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By J. Chipman, N. J. Grant, H. L. Bishop, H. N. Lander

Data of several studies on the equilibrium between molten iron and open hearth-type slags have been combined to determine some of the chemical reactions involved in steel-making. Effects of slag composition and temperature on the iron oxide activity, distribution of sulfur between slag and metal, and the carbon content of the metal are discussed. Also, an overall reaction for the equilibrium between sulfur and oxygen is presented. DURING the past 15 years, a number of significant equilibrium studies have been carried out between liquid iron and simple basic and acid slags in an effort to throw light on the chemical reactions involved in steelmaking. This paper is a summary of the experimental reports on investigations which have been conducted at the Massachusetts Institute of Technology, and of related work in other laboratories. The investigations summarized in this paper include the works of Fetters and Chipman1 and Taylor and Chipman,' which dealt with simple slags that are similar to those found in the open hearth. The sulfur determinations of the slag-metal tests of Fetters and Chipman as reported by Grant and Chip-man" are included. Also, the investigations by Win-kler and Chipman' and Grant and ChipmanQ f more complex slag systems are included in this summary. The experimental procedure is described in detail in each of these papers and will not be discussed. Since the previous reports have been somewhat independent, it is desirable to review and combine the data of the various investigations to determine, as accurately as possible, the reactions in the slag-metal systems of the open hearth. It is the object of this report to present the combined data in such a way as to enhance their utility and applicability. Oxidizing Power of Slags of the System (CaO+MgO)-Si0,-FeO in Equilibrium with Carbon-Free lron The slags selected to determine the iron oxide activity in equilibrium with pure liquid iron were those containing less than 2 pct each of P,O,, MnO, or A1,0, on a weight percentage basis. The method used to calculate activities of iron oxide in liquid slags was that developed by Taylor and Chipman.' The solubility of oxygen in molten carbon-free iron under pure iron oxide slags can be expressed by the following eauation —6320 log (pctO)-------------— + 2.734 [1] where T is the absolute temperature. The oxygen solubility values as determined from Eq. 1 were used throughout this study to calculate the iron oxide activity. The iron oxide activities of slags of various iron oxide contents are plotted in Fig. 1 as a function of the basicity, which is defined as the ratio (pct CaO + pct MgO)/pct SiO,, and are based on molecular percentage values of the components. The percent (FeO), is the total iron content in the slag calculated to FeO. Fig. 1 shows that as the basicity increases at constant mol pct (FeO),, the iron oxide activity increases rapidly and reaches a plateau which extends on the basicity scale from about 1.3 to 2.3; the iron oxide activity then decreases rapidly until a basicity of about 3.0 is reached, where it tends to level off. The solid portions of the curves represent the experimental data of Fetters and Chipman and Win-kler and Chipman. Their experimental heats were made in magnesia crucibles, and hence the slags were saturated with magnesia. The broken lines on the left represent the experimental data of Taylor and Chipman, who used a rotating crucible. In general, these slags contained less than 3 pct MgO. The absence of data for slags containing less than about 40 mol pct (FeO), and basicity ratios greater than about 2.5 made it necessary to calculate curves using ionic concepts of slags. The broken lines on the right, which disregard the solubility limits of di and tricalcium silicate and lime, were obtained by following the treatment of Flood and Grjotheim,"

Jan 1, 1957

US 4,134,618-Method for restoring an underground reservoir subsequent to the solution mining of an ore body of uranium, copper, nickel, vanadium, molybdenum, silver, rhenium, or selenium. Clean water a cycled through the mined area, via the injection and production wells used during mining, at a flow rate sufficient to entrain residual dissolved solids. The solids are separated at the surface and disposed of, e g., in a deep disposal well, while clarified water is recycled C A. Kossack, assigned to Atlantic Richfield Co. Jan 16, 1979 4 pp. (299-5) Filed. 12-29-77 (865,646) US 4,155,982-In situ leaching of a subterranean uranium ore deposit The ore is leached with a dilute aqueous solution of ammonium bicarbonate containing a small amount of hydrogen peroxide in order first to convert tetravalent uranium in the ore to the hexavalent state and second to dissolve the hexavalent uranium preferentially to the other metals or elements commonly occurring In such ore The uranium- enriched leach liquor IS brought to the surface, and the uranium recovered by means of adsorption on a particulate ion exchange resin, elution with an acid, and treatment with ammonia to precipitate relatively pure ammonium diuranate. G G. Hunkin, T P. Fife, and J R Stano, assigned to Wyoming Mineral Corp. May 22, 1979. 13 pp (423-7). Filed: 10- 9-74 (51 3,445). Same: Canadian 1,027,849, dated Mar. 14, 1978. US 4,157,847-In the mining of sulfur by the Frasch process hot water accumulating above subterranean sulfur from previous mining operations is recycled downward to contact and heat additional solid subterranean sulfur. Advantageously, pressurized and superheated drive water from above ground is commingled with the underground water to raise its temperature before it is recycled downward R. L Williams, R L Latiolais, J. L Gabriel, and R. L Bouis, assigned to Freeport Minerals Co June 12, 1979. 13 pp (299- 6) Filed 7-28-77 (81 9,879). US 4,158,76%1n this method for determining the uranium content of a solution obtained in the solution mining of an underground uranium ore deposit, the intensity of gamma radiation from the Th-234 daughter of U-238 emitted by the solution is determined as it impinges on a scintillator after being passed successively through filter foils of a ytterbium- tin alloy, a lutecium-tin alloy, and a hafnium-zirconium alloy This scintillation is evaluated as a measure of the uranium content To assure that the uranium-thorium conversion has reached a stable state, the measurement should be made about three months after the uranium solution has been produced R C Smith, assigned to Westinghouse Electric Corp. June 19, 1979 11 pp. (250-255). Filed. 10-20-77 (843,770).

