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By Benjamin Lustman, Robert F. Mehl

THE study of the high-temperature oxidation of pure metals, intensively pursued experimentally since the pioneer work of Pilling and Bedworth1 and supplemented by the recent theoretical work of Wagner2 is now well advanced. The important field of low-temperature oxidation-i.e., oxidation extending only through the temper color range of thicknesses with the formation of thin oxide layers in the range from o to 1000-2000 Angstroms-has not, however, reached so satisfactory a state, owing largely to the experimental difficulties that attend the formation and study of thin films; most of the work has been performed on abraded specimens whose surface irregularities approximated the thickness of the films formed. It has been pointed out that the rates of oxidation of different crystal faces are different and that the difference may be related to the orientation relationships that obtain between the metal crystal and the superimposed oxide crystal; it has also been suggested that this orientation dependence should manifest itself in rates of oxidation and perhaps also of corrosion in aggregates bearing preferred orientations. 3,4 An attempt to measure the rates of oxidation of different crystal faces of alpha iron demonstrated this difference in rate,4 but the dependence of rate on orientation was not simple; the method of measuring thickness, consisting of a color comparison with barium stearate multi-films of known thickness, was not wholly satisfactory. For these reasons it was felt that a study of the rate of oxidation of single crystals prepared with surfaces as smooth as possible, using a sensitive method giving true film thickness, should be profitable. Copper was chosen because of the ease of reduction of the primary oxide film and because the orientation relationships between metal and oxide and the composition of the oxide films formed at low temperatures are known; for thin films formed at low temperatures, Cu2O alone occurs.22-24 EXPERIMENTAL PROCEDURE Various methods of surface preparation were attempted in order to obtain a surface that would oxidize uniformly and reproducibly. Electrolytic polishing by the method of Jacquet5 and electrolytic and mechanical polishing followed by annealing in vacuum and in purified hydrogen at various temperatures were tested. The procedure finally adopted consisted in a fine metallographic polish followed by an anneal in purified hydrogen at temperatures of 900º to 1000°C. for 12 hr. or more. The surface so produced was very bright and smooth, with no trace of specular etching (though some grain-boundary etching was observed); indeed, fine scratches produced by the final polish were entirely removed by the high-temperature anneal.

Jan 1, 1941

By Henry P. Ehrlinger, James C. Bradbury

Tripoli is a naturally occurring, very finely divided form of silica found chiefly in some midwestern and southeastern states and used commercially as fillers and abrasives. Definitions Tripoli is a microcrystalline, finely particulate, more or less friable form of silica that appears to be the product of leaching of siliceous limestone or calcareous chert. The term was originally applied to a deposit near Seneca, Mo., that resembled material of that name found near Tripoli in North Africa (Hovey, 1894). The two deposits were subsequently found to have different physical characteristics -the North African tripoli, now called tripolite, is a diatomite, composed of the siliceous skeletons of microscopic marine plants called diatoms, and the Missouri tripoli contains no diatom remains; the term tripoli, however, continued to be used for the Missouri material and is now applied in a general way to most silica deposits similar to it in characteristics and geologic origin. In commercial trade tripoli is commonly understood to designate material from the Missouri-Oklahoma field; silica from southern Illinois, the other major producing area, is referred to commercially as amorphous silica. Each term, however, may be used commercially for material, regardless of place of origin, that has the characteristics or uses commonly ascribed to the material from one or the other major producing area. For example, in the commodity price listings, Engineering and Mining Journal routinely lists under Tripoli, prices "f.0.b. Elco, III." and "f.0.b. Seneca, Mo., and Rogers, Ark.," and under Silica, amorphous, prices "f .o.b. Ill.," and "f .o.b. Dierks, Ark." Amorphous silica, the commercial designation given to southern Illinois tripoli, is, like the term tripoli, a misnomer. Mineralogically, the southern Illinois deposits are composed of microcrystalline quartz, and no amorphous material has been detected during X-ray and scanning electron microscope investigations (Leamnson, Thomas, and Ehrlinger, 1969; Thomas et al., 1970). Soft silica is another term that has been applied to Illinois and Tennessee tripoli, presumably to distinguish it from the more compact Missouri material. It has also been used in the ceramic trade to distinguish tripoli from "hard" silica, or silica flour, produced by pulverizing silica sand (Heinz, 1937). Rottenstone, produced commercially in Pennsylvania, is similar to tripoli in that a major constituent is finely particulate silica, and its uses are much the same as those of tripoli- as abrasives and fillers. The origin of rottenstone also is similar to that of tripoli-decomposition of a siliceous sedimentary rock. The parent rock is defined as a siliceous limestone (Gary, McAfee, and Wolf, 1972; Thrush, 1968) or as shale (personal communication). Heinz (1937) quotes a brief statement describ-

