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By W. D. Robertson, E. Scala

Electrical resistivity of a number of pure liquid metals and alloys has been measured as a function of temperature and composition. The data show a close correspondence between the liquid and solid states with respect to thermal, structural, and compositional relationships. STUDY of diffuse scattering of X-rays by liquid metals1 has demonstrated that some degree of order persists above the melting point and that the atomic constitution of liquids is more analogous to the solid state than to a gas. Consideration of the change in various thermodynamic properties that accompanies transformation from solid to liquid leads to the same general conclusion.² evertheless, specific knowledge of the constitution of the liquid state is limited when compared with that of the solid and gaseous states owing, in part, to the difficulty of interpreting the X-ray data and in part to the indirect character of deductions based on thermodynamic data. Of the structure-sensitive physical properties, electrical resistivity of liquid metals is perhaps the most easily interpretable, particularly when comparison is made with the solid state. According to the available data, most of which was obtained prior to 1914, cubic metals exhibit a normal linear and positive temperature dependence in the liquid state and the data have been accepted without question. The divalent metals, zinc and cadmium, are apparently exceptional in that resistivity is not linear with temperature and it passes through a minimum. Mercury also exhibits a nonlinear temperature dependence but the slope is always positive. Important comparisons with magnesium could not be made at the time the following work was undertaken because the necessary experimental data were not available. Data on liquid solutions are very limited and are largely from a single source."-" Based on Bornemann's work, Norbury7 pointed out that the resistivity of liquid copper alloys appeared to be dependent on the valence of the solute and that the increase due to the solute was of the same order as in the solid state. However, large extrapolations were involved and no quantitative relationship was developed. Therefore, before proceeding with additional deductions regarding the resistivity of liquid metals and interpretation in terms of structure, it appeared necessary to verify and extend the previous work with particular emphasis on divalent metals and the effect of alloying elements of different valence in dilute liquid solutions. The present work includes: 1—A determination of the resistivity of high purity liquid magnesium, tin, indium, copper, zinc, and cadmium as a function of temperature. 2—The effect of 1 atom pct of copper, cadmium, aluminum, tin, antimony, and

Jan 1, 1954

By H. G. Dwyer

CONSIDERATION for future expansion influenced the design of the new smelter at Chuquicamata. The section of the smelter now going into operation, while large, represents only little more than half of the ultimate plant. Equipment for the direct smelting of raw concentrates has been arranged in the conventional manner although needless details have been eliminated wherever possible while mechanical and electrical features not usually found in copper smelters have been incorporated. Access is afforded to all equipment but platforms and walkways have been held to a minimum. The poling and other platforms in the converter aisle, normally subjected to battering by ladles and other heavy equipment in transit, are of concrete construction with steel grid armor embedded in the exposed surfaces. Noticeably absent are the many platforms formerly required for the handling of converter flux since this material is charged to the converters through the side walls of the converter uptake hoods. Clear space with ample headroom is provided under each converter and converter puncher's platform to permit clean-up by small bulldozers. Remote controls have been introduced at many points. Electrical control rooms and control centers have been conveniently located. An electrical tunnel with cross tunnels and escapeways is situated under the entire length of the converter aisle for power feed lines. Skull breaking facilities are in a separate building near the smelter. A silica-slurry building with brick storage area is adjacent to the smelter building so that elevator service is available to both buildings. A smelter office, a change house and lunchroom are provided in convenient locations. Units of the smelter as presently constructed are shown in the plan and table on page 1194. The ultimate smelter will house 7 reverberatory furnaces, 14 waste-heat boilers, 9 Peirce Smith converters, 4 casting furnaces serving 2 casting wheels, and one holding furnace serving a straightline casting machine. Additional crane requirements in the converter aisle will necessitate the installation of special hoisting equipment in space already provided in a raised section of the roof over the casting end of the aisle. Thus a complete crane may be lifted high enough above the crane rails to permit the passing of another crane underneath thereby giving all cranes full use of repair facilities already installed. For the collection of gases, 2 dust chambers, each with separate stacks, will collect converter gases and 2 balloon flues with separate stacks will collect reverberatory furnace gases. Extensions necessary to complete the ultimate plant will be possible with little interruption to normal operations since the future converters and reverberatory furnaces will be added at the east end while additional casting facilities will be added at the west end of the present plant. The future units may be added singly or all at one time depending on requirements.

