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By Shiro Ban-ya, John Chipman

Using the same experimental method previously described, the activity of sulfur in a number of quaternary and more complex liquid iron alloys at 1550oC is determined. A "cross-product term zj.zk is determined for each of the quaternary alloys to take account of the mutual effects of the combinalion on the indi-vidual contributions to In 5 The interactiotl coefjicienls delermined for ternary solutions and cross-pvoducl coefficierlts from the quaternary systems are used to estimate the activity coefficient of sulfur in more complex alloys. OUR recent papers 1,2 have described new determinations of the activity of sulfur in Fe-S binary and Fe-S-j ternary solutions, but the practical applications of these data require the estimation of activity of sulfur in more complex systems. Previously, Sherman and chipman3 devised an approximate method for calculating the activity of sulfur in complex systems by summing the contributions to the logarithm of the activity coefficient of each element in the alloy. This procedure is more successful, as one of us has pointed out,4 when the concentration variable is taken as zs = ns/(nFe — nS t CLJ~ nj) rather than the conventional atom fraction x~ = nS/(nF, + nS + Enj). In the former definition, which is based on analogy to interstitial solutions, the value assigned to uj is normally +1 for metallic and -1 for nonmetallic elements." In addition, however, the effects of mutual interaction between alloying elements must be considered for the accurate estimation of the activity of sulfur in more complex systems. The purpose of this investigation has been to devise a more reliable method for estimating the activity coefficient of sulfur in nmIticomponent iron alloys. The measurements were carried out on some quaternary systems Fe-S-j-k for combinations of silicon, chromium, nickel, cobalt, molybdenum, and tungsten. Manganese was not included since the experimental method has been found unsatisfactory for volatile, sulfide-forming elements. The experimental method was the same in every detail as described previously. 1,2 The concentrations of sulfur, silicon, chromium, and copper in the quenched metals were determined by chemical analysis but those of nickel, cobalt, molybdenum, and tungsten were calculated from charged amounts. Iron sulfide was included in the charges in amounts estimated to furnish approximately the final sulfur content. CALCULATION W2 have shown2 that when zs and zj are the concentration variables in a ternary Fe-S-j solution the logarithm of the activity coefficient S = a~/zg is a linear function of the variables as and aj defined as follows:

Jan 1, 1970

By D. L. Murphy

As the world's demand for iron ore increases and available sources are depleted, increasing attention will be centered on deposits in the Quebec and Labrador portions of the Labrador Trough. Improvements in the beneficiation of low grade iron ore stimulate exploration for deposits amenable to concentration. This study is centered on the Mt. Wright-Lake Carheil area, lying between Wabush Lake and Mt. Reed in Quebec. Described in detail are the general lithology, structural and economic geology, and mineralogy of the iron-formation. The iron ore province of Quebec and Baffin Island extends from the southern shore of Baffin Island southeasterly through the Labrador Trough to Matonipi Lake, approximately 185 miles northwest of Seven Islands. (See Fig. 1.) Future geologic field studies will very likely extend the limits of the province to include the ferruginous and associated rocks of the Lake Mistassini area. At present, only the deposits near Knob Lake and Lake Jeannine (Mt. Reed) have been brought into production although in the near future several other properties including those at Wabush Lake will commence operations. Within the next decade or so, as the world's demand for iron ore increases and available sources are depleted, this region will undoubtedly become a major mining district. Initial reports of iron-rich rocks in Labrador date back to the investigations undertaken by A. P. Low near the turn of the century. During the ensuing years the country was prospected chiefly for precious and nonferrous base metals because of its inaccessibility and the low tenor of the iron ore. In 1945 an evaluation of the direct shipping ores near Knob Lake indicated that sufficient reserves were present to justify the enormous capital expenditure required to bring the deposits into production. Initial open-pit mining began in 1954 following the construction of a townsite, a 360-mile long railway to Seven Islands, and an elaborate loading dock. Recent improvements in the beneficiation of low-grade iron ore have stimulated widespread exploration for deposits amenable to concentration, particularly along the southwest extension of the Trough. The Mt. Wright-Lake Carheil area, bounded by longitudes 66O45' and 67 30' west and latitudes 52 30' and 52 45' north, is a nearly rectangular tract of slightly less than 500 sq miles. It is in Saguenay County, 174 miles north-northwest of Seven Islands (see Fig. 1). Except for the periods of the spring breakup and the fall freeze up, the area is readily accessible by air.