Jan 1, 1980

By d&apos, C. Antonio, S. H. Reichman

In the course of our studies of the annealing behavior of vapor-deposited silver films we have determined the electrical resistivity as a function of annealing temperature for films in the thickness range of 630 to 3240A. Fig. 1 shows the resistivity of the silver films vs film thickness in as-deposited and annealed conditions. The films were prepared by depositing 99.999 pct pure silver from molybdenum boats onto Vycor substrates. Deposition was conducted at a residual pressure of 5 x 10"6 Torr at rates of 20 to 408, sec-'. Thicknesses were determined using a multiple-beam interferometer. During annealing, resistance was measured using the four-probe method. Measurements were made every 5°C during two consecutive anneals to 300°C under a continuous vacuum of 2 x X6 Torr. The heating and cooling rates during annealing were approximately l° and 2°C min-', respectively. Typical resistivity vs temperature curves are shown in Figs. 2 through 4. There is an inflection point evident at 120°C on Fig. 2, the first anneal of a 3240A film. This inflection point was found on all films above approximately 1!00A on both first and second anneals. Below 1400A the inflection occurred at approximately 180°C. Figs; 3 and 4 show the first and second anneals of a 1370A film. The inflection point occurs at 180°C on the first anneal and approximately 120°C on the second. Our interpretation of this phenomenon is based on oxygen liberation from the film surface. It is well-documented that the presence of oxygen on silver surfaces causes a reversible increase in resistivity.1"3 The liberation of this oxygen, for example during vacuum annealing, would therefore cause a decrease in resistivity as observed on Figs. 2, 3, and 4 as a change in slope. This is accounted for by the decomposition of Ag20 on the film surface. The free energy of AgzO becomes positive between 125" and 225°C.4 The thickness dependence of the inflection points can be explained as an orientation effect. The films used in this study were preferentially oriented with their (111) planes parallel to the Substrate.''~ In addition it has been sten that the thinner films, below approximately 1500A, possess a decided "hill and valley"

Jan 1, 1969

By E. O. Kirkendall

The investigation reported herein was undertaken to obtain data to supplement those presented in an earlier paper,l particularly for longer times at a higher temperature. This information may further develop our knowledge of the mechanism of diffusion in substitutional solid solutions. Diffusion of solute atoms interstitially dissolved is not difficult to visualize: it can take place without much disturbance of the solvent atoms. The mechanism of diffusion of solute atoms substitutionally dissolved is not so easily understood. Many theories have been advanced. Rosen-hain,2,3 Frenkel,4 Smekal,5 Langmuir,3,6 Steigman, Shockley and Nix,' and Johnson8 all proposed theories to explain diffusion. Langmuir's proposed mechanism consisted of a simple cyclic interchange of atoms involving an interchange in lattice positions of four or more atoms. This mechanism, accepted by the author at the time of his previous publication,1 and apparently quite generally accepted, required a net exchange in positions of both solute and solvent atoms in equal numbers. In other words, the rate of diffusion of the solvent and solute atoms would be the same. That this cyclic interchange in lattice positions of solute and solvent atoms in equal numbers is the only true mechanism of diffusion is denied by the evidence presented in this paper. Experimental Procedure This modification of similar procedure1 will be outlined briefly. The method consisted of the following steps: I. A pure Muntz metal (60.6 per cent Cu, 0.1 per cent total impurities) that was almost all beta brass at 780°C. was chosen. 2. The brass was turned between centers in a lathe to a diameter of 0.5965 inches. 3. After the brass was cleaned, it was electroplated with pure copper to a diameter of about one inch. 4. The sample was heated slowly to 400°C. under reduced pressure and held at that temperature for 4 hr. to remove occluded gases. It was then cooled to room temperature. 5. The sample was heated to 780°C. ± 3°C. and held at that temperature for different lengths of time; then quenched. Samples were cut off each time after quenching. Metallographic samples 1/4 in. thick were removed at I hr., 6 hr., 24 hr., 96 hr. and 701 hr. After 96 and 701 hr. samples of about I in. were removed for X-ray analysis. 6. The metallographic samples were polished on the cross section and photomicrographs were taken. 7. The I-in. samples were polished and etched on both ends. With the aid of a microscope each was carefully mounted in a four-jaw chuck in a lathe, so that they could be accurately bored for an arbor. 8. Turnings were taken for each X-ray sample. After each set of turnings, the sample was heated in an oil bath for about 1/2 hr. at 300°C. It was then etched in 25