Jan 1, 1975

By E. I. Larsen, E. F. Swazy, F. R. Hensel

EXPERIENCE has indicated that hard bronzes are not suitable for bearing applications where high bearing loads and speeds are involved. It is the general practice to utilize softer materials for these purposes, such as copper, lead, silver, babbitt, lead-base alloys, and more recently aluminum-base alloys, preferably supported by a steel backing. It was the objective of the present investigation to study a new material produced by powder metallurgical methods susceptible to precipitation-hardening. TEST MATERIALS Preliminary tests were made with compacts containing copper, nickel and silicon in quantities sufficient to form 3 to 5 per cent nickel silicide. It was found that this type of alloy was susceptible to the formation of a soft surface shell when sintered in tank hydrogen. The depth of the shell depended on the length of sintering time and sintering temperature, and varied in thickness from a few thousandths to as much as one eighth inch. This soft shell resulted from the preferential oxidation of silicon, thereby reducing the efficiency of age-hardening by the nickel silicide compound. The body of the sintered compacts below the soft shell could be precipitation-hardened to a hardness of 70 to 85 Rockwell B, by quenching from. 900°C. and age-hardening at 450°C. A series of tests was made with various addition agents, in order to decrease the rate of preferential oxidation, and it was found that phosphorus was most beneficial in this respect. After considerable experimentation, the following nominal composition was accepted as standard: 2.4 per cent nickel; 0.8 silicon; 0.3 phosphorus; balance copper. The physical properties and certain bearing properties of this alloy are described in the present paper. PREPARATION OF COMPACTS Several methods of incorporating the hardening ingredient (nickel silicide) were studied. Compacts formed from copper, nickel and silicon powders were found to be inferior to those fabricated from prealloyed nickel silicide master alloys, because of the rapid oxidation of pure silicon during sintering. The use of a prealloyed nickel silicide hardener containing 25 per cent silicon and 75 per cent nickel could be further improved by preparing a master alloy, incorporating nickel, silicon, phosphorus and copper, having the following nominal composition: 25 per cent nickel; 7 silicon; 3 phosphorus; 64 copper. This alloy is brittle in. the cast condition and can be readily powdered. SINTERING PROCEDURE The blended powders were pressed at 25 to 40 tons per sq. in., the pressure depending on the size and shape of the compacts. Sintering was carried out in hydrogen or cracked ammonia atmospheres at

