' Important engineering and production problems such as calculation of gas deliverability into a pipeline at a predetermined line pressure, design and analysis of gas-gathering lines, determinations of spacing and number of wells to be drilled during field development to meet future market or contract obligations, etc., all depend, at least in part, on the availability and use of reliable back-pressure curves.' In the past the behavior of gas wells was evaluated

Jan 1, 1958

By G. Gutzeit

An inner complex is a cyclic chemical structure containing an inorganic cation that is bound simultaneously to several atoms in a single organic molecule; on the one hand by means of ordinary valence bonds (electron exchange), on the other hand through the action of the electric field thus created, which satisfies the so-called secondary valences. The relative positions of the salt-forming and complex-forming groups are such that most frequently a four, five, or six-membered ring results through this double attachment of the cation.1-6 The formation of inner-complex ring systems depends not only upon the nature and suitable position of the salt-forming and complex-forming groups for ring closure, but, to a great extent, also on the nature of the metallic cation entering the reaction. This selective character of chelate-forming organic compounds is one of their most interesting and most valuable properties. As a matter of fact, the largest number of their practical applications is based upon their specificity.4,7-l3 Once a chelate compound is formed, its character is definitely "organic" in nature. In other words, its properties are conditioned to a much larger degree by the carbon chains or rings than by the metallic atom. Many inner complexes are soluble in nonpolar solvents such as benzene, paraffin oil or carbon tetrachloride, while the chelate-forming reagent before closure of the metal-organic ring is water soluble. (Example: copper complex of salicyl-aldoxime') It is obvious that such particular properties as those indicated above can be utilized whenever specificity and practically complete binding of inorganic ions into an undissociable complex are required. One of the well-known applications of chelate-forming compounds has been the development of specific reagents in analytical chemistry, creation of the spot-test method,4,14-16 and the application of the same principles to the contact print method for determining minerals." Chelate-forming Compounds as Collectors In the field of flotation, where selectivity is often a quality of paramount importance for the collector, various workers have lately attempted to apply their knowledge of specific organic analytical reagents to this purpose. A. C. Vivian18 has concentrated cassiterite by using ammonium nitrosophenylhydroxyl-amine (Cupferron) C6H5NO(=NONH4). Holmanl9 has tested dimethylglyoxime for the flotation of nickel oxide minerals, while deWitt has shown in a series of systematic experiments that alpha-diox-imes were generally selective collectors for nickel ores. Taurin NH2(CH2)2S03H has been proposed for the concentration Of Oxidized lead ores.19 Diphenylthio-carbazone

Jan 1, 1947

By G. Gutzeit

An inner complex is a cyclic chemical structure containing an inorganic cation that is bound simultaneously to several atoms in a single organic molecule; on the one hand by means of ordinary valence bonds (electron exchange), on the other hand through the action of the electric field thus created, which satisfies the so-called secondary valences. The relative positions of the salt-forming and complex-forming groups are such that most frequently a four, five, or six-membered ring results through this double attachment of the cation.1-6 The formation of inner-complex ring systems depends not only upon the nature and suitable position of the salt-forming and complex-forming groups for ring closure, but, to a great extent, also on the nature of the metallic cation entering the reaction. This selective character of chelate-forming organic compounds is one of their most interesting and most valuable properties. As a matter of fact, the largest number of their practical applications is based upon their specificity.4,7-l3 Once a chelate compound is formed, its character is definitely "organic" in nature. In other words, its properties are conditioned to a much larger degree by the carbon chains or rings than by the metallic atom. Many inner complexes are soluble in nonpolar solvents such as benzene, paraffin oil or carbon tetrachloride, while the chelate-forming reagent before closure of the metal-organic ring is water soluble. (Example: copper complex of salicyl-aldoxime') It is obvious that such particular properties as those indicated above can be utilized whenever specificity and practically complete binding of inorganic ions into an undissociable complex are required. One of the well-known applications of chelate-forming compounds has been the development of specific reagents in analytical chemistry, creation of the spot-test method,4,14-16 and the application of the same principles to the contact print method for determining minerals." Chelate-forming Compounds as Collectors In the field of flotation, where selectivity is often a quality of paramount importance for the collector, various workers have lately attempted to apply their knowledge of specific organic analytical reagents to this purpose. A. C. Vivian18 has concentrated cassiterite by using ammonium nitrosophenylhydroxyl-amine (Cupferron) C6H5NO(=NONH4). Holmanl9 has tested dimethylglyoxime for the flotation of nickel oxide minerals, while deWitt has shown in a series of systematic experiments that alpha-diox-imes were generally selective collectors for nickel ores. Taurin NH2(CH2)2S03H has been proposed for the concentration Of Oxidized lead ores.19 Diphenylthio-carbazone