Jan 1, 1952

By Walter S. Weeks

THE process of cooling air by allowing it to expand and do work in an engine is well known, but the theory of obtaining cold air by free expansion without the aid of an engine operating with cutoff has been little discussed. Case 1 If compressed air is allowed to expand to the atmospheric pressure through an orifice in an sir line that is supplied by a running compressor, no cooling results except the negligible one due to the Joule-Thompson effect, which will not be considered in this discussion. The effect of moisture will also be neglected. Symbols P1 Absolute pressure in pipe line, lb. per sq. ft. P3 Atmospheric pressure, lb. per sq. ft. V1 Volume occupied by 1 lb. air in pipe. V3 Volume occupied by 1 lb. air at P3. Cv Specific heat of air at constant volume, B.t.u. per lb. per deg. F. Cp Specific heat at constant pressure, B.t.u. per lb. per deg. F. T1 Absolute temperature of air in pipe, deg. F. T3 Absolute temperature of air outside after expansion and mixing and coming to rest. J Mechanical equivalent of heat (778 ft. lb.) R Gas constant for air, ft-lb. per deg. F. = 53.3. Formulas Consider 1 lb. of air moving out of a pipe. The air behind it does work on it to the extent of P1V1 ft-lb. This work is really done by the thrust of the piston of the compressor and does not come from any energy that exists in the air in the pipe. The pound of air contains

Jan 1, 1937

By Walter S. Weeks

The process of cooling air by allowing it to expand and do work in an engine is well known, but the theory of obtaining cold air by free expansion without the aid of an engine operating with cutoff has been little discussed. Case I If compressed air is allowed to expand to the atmospheric pressure through an orifice in an air line that is supplied by a running compressor, no cooling results except the negligible one due to the JouleThompson effect, which will not be considered in this discussion. The effect of moisture will also be neglected. Symbols P1 Absolute pressure in pipe line, lb. per sq. ft. P3 Atmospheric pressure, lb. per sq. ft. V1 Volume occupied by 1 lb. air in pipe. V3 Volume occupied by 1 lb. air at P3. C, Specific heat of air at constant volume, B.t.u. per lb. per deg. F. C, Specific heat at constant pressure, B.t.u. per lb, per deg. F. T1 Absolute temperature of air in pipe, deg. F. T8 Absolute temperature of air outside after expansion and mixing and coming to rest. j Mechanical equivalent of heat (778 ft. lb.) R Gas constant for air, ft-lb. per deg. F. = 53.3. Formulas Consider 1 lb. of air moving out of a pipe. The air behind it does work on it to the extent of P1V1 ft-lb. This work is really done by the thrust of the piston of the compressor and does not come from any energy that exists in the air in the pipe. The pound of air contains

Jan 1, 1937

By R. E. Crater

Brown, Gaudin, and Loeb in their study of intergranular comminution by heating attempt to find one explanation for all types of rock in terms of the properties of the phases present. The only necessary condition for intergranular cracking by heating is the setting up of high stresses at the grain boundaries. Such stresses may be set up in multiphase isotropic mixtures if the thermal expansions of the phases are different, in non-cubic single phases because of the anisotropy of thermal expansion in the various crystallographic directions, and in materials containing quartz because of the a-ß transformation at 575°C. In addition, for intergranular comminution by heating, the cooling and not the heating is most important.