Jan 1, 1946

By John H. Walthall, Raymond L. Copson, Travis P. Hignett

In October 1942, the War Production Board requested the Tennessee Valley Authority to undertake investigations to determine the feasibility of producing alumina suitable for reduction in aluminum cells, from clays and other domestic materials, by a lime-sintering, soda-ash leaching process. The work was undertaken by the chemical engineering staff of the Authority under the general direction of the War Metallurgy Committee of the National Academy of Sciences. The investigation included small-scale tests to determine the most suitable conditions for the process, and construction and operation of a pilot plant to obtain data for evaluation of the process and for design of a plant. The results of this investigation are described in the present paper. Sources of Alumina Alumina for the commercial production of aluminum is obtained from bauxite by the Bayer process. The tremendous demand for aluminum for wartime uses is causing rapid exhaustion of the high-grade bauxite deposits in the United States. On the other hand, there is an abundance of aluminous materials such as clay and lower grades of bauxite, which are not suitable for treatment by the Bayer process because of their high silica content. The Tennessee Valley Authority has conducted research and pilot-plant work for more than 5 years on methods for the production of alumina from clay and low-grade bauxite. Particular attention has been given to the high-grade white kaolin found in Carroll County, Tennessee. Exploratory drilling has demonstrated that at least 4 1/2 million tons of kaolin containing in excess of 34 per cent AlzOI is available in this area by strip-mining methods. It has been estimated that hundreds of millions of tons of clay of similar quality occur in the Tennessee Valley region. The Process The process is illustrated in the flowsheet (Fig. I), and consists essentially of the following steps: I. Heating a mixture of clay and limestone to form a sinter containing calcium aluminate and dicalcium silicate. z. Leaching this sinter with a dilute sodium carbonate solution, to form a sodium aluminate solution and a calcium carbonate, calcium silicate residue, which is discarded. 3. Treating the sodium aluminate solution with carbon dioxide to precipitate aluminum trihydrate and regenerate the sodium carbonate solution, which is recycled. 4. Heating the aluminum trihydrate to produce alumina. The process was considered promising because of the abundance and cheapness of the two raw materials, clay and limestone; and because, as compared with an acid process, smaller amounts of critical

Jan 1, 1944

By D. A. Dahlstrom

Although the liquid-solid cyclone is a relatively recent innovation in the field of coal preparation, various authors have already indicated three distinct applications to operations encountered in the modern tipple. Driessen's articles and work at the Dutch State Mines exhibited its possibilities in the bene-ficiation of fine coal with apparently high efficiencies down to the 200-mesh fraction. l,2,3,4 Other publications point out its use as a recoverer, thickener, and preliminary dewatering agent of fine coal which in too many cases is being wasted due largely to former high operating cost limitations.M Finally, certain authors have emphasized the practicability of applying the cyclone to the elimination of coarse and fine solids from water slurries in the tipple in order to produce a water suitable for recycle purposes containing only minute particles far below the 200-mesh size.6 This would result in a closed water system for many cases, with its accompanying economic and operating advantages to locations where water quantity and quality problems are severe; better operation of washing equipment using a consistent water devoid of injurious fine particles; lowered maintenance costs due to the lesser abrasion resulting when the fine abraiding particles are removed; and the greater ease of disposing of refuse streams of reduced volume containing greater percentages of solids. While the three applications have been indicated to be feasible, only a meager amount of data is available on capacities and solid elimination eficiency as a function of design variables and cyclone friction loss. This information is essential for the optimum use and construction of the solid-liquid cyclone, and accordingly, work on the problem was initiated at Northwestern University. For the unfamiliar reader, briefly the cyclone consists of a cylindrical section mounted above a truncated cone. The feed nozzle enters the cylindrical ring tangentially with the underflow nozzle permitting discharge of the concentrated solids located at the apex of the cone. The overflow nozzle through which the clarified water exits is centered in the cylindrical section at the top of the cyclone. Half sections of experimental cyclones will be found in Fig la and 6. The feed slurry enters with a tangential velocity, thus creating a spiral pattern of high centrifugal force. The solid particles of sufficient size and gravity are ejected outward to the walls and spirally discharge to the underflow. Most of the water with uneliminated fine solids moves radially inward along the path of the outer