Jan 1, 1947

By L. Sturkey

Quantitative X-ray diffraction studies of the precipitation of thorium in a Mg + 3.3 Th + 0.51 Zr alloy (HK31A) in both the as-cast and cold-worked states show that the precipitation may be described by f = 1 - e(t/T)1/2 over most of the aging period. The effects of cold work and temperature changes are determined. The precipitation of tile equilibrium Mg-Th compotund is Preceded by the formation of a transition phase of higher thorium content, with the cowposition Mg2Th and with a Laves-phase structure. Thorium-containing alloys of magnesium have assumed considerable commercial importance, especially for applications requiring exposures to temperatures greater than 500°F for appreciable lengths of time. The principal commercial wrought alloys in this system are HK31A, containing nominally 3 pet by weight thorium and about 0.7 pet by weight zirconium: and HM21A. containing 2 pet by weight thorium and 1 pet by weight manganese. These two alloys retain a high level of properties even after exposures of 100 hr at 600°F, while the more common alloys containing aluminum and zinc are badly overaged by these conditions. Therefore, in order to obtain some insight into the mechanism by which thorium produces high temperature stability in these wrought alloys, it seems desirable to investi- gate the effect of temperature and mechanical working on the precipitation processes involving thorium. Since the scattering power of a thorium atom for CuKa X-ray radiation is about ten times that for a magnesium atom, the magnesium alloys containing about 3 pet by weight thorium are ideal for quantitative measurements by X-ray diffraction of the amount of Mg-Th compound present at any time. Such quantitative measurements should be of theoretical importance in the study of the effects of time, temperature, and deformation on precipitation and precipitation hardening. Of the two commercial alloys, HM21A and HK31A, the latter is certainly the most suitable for study: In the Mg-Th-Zr2 system, only Mg-Th compounds need be considered, since no ternary compounds or binary Th-Zr3 and Mg-Zr4 compounds exist. The Zr is added to this alloy as a grain refining agent and probably plays a secondary role in precipitation. On the other hand. thorium and manganese form many

Jan 1, 1961

By Hans Neuberger

INTRODUCTION IN our everyday life, visual perception plays perhaps a more important role than any of the other senses with which we are equipped by nature. It is, therefore, quite understandable that the average person associates 'with the term "atmospheric pollution," clouds of dust, palls of smoke or deposits of soot, phenomena which are so familiar to the residents of industrial cities. On the other hand, "air" is usually considered the prototype of the invisible, of the intangible, and any suspensions in the air which do not conform to this concept, are regarded as foreign to the atmosphere and thus as "pollution." According to Webster, the term "pollution" implies uncleanness, impurity, in short, something undesirable. Although the scientist often accepts popular concepts, he is generally inclined to suspect that apparently "obvious" phenomena imply, literally, "more than meets the eye." To show that this suspicion is also justified with regard to atmospheric pollution, is the objective of this discussion. It will be shown that what seems foreign to the air at first sight, is by nature an integral part of it, and that the more important aspects of pollution generally escape attention. THE ATMOSPHERIC CONSTITUENTS We can distinguish two classes of atmospheric constituents: the permanent gases, chiefly nitrogen, oxygen, traces of argon, neon, and others, and the variable constituents which include water in its different states, carbon dioxide, ozone, and various suspensions, either in gaseous, liquid or solid form. These suspensions, known by the collective term "Aerosol,"20 will be considered in detail. DUST There are two general types of aerosols: the first type is represented by the socalled "neutral" particle 3, commonly known as dust and experienced by everyone, as it is the more conspicuous type of suspensions. . It often represents a special problem to the mining engineer, the mechanical engineer, the industrial engineer, and many other professional men. Dust consists of finely divided solids derived from weathering, drilling, handling and preparation of rocks and coal. Dust may also consist of organic or inorganic particles resulting from manufacture of a variety of products such as flour, rubber, lime and steel, from traffic on land be it on the highways, on rails or in city streets, from decomposed vegetation or from volcanic eruptions. Perhaps the most reviled member of this class of suspensions is the soot and fly ashes from coal fires and other combustion processes. The cosmic source of dust, namely the injection of meteoric matter into the atmosphere, is of minor significance because the concentration of particles is exceedingly small despite the relatively large mass of material invades the earth’s atmosphere from space