Jan 1, 1962

By B. Trentini

In the spectacular development of pure oxygen steel-making, the process using the vertical lance converter LD, is at the present time the most widely employed. Proper control of slag composition during the steel-making process appears to be essential in achieving satisfactory blowing from both the metallic yield and metallurgical points of view. The paper illustrates the primary importance of the presence of a large quantity of metal droplets in the slag during the process. In the case of both phosphorus and hematite pig iron, it can be deduced from the phase diagrams and confirmed by experimentation that nonhomogeneous slags are one of the causes of slag overflowing during the blow. The problem is however a complex one and further physicochemical studies appear necessary. Finally, the new continuous steelmakingprocess developed by IRSID is described. PEOPLE who knew Henri Marion Howe have said that he took great pleasure in speculating on the future of metallurgical processes. It is therefore not inappropriate to devote, in his memory, some description and discussion to processes unknown to the world of his time, in particular oxygen steelmaking and continuous steelmaking. The first industrial application to steelmaking of tonnage oxygen produced by air liquefaction was made in Germany just before the war and consisted in enriching the air blown through the bottom of a basic Begsemer converter in order to melt a higher proportion of scrap and to produce steels with lower nitrogen content than is achieved with conventional practice. While this process was being developed after the war, mostly in Western Europe, steelmakers were becoming increasingly familiar with the technique of blowing pure oxygen from the top, first by means of consumable steel pipes, with or without refractory shielding, and later by water-cooled lances, designed for the purpose and affording longer life. The field was then open for the wide use of pure oxygen in steelmaking, either in existing processes such as open-hearth or electric furnace, or in new processes. These new processes can be broadly classified according to the category of furnace employed. In the case of the vertical converter taken as the first category, bottom-blowing of pure oxygen causes extremely rapid wear of the refractory tuyeres, and although various expedients have been tried to overcome this drawback (such as mixing oxygen with CO2 or H2O or using high pressure oxygen), they have had to be abandoned. The solution for vertical converters has been found in top-blowing with a vertical water-cooled lance; this is known as the LD process or basic oxygen converter process.

Jan 1, 1969

By E. W. Shaw

Continued discussion of the paper of Roswell H. JOHNSON, presented at the New York meeting, February, 1915, and printed in Bulletin No. 98, February, 1915, pp. 221 to 226. See also Bulletin No. 101, May, 1915, pp. 1157 to 1162. E. W. SHAW, Washington, D. C. (communication to the Secretary+). -With the word petrology-literally the science of rocks-being used primarily for igneous rocks, and with geophysics coming to mean the study of lavas and the rocks into which they solidify, contributions to the knowledge of the physical chemistry of sedimentary rocks, even though only ideas which may be used as working hypotheses, become most welcome. The forces which control the formation and subsequent history of the stratified portions of the earth's crust are so little known that no one has yet been able to settle finally the questions as to whether petroleum is of organic or inorganic origin; whether it originated far from its present position, or nearby. Yet both the chemical and physical problems of the rocks in which oil occurs seem to be more simple than those of the igneous rocks. The oil-bearing rocks of western Pennsylvania, for example, have in all probability never been subjected to a pressure exceeding 3,000 or 4,000 lb. to the square inch, nor to a temperature higher than 100° or 200° C. These pressures are considerably below the crushing strength of rocks, and the temperature far below their melting point. The igneous rocks,, on the other hand, have been affected by enormous pressures and very high temperatures and yet steady progress is being made in reproducing in the laboratory the conditions of their formation and subsequent modification within the earth. The solution of the sedimentary-rock problems would seem to be fully as important as those of igneous rocks, and yet we must content ourselves with reasoning backward and our inferences as to what has happened are oftentimes little more than guesses.1 One of the fundamental problems is the origin of the salt water in oil fields. Is the salt water fossil sea water; has it been formed by the solution o-f salts of various kinds from distinct beds, from disseminated par-ticles, and from the weathering of suitable grains in the rock; or is it of deep-seated origin? Its general resemblance to sea water points to the first, but the principles held by some concerning the free circulation of water throughout the earth's crust, and certain peculiarities of composition indicated by the few analyses available, seem out of harmony with such an explanation.