Jan 1, 1950

By R. I. Parsons, M. B. Standing, E. N. Lindblad

The recovery of the heavier components from a gas cap or retrograde pool is shown to be the greatest when the sand is cycled with a dry gas at a low pressure. This conclusion is in direct opposition to the belief that the most efficient production program is pressure maintenance and cycling at or near the dew point. The results are calculated from: (I) constant volume, variable composition pressure-volume-temperature tests on a mixture of trap gas and liquid from a producing well; (2) published equilibrium constant data and the measured composition of the dew-point material; and (3) the fact that in a sand section of homogeneous permeability, injected gas displaces reservoir gas nearly, quantitatively. The results are based on the simplifying assumption that variable permeability systems may be defined by the ratio of two statistical parameters, and that gas injected into an actual sand will behave as though the sand were composed of many layers, each of constant permeability. Introduction Pressure decline in gas-condensate type reservoirs is accompanied by the formation of a liquid phase throughout the reservoir. Over the past ten years the processing of the material from these types of reservoirs for the heavier hydrocarbon components and the return of the light fractions to the reservoir ("cycling") has become increasingly popular. It has often been stated that the purpose of such a program is to prevent the loss of the retrograde liquid phase formed in the reservoir. The purpose of this paper is to present the results of laboratory tests and computations concerned with several possible methods of producing a gas cap or condensate type of reservoir. The results show that the recovery of heavier hydrocarbons for this type of reservoir is not a maximum under conditions of cycling at or near the dew-point pressure. Instead, variations in permeability and the ability of the dry injected gas to revaporize condensate, point to cycling at a considerably reduced pressure as the optimum production-method. In addition the paper suggests a way of evaluating sands for their permeability variation. The calculations presented in the following sections of the paper are in terms of the production of the butanes and heavier fraction from the gas cap of a field which had an original pressure of approximately 3000 psi. Specifically, the calculations show: 1. To what extent the condensate formed in the reservoir after pressure decline can be recovered by the cycling of a dry absorber-plant gas through the sands. 2. Whether there would be greater recovery of hydrocarbons if cycling were instigated at the original reservoir pressure.

Jan 1, 1948

By James T. Gow, Oscar E. Harder, Anton de S. Brasunas

This paper deals with the results obtained and the techniques employed in determining: 1. Liquidus and solidus temperatures of the HH and HT type heat-resistant alloys. 2. The relation of true temperatures (thermocouple) to apparent temperatures (optical pyrometer) for the molten HH and HT type alloys. This work was the outgrowth of needing to know something definite about these temperatures in order to study the effect of pouring temperatures, shake-out times, and heat-treatments on the properties of some heat-resistant alloys. The information developed is thought to be of interest to industry for guidance in foundry practices and the industrial heat applications of the alloys. This paper is based upon work that has been done for the Alloy Casting Institute at Battellc Memorial Institute. Liquidus and Solidus Temperatures of HH and HT Type Alloys Experimenta1 Procedures Temperature-time curves were obtained during the cooling and solidification of several HH and HT type alloys. The metal was melted in an Ajax high-frequency, induction furnace and poured into a core-sand mold for cooling. The temperature measurements were obtained by means of a platinum, platinum-rhodium thermocouple contained within a fused silica sheath, which was extended through the side wall of the dry core-sand mold to a point at about the center of the mold cavity, which was 3 in. in diameter by 5 in. deep. The cold junction of the thermocouple was kept in an ice bottle, and the temperature was recorded automatically on a direct-reading potentiometer recorder. Through a switching arrangement, the temperature recorded was checked occasionally with a portable Leeds and North-rup potentiometer indicator. Less than a 5°F. variation in the two instruments was always found. This is within the limit of accuracy of readings. The thermocouple used was checked for accuracy against a standard couple, both before use on this work and after completion of the work, by the instrument laboratory. Temperature-time Cooling Curves Fig. I is an enlarged reproduction of a part of one of the cooling curves over the temperature range of 2600' to 2200°F. for an alloy of the HT type with 0.45 per cent carbon, 16 per cent chromium, and 36 per cent nickel. This is a typically shaped cooling curve as obtained for the alloys. It will be noted that two temperatures "re shown on Fig. I for the liquidus temperature. It is thought likely that the higher temperature, A, at the point at