Jan 1, 1942

By E. O. Kirkendall

The investigation reported herein was undertaken to obtain data to supplement those presented in an earlier paper,l particularly for longer times at a higher temperature. This information may further develop our knowledge of the mechanism of diffusion in substitutional solid solutions. Diffusion of solute atoms interstitially dissolved is not difficult to visualize: it can take place without much disturbance of the solvent atoms. The mechanism of diffusion of solute atoms substitutionally dissolved is not so easily understood. Many theories have been advanced. Rosen-hain,2,3 Frenkel,4 Smekal,5 Langmuir,3,6 Steigman, Shockley and Nix,' and Johnson8 all proposed theories to explain diffusion. Langmuir's proposed mechanism consisted of a simple cyclic interchange of atoms involving an interchange in lattice positions of four or more atoms. This mechanism, accepted by the author at the time of his previous publication,1 and apparently quite generally accepted, required a net exchange in positions of both solute and solvent atoms in equal numbers. In other words, the rate of diffusion of the solvent and solute atoms would be the same. That this cyclic interchange in lattice positions of solute and solvent atoms in equal numbers is the only true mechanism of diffusion is denied by the evidence presented in this paper. Experimental Procedure This modification of similar procedure1 will be outlined briefly. The method consisted of the following steps: I. A pure Muntz metal (60.6 per cent Cu, 0.1 per cent total impurities) that was almost all beta brass at 780°C. was chosen. 2. The brass was turned between centers in a lathe to a diameter of 0.5965 inches. 3. After the brass was cleaned, it was electroplated with pure copper to a diameter of about one inch. 4. The sample was heated slowly to 400°C. under reduced pressure and held at that temperature for 4 hr. to remove occluded gases. It was then cooled to room temperature. 5. The sample was heated to 780°C. ± 3°C. and held at that temperature for different lengths of time; then quenched. Samples were cut off each time after quenching. Metallographic samples 1/4 in. thick were removed at I hr., 6 hr., 24 hr., 96 hr. and 701 hr. After 96 and 701 hr. samples of about I in. were removed for X-ray analysis. 6. The metallographic samples were polished on the cross section and photomicrographs were taken. 7. The I-in. samples were polished and etched on both ends. With the aid of a microscope each was carefully mounted in a four-jaw chuck in a lathe, so that they could be accurately bored for an arbor. 8. Turnings were taken for each X-ray sample. After each set of turnings, the sample was heated in an oil bath for about 1/2 hr. at 300°C. It was then etched in 25

Jan 1, 1942

By G. M. Willis, F. L. Hennessy

The oxygen pressure in equilibrium with silver and Ag2O-B2O3 melts has been measured between 800' and 900°C, to obtain the thermodynamic properties of the liquid. The compound Ag20. 4B20:1 appears to exist in the liquid, which shows marked heat content and entropy effects. A KNOWLEDGE of the thermodynamic properties of binary liquid silicates, borates, and phosphates would be of considerable assistance in the interpretation of the behavior of multi-component metallurgical slags. However, the literature contains comparatively few studies of the thermodynamics of binary slags. The system Ag20-B,O, attracted our attention as it was known to give a single liquid phase,',' in which high contents of silver could be obtained (up to 61 pct Ag according to Foex2). Further, it would be expected that the partial pressure of oxygen over melts in equilibrium with metallic silver could be used to determine the activity of Ag2O in the Ag,O-B,O, system. In many respects, it may be expected that the reaction of a basic oxide with boric oxide would be analogous to its reaction with silica. Liquid immiscibility frequently occurs in both borate and silicate systems. With B2O3 and SiO reaction with a basic oxide presumably involves a breakdown of the three-dimensional network of the acid oxide by reaction with oxygen atoms common to more than one silicon or boron atom. Ag2O-B2O3 was therefore investigated as a model of a slag system in the hope that its thermodynamic properties would assist in understanding those of other systems. Several methods for determining the activity of a component in a slag have been described in the literature. Chang and Derge" used high temperature electromotive force measurements to obtain the activity of SiO2 in CaO-SiO2 and Ca0-Al203-Si02 slags, but the cell reaction in their work is not clear. low has used rate of volatilization and vapor pressure measurements combined with phase diagrams to obtain activities in the systems KO-SiO,, Na,O-SiO, and Li,O-SiO," and PbO-SiO26 Taylor and Chipman7 extrapolated their results for the distribution of FeO between liquid iron and CaO (+Mg0)-FeO-SiOl slags to obtain the activity of FeO in the binary FeO-SiO2 system. In principle, one of the most direct methods for obtaining the activity of a metallic oxide in a phase is by comparison of the equilibrium oxygen pressure for the system metal-pure oxide with that of metal oxide-containing phase. Schenck and othersa have studied the stabilization of Ag2O on combination with other oxides (MO,) in the solid state by measurements of the oxygen pressure in systems of the type Ag-Ag,O-xM0,-MOy-0, (gas). Schuhmann and Ensio" have determined the activity of FeO in iron silicate slags in equilibrium with solid iron, using CO/CO2 mixtures to establish known partial pressure of oxygen. Although the method gives the activity of FeO without ambiguity, the slag is not a binary system, and interpretation of the results in terms of the hypothetical binary system FeO-SiO, is not possible. If a metal is solid at temperatures at which the properties of the slag containing its oxide are to be studied, this method has the considerable experimental advantage that the metal can be used as the container for the slag, and contamination by contact with refractories is avoided. In this work, crucibles for Ag2-B,O, melts were made from silver, and the liquid brought to equilibrium with definite pressures of oxygen gas. The oxygen pressure PO, thus fixes the activity of Ag20 in the liquid silver borate. For the reaction at a given temperature. is substantially constant, is directly proportional to the square root of the equilibrium oxygen pressure. Varying the oxygen pressure changed the silver oxide content of the liquid and it was possible to obtain the activity of Ag2O over a range of composition. Experimental Procedure In principle, the method consisted of bringing melts in silver crucibles or boats to equilibrium at a fixed temperature under a definite pressure of oxygen and analyzing the glass after solidification. Materials: B2O3 glass was prepared from A.R. quality boric acid by fusion in platinum. The silver