Jan 7, 1915

By Franz R. Dykstra

DEFINITIONS The ores of iron are classified in three general categories: direct shipping, concentrates, and agglomerated-i.e., pelletized or sintered. Direct Shipping As the name implies, direct-shipping ores are shipped as mined or, perhaps, after screening. Generally, direct-shipping ores are hematitic (R203), magnetitic (R304), or limonitic (2Fe2O3.3H20) in nature. Grades of direct-shipping ores vary widely. Prices are frequently related to the historical Mesabi standard of 51.5% iron, although certain premium lump ores may contain up to 68% iron. The use of direct-shipping ores is diminishing as the advantages of beneficiated ores become evident and reserves are depleted. Concentrates Where the nature of the deposit and economics allows, certain ores are upgraded. This may include no more than washing and screening, or may be as elaborate as fine grinding followed by magnetic, gravity, or even flotation procedures for separation. Coarser concentrates may be smelted "as is.'; Fine concentrates usually are sold as sinter feed. (Sinter, as used here and in the following, refers to a process by which a fine ore-carbon mixture is agglomerated at elevated temperatures on a direct-fired moving grate to eliminate fines and improve chemical and physical homogeneity.) Agglomerates-Pellets or Sinter The development of economic techniques of mining and concentrating taconite (fine-grained, ferruginous jasperoids) led to the introduction of the iron-ore pellet, which is now becoming the major form in which iron is introduced into the furnace. The tremendous reserves of magnetic taconites of the northern United States and Canadian Precambrian shield had been recognized for many years. A century of mining has seen the reserves of the direct-shipping or "red ores" of the Minnesota, Michigan, and Wisconsin ranges approach depletion. Research started in the 1930s has seen the evolution of motives and techniques to concentrate these stubborn refractory ores. The efficacy of concentrate pellets in iron-making has been such as to induce mines throughout the world to grind, concentrate, and pelletize otherwise shipping-grade ores. Table 14.1A.1 shows typical analyses of iron ore. Marketing-Prices of iron may be quoted on a value per long-ton (2240 lbs) or metric-ton (1000 kg or 2204 lb) basis, or on a value per long-ton-unit or metric-ton-unit basis. One iron unit represents 1 % of contained iron per ton. (Thus, a price of $0.45 per iron unit for ore containing

Jan 1, 1976

By Paul A. Schafer

BALATOC mine, the principal gold-producing mine in the Philippines, is 10 miles southeast of Baguio, in the Cordillera Central of northern Luzon.1 The region is a deeply dissected plateau, ranging in altitude from 3000 t0 5000 ft. above sea level. The rocks consist chiefly of granodiorite, diorite, and remnants of metamorphosed sediments, cut by dikes of andesite porphyry and quartz-diorite porphyry. All are intruded by a volcanic breccia plug, oval in horizontal section, about 3200 ft. long and 2300 ft. wide, which is the north central part of the mineralized area. Three main vein systems have been developed (Fig. 1): q6, 231 and 364, which strike about N.70°E. and dip 5o to 90°S. Each system is a braided zone consisting of many individual components. They are disturbed by a series of premineral faults or shear zones striking about N.45°E. Twelve of these produce important effects on the persistence, character, and quality of veins. From west to east the faults are named (after claims): Hog, Big Gun, Bull, Pine, Lolita, Bar No. I, Bar No. 2, Curt, Sun, Helen, Itoe, and Frog. They are early breaks formed prior to the N.70°E. vein fractures. Mineralization occurs on them but, with several prominent exceptions, they are too low grade to mine. A number of northwesterly striking faults complete the structural pattern. Although they are relatively abundant, the effect on the veins is so small that they do not present any problems in mining or development. All of these faults that have been observed are later than the N.70°E. veins and offset them to the left. NORTHEAST FAULTS The early northeast faults* are notably continuous in spite of their small displacements, 20 to 100 ft. Frequently they appear so weak that their importance is masked and their identity clouded. The gouge along any of these faults may vary from exceedingly weak at one point to very strong at another point only a short distance away. In other words, the amount of gouge depends on the changes of attitude of the fault plane, and is no indication of the extent of the movement. Places where walls are spread apart are filled with gouge squeezed from tight places. Also, mineralization sometimes obscures fault gouges by replacement. The mineralization of northeast faults has produced several important ore bodies; namely, 231 west on Pine fault and q6 vein on the same fault. To a smaller extent, Lolita, Curt, Bull, Bar No. I, and Sun

