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By George C. Ference

Sulfur is the 13th most common element in the earth's crust, constituting approximately 0.05% of the total. It occurs naturally in its elemental form, as metallic sulfides, nonmetallic sulfates, and as combined or free sulfur in natural gas, crude oil, and coal. COMMERCIAL SOURCES Most of the sulfur that is consumed is converted into sulfuric acid before use; therefore, it is not necessary to recover sulfur solely in its elemental form. Processes for recovery are peculiar- to the types of reserves being processed. The major commercial processes as well as the general geographic locations where the appropriate reserves occur are listed in the following. It should be noted that the sulfur values may be recovered as the primary product, as a coproduct with other materials, or as a byproduct. Elemental Sulfur 1) Frasch mining is used for subterranean deposits of elemental sulfur around the Gulf Coast areas of the United States and Mexico. Generally, but not exclusively, such deposits are located in salt dome structure. 2) Autoclaving, flotation, or solvent extraction of surface deposits of elemental sulfur is practiced throughout the world. 3) Extraction and conversion of hydrogen sulfide from sour natural gas into elemental sulfur is done principally in Canada, France, and the United States. 4) Conversion of metallic sulfides from pyrites into elemental sulfur is done via the Outokumpu process in Finland. 5) Catalytic cracking and hydrocracking of sulfur-bearing crude oils to produce elemental sulfur is done worldwide. Desulfurization of refined petroleum products also yields elemental sulfur. 6) Recovery of elemental sulfur from sulfur-bearing oil sands (Athabasca tar sands) has been initiated in Canada. 7) As of this writing (1970), a plant has been constructed for the thermal decomposition of gypsum to produce elemental sulfur in the United States. Sulfuric Acid Sulfur values in the form of sulfuric acid are recovered via: 1) Recovery from smelter gases throughout the world. 2) Roasting of pyrites throughout the world with iron sinters as a byproduct. 3) Roasting of anhydrite with cement as a coproduct, primarily in Europe. 4) Processes currently are being developed for recovery of sulfuric acid from combustion gases resulting from the burning of high-sulfur-content fuel. Other Sulfur values also are recovered from waste products which normally occur in highly industrialized areas. Some examples are: coke-oven gases, sludge sulfuric acid, and pickling liquors (ferrous sulfate).

Jan 1, 1976

By C. D. King

THIS year the American Institute of Mining and Metallurgical Engineers celebrates its seventy-fifth anniversary as well as the same anniversary of iron and steel in this country as we now know it. The society's span of life comprehends the very beginning and gradual development of the present-day iron and steel industry and its TRANSACTIONS are rich with the trials and achievements of the pioneers in this field. It is difficult to believe that in the first year of the Institute's existence there was produced in this country only 84,000 net tons of ingots, of which only 2000 tons was made by the open-hearth process; that the bessemer process was just barely beginning; that charcoal and anthracite were virtually the only blast-furnace fuels; that Mesabi ores had not been used in blast furnaces, and such pig iron as was then made was produced at a number of small units, each adjacent to its ore and fuel supply. The growth from 84,000 net tons production of steel ingots to 95,500,000 tons in 1945 eloquently tells the story of America's industrial growth.

Jan 1, 1947

By T. B. Counselman

AfteR several years study, the Universal Atlas Cement Co. decided to rebuild its plant at Leeds, Alabama. The entire old plant, which was to operate during the new construction, was then to be scrapped with the exception of two kilns. The quarry was to be mechanized, new and larger kilns installed, with the most modern type of equipment all through the plant. Raw grinding operations at all of the Universal Atlas plants were dry. However, the dust hazard of this operation and the growing emphasis on occupational diseases made wet grinding attractive. Coal at Leeds is cheap, so that a slightly higher coal practice was unimportant. Power was cheap, so that waste-heat boilers were not desirable. Since new kilns were to be installed, these could be made long enough to make filters unnecessary. Wet raw grinding could be either the old practice of open-circuit compartment mills or closed-circuit grinding in accordance with metal-lurgical practice. The latter saved power and steel wear and saved initial investment. This had been demonstrated in cement plants. Also, the elimination of tramp oversize was a most important advantage. Ease of chemical control was another factor. Blending in the thickener, with elimination of slurry mixers had been found practicable. Therefore, if wet raw grinding were used at all, the advantages were clearly in favor of closed-circuit grinding. Detailed layouts of the most modern possible closed-circuit dry-grinding plant and of a closed-circuit wet-grinding plant were prepared, and careful estimates were made of initial investment and operating costs. Full consideration of all the factors involved resulted in a decision to install wet closed-circuit grinding. The capacity of the new kilns was established at 4000 bbl. per day. Two new kilns were installed, each with a capacity of 80 bbl. per hour. Since 625 lb. of raw material is required to make a barrel of finished cement, the capacity of the grinding plant for the new kilns had to average only 1250 tons per day. Sufficient additional grinding capacity had to be provided for the two remaining old kilns, or their possible replacement by a third new kiln. The grinding rate, therefore, was set at 90 tons per