Jan 1, 1954

By Leland Russell van Wert

In 1888, Howard,1' working at the Watertown Arsenal on the tensile properties of ferrous materials at various temperatures, noted the curious fact that the stress-strain diagrams of low-carbon steels tested within a certain temperature range (200" to 350" C.) departed more or less from the normal regularity of such diagrams as secured by testing at either above or below these temperatures. This same jagged appearance of similar diagrams for steels has been observed by at least one other investigator, and de Forest2 has reported similar irregularities in the tensile testing of some nonferrous alloys. Recently again, this anomaly in diagram contour has been shown in a most striking fashion, apparently because of its accentuation by the method of testing employed, by Dr. Albert Sauveur.~ He described (for nonaustenitie steels) two quite distinct types of torsional stress-time diagrams: (1) those with a regular and smooth outline, derived normally by testing at temperatures above 300" C., or below 200" C. (as, for example, Figs. 4a or e); and (2) those presenting a decided "stepped" appearance, which are invariably produced when twisting is done within the 200" to 300" C. range (examples, Figs. 5a and b). The torsion test brings out so much more sharply (and convincingly) the irregularities occurring at 200' and 300" C. than does the tensile test that they can no longer be considered as resulting from simply idiosyncratic or accidental and inconsequential causes. Clearly, from the temperatures involved, the "stepped" type of diagram, or more accurately, the peculiar manner of response to torsional stress which manifests itself in the diagram, is an aspect of the "blue-heat" phenomenon. One's curiosity, if nothing else, prompts an inquiry as to the nature and significance of these "steps." What do they mean? What causes them To these questions there are no completely satisfactory answers. The following experimental observations are offered as suggestions towards the solution of the problem.

Jan 1, 1931

By J. A. M. van Liempt

SINCE the discovery of von Laue, that a crystal forms a natural grating for X-rays, our knowledge of the structure of solids has gone forward with rapid strides. This progress is not only of purely scientific interest, but has also yielded direct technological results. One of the most valuable results is the broadening of our knowledge of the structure of pure metals and alloys. To promote these studies it is often desirable to have at our disposal pieces of metal consisting of one single crystal. As is so often the case in the natural sciences, we obtain the best results by making our earliest experiments on pure, simple materials and avoiding unnecessary complications. The Cryogen Laboratory at Leyden followed this method with much success, because the work was done at such low temperatures that the heat movement of the atoms was almost absent. Similarly we can simplify the studies of metals by leaving out of consideration the influence of the grain boundaries and the mutual influence of the crystals by using unicrystalline instead of polycrystalline metal. Methods of making single crystals have been scientifically studied during the past few years. Some methods were already known in the arts, but these have been improved and new methods have been developed. The methods for making metallic single crystals may be divided into the following groups: A. From the liquid state B. From the gaseous state C. Electrolytically D. By recrystallization in the solid state METHOD A 1. Tammann's Method. 1-Tammann succeeded in making bismuth single crystals of a maximum length of 20 cm. by undercooling the molten metal 0.1 to 0.3° G. below its melting point in glass tubes of a maximum

Jan 1, 1928

By Alex McCoy

SAMPLING of the fluid from oil wells for percentages of oil, emulsified oil, and water during the last two years has brought out some interesting facts concerning oil-water emulsion. This result led to a laboratory investigation of emulsion, which substantiated the conclusions made from the field observations. The purpose of this paper is to present the information collected, the laboratory experiments, and our interpretation of the same. In order to define emulsified oil exactly, give its synthesis and origin, and to show how and when it is formed in the wells, the work was necessarily divided into two separate lines-laboratory work and field observations. It is hoped that this study may lead to a discussion of such points so that the petroleum engineer, geologist, or technologist may be benefited by its practical bearing on oil-field management. Special credit is due Mr. Everett Carpenter, chief geologist of the Empire Gas & Fuel Co., for his assistance and cooperation in this work. LABORATORY INVESTIGATIONS ON EMULSIFIED OIL Laboratory investigations were conducted in an attempt to learn the composition and some of the properties of emulsified oil, or B. S., as it is more commonly called, also to demonstrate, by laboratory methods, how B. S. may be formed under conditions similar to those existing at the time a well is being pumped, and how it may be broken down. Literature bearing on this subject is widely scattered and very limited in scope. Bacon and Hamor define B. S., or bottom settlings, as "earthy matter, inert organic matter, or, in the case of Pennsylvanian petroleum, an emulsion of paraffin wax and water, which accompanies crude oil." In this discussion we will limit the term B. S. to that heavy,

Jan 8, 1919

By A. T. Churchman

The deformation modes of rhenium have been identified as those typical of the hexagonal metals, titanium, zirconium, and beryllium whose c/a ratios, in common with rhenium, are less than ideal for close packing. Slip is observed on (1010), (1011), and (0001) planes and twinning on (1121), (1122), and (1012) planes. The very high rate of work hardening is believed to be associated with intersecting partial dislocations on two (1010) systems which can combine to form sessile barriers. If the stacking fault energy is low, as postulated by Seeger, these barriers should be strong and not easily bypassed by cross slipping. Such an explanation could also account for the very small temperature dependence of the yield stress which was observed. RHENIUM is interesting scientifically as a member of the group of high melting point hexagonal metals: titanium, beryllium, and zirconium with a c/a ratio less than that for ideal close packing. Unlike them, however, it work hardens at a very high rate. This rate is greater and continues to a much higher degree of deformation than for nickel, normally considered to have a high rate of work hardening. This paper presents experimental observations on the modes of deformation of rhenium and, by comparison with other hexagonal metals, some speculation on the cause of the high work hardening. MATERIALS Johnson, Matthey rhenium powder of both 99.9 pct and 99.5 pct purity, see Table I, was compacted at 10 tons per sq in., part sintered at 1350°C in vacuo, and finally arc melted in a "gettered" argon atmosphere arc furnace to produce small buttons. Little difference was observed in the as-cast hardness or working down behavior of the two purities suggesting that either silicon and potassium do not have a significant effect on the working properties of rhenium or they were lost during arc melting. SPECIMEN PREPARATION The cast structure was broken up by cold-rolling with inter-stage annealing at 1600o or 1800°C in a vacuum high-frequency furnace using a tungsten susceptor. Strip for tensile testing was taken from two thicknesses of material 0.011 and 0.064 in. The former with intermediate anneals at 1800°C had a grain size of 900 grains per sq mm, while the latter with inter-stage annealing at 1600°C had a grain size of 3600 grains per sq mm. A coarse grain size was obtained by secondary recrystallization in a half button cold-worked by 30 pct reduction. Annealing times of from half an hour to several hours at 2200° to 2600°C in a "gettered" argon atmosphere arc furnace1 resulted in grains of up to 2 mm diam.