Jan 1, 1942

By Charles C. Hawes

DETERMINATION OF SILICA OXIDE iron ores usually are found in intimate association with silica and phosphorus compounds. Their quantitative separation and purification sometimes present difficult problems to the chemist. Silicic acids may represent various degrees of dehydration. They are exceedingly weak, but combine with metallic acids and form some of the most stable oxides in nature, the silicates. When iron ores are treated with hydrochloric acid, they yield practically all their iron. However, apart from rare exceptions, varying amounts of insoluble residues of silica, alumina, lime, magnesia and compounds of phosphorus, sulphur, titanium, chromium and others will be left. If the oxides of silicon, aluminum and titanium are present in small quantities, the insoluble residue is generally very small, but the presence of these oxides more usual in larger quantities. Therefore, only a special treatment can break the bond between these elements. Ore Residues Acids remove the soluble constituent of the ore, leaving the insoluble residue, which chemically is rock or gangue and must be treated accordingly. Alkali carbonates are used frequently to break up the residue, but other fluxes have also been recommended, such as a number of lead and boron salts. The introduction of these salts, which offers certain advantages, requires, however, their removal before the other constituents can be analyzed, and this elimination is sometimes difficult. Usually in quantitative analysis silicates are dissociated by fusing them in a platinum crucible with sodium carbonate, thereby forming sodium silicate, Na2SiO3, sodium aluminate, Na2A1204, sodium titanate, Na2TiOs, and carbonates of other elements. All the carbonates are soluble in hydrochloric acid, but also some silicic acid is formed that must be rendered insoluble. To this end the solution is evaporated several times, as the first evaporation still leaves as much as 5 per cent of the silica soluble. Even after a number of evaporations, minute quantities of silica may be found with the iron and alumina present. Perchloric Acid as an Agent for Dehydrating Silicic Acid Perchloric acid, HCI04, (60 per cent), has been used for years as a solvent, but few chemists have used it to dehydrate silica. It is derived from anhydrous perchloric C1207, which is most unstable and dangerous. Perchloric acid is a strong oxidizing agent, which boils at 203°C. It is more effective in rendering silica insoluble than any other known agent, and most rapid in action. After perchloric acid is added to a mixture containing silicic acid, the resultant solution is

Jan 1, 1945

By Ralph Hultgren, Bernard York, David W. Mitchell

It is a well-known fact that magnesium-alloy castings are apt to be coarse grained if the melt is not superheated several hundred degrees above the melting point before casting. (The casting temperature varies according to the shape of the mold. A typical casting temperature is perhaps 1400°F.) British practice is to heat to 900°C. (1650°°F.) for 15 min., cool rapidly to casting temperature, and cast.1 In Germany superheating is carried out at 850° to 900°C. (1560° to 1650°F.) depending on the amount of scrap used. It is stated that further refinement will be obtained by prolonging the period of superheating or by increasing the superheat temperature to 950°C. (1740°F.).2 In the United States superheating is carried out at i600° to 1700°F. (871° to 927°C.), perhaps even higher in some places. It is stated that superheating effects are found as low as 1500°F. (816°C.), but several hours are required.3 These commercial treatments lead to grain sizes in sand castings that may vary from 4 to 8 grains per sq. mm.§ in heavy sections and from 60 to l00 in 3-in sections to perhaps 380 in thin sections. It is also generally known that the refining effect of superheating is lost if the melt is held for some time at lower temperatures before casting. Aside from these very qualitative statements, there is little to be found in the literature as to the effect of temperature and time of superheat on the final grain size. Because of the uncertainty of these factors, the Office of Production Research and Development of the War Production Board placed a research contract with the University of California, supervised by the War Metallurgy Committee. This research, which was done under the "Restricted" Project NRC-550, is the basis of this paper, which has been released for publication by the O.P.R.D. The material studied was an alloy prepared from carbothermic magnesium. The temperatures required for grain refinement proved to be widely different from those used in practice, as described in the statements in the first paragraph. This difference is attributed to the fact that the magnesium in the specimens was of carbothermic origin instead of the electrolytic magnesium in common use. MATERIALS AND METHODS The magnesium alloy studied was one of the most popular sand-casting alloys, with a nominal composition of 9 per cent aluminum, 2 per cent zinc, and 0.r per cent (minimum) manganese and the balance magnesium. This is designated

Jan 1, 1945

Discussion of the paper of W. R. Shimer and F. O. Kichline, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 81, September, 1913, pp. 2361 to 2377. ALLERTON S. CUSHMAN,* Washington, D. C.:-I have been much interested in Mr. Shimer's valuable contribution. The apparent fact that the oxides of certain metals which are not reduced by hydrogen per se, are reducible when the oxides are dissolved in iron in small quantity, is brought out for the first time, and is worthy of the careful attention of investigators. The Ledebur method has been subjected to considerable criticism, owing to the alleged fact that it did not measure the oxygen combined with impurities. Personally I have found the method extremely helpful in spite of the minute quantities of oxygen with which it deals. Mr. Shinier points out that the highest oxygen he obtained by over-blowing was 0.074 per cent., while the minimum quantity in a properly finished steel was in the neighborhood of 0.02 per cent. The Ledebur method is used as a constant check on the quality of heats made in practice under my direction. In dealing with a very pure commercial iron, we should expect to find and would find difficulty in galvanizing sheets made from a heat running 0.07 per cent. oxygen. In fact, we do not like to have the oxygen rise above 0.03 per cent. I am inclined to agree with the author that excessive oxygen leaves a bath of metal in a very short time, but nevertheless I believe it takes only a very little combined oxygen to begin to make its presence felt in the pickling and galvanizing department, when sheet metal is the product manufactured. As Mr. Shimer points out, the higher the carbon, the lower the oxygen danger, and it is partly for this reason that the manufacture of carbon-free metal in the open-hearth furnace has to be so very carefully watched and controlled from the furnace through to the finished product. It is quite possible that, there is a critical temperature of dissociation between iron and oxygen, although the critical points may vary in baths of different carbon content. Unfortunately, the accurate determination of the temperature of a molten bath at the time of pouring or teeming is a very difficult matter. For a long time I have been wishing that there were some reliable data which would indicate the effect of the tem-