Jan 1, 1945

By M. B. Standing, R. I. Parsons, E. N. Lindblad

The recovery of the heavier components from a gas cap or retrograde pool is shown to be the greatest when the sand is cycled with a dry gas at a low pressure. This conclusion is in direct opposition to the belief that the most efficient production program is pressure maintenance and cycling at or near the dew point. The results are calculated from: (I) constant volume, variable composition pressure-volume-temperature tests on a mixture of trap gas and liquid from a producing well; (2) published equilibrium constant data and the measured composition of the dew-point material; and (3) the fact that in a sand section of homogeneous permeability, injected gas displaces reservoir gas nearly, quantitatively. The results are based on the simplifying assumption that variable permeability systems may be defined by the ratio of two statistical parameters, and that gas injected into an actual sand will behave as though the sand were composed of many layers, each of constant permeability. Introduction Pressure decline in gas-condensate type reservoirs is accompanied by the formation of a liquid phase throughout the reservoir. Over the past ten years the processing of the material from these types of reservoirs for the heavier hydrocarbon components and the return of the light fractions to the reservoir ("cycling") has become increasingly popular. It has often been stated that the purpose of such a program is to prevent the loss of the retrograde liquid phase formed in the reservoir. The purpose of this paper is to present the results of laboratory tests and computations concerned with several possible methods of producing a gas cap or condensate type of reservoir. The results show that the recovery of heavier hydrocarbons for this type of reservoir is not a maximum under conditions of cycling at or near the dew-point pressure. Instead, variations in permeability and the ability of the dry injected gas to revaporize condensate, point to cycling at a considerably reduced pressure as the optimum production-method. In addition the paper suggests a way of evaluating sands for their permeability variation. The calculations presented in the following sections of the paper are in terms of the production of the butanes and heavier fraction from the gas cap of a field which had an original pressure of approximately 3000 psi. Specifically, the calculations show: 1. To what extent the condensate formed in the reservoir after pressure decline can be recovered by the cycling of a dry absorber-plant gas through the sands. 2. Whether there would be greater recovery of hydrocarbons if cycling were instigated at the original reservoir pressure.

Jan 1, 1948

By L. A. Willey

Although the interierometric method for the determination of length changes was devised by Fizeau more than three quarters of a century ago, it has not achieved the widespread use in the metallurgical field that its precision and simplicity would seem to warrant. The interferometer and the basic principle are both very simple. When optically plane surfaces held at a very slight angle to each other are illuminated by monochromatic light, rectilinear, equally spaced interference fringes arc formed. Each fringe corresponds to a defiuitc thikness of the wedge formed by the optical flat.;. The difference in wedge thickness between two consecutive fringes is cqual to one half the wave length of the illuminating light. Instruments for vicwing the intertero~ncter have passed through a number of modifications. Outstanding among the improvements were those Abbe. in 1884. His improved instrument permitted micrometric mcasurements to the order of one-hundredth of the width of an interference fringe (i.e., lengths were measured to the order of one two-hulldredth of the mave length of light ). It also permitted the consecutive use of light of several wave lengths. which made possible the determination of the order number of any fringe and therefore the absolute thickness of the wedge at any point. The Abbe dilatometer and methods of measuretment, including corrections to he applied for the change of index of refraction with change in tempcrature and barometric pressure in an air wedge, have been thoroughly described by Pulfrich.' Pulfrich2 made further improvements in the interference measuring apparatus. His instrument embodied all the features of the Abbe dilatometer but was made more versatile by its complete mechanical separation from the interferorneter. The introduction of an Amici prism in the piece permitted the simultaneous observ tion of the whole set of fringe systems developed in the interferometer from the visible light of a geisler tulle. .Also, the introduction of a direct-vision, reflecting prism made it possible to set the fringes parallel to the two vertical fiducial line. of the instrument without the necessity of rotating the interierometcr. Interferometric methods employed ill this country have been developed and dcscribed by Priest, Pelers and Cragoe," Austin,5 Merritt,= Saunders,? and Nix and MaNair. Since none of these authors used the type of instrument that was employed in the present investigation, they Will not be discussed here. This paper will be limited to the description of the interfernmetric apparatus and method used at the Aluminum Research Laboratories and to the presentation of data so obtained. Apparatus and Procedure A general view of the dilatometer, not including equipment for controlling and