Jan 1, 1961

By Adrian C. Dorenfeld

Laboratory data form the basis for the design of flotation circuits. These data, obtained from testing samples of the ore, should show the optimum con- ditions for concentrating the ore and the effects of change in process vari- ables. Among the more important variables commonly met in flotation practice are: Liberation Size-This is the particle size at which substantially all of the valuable minerals are detached from the gangue minerals. Reagent Additions- Experimental data will show the reagents used and their quantity, quality, and point of addition. Pulp Density-This is an important variable in the design of the flotation circuit because it is one of the factors determining the size and number of flotation cells. Flotation Time-The time necessary to make the separation into concentrate and tailing depends on such factors as particle size and reagents used and must be known for determination of the size and number of flotation cells in the plant. Temperature of Pulp-Temperature affects flotation reactions. Water at approximately room temperature is satisfactory for most flotation separations, but some minerals such as fluorspar are best floated in hot water. Type of Circuit-Many types of circuits can be designed, as discussed in detail later. The laboratory tests should provide data for design of the plant circuit best suited to the ore. Water-Knowledge of the quality of the future plant's raw water is important because water quality may drastically affect flotation results. If possible, flotation tests should be made using samples of the water to be used in the plant. Flotation results may vary with seasonal temperatures and with circulation of reclaimed water. Experimentation can show whether it will be necessary to provide for heating, cooling, treating, or reclaiming the water. Uniformity of Ore-The extent of variation of the ore in hardness, grind- ability, mineral content, and floatability should be investigated so that the designer can ascertain methods to overcome problems caused by ore variations. Settling and Filtration Data-To design the plant flotation circuits, settling and filtration rates and ultimate percentage solids of the various products must be determined. Corrosion and Erosion-Corrosion and erosion tests should be made on the flotation pulps, particularly if the pulps are acid or at an elevated temperature, so that suitable materials of construction can then be chosen.

Jan 1, 1962

By J. W. Clark, C. T. Sims

Wrought chromium-base alloys containing yttrium, cubic monocarbides of the Ti(Zr)C type, and similay alloys containing manganese and rhenium have been melted and fabricated. Strength has been studied by hot hardness and elevated-temperature tensile and rupture measurements, low-temperature ductility by tensile testing, and surface stability by oxidation testing. In additiod, studies have been conducted of the carbide stability, and of aging behavior. The carbide dispersion generates effective elevated-temperature strength, which is further enhanced hv strain-induced precipitation. The dispersion exhibits classical dissolution and aging response. The ductile-to-brittle transition temperature of these alloys is above room temperature. The alloys reported show fairly good oxidation resistance, but nitrogen contamination can cause fortnation of a hard Cr2N layer under the oxide scale. Manganese does not appear to be a promising alloying element in chromium. In the years 1945 to 1950, the metal chromium was considered as a possible base for alloy systems due to its considerably higher melting point than superalloys, its low density, its high thermal conductivity, and its apparent capacity for strengthening. However, this interest in chromium was short-lived. It was found difficult to melt and cast, to be exceptionally sensitive to the effect of minor imperfections, to have a lack of ductility at both room and elevated temperatures, and to be subject to a deleterious effect of alloying elements upon the ductile-to-brittle transition temperature.' Since then, chromium, as a practical alloy base, has remained virtually unstudied. Further, purposeful ignoring of chromium has been promoted by statements that its bcc structure would not allow it to be strengthened to useful values, when compared to the "austenitic" alloys.2 Recently, a new look has been taken at chromium-base alloy systems. Study of the literature will show that chromium, providing some of its disadvantages could be eliminated or minimized, actually has a rather attractive potential as an alloy-system base. Analysis of rather scattered data suggests that chromium is quite capable of being strengthened to high levels. Also, significant strengthening of its two sister elements in Group VI-A, molybdenum and tungsten, has been demonstrated in a number of commercial and exploratory alloys. Chromium should be similar. Since chromium does not readily form a volatile oxide like tungsten or molybdenum, it offers a much higher probability of giving birth to alloy systems with useful oxidation resistance. Concerns about possible high elemental vapor pressure have been mitigated by recent data.3 In addition, the physical properties exhibited by chromium are attractive for application as a high-temperature structural material. For instance, its thermal conductivity varies from 49 to 36 Btu-ft/hr-sq ft-°F over its range of usefulness (which is two to four times higher than most superalloys), its density is about 7.2 g per cc (20 pct less than most nickel-base alloys), its coefficient of thermal expansion varies from 4 to 8 x 10-6 per OF, and it has a relatively high modulus of elasticity, approximately 42 x 10' psi.4 Alloying studies on a chromium base in the past have usually encompassed rather sweeping solid-solution alloy additions for strengthening. This is not consistent with contemporary alloying practice in Group VI-A. For instance, molybdenum, also in Group VI-A, is primarily alloyed for strength improvement by use of heat-treatable carbide dispersions.5 Chromium and molybdenum are similar in their chemical activity and other properties. Thus, strengthening of chromium by carbide dispersions was studied. Chromium-base alloys are plagued with room-temperature brittleness, although high-purity unal-loyed chromium can be made ductile.4,8 Use of yttrium as a scavenger has done much to improve ductility and resistance to nitrogen embrittlement in chromium systems,7 so it was utilized in this program. It has also recently been found8 that small rhenium additions (1 to 5 pct) create improvement in the ductility of Type 218 tungsten wire. This is apparently related to the remarkable effect of rhenium additions near its terminal solid solubility in all Group VI-A metals.9'10 Investigation to establish if dilute concentrations of rhenium would also be effective in chromium appeared to be logical for this program. Since rhenium is too expensive to be practical in alloys for application as structural components, ductility improvements through solid-solution alloying were also sought by substitution of manganese for rhenium; manganese, like rhenium, exists in Group VII of the periodic system. The optimum amount of carbide dispersion for chromium-base alloys was obtained by analogy with molybdenum. Strengthening in molybdenum is achieved by use of Ti-Zr carbide dispersions. A