Jan 12, 1913

By Carl F. Floe, John Chipman

THE system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or C02 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modem metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100° to 1500°C., and pressures from about 20 mm. of mercury to somewhat above atmospheric. REVIEW OF PREVIOUS WORK The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as 02, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: [2M -}-G2 = 2MGK =G) IYf X[I]] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: [MG = Ki Pa,[2]] Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: [6Cu + S02 = Cu2S + 2Cu20[3] K Cu2S X (Cu20)2(Cu)e(Psm)[4]] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: [K1 =or Vdo,= K2/PBO [5] PsO]

Jan 1, 1941

By Nathaniel Herz

The use of zinc dust for precipitating the pecious metals from cyanide solutions is well established now in many places, and has many advantages over the shavings method of precipitation. Although much work has been done o,n methods of testing zinc dust, as yet. no absolutely positive test has been devised to determine the value of the material. Certain facts are known, but often it happens that results on a working scale are not as expected from the laboratory tests. The purpose of this paper is to record some obscrvations made while testing a large variety of zinc-dust samples in the laboratory. W. J. Sharwoodl has described standard analytical methods, which have been followed, with the changes noted. The regular determinations include zinc oxide, by solution in ammonia and ammonium chloride, lead, and precipitating efficiency. In some cases cadmium was determined by a method similar to that described by J E Clennell.2 I will discuss the precipitating-efficiency test in detail. The procedure is as follows: "A solution of potassium silver cyanide is prepared by dissolving 10 grams of silver cyanide (AgCN) and 5 grams of 99 %' potassium cyanide in a little water and diluting up to 1000 cc. It is then adjusted by addition of a little more XCN or AgCN until the solution indicates from 0.12% to 0.15% free KCN by titration with standard silver nitrate. The titration is best made by using a 10-cc. or 20-cc. sample, adding 1 CC. of 2 % potassium iodide, and a slight excess of ammonia, as the end point is then sharper. Or 15 grams of pure crystallized XAg(CN)2 may be dissolved in a liter of water and 1.5 grams XCN added. " Weigh out 0.5 gram zinc dust into a 300-cc. beaker. Add a few cubic centimeters of watcr and stir until zinc is well mixed, then pour in 250 cc. of the prepared solution, stirring vigorously. See that all lumps are broken up, and continue stirring for fully five minutes. Stir occasionally (at least every 10 minutes) until the end of two hours from the addition of the solution. Then filter upon an 11-cm. filter, wash precipitate thoroughly, sprinkle with test lead, wrap it carefully in the paper, place in a scarifier with about 20 grams test lead, burn paper cautiously in muffle, scorify five minutes, cupel at low temperature and weigh silver. Milligrams silver obtained from 0.5 gram zinc X 0.0606 = percentage precipitating efflciency."³

Jan 1, 1916

By Clarence Zener

IT has long been known that the density of a metal usually decreases with cold-work. Thus O'Neill1 observed as early as 1861 that cold hammering of commercial hot-rolled copper is accompanied by a decrease of density of 0.2 per cent, and that subsequent annealing restores the original density. The origin of this density change, however, has remained obscure. In particular, experiment has not yet decided whether it is due to the presence of small cavities and an increase in intergranular surface or to an actual expansion of the lattice itself. This uncertainty in the origin of the change in density is a reflection of our uncertainty as to the changes induced in a metal by cold-working. One school regards cold-working as a breaking up of the original grains into a large number of perfect crystallites somewhat randomly orientated with respect to one another.2 According to this viewpoint, the mere introduction of a large intercrystallite surface induces a net volume expansion. Another school regards cold-working primarily as a distortion of the grains. It is not obvious that this second viewpoint will lead to a net volume expansion. The purpose of the present paper is to show that this is indeed the case, and that this expansion is of the right order of magnitude to explain existing experimental data. The physical basis for the association of an expansion with distortion lies essentially in the variation of the elastic moduli with volume. This variation is considerable. Thus from Table I we see that a I per cent increase in volume for the case of copper will decrease the bulk modulus K by 10 per cent, the shearing modulus µ by 3.8 per cent. If we thus twist a rod through a given angle, we shall do less work upon it if it increases slightly in volume, thereby reducing the torsion modulus that involves as a factor the shearing modulus. A general principle' in physics states that the rod will so adjust itself as to have a minimum potential energy consistent with the end restraints. It will therefore expand. [ ] In order to obtain a quantitative comparison with experiment, we follow Maier4 in comparing the lattice expansion with the latent energy of cold-work. This latent energy has been measured directly by Taylor and Quinney5 on copper rods subjected to torsion, and may amount to as much as 15 per cent of the total work done upon the specimens. We shall assume that this