Jan 1, 1939

By T. B. Counselman

AfteR several years study, the Universal Atlas Cement Co. decided to rebuild its plant at Leeds, Alabama. The entire old plant, which was to operate during the new construction, was then to be scrapped with the exception of two kilns. The quarry was to be mechanized, new and larger kilns installed, with the most modern type of equipment all through the plant. Raw grinding operations at all of the Universal Atlas plants were dry. However, the dust hazard of this operation and the growing emphasis on occupational diseases made wet grinding attractive. Coal at Leeds is cheap, so that a slightly higher coal practice was unimportant. Power was cheap, so that waste-heat boilers were not desirable. Since new kilns were to be installed, these could be made long enough to make filters unnecessary. Wet raw grinding could be either the old practice of open-circuit compartment mills or closed-circuit grinding in accordance with metal-lurgical practice. The latter saved power and steel wear and saved initial investment. This had been demonstrated in cement plants. Also, the elimination of tramp oversize was a most important advantage. Ease of chemical control was another factor. Blending in the thickener, with elimination of slurry mixers had been found practicable. Therefore, if wet raw grinding were used at all, the advantages were clearly in favor of closed-circuit grinding. Detailed layouts of the most modern possible closed-circuit dry-grinding plant and of a closed-circuit wet-grinding plant were prepared, and careful estimates were made of initial investment and operating costs. Full consideration of all the factors involved resulted in a decision to install wet closed-circuit grinding. The capacity of the new kilns was established at 4000 bbl. per day. Two new kilns were installed, each with a capacity of 80 bbl. per hour. Since 625 lb. of raw material is required to make a barrel of finished cement, the capacity of the grinding plant for the new kilns had to average only 1250 tons per day. Sufficient additional grinding capacity had to be provided for the two remaining old kilns, or their possible replacement by a third new kiln. The grinding rate, therefore, was set at 90 tons per

Jan 1, 1939

By J. B. Austin, R. L. Rickett

MEASUREMENTS Of the rate of decomposition of austenite at constant temperature are commonly represented by plotting the percentage transformed on linear coordinates against time on either a linear or a logarithmic scale, a method that yields a curve that in shape resembles an integral sign (Fig. 1). A graph of this kind is not always convenient because extrapolation to the beginning or end of the transformation, or even interpolation, may be uncertain unless there are a large number of observations, which seldom happens; furthermore, the degree of consistency of a set of measurements is difficult to judge from such a curve. It is desirable therefore to find some mode of plotting, or even better to find a standard variety of graph paper, that gives a straight line instead of the integral shape. The straight line has many advantages; the number of readings required to fix the position of the curve is greatly reduced, interpolation is easy and rapid, extrapolation can be carried out with greater confidence and, finally, the consistency of the measurements is readily estimated from the scatter of the points. The last advantage is particularly valuable when the data are obtained by direct microscopic examination alone, because they are influenced by the skill of the observer in estimating the relative size of areas, possibly also by undetected inhomogeneity of the specimen. A search for ways of representing the observations as a straight line yielded two methods which are described in this paper. The paper also includes an account of some interesting relations brought to light in applying these methods to the available experimental data. Usually the best way to derive such a method of plotting is to base it on established principles of chemistry and physics, as has been done, for example, for the temperature variation of the equilibrium constant of a chemical reaction. But so little is known of the mechanism of the decomposition of austenite, and so little is available in the way of well established background for changes of this kind, that it is simpler to rely upon purely empirical means. The general plan therefore is to study existing data with a view to finding some function of the direct observations that will

Jan 1, 1938

By Nicholas J. Grant, John Chipman

A full understanding of the behavior of sulphur in the basic open-hearth process has been delayed by lack of dependable data covering a wide range of slag conditions in the absence of other complicating factors that are likely to be present under operating conditions. It has been generally accepted that strongly basic slags will dissolve more sulphur than will those in which the acidic and basic constituents are more nearly balanced. It has been known that both slag and metal would absorb sulphur from the flame when the sulphur content of the fuel is high. It has been generally believed that manganese assists in the transfer of sulphur from metal to slag. Almost nothing has been known of the effect of temperature upon desulphurization;the data have been conflicting and there has been a tendency to depend rather heavily upon analogy with the better understood desulphurizing reaction of the blast furnace. Many attempts have been made to build up from open-hearth data a satisfactory theory of the chemical reactions involved in the process. That this has been an extremely difficult task is owing to two reasons that have been very generally recognized. The first is the parallel and simultaneous reaction of sulphur transfer between flame and bath. The second is the difficulty of distinguishing between the factors that ultimately limit the transfer from metal to slag—i.e., equilibrium conditions—and those whose influence is only upon the rate of transfer. It has been the object of the work here recounted to study the equilibrium distribution of sulphur between slag and metal in the absence of these complicating factors, with the hope that a better understanding of the equilibria involved would lead to a better control of the over-all process in the open-hearth furnace. A review of the literature on steelmaking reveals almost complete agreement with respect to the paramount importance of lime in promoting desulphurization. In expressing this effect in quantitative terms, however, and in formulating the relationships between the concentrations of other slag components and the desulphurizing power, there is little agreement. For instance, the "basicity" or basic strength of the slag is commonly measured by some kind of ratio of concentration of basic to acidic oxides. Of these, the following have been reviewed by Schenck:20 V radio = % CaO/%SiO, Körber and Oelsen's _ % CaO'. 100/% CaO + % SiO2 where (%CaO') = % CaO- 1.18% P2O5. Herty's B ratio = % CaO - (0.93 . % SO2) - (1.18% P205) Among others there appear the following: 20 References are at the end of the paper.