Jan 1, 1964

By W. H. Emmons

MOST mineral deposits change as they are followed downward on their dips. Some of these changes are due to primary arrangement; different ores were precipitated at different depths when the deposits were formed. Other changes are due to weathering or secondary enrichment. The chief changes resulting from weathering, in the main, are understood and standard changes are recognized. The processes are relatively simple. They take place at ordinary temperatures and pressures and can be duplicated in the laboratories. Moreover, there are thousands of deposits available for study, because the processes take place near the surface where the development of mines is begun. The changes due to primary arrangement of the deposits of the metals are not so well understood. Deposition has taken place at higher temperatures and our knowledge of the chemistry of the processes leaves much to be desired. Very few experimental data are available. The deposits, moreover, offer fewer examples because many mines are not, developed to depths where the changes can be studied and a change to unprofitable material usually results in stopping work. Most, students of ore deposits now accept, as confirmed, the hypothesis that nearly all lodes and related deposits were formed by solutions originating in intrusive igneous masses. Outward from these masses, the deposits at many places are grouped in zones and the arrangement noted from the intrusions outward are commonly the reverse of the changes noted from the surface downward in a single lode. A study of the changes in groups of deposits, from the parent intrusion outward, will throw light on the changes to be expected in a single lode downward. Because the changes in series of deposits from the intrusive outward may all be observed near the surface, where more data are available, it is possible to increase the number of examples many fold and to apply the statistical method of study with greater confidence of avoiding error.

Jan 3, 1924

By W. H. Smith

IN the course of an investigation on chromium containing minor amounts of alloying elements, the information herein has been obtained on the crys-tallographic orientations resulting from arc melting, rolling, and annealing. The chromium used in this investigation was electrolytic flake obtained from the Electro Metallurgical Co. This material was heated for 20 hr at 1600°C in hydrogen with a dew point of about — 100°C. The oxygen and nitrogen content of the chromium after this treatment was 0.0003 pct 0 and 0.005 pct N. Five pounds of this chromium were arc melted in a water-cooled copper crucible. After arc melting, the oxygen and nitrogen contents were 0.002 and 0.025 pet, respectively. A section of this ingot is shown in Fig. 1. By means of a back-reflection Laue technique, the crystal habit of the cast ingot was determined. As expected, it was found that the [loo] was approximately the axis of the columnar grains. In this respect, chromium behaves like other body-centered-cubic metals in that a cubic axis is normal to the cold surface of the mold. A slab cut from this ingot was rolled at 600°C as follows: four 30 pct reductions were made with intermediate anneals at 1200°C for 15 min. Rolling was done with the [loo] of the columnar grains in the rolling direction. Following the final anneal, an 80 pct reduction was taken at 600 °C. The final sheet thickness was ten mils. By polishing and etching, the thickness was reduced to four mils and the grain orientation determined by the transmission Laue method using molybdenum radiation with a zirconium filter. Fig. 2 is the (110) pole figure for this material with the ideal (100) [011] and (111) [112] orientations indicated. The orientation is typical of most cold rolled body-centered-cubic metals having the [llO] of the grains approximately in the rolling direction and the (100) planes approximately in the plane of the rolled sheet. There is also evidence of some 10) [1 orientation. The grain orientation of sheet rolled 40 and 80 pct in the same direction as before at 600°C followed by recrystallization at 12000 C for 15 min was determined by a back-reflection Laue technique. A random texture was found in both cases. This 1200°C 15 min anneal was found to give complete recrystallization and some grain growth.

Jan 1, 1956

By C. A. Stetefeldt

IK the dry-crushing of ores, either by stamps, rolls, or other machinery, it is essential that the material should be free from moisture. Hence a contrivance which effects this with economy, and is of durable and compact construction, is a great desideratum. It is claimed for the below-described shelf dry-kiln, that it possesses these qualifications in a high degree. The construction of the shelf dry-kiln is based on the Hasenclever principle. That is to say, a number of inclined shelves are arranged zig-zag above each other in a vertical shaft, having openings or slits where they meet, on which the ore rests in a stratum, the thickness of which is governed by the width of the slits and the inclination of the shelves. If a portion of the charge is removed at the end of the bottom shelf, a sliding motion of the ore takes place on all shelves above, and the top shelf is replenished from a hopper set over it. It will be seen that the shaft is divided by the shelves into a number of triangular prismatic spaces. Through these the hot gases from a fireplace are made to circulate, each space communicating with the next one by a flue arranged in the sidewall of the shaft. These flues being located on alternate sides of the shaft, a continuous passage is formed through the whole structure. After thus stating the principle of the construction, its details will be easily understood by reference to the drawings, Fig. 1 to Fig. 5. The drawings, Fig. 1 to Fig. 4, represent two kilns united into one structure. The cast iron shelves(a) are 2 feet 4 inches wide and 5 feet long, with sides and a back 4 inches high, and are cast a full halfinch thick. How they rest on the brackets(d), and interlock each other, is shown in Fig. 5. Three such shelves, with an inclination of 38') are placed in one row in a brick shaft 7 feet 1/2 inch wide and 4 feet deep. The ore hoppers(g) rest on the iron bems(f). At the end of the bottom shelves are the discharge-doors(b), with shoots projecting beyond the front wall. A swinging apron(e) keeps the ore in place. By dropping it a car below the shoot is filled with dry ore. A number of extra-large pieces of ore may cause a stoppage in the slits ; for such an emergency the openings(e) are provided, through