Jan 1, 1941

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

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

Jan 1, 1949

By R. J. Wasilewski

The resistivity of single crystal and of polycrystalline metal has been determined between 77° and 1500°K. At comparable purity, the resistivity of the poly crystalline metal differs from that calculated from the axial resistivity values. The observed anisotropy is briefly discussed. A zone refined titanium rod was obtained from F. J. Darnell.1 The hardness of this material varied between 52 and 64 Bhn, indicative of its high purity. Single-crystal specimens were cut out from a few large grains, elongated predominantly along <1120>. Resistance measurements were taken with specimens immersed in liquid nitrogen, solid CO,, and acetone, and at ice point, and then recorded continuously between room temperature and 1200" to 1250°C, throughout at least one full heating and cooling cycle at a rate of l° to 3°C per min. Four probe measurements were taken using spot-welded Pt wire 0.003 in. in diam as potential terminals, and the electromotive force drop was determined poten-tiometrically. A standard resistance, in series with the specimen, served to determine the dc current (generally about 80 ma) in the circuit. In order to eliminate spurious thermal electromotive forces, the circuit polarity was automatically reversed at 5-min intervals, and the mean of the two adjacent readings taken as the true electromotive force value. The discrepancy between the readings at reversed polarities was generally of the order of a few µ v, as all the spot-welded joints were contained within a volume of some 5 mm cube. The relative resistance (R T/R 273o) variation with temperature is tabulated below, and shown in Fig. 1, as measured during the first heating run. The discontinuous drop in resistance, corresponding to the a — ß transformation, started for both initial orientations at 1170°K; i.e., some 15°K above the accepted value of 882°C (1155°K). Judging by the temperature ranse of transformation—some 30°K for the single crystal and 20°K for the polycrystal-line specimen—this difference is believed caused by the solution of the oxygen present initially on the surface of the specimens. The general trend of the resistance vs temperature shown in Fi,;. 1 is in qualitative agreement with that previously reported for polycrystalline titanium metal. 2,3 Significant anisotropy is, however, indicated by the crossing over of the curves for <1120> and <0001> orientations at 273°, 650°, and 1000°K. This difference is most startlingly shown in Fig. 2, where instantaneous temperature coefficients (l/R273 x dR /dT) are plotted for both the first heat-

Jan 1, 1962

By George Mah, Charles Wert

Internal-friction peaks caused by diffusion of oxygen and nitrogen have been observed in ytterbium. They are thought to be caused by the redistribution, under stress, of strain dipoles around an interstitial oxygen or nitrogen and a neighboring substitutional impurity. With the use of a simple geometrical model, diffusion coefficients for oxygen and nitrogen between special interstitial sites have been calculated. a) APPLICATION OF INTERNAL FRICTION TO MEASUREMENT OF DIFFUSION RATES IN DISSOLVED INTERSTITIAL ATOMS In bcc metals, the interstitial atoms occupy the centers of cube faces (0, 1/2, 1/2), or their equivalents, the center of the cube edges (0, 0, 1/2). An interstitial atom in this position causes an aniso-tropic distortion in the lattice. When stress is applied, mechanical relaxation can take place by the movements of the interstitial atoms. This relaxation has been used to obtain information concerning the movements of the interstitial atoms in the bcc metals. Data for these alloys have been compiled by Stanley and Wert. Other researchers have extended the investigation of interstitial diffusion to the close-packed metals. Gupta and weinig2 found an oxygen peak in a titanium, the height of which is linearly dependent on the oxygen concentration. They assumed, therefore, that they were dealing with movement of atomic ally dispersed oxygen in titanium. KG and wang3 determined that the diffusion coefficients of carbon in fcc steels and in nickel obtained by internal-friction methods were consistent with those obtained by macrodiffusion methods at much higher temperatures. Bisogni found oxygen and nitrogen peaks in hafnium by use of which he deduced the diffusion coefficient of these gases in hafnium. He observed further that the half-widths of these peaks corresponded almost exactly with those of a single-relaxation process; he assumed it to be caused by movement of atomically dispersed oxygen and nitrogen. From these studies, the deduction can be drawn that, in general, diffusion data can also be obtained for the interstitial diffusion in close-packed metals (or more precisely, in slightly impure close-packed metals). One group of such metals for which little data exist for the diffusion of dissolved oxygen and nitrogen is the rare earths. They have great affinity for gases, which enter solution interstitially. In this investigation results were obtained for the Yb-O and Yb-N interstitial solid solutions with traces of substitutional impurities; these solid solutions are of fcc structure. b) MECHANISM OF THE RELAXATION IN FCC CRYSTALS In the fcc structure, an interstitial gas atom is usually situated in the octahedral position (1/2, 1/2,