Jan 1, 1947

By Nicholas J. Grant, John Chipman

A full understanding of the behavior of sulphur in the basic open-hearth process has been delayed by lack of dependable data covering a wide range of slag conditions in the absence of other complicating factors that are likely to be present under operating conditions. It has been generally accepted that strongly basic slags will dissolve more sulphur than will those in which the acidic and basic constituents are more nearly balanced. It has been known that both slag and metal would absorb sulphur from the flame when the sulphur content of the fuel is high. It has been generally believed that manganese assists in the transfer of sulphur from metal to slag. Almost nothing has been known of the effect of temperature upon desulphurization;the data have been conflicting and there has been a tendency to depend rather heavily upon analogy with the better understood desulphurizing reaction of the blast furnace. Many attempts have been made to build up from open-hearth data a satisfactory theory of the chemical reactions involved in the process. That this has been an extremely difficult task is owing to two reasons that have been very generally recognized. The first is the parallel and simultaneous reaction of sulphur transfer between flame and bath. The second is the difficulty of distinguishing between the factors that ultimately limit the transfer from metal to slag—i.e., equilibrium conditions—and those whose influence is only upon the rate of transfer. It has been the object of the work here recounted to study the equilibrium distribution of sulphur between slag and metal in the absence of these complicating factors, with the hope that a better understanding of the equilibria involved would lead to a better control of the over-all process in the open-hearth furnace. A review of the literature on steelmaking reveals almost complete agreement with respect to the paramount importance of lime in promoting desulphurization. In expressing this effect in quantitative terms, however, and in formulating the relationships between the concentrations of other slag components and the desulphurizing power, there is little agreement. For instance, the "basicity" or basic strength of the slag is commonly measured by some kind of ratio of concentration of basic to acidic oxides. Of these, the following have been reviewed by Schenck:20 V radio = % CaO/%SiO, Körber and Oelsen's _ % CaO'. 100/% CaO + % SiO2 where (%CaO') = % CaO- 1.18% P2O5. Herty's B ratio = % CaO - (0.93 . % SO2) - (1.18% P205) Among others there appear the following: 20 References are at the end of the paper.

Jan 1, 1947

By V. F. Leferrer

A new process for the treatment of silver crusts from desilverization of lead has been developed by Societe de Penarroya. The zinc contained in the crusts is recuperated by vacuum distillation at low temperature. The use of special retort crucibles is avoided. AT Noyelles-Godault the Parkes process (zinc addition to a silver-bearing lead melt) is used to desilverize lead bullion from the blast furnace. The crust which rises to the surface of the bath is removed and pressed by a well-known process in a press of the Howard type. The pressed crust, called zinc crust or silver crust, contains 10 pct Ag, 30 pct Zn, and 60 pct Pb. It is melted under a salt bed in a small, narrow, and deep kettle heated only in its upper part. A liquid concentrated alloy is obtained which is called T.A.C. in France (triple alliage concentr6) analyzing approximately 25 pct Ag, 65 pct Zn, 8 to 10 pct Pb, and 1 to 1.5 pct Cu. This T.A.C. is a real metallic alloy, completely deoxidized, and can be stored indefinitely. The process used at Noyelles-Godault consists in distilling this alloy in a tight furnace, under low vacuum and at low temperature, so that only the zinc distills and is condensed into liquid form. The residual silver-bearing lead is almost entirely free from zinc and oxidized dross. The vacuum dezincing equipment, see Figs. 1 and 2, consists of: 1) A furnace, constituted of a casing of steel plate lined with refractory bricks, heated internally by means of graphite resistors. The temperature of the furnace is measured by a thermocouple device and controlled by an automatic temperature regulator which acts upon the flow of the current passing through the resistors. Two doors, numbered 1 and 2 in Fig. 2, are provided for, one for charging the T.A.C., the other for tapping the high silver-bearing lead. 2) A condenser, and an ordinary room lined with good heat conductor refractory material. This condenser is provided with a graphite resistor which serves to bring to temperature when starting the furnace. A thermocouple records the temperature of the zinc melt and controls the temperature in the furnace, that is, the flow of current through the resistors, by means of the above mentioned regulator, so that the distillation rate in the furnace does not exceed that of the condensation. The condenser is connected to the vacuum pump by a filter. The whole equipment should, of course, be fluid-tight. The operation is carried out under a vacuum of about 10 mm Hg.