Jan 1, 1884

By J. B. Morrow, D. H. Davis

THERE are two general approaches to the problem of increasing profits from an operation. One is to lower expense; the other is to raise income. Mechanical preparation of coal may be used for either purpose but a prudent consideration of many details must precede any decision lest the results be negative instead of positive. It is quite possible that any net gain will result from a combination of the two. Since mechanically prepared coal invariably is a better product qualitatively than a hand-picked coal from the same mine, it is a reason- able expectation that the customer will be willing to increase the producer's income by paying a higher price. Or there may be the possibility that a combination of mechanical mining plus mechanical cleaning will give a lower over-all production cost for the coal in the railroad car. More likely, there will be found a combination of these two factors. From the customer's point of view, the competitive delivered cost per B.t.u. considered in relation to such incidental factors as dust nuisance, handling properties, ash disposal, and ash fusibility determines what he will pay. In a bulk tonnage product such as coal, freight is a very considerable part of the delivered fuel cost, and obviously freight paid on incombustible ash has no economic attractions. INCENTIVE FOR CLEANING Coal is prepared in four major ways: 1 (I) by screening or sizing, (a) by mixing or blending, (3) by cleaning, including hand picking and mechanical cleaning, (4) by dustless treatment. By a combination of any or all of these methods, coal can be prepared to standard specifications. It is easily possible to have good cleaning and still get a poor final product because of faulty screening or mixing,

Jan 1, 1943

By C. M. Young

THE safety lamp is the most common and convenient apparatus for detecting inflammable gases in mines, the presence of gas being shown by a blue flame, called the cap, if the wick has been lowered to suppress the luminous flame. The height of the cap increases with the proportion of gas and with the temperature of the lamp flame. Lamps of the Wolf type, the fuel of which is benzine, have a hotter flame than lamps in which vegetable oils are used, such as the Davy, and the Clanny, and are more sensitive than the latter and their many modifications. The Piehler alcohol lamp gives a still higher cap while the Clowes hydrogen lamp is most sensitive of all. While the effect of the temperature of the source of ignition is well known, the writer knows of no previous attempt to correlate the change of this temperature with change of the height of the cap produced. In order to determine the height of the cap at various temperatures, it was necessary to have a source of ignition the temperature of which could he accurately controlled over a considerable range. This condition was met by a coil of wire of high fusing point heated by an electric current controlled by a variable resistance. The use of a coil offered the further advantage of freedom from complications due to the flame of a burning fuel. Such a flame, being itself of variable height, would to some extent raise or lower the elevation of the base of the cap and therefore add to the difficulty of determining the height of the cap. Besides this, the presence of a small cap from the lamp fuel, commonly known as the "fuel cap, " would interfere with the observation of small gas caps. After some experiment, a coil was made of platinum wire, No. 26, diameter 0.016 in. The coil was 17/64 in. (6.746 mm.) in outside diameter and had eight full turns in a length of ½ in. (12.69 mm.). This was connected to an electric circuit through an adjustable resistance, as shown in

Jan 8, 1919

By J. D. Rice, H. H. Rachford, G. H. Bruce, D. W. Peaceman

The problem of unsteady-state gas flow through porous media leads to a second-order non-linear partial differential equation for which no analytical solution has been found. In this paper a stable numerical procedure is developed for solving the equation for production of gas at constant rate from linear and radial systems. An electronic digital computer is used to perform the numerical integration using an implicit form of an approximating difference equation. Solutions are presented in graphical form for various values of dimension-less parameters. The solutions are compared with the laboratory study of gas depletion in a linear system. INTRODUCTION Production of fluids from porous rock reservoirs is essentially a transient process. Transient gradients develop as soon as production begins, and further withdrawals continue to cause disturbances which propagate throughout the reservoir, each adding in some way to the prior ones. A correct mathematical analysis of this behavior is complicated by the fact that the transient or unsteady-state flow of compressible fluids must be described by difficult second-order partial differential equations. As a practical matter, three distinctly different cases arise: 1. Flow of single-phase liquid 2. Flow of gases 3. Multiphase flow The first of these has been found to give a linear second-order equation similar to the well-known heat flow equation. where 7 is fluid density, 8 is time, and a a constant for the system, provided d 7 = r cdp, where the compressibility, c, is constant over the range of pressure, p, considered. Solutions of Equation (1) for both linear and radial flow are available in several forms.2'3' On the other hand. the second case, which is the flow of gas, gives a non-linear second-order equation, the solution of which is not known. Although a number of approximate solutions have been proposed, each is limited in value by the associated simplifying assumptions. Inasmuch as the analysis of transient flow is limited to liquid systems, a solution of the second case is necessary if further progress is to be made in studying underground fluid movement. For this reason a solution of Equation (2) was undertaken by means of numerical integration of approximating difference equations. BASIC DIFFERENTIAL EQUATION Equation (2; is derived by combining the equation of continuity, the perfect gas law, and Darcy's law to give the basic differential equation Strictly speaking, the fluids present in a gas reservoir are not perfect gases. Furthermore, there are indications that over certain velocity ranges, Darcy's law is not applicable. It would not be practicable. however, to attempt to obtain numerical solutions which would take into account all the possible variations from these laws which could occur in actual systems. The