Jan 1, 1964

By R. E. Hurst, D. E. Ramsey, J. M. Moore

The "frac" method of well stimulation has been applied successfully to all producing formations in the Permian Basin area. During the five years since its development, many changes and improvements have been made in treating materials. procedures, and equipie11t. A number of fluid carrying agents, having different physica1 and chemical properties, have been developed to meet variorus well requirements. The current trend is toward larger gallonage treatments, employing higher injection rates. The use of "down-the-casing" techniques has greatly reduced high surface working pressures, attributable to friction losses resulting from injection throrugh tubing. Petrographic studies of various Permian Basin formations, coordinated with laboratory and well log data, have been found a valuable guide in planning frac treat111o1t.s. A knowledge of the extent (and orientation of naturally occurring fractures and planes of weakness in the formation, aid in predicting the ultimate drainage pattern resulting from the frac treatment. INTRODUCTION The South Permian Basin covers an area in Wcst Texas and New Mexico about onc-half the size of the state of Texas, This vast region has been called the "Permian Basin" for so long that the term will he used here. It includes an area south of the Matador Arch. approximately 250 miles wide and 300 miles long. Structural features of importance within the basin are the Northwest Shelf, Eastern Platform, Midland Basin, Central Basin Platform, and Delaware Basin. The principal producing formations include sand, limestone and dolo-mite, with lesser amounts of shale, anhydrite. chert. and various silicates. All of the producing formations in the Permian Basin have responded to some type of frac treatment. Essentially, a frac treatment may be defined as the injection, into a formation. of a fluid carrying agent containing a particulated solid (usually sand), for the purpose of increasing production. The application of this method of well stimulation to many differing Permian Basin reservoirs has necessitated numerous changes and improvements in carrying agents, solids, service equipment. well equipment. and treating techniques. CARRYING AGENTS A number of different types of fluid carrying agents have been developed since the introduction of the frac method of well stimulation. These agents have different physical and chemical properties, and in many cases the extent of production increase derived from the frac treatment depends on the choice of fluid carrier. Unfortunately, due to many different systems of nomenclature used in the oil field, these differences are not always recognized by the oil Operator. In general, carving agents may he divided into the following broad classi-

Jan 1, 1956

By W. L. Phillips

Stress-strain data are reported for sodium chloride, lithium fluoride, and magnesium oxide tested in compression at diffevent strain rates in the telrlperature range from 70° to 873°K. Quantitative equations are given for the stvain-rate dependence of the critical resolved shear stress and the initial rate of work havdening. The properties so determined are compared with results previously reported for metals. ALTHOUGH the effects of strain rate and temperature on the stress-strain characteristics of metals have been extensively investigated1,2 these effects have not been studied in detail in ionic crystals. In the only previous investigations on the effect of strain rate on the deformation of ionic crystals. Gilman and gohnston3 and Hulse and pask4 have shown that the yield stress of lithium fluoride and magnesium oxide at room temperature is proportional to the ninth or tenth root of the strain rate. CRYSTAL PREPARATION Lithium fluoride, sodium chloride. and magnesium oxide single crystals were purchased from the Har-shaw Chemical Co. The compression fixture and sample preparation have been described in detail previously.5 The detectable impurities in MgO were eight parts in 105 of Fe and six parts in 105 of Si; in LiF, six parts in 105 of Mg; and in NaC1, two parts in 105 of Fe and four parts in 10&apos; of Mg. The cleaved samples measured - 0.1 in. by 0.1 in. by 0.3 in. Prior to testing all samples were annealed at -0.8 of their melting point and cooled to room tempera- ture at 50 C per hr.&apos; Samples were strained at rates (<) of 0.1, 0.01, 0.002, and 0.0002 in. per in. per min. EXPERIMENTAL RESULTS Fig. 1 is a plot of the critical resolved shear stress a,. (extrapolation of slope of easy glide region to zero strain) of sodium chloride, lithium fluoride, and magnesium oxide tested at different strain rates as a function of temperature. In all crystals at all strain rates a, decreases with increasing temperature according to an equation of the type397 where uo is a stress constant, K is a constant, and T is the absolute temperature. The points in Fig. 1 are the average of six tests. It is evident that there is a break in the log 0,- temperature plots at a characteristic temperature T,. The constant K of Eq. [I] is dependent on strain rate, Fig. 2. The relationship