Jan 1, 1958

By Nicholas J. Grant, John S. Benjamin

A series of composite alloys containing a high volume of NiAl, Ni3Ah or CoAl, bonded with 0 to 40 vol pct of a ductile metal phase, were prepared by powder blending and hot extrusion. The binder metals were of four types: pure nickel or cobalt, near saturated solid solutions of aluminum in nickel and cobalt, type 316 stainless steel, and niobium. Sound extrusions were obtained in almost all instances. Studied or measured were the following: interaction between the alunzinides and the binders, room-temperature modulus of rupture values, 1500° and 1800°F stress rupture properties, hardness, structure, and oxidation resistance. Stable structures can be produced for 1800°F exposure, with interesting high-temperature strength and good high-temperature ductility. Oxidation resistance was excellent. A large number of experimental investigations have been made of the role of structure on the properties of cermets and composite materials. Gurland,1 Kreimer et al.,2 and Gurland and Bardzil3 have indicated the preferred particle size in carbide base cermets to be about 1 µ, with a hard phase content of 60 to 80 vol pct. The optimum ductile binder thickness was noted to be 0.3 to 0.6 µ.1 Complete separation of the hard phase particles by the binder is important in reducing the severity of brittle fracture.' The purpose of the present study was to produce structures comparable to the conventional cermets, using a series of relatively close-packed intermetal-lic compounds rather than carbides as the refractory hard phase, and to study the effects of binder content and composition on both high- and low-temperature properties. The selected intermetallic compounds were particularly of interest because of the potential they offered in yielding room-temperature ductility. The highly symmetrical structures are known to possess high-temperature ductility and room-temperature toughness. Based on a ductile binder, the alloys were prepared by the powder-metallurgy route to avoid melting and subsequent alloying of the matrix, and were extruded at relatively low temperatures. It was expected that the composite alloy would retain useful ductility. In contrast, infiltration and high-temperature sintering led to alloying of the matrix and to decreased ductility. The systems Ni-A1 and Co-A1 were selected for this study. In the Ni-A1 system the compounds NiA1, having an ordered bcc B2 structure, and Ni3Al(?1), having an ordered fcc L12 structure, were chosen. In the system Co-A1 the intermetallic compound CoAl with an ordered bcc B2 structure was used. ALLOY PREPARATION The intermetallic compounds, see Table I, were prepared by using master alloys of Ni-A1 and CO-A1, with additions of either cobalt or nickel to achieve the desired compositions. The master alloy in crushed, homogenized form, was melted with pure nickel or cobalt in an inert atmosphere, cold copper crucible, nonconsumable tungsten arc furnace. The resultant intermetallic compounds were homogenized at 2192°C in argon, crushed, and dry ball-milled in a stainless mill to -100 and -325 mesh for the Ni-A1 compounds and to -325 mesh for the CoAl compound. Finer fractions were separated for some of the composite alloys. Several ductile binders were utilized. These included Inco B nickel, 5µ ; pure cobalt, 5 µ, from Sher-ritt Gordon Mines, Ltd.; fine (-325 mesh) niobium hydride powder; fine (15 µ) type 316 stainless-steel powder; and near-saturated Ni-A1 and Co-A1 solid-solution alloys, also in fine powder form. The niobium hydride was decomposed above about 700°C in processing of the compacts in vacuum to produce niobium powder. The Ni-7.1 pct A1 and the Co-5.3 pct A1 solid-solution alloys were prepared from pure nickel or cobalt and pure aluminum by nonconsumable tungsten arc melting under an inert atmosphere. The ingots were homogenized, lathe-turned to fine chips, and dry ball-milled in air to -325 mesh powder. These solid-solution alloys are designated NiSS and CoSS; see Table I. Subsequently the hard and ductile phases were dry ball-milled as a blend. Experiments clearly established the need to coat the hard particles with the ductile binder to optimize subsequent hot compaction by extrusion. Ordinary dry mixing usually resulted in nonhomogeneous alloys which were quite brittle. Conventional cermets are consolidated by liquid phase sinteiing or infiltration, which resulis in undesirable and uncontrolled alloying of the binder phase. For this study, a loose (unsintered) powder-extrusion process was emploved, minimizing reactions between binder and hard particle, thereby permitting much greater control of composition and structure. The constituent powders were first mixed in the desired