Jan 1, 1945

By James T. Gow, Oscar E. Harder, Anton de S. Brasunas

THIS paper deals with the results obtained and the techniques employed in determining: I. Liquidus and solidus temperatures of the HH and HT type heat-resistant alloys. † 2. The relation of true temperatures (thermocouple) to apparent temperatures (optical pyrometer) for the molten HH and HT type alloys. This work was the outgrowth of needing to know something definite about these temperatures in order to study the effect of pouring temperatures, shake-out times, and heat-treatments on the properties of some heat-resistant alloys. The information developed is thought to be of interest to industry for guidance in foundry practices and the industrial heat applications of the alloys. This paper is based upon work that has been done for the Alloy Casting Institute at Battelle Memorial Institute. LIQUIDUS AND SOLIDUS TEMPERATURES OF HH AND HT TYPE ALLOYS Experimental Procedures Temperature-time curves were obtained during the cooling and solidification of several HH and HT type alloys. The metal was melted in an Ajax high-frequency induction furnace and poured into a coresand mold for cooling. The temperature measurements were obtained by means of a platinum, platinumrhodium thermocouple contained within a fused silica sheath, which was extended through the side wall of the dry core-sand mold to a point at about the center of the mold cavity, which was 3 in. in diameter by 5 in. deep. The cold junction of the thermocouple was kept in an ice bottle, and the temperature was recorded automatically on a direct-reading potentiometer recorder. Through a switching arrangement, the temperature recorded was checked occasionally with a portable Leeds and Northrup potentiometer indicator. Less than a 5°F. variation in the two instruments was always found. This is within the limit of accuracy of readings. The thermocouple used was checked for accuracy against a standard couple, both before use on this work and after completion of the work, by the instrument laboratory. Temperature-time Cooling Curves Fig. I is an enlarged reproduction of a part of one of the cooling curves over the temperature range of 2600° to 2200°F. for an alloy of the HT type with 0.45 per cent carbon, 16 per cent chromium, and 36 per cent nickel. This is a typically shaped cooling curve as obtained for the alloys. It will be noted that two temperatures are shown on Fig. r for the liquidus temperature. It is thought likely that the higher temperature, A, at the point at

Jan 1, 1945

By I. Fatt

This paper proposes the network of tubes as a model more closely representing real porous media than does the bundle of tubes. Capillary pressure curves are derived from network models and pore size distributions are calculated from these curves. In this way is shown the difference between the true and calculated pore size distributions when the capillary pressure curve is used to obtain pore size distribution for porous media. INTRODUCTION Despite the technological importance of the laws governing flow through porous media, many of these laws have not yet been clearly formulated. This is especially true of the laws governing multiphase flow. The static properties, such as the capillary pressure curve, are also not at present interpretable correctly in terms of the pore size distribution and other structural properties of porous media. In the absence of any well founded theoretical description of fluid flow through porous media, many empirical descriptions have been proposed. In addition to the strictly empirical flow equa- tions, some equations have been developed rigorously from simple geometrical models of the pore spaces. These equations are only as valid as is the model used in their development. The two models used in the past, the sphere pack and the bundle of tubes, have been too simple, and as a result, the equations derived from them have failed to predict the observed properties. Agreement between theory and observation has been achieved for these models by inserting parameters of doubtful physical significance. The work to be reported here was undertaken in the belief that the study of a model more closely resembling most real porous media than does the sphere pack or bundle of tubes would yield useful information concerning the structure of real porous media and the relation between structure and flow properties. There was no intention of developing any calculational procedures, as for example calculating relative permeability from capillary pressure data. The objective of the study was instead to develop a better qualitative understanding of the relation between the various measurable properties of porous media. The model chosen for study is the network of tubes in which each tube represents a pore space in the porous medium. Microscopic observations leave no doubt that sandstones and clastic carbonates are three-dimensional irregular networks of irregularly shaped pores. The irregularity of these structures makes any accurate theoretical study of their properties impossible. Results from an oversimplified model such as the bundle of tubes are worthless when applied to real systerns. The sphere pack model, on the other hand, not