Jan 1, 1948

By Max Y. Seaton

THE scope of this paper will be limited to finished materials that contain a large preponderance (around 80 per cent or more) of magnesium oxide. The large and commercially important production of refractory dolomite and modified dolomites is not discussed here, and the production of magnesium basic carbonate for use as a heat insulator is barely mentioned. The discussion is confined mainly to magnesias produced in comparatively great quantity by direct processing of naturally occurring raw materials and hence excludes secondary or highly purified products such as pharmaceutical products or U.S.P. light and heavy calcined magnesias of commerce. NOMENCLATURE The nomenclature of the magnesia products that will be discussed is somewhat confusing, in that it is customary in the trade to designate as "calcined magnesite" the materials that result from the calcining of magnesite to temperatures that remove the contained carbon dioxide. The finished product, therefore, is not magnesite at all but simply a more or less pure magnesium oxide or magnesia. Furthermore, partly for statistical and partly for commercial reasons, it has been customary, during recent years, to classify as "calcined magnesite" products that result from the heat-treatment of magnesium hydroxide precipitated from magnesium-containing brines; products that, obviously, have no relationship whatever to magnesite. In the listing of magnesia-containing materials, tonnages of which are regularly reported by the Bureau of Mines, reports ordinarily are made under two headings: "caustic calcined" magnesite, in which all of the varieties of products treated at relatively low temperatures are lumped; and "dead-burned" magnesite, in which are included both high-purity and low-purity, and particularly both high-iron and low-iron, materials that have been so heat-treated that the magnesium oxide occurs predominantly as crystalline periclase-materials used almost entirely for refractory purposes. In 1940 the apparent domestic consumption of "caustic calcined" magnesite was approximately 17,000 tons, about 95 per cent of which was produced in this country. The apparent consumption of "dead-burned" magnesite was approximately 172,000 tons, some 82 per cent of which was domestically produced. In both total quantity and percentage of material produced within the United States, these figures are record highs for many years past. UTILIZATION As indicated by these figures, the major tonnage outlet for magnesia is the refractories industry, in which magnesia is employed principally in three ways: (I) as dead-burned grain magnesite for the construction and maintenance of the hearths or bottoms of basic open-hearth furnaces; (2) in the form of refractory magnesite bricks and shapes; and (3) as a chemical