Jan 1, 1967

By W. C. Clarke

An empirical study of the nature of the embrittle-ment which occurs in martensitic and semiaustenitic precipitation hardening stainless steels upon exposure at temperatures of from about 550" to 875°F has been undertaken. This work was aimed at determining cazusation and means of controlling this phenomenon. A commercial copper bearing precipitation hardening alloy was used as a basic material for study. The effect of heat treatment variables was studied as was the effect of variations in analysis. It is concluded from the evidence that martensitic and semiaustenitic precipitation hardening stainless steels are subject to 885°F ernbrittlement similar to that observed in the straight chromium stainless steels. A characteristic of precipitation hardening stainless steels which has limited their use in certain applications is that they embrittle when held at temperatures in the range of from about 550" to 900°F. This is true to a more or less degree in all currently available alloys, either the basically martensitic type or the semiaustenitic type. The rate of embrittlement varies markedly with exposure temperature, being low at 550" to 600°F and in-creasing as the temperature increases. In spite of this embrittlement, these alloys with their unique combination of high mechanical strength, reasonable toughness, and good corrosion resistance are used in many hundreds of applications. Nevertheless, there are potential applications where the embrittle-ment described is a limiting factor. The purpose of this investigation was to study the embrittlement of these alloys and to find a way to control or eliminate it. GUIDELINES USED IN PRESENT WORK The work reported in this paper is based on a study of 17-4 PH*, a very widely used alloy. It has been used *Trademark of Armco Steel Corp., licensor. in pressurized water and boiling water atomic reactors operating at about 550°F for a number of years. As the life of such equipment is extended or operating temperatures are raised, the possibility of embrit-tlement becomes of increasing concern to materials engineers. Much investigation work was done with respect to the use of 17-4 PH at 550°F. K. C. Antony' states "Such estimation" (of an activation energy for the diffusion of chromium in iron) "would indicate W. C. CLARKE, Jr. is Senior Research Engineer, Advanced Materials Division, Armco Steel Corp., Baltimore. Md. This manuscript is based on a talk presented at the symposium on New Developments in Stainless Steel, sponsored by the IMD Corrosion Resistant Metals Committee, Detroit, Mich., October 14-15, 1968. significant secondary aging is improbable at temperatures less than 700°F within normal component service life". This statement is modified however by the recognition of the accelerating tendencies of applied stress and internal stress as well as the possible effect of irradiation. In this investigation of 17-4 PH, the H 1100 (1900°F-1 hr oil quench or air cool + 1100°F-4 hr-air cool) condition was used, partly because this condition is normally used in atomic reactors. As shown later, the precipitation hardening temperature has no real bearing on the rate of embrittlement. An exposure temperature of 800°F was selected since embrittlement at 800°F is rapid, permitting development of relative data in time periods of 400 to 500 hr. For those not familiar, a nominal present day analysis of 17-4 PH is: C Mn P S SiCrNiCuCbN 0.04 0.30 0.015 0.015 0.60 16.00 4.30 3.25 0.23 0.030 TYPICAL BEHAVIOR OF 17-4 PH Figs. 1 and 2 show the behavior of a commercial heat of 17-4 PH under the conditions defined. Characteristically, 800°F exposure causes a rapid drop in Charpy V-notch impact strength. Tensile and yield strengths gradually increase and a gradual loss of elongation and reduction of area occur, accompanied by an increase in hardness. Notched tensile strength increases to 125 hr exposure and then sharply decreases after exposure for 500 hr. The notched vs un-notched tensile ratio remains virtually constant to exposure for 125 hr (1.67 to 1.56) but drops to 1.15 after 500 hr. Tensile ductility is not alarmingly affected even after much longer exposure times than these. For example, samples aged at 1100°F for 1 hr exposed at 800°F for 4000 hr showed a drop in elonga-tion of from 13 to 11 pct and in reduction of area of from 58 to 37 pct. Notched impact is the property SmIgth KSI 3JJ[/__________^UTS-Nrteh 260 ;/- 240 —^ 200 UTS-Smooth________._, o ioo mo Sob" m Too Hours Exposure Fig. 1—Effect of exposure at 800°F for various times on notched tensile strength and smooth tensile and 0.2 pct yield strength of 17-4 PH in the H 1100 condition.

Jan 1, 1970

By B. M. Loring, I. R. Kramer, F. M. Walters

No observations on the mechanical properties of iron-manganese alloys have been published since pure manganese became readily available, either distilled manganese or electrolytic manganese. The purpose of this investigation was to determine whether iron-manganese alloys are essentially brittle, as reported by Hadfield,1 or whether the lack of ductility observed was due to impurities in the alloys that he studied. EXPERIMENTAL METHODS The alloys were melted in a 100-lb. high-frequency induction furnace with a magnesia crucible, using ingot iron and electrolytic manganese. The heats were split, the first giving six 18-lb. ingots and the second three. Each successive heat was higher in manganese and about 0.3 per cent silicon [ ] was added as ferrosilicon. The alloys forged without difficulty-and were given a 90 percent reduction to 3/4-in. rounds. The chemical analysis of the alloys is given in Table I. The forged rods were homogenized for [ ] 24 hr. at 1150°C. (2100°F.) and air-cooled. The alloys were tested in two conditions of heat-treatment: (I) as normalized from 870°C. (1600°F.) and (2) normalized from 870°C. and tempered for z hr. at 540°C. (1000°F.) and air-cooled. The tensile specimens were 0.505 in. in diameter with a 2-in. gauge length, and the impact specimens were V-notch Charpy. The proportional limit and yield strength were taken from the stress-strain diagrams drawn by a Peters recorder. The data obtained from the tensile test and the hardness measurements are given in Table 2. Specimens that were normalized are designated by N; those that were normalized and tempered by T. Alloy G was tempered after forging (D).