Jan 3, 1959

By G. C. Wallick, J. S. Aronofsky

This paper presents an experimental verification of numerical solutions of the differential equation describing the transient flow of an ideal gas through a porous material including gas slip effects. Several experiments previously proposed by one of the authors are described together with the correlation of the experimental results with the numerical solutions. Excellent agreement is shown between experiment and theory, thus demonstrating the validity of both the basic assumption made in the derivation of the differential equation and of the numerical solutions of the differential equation. INTRODUCTION In a recent paper,' one of the authors has discussed a numerical solution of the differential equation describing the unsteady flow of an ideal gas through a porous material. This paper was primarily concerned with the effect of gas slip on the flow behavior. In steady state measurements, Klinkenberg2 and others have observed that the apparent gas permeability Kn of a porous material may be expressed as a linear function of the reciprocal average pressure 1/P of the form, ka = b + m/P........(1) where the intercept b is a constant for a given porous material and the slope m is a constant for a given porous material-gas combination. Aronofsky1 assumed that Equation (1) could be used to describe transient flow if P was replaced by the average pressure in an infinitesimal volume element. A number of numerical solutions of the resultant differential equation were presented and specific flow experiments were proposed as a means of testing the numerical solutions. The purpose of the present paper is to describe the results of several of these experiments and the correlation of the experimental data with the results of the numerical analysis. Reference should be made to the previous paper' for details of the mathematical and numerical analysis. EXPERIMENTAL PROCEDURE A simplified schematic drawing of the experimental apparatus is shown in Fig. 1. An 8.89 cm diameter limestone core of length L = 14.82 cm was mounted in a conventional rubber sleeve permeameter cell. The external sleeve pressure in this cell was maintained equal to 500 psig during all experimental tests, thus permitting only longitudinal flow through the core. One end of the core, X = L, was connected to an adjustable cavity of volume V as well as a pressure gauge or manometer. The other end of the core, X = 0, was connected to a Nullmatic pressure regulator which was in turn connected to a nitrogen cylinder or vacuum pump. In each experiment, the core and adjacent dead volume were charged with nitrogen to a uniform gas pressure P1. The pressure at X = 0 was then suddenly raised or lowered to a constant pressure P, and the resulting pressure buildup or pressure decline at X — L was recorded as a function of the time. The porosity + and the permeability constants m and b were determined using the transient method which was suggested by the results of the numerical analysis and which was described in the earlier paper.' The following average values for these constants were obtained as a result of 19 separate evaluations: 171 -0.259 2 0.005 md-atm; b = 0.374 5 0.008 md; and F = 0.098 ± 0.005*. It should be noted that in order that transient phenomena will be slow enough to be observed conveniently, it is desirable to use a porous material of very low permeability, e.g., less than I md. Moreover, it is in this low permeability range that the gas slip effects are most significant. Thus, such a low permeability sample is very suitable for use in an experimental verification of the numerical solutions previously described.

Jan 1, 1955

By J. C. Smock

The primitive mode of mining clay by open workings, in which the overlying beds of earth (commonly termed the " bearing ") were removed, and the clay then dug out by sinking shallow pits, is still the prevalent and almost universal mode of extraction. This is particularly true of our cretaceous and tertiary clays, which are generally earthy in character, and but slightly covered by drift and alluvium. The most accessible beds in many of our clay districts have been worked out, and clay miners are compelled to search for new outcrops, or to remove thicker beds of top dirt or bearing. Under this stimulus subterranean working, or mining proper, has been suggested. A brief notice of this new mode, as employed by Mr. Otto Ernst, near the head of Chesquake's Creek, three miles south of South Amboy, New Jersey, is here presented for your consideration. Previous to mining, the old mode of extraction, digging pits, was found to be too expensive, in' consequence of the heavy amount of top dirt and the excessively large amount of water in these overly

By J. C. Smock

THE primitive mode of mining clay by open workings, in which the overlying beds of earth (commonly termed the "bearing") were removed, and the clay then dug out by sinking shallow pits, is still the prevalent and almost universal mode of extraction. This is particularly true of our cretaceous and tertiary clays, which are generally earthy in character, and but slightly covered by drift and alluvium. The most accessible beds in many of our clay districts have been worked out, and clay miners are compelled to search for new outcrops, or to remove thicker beds of top dirt or bearing. Under this stimulus subterranean working, or mining proper, has been suggested. A brief notice of this new mode, as employed by Mr. Otto Ernst, near the head of Chesquake's Creek, three miles south of South Amboy, New Jersey, is here presented for your consideration. Previous to mining, the old mode of extraction, digging pits, was found to be too expensive, in' consequence of the heavy amount of top dirt and the excessively large amount of water in these overly-