Jan 1, 1942

By Gilbert H. Cady

Extensive sampling of coal in Illinois during the past 10 or 12 yegrs by the State Geological Survey, in cooperation with various organizations, such as the U. S. Bureau of Mines, the University of Illinois, and the Illinois Cooperative Mining Investigations, has made possible the delineation of two areas of low-sulfur coal in the southern part of Illinois. The $fur content is less than 1.25 per cent., so that, if otherwise suitable, these coals can be employed for metallurgical uses and for the manufacture of water-gas and retort gas. One of these areas is small and lies in Jackson County, near Murphysboro, the other is much larger and includes a large part of the famous Franklin County field. A small area of No. 2, or Murphysboro, coal has been worked for many years near the town of Murphysboro, Jackson County, Ill. In two mines, at least, the coal has a sulfur content of less than 1.25 per cent. It is doubtful, however, whether this field will ever be a source of large tonnage as the total area underlain by low-sulfur coal in workable thickness is probably less than 15 sq. mi. (24.14 sq. km.), and a large part of it has already been worked out.. The location of the area of low-sulfur coal in the Franklin County field is shown in the accompanying map. The small area underlain by the Murphysboro low-sulfur coal is shown near the town of that name in the central part of Jackson County. The larger area lies in the west side of Franklin County, extending also about 6 mi. (9.65 km.) south into Williamson County, about 4 mi. (6.43 km.) west into northern Jackson and western Perry County, and northward an undetermined distance into Jefferson County. All but the northern limit of the area is fairly well defined by sampling in numerous mines. The inner cross-lined area is underlain by coal having less than 1 per cent. sulfur, the outer boundary surrounding the area underlain by coal having less than 1.25 per cent. sulfur. The coal mined in the district is No. 6 or Herrin coal, commonly known as the Carterville or Franklin County coal. The bed has a thickness varying from about 8 ft. (2.4 m.) on the border of the low-sulfur area up to more than 10 ft. (3 m.) in the central portion, locally having a thick-

Jan 1, 1920

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 microporosity. 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 microscope 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, Aborn, 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 measurement. The A.S.T.M.. recommends that measurement be made by comparison with a standard chart, by means of Jeffries' planimetric method' 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.', The chart was constructed by photographing at i00 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 enlargement 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

By Gerald Edmunds

In a paper1 before this Institute in 1940, the writer reported that the surface orientation texture of zinc and cadmium differed from the texture existing within the casting, in that basal planes were parallel to the surface. He was unable to rationalize the , origin of this surface texture. It is conceivable that the surface orientation texture is influenced by the atomic force fields, which are different at the surface and within the body of metal. It was considered that a radical changc in the surface against which the metal is cast might alter the surface texture. In trial of this, zinc has been cast against a surface of molten lead, but the same result has been obtained—i.e., (001) parallel, ± 2oo, to the surface—as was obtained when it was cast against air, Transite or iron.' Into the bottom of an open cast-iron tray, 7 by 14 in. by 2 in. deep, preheated to about 275°C., about 1/4 in. of lead, then 1/2 in. of zinc was poured, and the whole was covered with an electric heater to enforce freezing from the bottom upward. After a lapse of time sufficient for the zinc but not the lead to solidify, the zinc slab was raised free of the molten lead. The bottom surface of the zinc casting was coated with a thin layer of lead. A specimen of the slab 136 in. square was metallographically polished to flatten it and remove the slight film of lead, and the orientation was determined by the method used before,' with the result stated above. Some determinations have also been made on other metals, as follows: Surface orientation determinations were made on the 3/8-in. diameter grip section of two 1/4-in. diameter aluminum-alloy die-cast tensile bars and on a 1/8 by 1/2-in. flat aluminum-alloy die-cast tensile bar. None of these three aluminum die castings exhibited any preferred orientation at the surface. A brass die casting (nominal composition: 60 Cu, 37.75 Zn, 1.00 Sn, 1.00 Pb, 0.10 Al, 0.15 Si) furnished by C. S. Smith was also examined. The surface showed a random orientation of alpha and beta. Summary A zinc casting solidified against a molten lead surface was found to have the same surface orientation texture, (001) parallel to the surface, as other zinc and cadmium castings. Aluminum and alpha-beta brass die castings were found to have random grain orientation textures at the surface. Acknowledgment The X-ray determinations were conducted by M. L. Fuller.