Jan 1, 1941

By C. B. Alcock, R. A. Oriani

Some simple models of solutions are described; these include the regular solution, the subregular solution, and the quasichemical model. The assunzption underlying these models, the physical signzficance thereof, and the experimental manifestations are discussed. Examples are presented from the fields of liquid and solid metallic solutions, liquid slags, mattes, liquid and solid ionic solutions, and mixed carbides to show under what conditions and for which systems these solution models are fair descriptions. The deviations of real solutions from the models are of theoretical interest. Some such deviations, both for dilute and for concentrated solutions, arc pointed out and their Physical sigtzzficance discussed. DURING the past half century there has been a gradual accumulation of thermodynamic data for systems of interest to the metallurgist. There remain many gaps in the data, however, and the metallurgist must often face the problem of estimation of thermodynamic quantities where measured values do not exist. One might hope that the experimental progress would be matched by theoretical advances which would make such estimations possible with a high degree of confidence. However, theoretical progress has been disappointingly slow even for the simplest kinds of solutions, and since the multicomponent systems in which the metallurgist is interested are very complex, one cannot expect theory to be of much help to the metallurgist. In this situation, therefore, it seems worthwhile to examine some simple models of solutions from two points of view: firstly, to see if such crude models represent the thermodynamic facts in as many types of solutions as possible sufficiently well for the needs of the metallurgist, and secondly to see what the deviations from such models show to be important for consideration by theorists. BOND ENERGY MODELS OF SOLUTIONS The simple models that we will examine from these points of view may be termed statistical models, in that they are concerned with the thermodynamic consequences of some simple assumptions about the energy of an assembly of atoms, molecules, or ions, and do not inquire into the physical basis of the interaction. The underlying assumption of these models is that the energy of an assembly of molecules (by which we include also atoms or ions) is given by the sum over all interaction energies of molecules taken two at a time; we will discuss only those models in which the pairwise interactions are restricted to those between nearest neighbors. Thus, in a pure substance of bond energy EAA, the internal energy (with respect to some specific reference state) will be expressed as NAA EAA where NAA is the number of nearest-neighbor pairs. A solution of molecules A and B will be characterized by NAA EAA + NBB EBB + NAB EAB where the Eij represent the bond energies of the nearest-neighbor i-j pairs. If one assumes that the EAA and EBB are the same in the pure components as in the solution, and that the coordination numbers in the two pure substances and in the solution are the same, then the energy of the solution with respect to the pure components (i.e., the energy of solution) is a function of the following linear combination of the bond energies: EAB - 1/2(EAA +EBB) = w. The thermodynamically ideal solution is defined as one in which the activity of each component is equal to the mole fraction of that component at all concentrations and all temperatures. It follows that

Jan 1, 1962

By Grimes, J. A.

EXTENSIVE discovery 'and rapid exploitation of orebodies within the past half century have attracted many able geologists to the mining industry and furnished them a wealth of data from which to develop theories concerning ore genesis. By tosting and elimillating theories which are not sufficiently sup- ported by fact, or which are based on inaccurate observation of field data, the trend of geological opinion has . moved strongly in certain directions until, at the present time, large numbers of geologists subscribe to a broad concept of .ore genesis that I would summarize as below:

Jan 1, 1928

By Max Ball

AN intelligent discussion of the oil situation and its needs, whether from the standpoint of the prospector, the operator, the engineer, or the public administrative officer, must be founded upon a knowledge of the law under which oil lands are obtained. A consideration of new legislation must be prefaced by an understanding of the present law and its results. This paper undertakes to present no new remedy for the ills of the present situation, no new solution of the problems the oil business is facing. It attempts merely to summarize the present law, its provisions, its origin, its development, and its effects. The discussion does not pretend to be exhaustive from a legal standpoint. It aims to avoid legal intricacies Which tend to confuse rather than clarify. It seeks but to present the essentials of the existing situation. The title to government lands known to contain valuable deposits of petroleum may be acquired only under the terms of the placer law as embodied in Section 2329 et seq. of the Revised Statutes. As a preliminary to considering the desirability of this situation it is profitable to examine into its origin. ORIGIN OF THE LAW Congress has left no room for doubt as to the legal applicability of the placer law to oil lands. The Act of Feb. 11, 1897 (29 Stat., 526), provides: "that any person authorized to enter lands under the mining laws of the United States may enter and obtain patent to land containing petroleum or other mineral oils, and chiefly valuable therefor, under the provisions of the laws relating to placer mineral claims."