Jan 1, 1957

By H. S. Kalish, F. J. Dunkerley

Introduction and Previous Work THE determination of the low temperature tensile properties of tin and tin-lead alloys was initiated as part of an extensive research program on the phasial equilibria of tin binary systems below 13.2°C and the property changes associated therewith. A survey of the literature revealed that, although some room temperature tensile data were available for tin and a few tin-lead alloys, there existed no survey report of the low tcmPerature tensile properties of these alloys. Accordingly, the tensile data for tin and a series of pure tin alloys containing from 0.01 to 50 pet lead were measured at eleven temperatures horn — 196 to +20°C and are presented here in survey form. In addition to the importance of these tensile data as a preliminary to certain fundamental research, this information promises also to be of commercial importance because of the extensive use now being made of tin-lead solders in refrigeration and gas liquefaction equipment. Occasional failures of the solders in low temperature service have been attributed by some metallurgists to low temperature embrittlement, while others hold that failure results from the transformation of the tin-rich phase of the solder from the solid white (beta) to the powdered gray (alpha) form. From the data previously available in the literature, neither of these explanations can be completely corroborated. cohen and van Lieshout have estab-lished the beta to alpha tin transformation at 13,2°C and have shown that strain accelerates the transformation. Further, they showed that although I pct lead retarded the transformation, it was not eliminated. It will be pertinent, then, to note whether the beta to alpha transformation of the tin.rich phase will occur in a short-time tensile 'test. polanyi and schmid2 studied the tensile properties of tin single crystals at — 185°~ and report that tin is britlle at this tem-perature. In 1946, Kostenets3 reported that pure tin was brittle at —Ig6 and — 253°~, while lead remained ductile at both these temperatures. He also studied the tensile properties of tin-lead alloys containing from 10 to 75 pet lead at —253, —196 and + I~OC. The ultimate tensile strength increased more than two times in going from room temperature to — I96°C and about three times that value on further cooling to — 253 C- All the alloys were brittle at — 196'C except those containing more than 75 pct lead. Even at — 253'C, the 75 pct lead alloy retained 36 pet elongation in a 30 mm-ga. length. Creep is also an important phenomenon

Jan 1, 1949

By Robert M. Yonco, Irving Johnson, Martin G. Chasanov

The thermodynamics of the cadmium-rich portion of the Pu-Cd system has been studied with a high-temperature galvanic-cell method. The partial phase diagram of the Pu-Cd system was determined. The existence of the intermediate phases PuCd11 (cubic BaHg11 structure, ao= 9.282) and PuCd6 (cubic, CeCd6 structure, a, = 15.59) was established. The existence of at least one other intermediate phase richer in plutonium was indicated. PuCd11 was found to peritectically decompose into PuCd6 and liquid at 406" * 2°C. The solubility of plutonium in liquid cadmium may be represented by the equations: (355' to 399°C) log (at. pct Pu) = 6.223 -4282T-1 (399° to 632°C) log (al. pct Pu) - 5.148 - 5277T-1 > 1.156 x 106 T-2 The free energy of formation values (kcal per mole) of the two intermetallic phases are given by the equations: (PuCd11), ?Gf= -45.9 + 35.7 x 10-3 T (PuCd6), ?Gf0- -39.27 + 25.86 X 10-3T The excess free energy (kcal per mole) of plutonium in liquid cadmium may be represented by the equation: -(-16.72 * 29.54 NPu) 10-3T in which Npu and Ned are the atom fractions of plutonium and cadmium. The thermodyanamics of the U- Cd and Pu-Cd systems are compared. THERMODYNAMIC information on systems of the actinide metals with low-melting metals, such as zinc and cadmium, is useful in the design of pyro-metallurgical processes for the purification of nuclear reactor fuels. The thermodynamics of the Pu-Zn,1 Th-Zn.2,3 U-Zn,4-5 and U-Cd6 systems have been reported. The present report on the Pu-Cd system concerns the liquidus composition in the cadmium-rich region, the characterization of the two most cadmium-rich intermetallic phases, and the thermodynamic properties of these intermetallic phases and dilute liquid solutions of plutonium in cadmium. EXPERIMENTAL Phase Studies. The liquidus composition was determined by analysis of filtered samples of the liquid phase withdrawn at a series of temperatures. The apparatus and procedure were identical to that used in the previous study of the Pu-Zn system.' Briefly. a sample of the melt was withdrawn into a tantalum tube fitted with a porous tantalum filter (30-µ pore). the entire sample dissolved in hydrochloric acid (to avoid errors due to segregation