Jan 1, 1953

By Edward W. Parker

This plant was built in 1907 at the Bankhead mines to manufacture briquettes by the Zwoyer process under license from the Zwoyer Fuel Go., of New York, N. Y. The building was constructed to contain two units, each of a capacity of 10 tons per hr.; one unit was installed at the time the building was constructed, and the second unit is now being built. The coal used is an anthracite, which is more friable than that of Pennsylvania, and, as a consequepce, a larger percentage of dust or waste is produced, which was formerly thrown upon the slack-pile as waste, but is now passed to the " dust-bin " in the breaker, from which it is conveyed to the briquette-plant. An average analysis of the coal, published by Lewis Stockett and 13. R. Warden,' is as follows: Per Cent. Moisture,.........0.50 Volatile,..8.00 Fixed carbon,... 83..50 Ash,.......8.00 Total,.100.00 Sulphur,.........0.40 per cent. Specific gravity,...... 1.40 Color of ash,.white Heat value,.......14,000 B.t.u. The plant is run under two 12-hr. shifts, the force consisting of 1 superintendent for both shifts, 1 engineer for each shift, 1 briquetter for each shift, 1 helper for each shift, 1 laborer cleaning up for each shift. In the pitch-melting house, 2 men are on duty for one shift. The steam for the engine is furnished from a central boiler-plant, which also supplies steam for the breaker, the electric light and power-plant, machinery-shop, and boiler-shop. During March, April, May, and half of June, in 1907, the

Jan 1, 1909

By G. Krauss, W. Pitsch

The fine structure of the bcc martensite formed in an Fe-33 wt pct ATi single crystal of arrstenite is sho~on by transmission electron microscoPy to consist of combinations of transformation twins, stacking faults, deformation twins, and regular arrays of parallel screw dislocations. These structures constitute evidence for the multiple lattice-invariant deformations which operating during the formation of martensite could produce the real habit-plane scatter measured by a two-surface analysis of the plates formed in the single crystal of this investigation and reported in the literature for other Fe-Ni rnartensites. CRYSTALLOGRAPHIC theories1,2 of martensitic transformation show that the habit plane of martensite in a parent lattice is dependent in part upon an inhomogeneous distortion or lattice-invariant deformation which takes place on a fine scale within a martensite plate during its formation. Several recent theoretical papers3,4 have addressed themselves to an analysis of a wide variety of conceivable lat-tice-invarient deformations and the habit planes which they produce, while experimental investigation have been concerned with either the measurement of habit planes or the description and identification of the martensitic fine structure which reflects the nature of the lattice-invariant deformation operating during transformation. In Fe-Ni alloys with subzero Ms temperatures, the group of alloys with which this paper concerns itself, habit planes have often been found to scatter an amount greater than might be expected from possible experimental errors,5-7 and fine twinning has been identified as a major constituent of the fine structure of martensite.8-11 It has been suggested3,4 that more than one type of invariant shear occurs during martensitic transformation. This possibility has been experimentally supported12,13 by the observation of both dislocation configurations and twinning in a single martensite plate. The purpose of this paper is to report additional evidence for multiple lattice-invariant deformations in martensite and so to account for the real scatter in the habit planes of the martensite plates formed in Fe-Ni alloys. EXPERIMENTAL PROCEDURE The Fe-Ni single crystal was produced by pulling a high-purity iron and nickel charge through a single-crystal vacuum furnace in an alumina crucible. The crystal was double-melted to promote homogeneity and to increase its size by further additions on the second pass. In its final form the crystal was 4 cm in diam and 5 cm long. The nickel and carbon contents were analyzed at 32.9 and 0.006 wt pct, respectively. The austenite of this alloy first transformed to martensite by bursts at about -120°C, and, to preserve as much of the austenite as possible, all transformation was performed just below -120°C. Some observations were made on transformed samples which had been heated for 2 min at 340°C. It is assumed that the features of the martensite of these samples, Figs. 1 and 4, are the same as those of the as-quenched martensite. Orientation of the crystal by X-ray diffraction established 10.735 0.609 0.3161? as the axis of the crystal, an orientation that was checked within 2 deg by neutron diffraction. Further checks by electron diffraction of samples cut normal to the axis confirmed this orientation within the larger limits of error inherent in electron diffraction of thin foils. The X-ray orientation was the one used for the two-surface analysis of the martensite habit planes. A two-surface analysis was performed on the quadrant of the single crystal which had been oriented by both X-ray and neutron-diffraction techniques. Photomicrographs at X50 were made on two surfaces along an edge 2 cm long. Fiducial marks and the fact that many of the plates were almost completely surrounded by retained austenite made good matching of individual plates on two surfaces possible. The habit-plane trace on a surface was taken as the best line parallel to the long axis of a plate. A measure of the accuracy afforded by this criterion was provided by a family of very large plates which appeared at intervals along the entire 2 cm length of the edge. The plates all had habit-plane traces within 2 deg of one another. Many of the plates did not show midribs and, therefore, the use of midribs7 to represent habit-plane traces was not feasible in this investigation. The over-all experimental accuracy is estimated to be better than ±2 deg. Samples for transmission examination in a Siemens Elmiskop I at 100 kv were prepared by cutting 2-mm-thick discs from the single crystal, removing about 0.5 mm by chemical polishing,14 trans-

Jan 1, 1965