Jan 6, 1914

Society of Chemical Industry (London), American Section. Foster D. Shell, Secretary, 130 Clinton St., Brooklyn, N. Y. Publications of this Society are not of direct interest in this directory but the address of the Society is listed that the reader may have it on record for reference. Subscription to the Journal (A the Society costs £ 2 10s, or $12.50 at the normal rate of exchange. Individual copies are is 9d, postage extra.

Jan 1, 1933

By D. R. Walker, M. C. Shaw

The laws of Kick and Rittinger are explained as functions of particle size with metal cutting theory. Comminution is shown to be basically the same process as metal grinding. The machine shop type of grinding operation is used to study mineral crushing. Evidence indicates that plastic flow occurs in comminution. THE laws of comminution of Kick and Rittinger have been debated for many years. Certain data obtained from ball mill and drop tests are found to be in approximate agreement with Rittinger's law while other data would seem to support Kick's law. In all these tests the energy required to produce a wide variety of particle sizes has been studied. Surface area has also been measured with considerable difficulty, at first because it was thought that the energy associated with crushing was that required to create new surface, later because of precedent and because a more fundamental variable was unknown. Tests made with the machine shop type of grinding process show that normally brittle materials that are usually crushed can behave like the more ductile metals. Brittleness is then a relative prop- erty largely dependent on specimen size and stress state. The machine grinding operation offers a convenient means for studying the comminution of materials in which the important size variable retains its identity. The energy required to grind a certain volume of material is shown to be strongly dependent on size. Kick's law is found to hold very well for particles below 1 micron in size, while Rittinger's law holds approximately in the comminution of larger particles. While a physical origin of Kick's law is established in terms of the theoretical strength of materials having a perfect lattice structure, there is found to be no physical basis for Rittinger's law. Because of its industrial importance, comminution has commanded considerable technical attention and has been the subject of continuous study for nearly a century. A number of empirical rules have been proposed to make it possible for grinding energies to be predicted. Of these so-called laws of comminution those bearing the names of Kick and Rittinger have been most widely applied and debated.

Jan 1, 1955

By E. Lancaster-Jones

THE gravity magnitudes obtained by means of observations with the Eötvös balance in the field are necessarily resultant or total effects due to all abnormalities of mass distribution, including even the effects due to the ellipticity and rotational motion of the whole earth. Since the object of the survey is to isolate the effects which arise solely from some particular subterranean feature, and to deduce therefrom the configuration and extent of this feature, the first step is to eliminate from the observed effects all those due to "disturbing" (i, e., unwanted) features, whether above or below the surface of the ground. The disturbing features have different characteristics, according to their situation relative to the center of the balance and to the horizontal plane through the foot of the balance, or station point; this diversity was recognized by Eötvös, who divided the total effects into so-called Normal, Terrain, Topographical, Cartographical and Subterranean effects. This classification has been adhered to by most subsequent investigators, but the writer prefers to employ the term "three-dimensional," which really indicates the essential character of the class of effect known as "Subterranean," at any, rate from the standpoint of the computer of effects. Before disturbing effects can be eliminated, the features must be measured up or surveyed, whether by topographical, mining, or boring methods, and then the effects of each feature calculated and subtracted from the total observed effects. After this the problem of interpreting the residual effects will itself necessitate the computation of the assumed feature, or even a series of trial features.