Jan 1, 1875

By Arthur Taggart

FLOTATION of sulphide minerals and native metals is no longer a practical difficulty. The underlying scientific principles of the method, although not explored in anything like complete detail, have been formulated with sufficient breadth so that the direction of attack on any specific case is clearly indicated. It has been known since the earliest clays of flotation that certain of the nonsulphide nonmetal minerals-e.g., sulphur and graphite-would respond to flotation by oils as sulphides do; therefore they have been grouped with sulphides in many patents. But since the development of the chemical theory of collection,1,2,3 this similarity in action has been one of the facts cited in disproof of the theory by opponents of the hypothesis.4,5,6 Air levitation? of certain oxidized minerals, both metalliferous? and nonmetalliferous, and separa-tion thereby from other oxidized minerals, is a recent development in practice, although the discovery of the method dates back 17 years.7 This paper presents evidence that the principles underlying the air levita-tion of the nonsulphide nonmetal minerals are the same as those utilized in the flotation of the sulphides and native metals. It will be apparent immediately to anyone with knowledge of mineral concentration that separation of air-levitated minerals in water from minerals not so levitated is a simple matter of water-gravity concentra-tion, the separating device employed depending solely upon the size of the particles treated and the buoyancy differences effected by the levita-tion, The usual separating means employed are: (1) a flotation machine for fine, slimy and for well aerated granular material; (2) shaking tables for granular less aerated material.

Jan 1, 1937

By G. E. Klinzing, S. H. Chiang, R. M. Kakwani

Filtration and dewatering results of -500 µm (-32 mesh) Pittsburgh seam coal are discussed with reference to the microscopic structure parameters, i.e., particle segregation in the cake and particle and pore size distributions at different layers. At low solid concentration of 0.33 kg coal/kg water, a non-uniform cake structure is observed where particle and pore sizes increase from the top to bottom layers in the filter cake. An increase in the solid concentration in slurry produces more uniform cake structure and higher filtration and dewatering rates. Air bubble entrapment in the coal filter cakes is also discussed.

Jan 1, 1985

By A. L. Fentress, P. R. Bucky

The purpose of this paper is to present a scientific method for determining the proper span and shape of roof for safe and economical mining; at present, these two vital factors wherever pillars are left to support the roof are determined by local practice or general experience. To develop the method described here, experimental laboratory work was done. The arch adopted was a segment of a circle, a flat roof being considered an arch with an infinite radius. Hitherto, arches have been used underground without the background of stress analysis that generally precedes arch construction on the surface. In many cases results have not been as expected, because of the lack of knowledge of the factors affecting its strength and behavior. A theoretical and experimental study of arches should furnish information that will make it possible to design safe and economical surface structures as well as underground openings. For example, on the subject of mine drifts and tunnels, the present idea is that arching their backs increases their strength; this paper will indicate that this is not always true, and if it can be shown that under certain conditions arching becomes unnecessary an economic saving will result. In room-and-pillar work a question may arise as to whether arching the roof and gobbing the excavated material will result in timber saving, and a decrease in the dangers from falls of roof. It is to be distinctly understood that each mine must be treated as an individual problem, and that answers to these questions and many others can now be found after experimental laboratory data have been obtained. Mine-Arch Structure Fig. 1 shows the elements that affect the strength or behavior of the experimental arch. They are the span, crown thickness, radius of curvature, rise and restraint. The restraint in all cases was made sufficient to cause the arch to fail without displacing the restraining sides. Fig. 2a is a photograph of a model arch prepared for testing in the centri-