Jan 1, 1945

By William J. McCaughey, Richard L. Barrett

FOR sixty years-in fact, ever since the inception of the basic steelmaking process -basic slags have been the subject of study by chemists, metallurgists and petrographers, with the purpose of providing a better understanding of the reactions between the slag and the metal during the refining process. The result of this work and of the researches of mineralogists and physical chemists into the chemistry of oxide systems is a considerable body of literature dealing not only with slags themselves but with equilibrium relationships in systems synthesized from pure components. Since any actual slag is a multicomponent system more complex than any yet worked out in the laboratory, a complete solution to the problem is still far away. The writers have recently published a paper1 which they believe sheds light on the role of the slag in the elimination of phosphorus and it is the purpose of the present paper to discuss the metallurgical applications of that work. Since the pioneer investigations on the constitution of basic slags carried on by Stead and Risdale, Carnot and Richards, Hilgenstock and others in the 1880's, a considerable body of literature on this subject has appeared. Many of the more important of these papers were summarized in the previous paper,' therefore they will not be reviewed here. PETROGRAPHIC STUDY The present writers have had occasion, over a period of years, to examine petrographically a great number of basic steel- making slags having a very wide range of chemical compositions and made under various conditions of operating practice. Although certain of these slags exhibit some unusual features, it is a remarkable fact that the great majority of mature slags show certain typical characteristics, which persist throughout the wide range of chemical compositions. The typical mature slag usually appears under the microscope to consist of two phases. The phase of primary crystallization is light colored and doubly refracting. If separated mechanically and subjected to chemical analysis, it is found to consist essentially of SiO2, CaO, and P2O5. Sometimes, although not usually, two such silicate-phosphate phases are found. The other conspicuous phase is dark in color and optically isotropic, and occurs as the interstitial material between the grains of the light colored phase. This dark colored interstitial phase when analyzed is found to consist essentially of FeO,Fe2O3, MnO, and MgO. In some slags high in iron oxide, particularly those from low-carbon heats, dicalcium ferrite is found. This phase is dark reddish brown in color and anisotropic.

Jan 1, 1944

By Henry Mackay

THE interesting paper recently submitted by Messrs. Tobelmann and Potter' shows that chemical problems have developed which are of great interest in this new and important branch of metallurgy. Those who realize what a process of this kind really involves will agree that it deserves a better name than "leaching process." The word leaching conveys the idea that the copper is simply leached out of the ore with acid and then precipitated on iron; the chemistry of such a process would be of little interest. As, however, during the first year's operation of this plant 24,400,532 lb. (11,067,837 kg.) or about two-thirds of the produce, was electrolytic copper, while 7,992,033 lb., or about one-third, was cement copper, it would seem more appropriate to term the process electrochemical. It further appears, from the particulars given, that efforts have been made to have the entire production in the form of electrolytic copper. -This could be done if the chemistry of the problem were kept in balance, so that it would not be necessary to discard any solutions that carried copper and acid of commercial value. A process, such as that under consideration, in which the copper is precipitated from solution by electrolysis, the solvent being at the same time regenerated, is one that requires special chemical and electrochemical knowledge and experience if all the -copper in solution that has been extracted from the ore is to be successfully and economically produced as electrolytic copper. The object of this paper is to discuss, from the practical and theoretical standpoints, the chemical and electrochemical problems involved in the working of a process of this kind, and' which must be solved to keep it in chemical and electrochemical equilibrium. In such a process, if the chemical balance is maintained, a solution can be used alternately as a