Jan 1, 1928

By J. T. Norton, Pekka Rautala

The phases and equilibria in the W-Co-C system have been studied by X-ray diffraction methods, metallographic technique, and thermal analysis. In addition to the 7 phase, two double carbides, called 8 and have been revealed. The compositions correspond to CO3 W6C2 and Co3-W10C4. The reactions leading to these phases have been explained and tentative diagrams of stable and metastable equilibria proposed. The basic reactions in sintering cobalt cemented tungsten carbides are discussed. THE W-Co-C system is of fundamental importance in practical carbide manufacturing as well as for the understanding of the sintering mechanism. Surprisingly little is known about this system, for the probable reason that all the important alloys are of two-phase structure and that the diagram Co-WC has been treated as a quasi-binary. This obviously is incorrect, because WC decomposes before melting. One ternary phase, 7, of composition Co3W3C has long been known. It was first studied by Adelskold, Sundelin, and Westgren,1 although the isomorphous iron-tungsten carbide was known earlier. There have been in the literature several reports of two 7 phases.' " Also the 7 phase has been considered unstable by Takeda4 and Westgren.1 The Co-WC diagram has been studied by Wyman and Kelley5 and a quasi-binary diagram has been published by Sandford and Trent.2 Takeda has published a tentative Co-W-C diagram, considering both metastable and stable equilibria. However, the lines of two-fold saturation are shown only partially and it seems impossible to complete the diagram without violating the phase theory. Therefore it seemed desirable to examine the system in more detail. Experimental Procedure The alloys used in the present investigation were made of powders of tungsten, tungsten monocarbide, cobalt, and carbon and were of the grade used in manufacture of commercial cemented carbides. The powders were ground and mixed in small stainless steel ball mills, using balls of the same material. Benzene was used as a dispersing agent. The mixing period was 1 hr, since this was shown to give suffi- ciently good mixing of the powders without too great a contamination from the mill. After ball milling, the specimens were pressed in cylindrical or rectangular dies. No paraffin or other lubricant was used and the small compacts had sufficient green strength to be handled without difficulty. Several sintering furnaces were employed. The most satisfactory arrangement was a vacuum furnace based on the Arsem principle which employed a graphite helix as the resistance heating element. Specimens were placed on graphite stands and there was generally a slight carburization or decarburiza-tion of the specimen surface, depending on the carbon content of the alloy. The evaporation of the cobalt at a sintering temperature of 1400°C was not significant, but became severe at 1500°C and higher. The sintering time was 1 hr at 2000°C and 2 to 4 hr at lower temperatures. It was not possible to quench the specimens, but the cooling rates were rather fast, greater than 300°C in the first minute. In the system under investigation, the reactions are sluggish, and it is believed that the high temperature structures are satisfactorily retained. The principal method of investigating the sintered specimens was X-ray diffraction by the Norelco recording spectrometer. Approximate determinations of the phase boundaries were made by the disappearing phase method. Ternary Phases To study the phase formation in W-Co-C system, a series of specimens was sintered at 1400°C. In this experiment two ternary phases, called here ? and k were formed in addition to the well-known 7 phase. The 7 phase, which has been completely described by Westgren: showed a range of homogeneity from 7 to 20 pct C and from 38 to 48 pct Co. At 1400°C the 7 phase was found to be in equilibrium with monotungsten carbide, 8, tungsten, 8, #?, and liquid. The boundaries toward #? and liquid were difficult to determine and appeared to be very temperature sensitive. The other boundaries are believed to be well fixed. The homogeneity range of 7, as measured in this work, is considerably smaller than the one

Jan 1, 1953

ANY discussion of State-supported schools of mining and metallurgy needs to be prefaced by a definition, since the first school to offer a mining curriculum, the Pennsylvania. Polytechnic College, was established by a grant from the State. But, so far as can be determined, it received no further State support. It would be tiresome to go into precise details, and it will be enough to stipulate that by State schools are meant those which derive their main financial support from regular appropriations made by a State legislature. The University of Michigan was the first of these to. offer a mineral industry curriculum; its story, as well as those of Wisconsin and Illinois, has been related in the preceding chapter.* Arranging the others in chronological order involves making a decision as to what weight to attach to plans for giving instruction, as contrasted with its effective initiation. This may appropriately be illustrated by the history of mineral industry education in California. CALIFORNIA Among those who came to California in 1849 and the following years were many New Englanders who had a keen interest in education. Some of them, mostly Congregationalists and Presbyterians, sought to establish a school of higher education around San Francisco Bay and eventually succeeded in opening the "Scientific and Classical School at Contra Costa" in Oakland, at Broadway and 5th St., on June 90, 1853. This prospered so well that it was chartered by the State as the College of California" on April, 13, 1855. Developing so rapidly that its quarters became. cramped, in 1864 it not only bought a tract of

Jan 1, 1941

By L. C. Morganroth

From a geological standpoint, but scant attention has been paid to fire-clay beds. Only within the last few years have they been the subject of individual investigation, prior to this time having been considered only in their relation to coal seams. While the relative importance of coal and fire clay is still immeasurably in favor of coal, yet an industry as large as that of fire clay is entitled to a measure of attention. A discussion of the Carboniferous clays is practically a discussion of the clay beds in the Appalachian basin, since more than 90 per cent. of these clays mined are from this region. The clays are confined to the northern end of the basin, or the States of Pennsylvania, Ohio, Kentucky, Maryland and West Virginia, ranking in importance about in the order named. The clay deposits of the Carboniferous period have been divided into two classes; those found in the Pottsville conglomerate series of rocks, ' and all those that are found in the formations above, for the reason that the clay beds above the Pottsville series all resemble each other in properties, composition and appearance, and all are distinctly different from the bed found in the Pottsville formation. The bed of clay found in the latter formation is unique in that flint clay is practically restricted to it. (A variety of flint clay is occasionally found in these upper deposits but this is in such small amounts as to be negligible.) Carboniferous clays occur between stratified rocks; sandstones, limestones, etc., in the same manner as coal veins. They are often accompanied by a coal vein although where the clay is of a workable thickness, the coal is generally too thin to work. The clay beds are sometimes known by the name of the coal seam at which horizon they occur. Clay beds may be from a few inches up to 20 ft. in thickness. They may consist of all soft clay, all flint or both soft and flint. The Carboniferous clay beds of Pennsylvania are the most important of any of the clay beds found in the country, and are among the oldest ones worked. We know more about this clay geologically for the reason

Jan 1, 1916