Jan 1, 1934

By E. S. Grumell

The correct sampling of coal and coke is becoming important to an ever increasing number of producers and consumers. This, therefore, may be an opportune moment to examine where we stand with regard to existing and proposed methods. In this paper an attempt will be made to review, as briefly as possible, some of the considerable amount of painstaking research which has been done in the last 10 years, and which has unquestionably led to a much better understanding of the subject. In so doing we shall try, on the one hand, to make clear where substantial progress has been made, and on the other hand, to draw attention to points that require further investigation. The paper is divided into sections in order to emphasize the major divisions of the subject; further, in order to retain this emphasis, detailed consideration of some of the points has been relegated to appendixes. No attempt has been made to give a complete survey of the literature, as this has already been done by L. A. Bushell.2 The following abbreviations will be used: A.E., average error; P.E., probable error; S.W.R., size-weight ratio; B.S.I., British Standards Institution. Section 1.—Cost It has often been stated that the cost of sampling should bear some relationship to the value of the product, and since coal is a relatively cheap raw material it would be a major error to specify, for ordinary commercial purposes, elaborate and costly methods of sampling which nobody would adopt. Specifications must be of such a nature that they will be used. We believe that one of the achievements of the last 10 years has been to reduce the cost of sampling. There is, however, another point to be considered; via., that the cost of sampling should bear some relationship to the value of the investigation. Correct sampling is a cog (possibly a small one) in the wheel

Jan 1, 1940

By E. S. Grumell

The correct sampling of coal and coke is becoming important to an ever increasing number of producers and consumers. This, therefore, may be an opportune moment to examine where we stand with regard to existing and proposed methods. In this paper an attempt will be made to review, as briefly as possible, some of the considerable amount of painstaking research which has been done in the last 10 years, and which has unquestionably led to a much better understanding of the subject. In so doing we shall try, on the one hand, to make clear where substantial progress has been made, and on the other hand, to draw attention to points that require further investigation. The paper is divided into sections in order to emphasize the major divisions of the subject; further, in order to retain this emphasis, detailed consideration of some of the points has been relegated to appendixes. No attempt has been made to give a complete survey of the literature, as this has already been done by L. A. Bushell.2 The following abbreviations will be used: A.E., average error; P.E., probable error; S.W.R., size-weight ratio; B.S.I., British Standards Institution. Section 1.—Cost It has often been stated that the cost of sampling should bear some relationship to the value of the product, and since coal is a relatively cheap raw material it would be a major error to specify, for ordinary commercial purposes, elaborate and costly methods of sampling which nobody would adopt. Specifications must be of such a nature that they will be used. We believe that one of the achievements of the last 10 years has been to reduce the cost of sampling. There is, however, another point to be considered; via., that the cost of sampling should bear some relationship to the value of the investigation. Correct sampling is a cog (possibly a small one) in the wheel

Jan 1, 1940

By Howard I. Epstein, John R. Buzek

Thickeners are simply large tanks, usually circular in shape, which are designed to allow settling of solids and to operate with continuous overflow of clear water and underflow of thick pulp. The dimensions of the thickener are usually such that dewatering of very fine pulps may be accomplished while still overflowing clear water. Some thickeners such as the Center, Hardinge and Hydrotator types combine thickening with filtering2 while others such as the Dorr type are pure thickeners. l .2 , 3 A schematic diagram of the traction type Dorr thickener is shown in [Fig 1]. This type is appropriate for tanks over 15 m (50 ft) in diameter. This tank employs a rotating raking mechanism which moves the settled material toward the central discharge. For this and other thickeners, it is common to have a shallow conical tank bottom in order to conform to the geometry of the raking mechanism, and it is often desirable to elevate the tank for ease of access to the product. When the tank does not rest on the ground, the forces resisted by the cone are large, and thick plates must be employed. The fabrication of these tanks requires temporary supports in order to erect the cone. A flat-bottomed tank could also be used because the settled material would soon form a hardened conical surface. However, because of the presence of large bending forces, even larger plate thicknesses are required than for the conical bottom. Significant cost savings often can be realized by the use of a scalloped-bottomed tank such as the one partially shown in [Fig. 2]. The particular scalloped bottom discussed in this paper employs radial beams forming the outline of the cone-shaped bottom. These beams are supported directly by columns. Cone segments are hung between adjacent beams. The exact geometry of these segments depends upon the cone angle and radius, the number of radial beams, and their inclination. The geometry is chosen to satisfy certain clearance restraints and to utilize the material as efficiently as possible. The resulting thickness of these segments is significantly less than that of the equivalent plate for the tank with a conical bottom. This result, along with the simpler fabrication procedures required, accounts for the cost savings associated with this design. The raking mechanism employed may be the same as for the conventional conical bottom since the settled material soon forms a conical surface. Determination of the internal force mechanism for the scalloped bottom leads to designs that utilized material efficiently and thus maximize the cost savings. The complicated geometry of these bottoms along with the difficulty in analyzing the structure are factors which may have limited the use of scalloped-bottomed tanks to date. When such tanks have been built, the uncertainties associated with the internal forces have led to designs that are somewhat inefficient. In this paper, equations relating the geometric parameters are presented along with simplified closed-form solutions for the internal forces in the cone segments, from which the loads applied to the beams and the loads carried to the cylindrical tank shell can be deduced. An example is presented to show the magnitude of the savings which may be realized with this configuration.