Jan 9, 1919

By David R. Poirier

Activity data of carbon as a function of both temperature and composition throughout the stable austenite range is correlated by mearts of an equation derived from a quasi-chemical model. The carbon activity data of austmite for temperatures between 800° and 1200°C are utilized in conjunction with the activity of carbon calculated for the y solidus using the activity of carbon in liquid iron and published austenite-liquid equilibria. The results agree very well with Chip-man's correlation; however, a small difference in the activity of carbon in the high-temperature range of the austenite field is evident. Excellent agreement is found for the heat of solution of graphite in infinitely dilute austenite; from this study the value is 10,550 cal as compared with Chipman's value of 10,680 cal. AS part of a program to study microsegregation in dendritic solidification of ternary Fe-C-Cr alloys, it was desirable to be able to describe the equilibria between austenite and liquid iron in Fe-C-Cr alloys. In this regard, it was necessary to correlate existing data on the activity of carbon in Fe-C austenite as a function of both temperature and composition. At that time, Chipman's analysis1 of the thermodynamics of binary Fe-C austenite was not available. It will be shown that this study and Chipman's study agree rather well throughout the stable austenite range of temperature and composition; however, some small differences appear at temperatures greater than the eutectic temperature. Benz and Elliott 2 presented isoactivity lines for austenite superimposed on their revised Fe-C phase diagram. Using an expression from Darken and Gury 3 representing Smith's4 activity data between 800" and 1000°C, they found that the activities extrapolated above 1000°C to the solidus did not agree with the activities determined from the corresponding liquidus compositions. It is the purpose of the following argument to reconcile carbon activity data of austenite with the activity in liquid Fe-C alloys as determined by Rist and Chipman. 5 In addition, a simple analytical expression is sought for computational convenience. ACTIVITY DATA OF CARBON IN ZRON Fig. 1 shows the activity of carbon in Fe-C austenite as determined by Smith, 4 Schenck and Kaiser, 6 Scheil et a1.,7 and Bungardt et al.' The lines are merely drawn to separate the data into the respective isotherms. These data are inadequate to determine the activity of carbon at temperatures greater than 1200°C. The activity coefficient in Fe-C liquid alloys was assumed by Rist and chipmans to obey the following

Jan 1, 1969

By W. R. Opie

The object of this paper is to show the manner in which typical electrodeposits of hexagonal-close-packed metals—zinc, titanium, and zirconium—tend to form. The conditions of electrodeposi-tion markedly affect the nature of the deposits in regard to crystal size, orientation, and appearance. No attempt is made to correlate cell conditions with deposit quality but, rather, characteristic types of deposits were selected and a study made to show the relationship between outward appearance and crystal structure. The zinc deposits were made in aqueous electrolytes and the titanium and zirconium deposited from fused salt baths. ZINC deposits studied were made in the American Smelting and Refining Co.'s Central Research Laboratories. They were representative of bright, shiny, smooth deposits, which can be obtained by using proper current densities and electrolyte addition agents, and of deposits which are dull and tend to be nodular. Four deposits were selected which ranged from smooth and bright to very nodular and dull, and their classifications are shown in Table I. These were examined microscopically and were found to differ quite markedly in outward surface structure and in microstructure. The outward surface variation is illustrated in Figs. 1 to 4. At X50 the texture could be seen to progress from granular to platelike to smooth. The microstructures of the deposits' cross sections from starting sheet to outer surface are shown in Figs. 5 through 8. The dull nodular deposits (sample Nos. 1 and 2) show some tendency for acicular growth. The platelike sample (No. 3) shows tendency for columnar growth development and the smooth deposit (No. 4) has a well developed columnar structure. Back-reflection X-ray patterns of the deposit surfaces revealed some interesting information. The crystal orientation was random in all deposits except the smooth deposit. Fig. 9 is a typical back-reflection pattern of a nodular deposit. All planes are reflecting in the proper relative intensity. The pattern of the smooth deposit is shown in Fig. 10. The only planes which reflect are the (10.4). This series of planes is in the right position, with the FeKa radiation used, to satisfy the Bragg equation if the basal planes {00.1) are at right angles to the X-ray beam. The results were interpreted to mean that in the bright smooth deposit preferred orientation has occurred with the basal hexagonal planes oriented in the plane of the sheet but with all other planes randomly oriented around the c-axis.