Jan 1, 1962

By Carl F. Floe, John Chipman

THE system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or CO2 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modern metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100° to 1500°C., and pressures from about 20 mm. of mercury to somewhat above atmospheric. REVIEW OF PREVIOUS WORK The solubility of gases in most liquids has been found to obey Henry&apos;s law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as 02, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts&apos; law. It may be recognized as a special case of Henry&apos;s law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: [(MG) l 2M +G2 = 2MG K = Ma X Pa, [I]] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: [MG = Kl Pa,[2]] Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: [6Cu + SO2 = Cu2S + 2Cu20[3] K _ Cu2S X (Cu20)2 (Cu)6(Pso2)[4]] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: [8 =KI = Pte, or VSO2= K2 &apos;~/PeO, [S]]

Jan 1, 1941

By Clarence Zener

IT has long been known that the density of a metal usually decreases with cold-work. Thus O&apos;Neill1 observed as early as 1861 that cold hammering of commercial hot-rolled copper is accompanied by a decrease of density of 0.2 per cent, and that subsequent annealing restores the original density. The origin of this density change, however, has remained obscure. In particular, experiment has not yet decided whether it is due to the presence of small cavities and an increase in intergranular surface or to an actual expansion of the lattice itself. This uncertainty in the origin of the change in density is a reflection of our uncertainty as to the changes induced in a metal by cold-working. One school regards cold-working as a breaking up of the original grains into a large number of perfect crystallites somewhat randomly orientated with respect to one another.2 According to this viewpoint, the mere introduction of a large intercrystallite surface induces a net volume expansion. Another school regards cold-working primarily as a distortion of the grains. It is not obvious that this second viewpoint will lead to a net volume expansion. The purpose of the present paper is to show that this is indeed the case, and that this expansion is of the right order of magnitude to explain existing experimental data. The physical basis for the association of an expansion with distortion lies essentially in the variation of the elastic moduli with volume. This variation is considerable. Thus from Table I we see that a I per cent increase in volume for the case of copper will decrease the bulk modulus K by i0 per cent, the shearing modulus µ by 3.8 per cent. If we thus twist a rod through a given angle, we shall do less work upon it if it increases slightly in volume, thereby reducing the torsion modulus that involves as a factor the shearing modulus. A general principle&apos; in physics states that the rod will so adjust itself as to have a minimum potential energy consistent with the end restraints. It will therefore expand. [ ] In order to obtain a quantitative comparison with experiment, we follow Maier4 in comparing the lattice expansion with the latent energy of cold-work. This latent energy has been measured directly by Taylor and Quinney5 on copper rods subjected to torsion, and may amount to as much as 15 per cent of the total work done upon the specimens. We shall assume that this

Jan 1, 1941

By B. Silliman

The experiments detailed by Dr. Hunt,* having demonstrated the fact that the copper contained in the "clay ore" of Jones&apos;s Mine, was rendered completely soluble in the bath of ferrous chloride, used in the Hunt and Douglas process, after heating in contact with carbonaceous matter in a close vessel, I set myself to devise a form of muffle furnace adapted to the treatment of large quantities of these and similar ores by a continuous process. The result is shown in the diagrams on Plate X, reduced from the working drawings, after which this furnace was built early in 1876, at Phœnixville, by the Chemical Copper Company on their works at this place. The peculiar character of this ore determined the form, dimensions, and position, with reference to charging and discharging of these muffles. The ore arrived from the mine with from 20 to 25 per cent. of moisture, and when dried at 21o F., or more slowly at lower temperature, it falls to a light incoherent powder, with occasional lumps of undecomposed rock. In this condition it is readily mingled with coal-dust or any like reducing agent, and requires no other preparation for the muffle than the use of the shovel, to mix it well with the reducing agent. As it is a remarkably good non-conductor of heat, it was obvious that the mass, to be heated through in a reasonable time, must not be too thick, while the weight of the mass must be sustained in a way to avoid undue strain upon the walls of the muffle. These walls must be as thin as practicable, to favor the more rapid transmission of heat, and must, therefore, be so constructed as to admit of being stayed on the sides at frequent intervals to resist the lateral thrust of the very mobile mass of pulverulent ore, which, for obvious reasons, must be charged at the top and drawn from the bottom of each chamber. These considerations led to the form adopted, viz., two vertical muffles, standing upon very strong bridge tiles, seen in longitudinal section, on the line E, F, and in plan in Fig. 3, on the same plane. (Plate X.) The vertical section of the muffle is seen in Fig. 4, drawn in the plane G, H, of the longitudinal section, Fig. 6, which is the key to all sections. The walls of the muffles are built of the best firebrick, very care-