Jan 1, 1979

By Marling J. Ankeny

MINING research in the U. S. today is indeed complex, whether it involves the Government, a small private concern, or a large one. And it promises to become more so, despite great advances already made in developing equipment and technology. The U. S. Bureau of Mines is committed to place greater emphasis on mining research as expressed in a recent policy statement to Congress on the "Long Range Minerals Program," by Secretary Fred A. Seaton, quoted above.

Jan 1, 1958

By S. T. Wlodek, John Wulff

Dense, adherent, and ductile coatings of chromium can be applied to Molybdenum by selectively freezing out the chromium solute from a supersaturated copper-or tin-rich liquid alloy. The successful exploitation of this technique depends on the control of variables common to any freezing process. Under the most favorable combimtion of supersaturation, nucleation, and mass-transfey, coatings as thick as 0.004 in. can be obtained. In exploratory experiments it was found that a coating of chromium may be applied to molybdenum by immersing the molybdenum body in a supercooled copper-chromium or tin-chromium melt and selectively freezing out the contained chromium onto the molybdenum body. Supercooling of the liquid metal plating bath can be achieved by cooling, or the maintenance of thermal or concentration gradients in the melt. The technique is similar to conventional dip-plating procedures where the sample is immersed in a molten bath of the pure plating medium, except that in these studies, the plating medium consisted of a dilute solution of chromium in liquid tin or copper. The success of this method requires that the base material to be plated be isomorphous with the coating and insoluble in the plating bath. In addition, the plating bath, while having an appreciable solubility for the coating component, must have negligible solid solubility in the solid plate. Such relationships exist in the molybdenum-chromium, chromium-tin, and chromium-copper systems. Liquid tin and copper are satisfactory as the plating solvent, because although chromium is appreciably soluble in both of these liquid metals, solid inter-solubility is almost negligible, and no compound formation occurs. The same relationships exist between molybdenum and copper or tin except that the solubility of molybdenum in liquid tin or copper is insignificant. It is this combination of solubility relationships, as well as the completely isomorphous nature of the molybdenum-chromium system, which allows the formation of a chromium coating on molybdenum by the selective freezing mechanism. Since the main deterrent to the widespread use of molybdenum for high-temperature structural applications is its poor oxidation resistance, the formation of a dense and ductile chromium coating on molybdenum may well be of commercial significance. In addition, the basic principle of coating formation by selective freezing should be applicable to other metallic or even nonmetallic systems. The precipitation of the solute from a liquid metallic solution, for the formation of a protective coating, has not been previously considered in the literature. Frequently, however, a similar phenomenon has been described in the corrosion of metallic heat exchangers by liquid metals1 wherein temperature gradients in the liquid metal heat-transfer medium result in the formation of layers or deposits of metallic residue2 in the cooler portions of the system. Impregnating techniques using liquid baths have been tried as a plating process. Semchyshen and Barr, for instance, have successfully diffused chromium into molybdenum by immersing the molybdenum specimen in a liquid tin-chromium or copper-chromium alloy. This simple holding technique fails to produce a layer of pure chromium and requires prolonged immersion to allow for the diffusion-activated enrichment of the molybdenum. During the course of this investigation, most of the phase relations published for the copper-chromium4 and molybdenum-chromium4 systems, were found reliable. It was necessary, however, to investigate the solubilities of chromium and molybdenum in liquid tin as well as the solubility of molybdenum in liquid copper. These determinations were made by a simpie weight loss technique on materials of the same purity as used in the plating studies. The results of these solubility studies are given in Tables I and I1 and indicate that although the solubility of molybdenum in liquid