Jan 1, 1957

By William J. Harris, Morris Cohen

INTRODUCTION THE recent application of lineal analysis1,2 to the austenite-martensite reaction has made possible a quantitative study of the kinetics of this transformation during rapid cooling. Martensite range curves can thus be constructed to portray the onset of the reaction at [M.] and its subsequent progress as a function of temperature down to and below the ambient. It now seems in order to investigate other aspects of the martensite transformation, using this quantitative method of approach. One of the least understood characteristics of the austenite-martensite reaction is that of stabilization which has been defined by Troiano and Greninger3 as "a lowering of [M.], resulting from aging, without change in chemical composition of the parent solid solution." In other words, if the hardening quench is arrested at a predetermined subcritical temperature (Th) for a sufficient period of time, more austenite may be retained at a given lower or reference temperature (Tr) than if the steel had been cooled directly and rapidly to Tr in the first place. For the purposes of the work at hand, the extent of stabilization produced by the isothermal treatment at Th, is measured explicitly in terms of the excess austenite [(S)] that exists in the steel at Tr, over and above the amount that is normally present after direct quenching to Tr. Tr is conveniently taken to be room temperature, but this choice is not essential and is sometimes undesirable. The holding temperature (Th) may be above or below [M], and still cause stabilization depending upon the chemistry of the austenite. Stabilization has been found to occur in the presence of bainite4 and of martensite5,6,7,8 as well as in the absence of either.9 The phenomenon of stabilization is not concerned with (and may even be obscured by) ferrite formation or any other type of phase change occurring at Th that alters the chemistry of the remaining austenite. Such a structural change would obviously influence the martensite transformation during subsequent cooling. Stabilization, however, is more subtle; it appears to manifest itself without detectable variation of the austenite composition, whether in the presence or absence of transformation products. There are relatively few direct references to stabilization in the literature. The stabilizing effect of room temperature aging and tempering on the subzero transformation of retained austenite has been clearly shown in plain carbon,6.8 low alloy 6.7.8 and high alloy tool steels.10,5 Starting with the as-hardened steel, the degree of stabilization increases with tempering time and temperature through

Jan 1, 1948

By Walter R. Hibbard, George H. Eichelman, William P. Saunders

INTEREST in the various products of the austenite eutectoid transformation in iron-carbon alloys, particularly as produced by the isothermal sub-critical techniques introduced by Davenport and Bain,1 has resulted in the application of similar heat treatments to other eutectoid transformations. Studies2.3.4 of the beta copper-aluminum alloy eutectoid transformation revealed microstructures very similar to those found in iron-carbon alloys. Investigations5,6 of the kappa phase in the copper-silicon alloy system have established the eutectoid type transformation of this phase into terminal alpha and intermediate gamma phases. This transformation has been reported' as forming a eutectoid type structure in a very sluggish manner by a long time isothermal treatment. The purpose of the present investigation is to study the products of the kappa eutectoid transformation as affected by transformation temperatures by means of microscopic and hardness methods. PREPARATION OF ALLOYS The copper-silicon alloy equilibrium diagram is shown in Fig I. The kappa field converges to a minimum silicon solubility at the eutectoid composition and all other completely kappa alloys are hypereutectoid. Thus, kappa decomposition involves first the proeutectoid precipitation of gamma, followed by the eutectoid transformation of a lower silicon content kappa (5.2 pct). Smith5 has indicated that alloys containing between 5.4 and 5.7 pct silicon could be hot rolled, but that the latter composition was desirable in order to permit a wider kappa temperature range. The alloy was prepared by adding Baker's commercially pure silicon to an ingot of copper-silicon alloy containing 2.34 pct silicon remaining from the investigation of Brick, Martin and Angier.7 Following the casting techniques of Krynitsky, Saunders and Stern,8 the ingot was melted under a heavy layer of dried charcoal in a clay-graphite crucible in a gas-fired pot furnace. Small lumps of silicon were held under the melt surface with a graphite rod. After the silicon had dissolved, the alloy was chill-cast and then remelted without a cover, stirred thoroughly, skimmed and poured into a preheated cast iron mold. The cast microstructure is shown in Fig 2. The casting, 10 X 4 X ¾ in., was annealed at 750°C for 21 brand furnace cooled. About 1/16 in. was milled from all surfaces. The plate was cut in half longitudinally and the bottom half analyzed by A.S.T.M. methods.9 The composition by weight was as follows: copper 94.24 pct, silicon 5.56 pct, iron 0.11 pct.

Jan 1, 1948