Jan 1, 1961

By E. A. Gulbransen, W. S. Wysong

The behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a a Or as an important component in alloys in high temperature Oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a micro-balance study of the following problems: (1) the oxidation behavior in the ternperature range of 25 to 550°C (') the reduction with pure hydrogen Of thin Oxide films formed On tungsten, and (3) the volatility Of thin Oxide films On tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the Oxide to to ratio is greater than one, the oxide is not considered protective, ('1 the meta1 readily Oxidizes at temperatures from 30" to 55o°C (3) the oxides WO² and WO³ are reduced at temperatures as low as 500°C. by hydrogen, and (4) the Oxide WO3 is volatile at temperatures from 800 to 1100°C. Literature The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°c. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides, Schei14 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bed-worth's5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.? They have reported that WO3 is the stable oxide in contact with the metallic substrate up to approximately 600°C while wo³ forms first at 7oo°c. Hagg and Magneli8 have recently reported a study of the lattice structures . observed in the tungsten oxidcs using the X-ray diffraction method. In addition to an a-phase WO3 and a '-phase WO2, they reported the existence of two new phases. A 8' phase, homogeneous between

Jan 1, 1949

By E. A. Gulbransen, W. S. Wysong

THE behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a metal or as an important component in alloys in high temperature oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a microbalance study1,2 of the following problems: (I) the oxidation behavior in the temperature range of 25 to 550°C (2) the reduction with pure hydrogen of thin oxide films formed on tungsten, and (3) the volatility of thin oxide films on tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the oxide to metal volume ratio is greater than one, the oxide is not considered protective, (2) the metal readily oxidizes at temperatures from 300° to 550°C (3) the oxides W02 and WO3 are reduced at temperatures as low as 500°C. by hydrogen, and (4) the oxide W02 is volatile at temperatures from 800 to 1100°C. LITERATURE The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°C. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides. Scheil4 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bedworth5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.7 They have reported that W03 is the stable oxide in contact with the metallic substrate up to approximately 600°C while W02 forms first at 700°C. Hägg and Magneli8 have recently reported a study of the lattice structures observed in the tungsten oxides using the X-ray diffraction method. In addition to an a-phase W03 and a d-phase W02, they reported the existence of two new phases. A ß' phase, homogeneous between

Jan 1, 1947

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 Cecil H. Desch

The progress of metallurgical practice and the demands made by the engineering industry on our foundries and mills have made the crystalline structure of metals a subject of far more than academic interest. Metals and alloys are made up of crystals. Even if we accept the view, so ably maintained by some metallurgists, that the crystals are separated from one another by an amorphous layer, it remains true that all but a very minute fraction of any metallic mass is crystalline. The conditions which affect the growth of crystals are therefore of importance in metallurgy. It is not only castings whose properties depend on the arrangement of their crystals, for the more we learn of the behavior of forged, rolled and drawn metals, the more certain it becomes that it is profoundly influenced by the size and arrangement of the crystals in the original ingot, determining a structure which may persist in a modified form through a long series of mechanical operations and annealings. This is mainly due to the concentration of much of the impurities in the last portions of the liquid to freeze, so that the boundaries between single crystals or groups of crystals are marked out by a zone of segregated material, differing in properties from the mass, and offering a barrier to diffusion and equalization of composition throughout the whole. The importance of this fact has been fully recognized by steel manufacturers, who have to deal with ingots which are sometimes very large, and are cast at a high temperature, containing impurities which have a marked effect on the properties even when present in very small quantity. For this reason the Iron and Steel Institute has set up a committee to examine the whole question of the heterogeneity of steel ingots,(1)† and a report has been issued, containing an account of the structure of 16 ingots, ranging in weight from 15 cwt. to 172 tons, each of which was sectioned and examined by chemical analysis and by etching. A valuable body of data concerning segregation has thus been collected. The work of the committee is being prosecuted with great activity, and at the same time researches are in progress to determine the physical

Jan 1, 1927