Jan 1, 1965

By G. K. Manning, C. H. Lorig

TWO metallurgical tools have acquired wide use within the past several years as a means of studying the transformation characteristics of steel. One is a technique used first by Bain and Davenport for determining the transformation characteristics of a steel at constant temperature; the second is the end-quench hardenability test. Constant-temperature transformation curves like those of Bain and Davenport have done much to rationalize the metallography of steel; however, in commercial practices, constant-temperature transformation is seldom encountered, therefore only rarely can such curves be directly applied. The real reason for the determination of such curves lies in the fact that they provide a way of thinking about transformation that is both convenient and productive. The end-quench hardenability test is a more practical means of studying transformation, for, by correlating positions on the hardenability bar with shapes of different masses, an almost direct application of the results can be made. Unfortunately, the end-quench test, though practical, can do very little toward improving the metallurgists' way of thinking about transformation. These two metallurgical tools, dealing with precisely the same phenomenon, should be very closely associated in metallurgists' minds. Actually, they are frequently pushed into separate mental corners and considered as being more or less distinct and unrelated. The reason for this is that no strong connecting link between them has been developed. An attempt is sometimes made to relate these two tools by projecting the critical cooling rate on the isothermal transformation plot as illustrated in Fig. I. The critical cooling rate is considered as a constant rate-though in practical applications, cooling rates are never constant—and this constant cooling rate is given uniform significance from the Ae temperature down to the temperature of initial transformation. A little thought indicates the errors of such a procedure. Certainly the time interval spent just below point A of Fig. I cannot be as effective in promoting nucleation as is the time interval spent just above point B. Yet the procedure represented in Fig. I considers all the time spent between temperatures A and B to be just as effective in promoting nucleation as though all the time were spent at temperature B. Furthermore, change the shape of the isothermal curve between points B and C in any way desired, and the required critical cooling rate is not changed one iota. This cannot possibly be true. Such a way of thinking about critical cooling rates not only is incapable of giving any results that are quantitatively satisfactory but is likely to give very misleading qualitative results.

Jan 1, 1947

By G. K. Manning, C. H. Lorig

TWO metallurgical tools have acquired wide use within the past several years as a means of studying the transformation characteristics of steel. One is a technique used first by Bain and Davenport for determining the transformation characteristics of a steel at constant temperature; the second is the end-quench hardenability test. Constant-temperature transformation curves like those of Bain and Davenport have done much to rationalize the metallography of steel; however, in commercial practices, constant-temperature transformation is seldom encountered, therefore only rarely can such curves be directly applied. The real reason for the determination of such curves lies in the fact that they provide a way of thinking about transformation that is both convenient and productive. The end-quench hardenability test is a more practical means of studying transformation, for, by correlating positions on the hardenability bar with shapes of different masses, an almost direct application of the results can be made. Unfortunately, the end-quench test, though practical, can do very little toward improving the metallurgists' way of thinking about transformation. These two metallurgical tools, dealing with precisely the same phenomenon, should be very closely associated in metallurgists' minds. Actually, they are frequently pushed into separate mental corners and considered as being more or less distinct and unrelated. The reason for this is that no strong connecting link between them has been developed. An attempt is sometimes made to relate these two tools by projecting the critical cooling rate on the isothermal transformation plot as illustrated in Fig. I. The critical cooling rate is considered as a constant rate-though in practical applications, cooling rates are never constant—and this constant cooling rate is given uniform significance from the Ae temperature down to the temperature of initial transformation. A little thought indicates the errors of such a procedure. Certainly the time interval spent just below point A of Fig. I cannot be as effective in promoting nucleation as is the time interval spent just above point B. Yet the procedure represented in Fig. I considers all the time spent between temperatures A and B to be just as effective in promoting nucleation as though all the time were spent at temperature B. Furthermore, change the shape of the isothermal curve between points B and C in any way desired, and the required critical cooling rate is not changed one iota. This cannot possibly be true. Such a way of thinking about critical cooling rates not only is incapable of giving any results that are quantitatively satisfactory but is likely to give very misleading qualitative results.

Jan 1, 1947

By J. R. Long, T. R. Graham

THIS report is concerned with part of a series of investigations carried on by the Federal Bureau of Mines on alloys, particularly nonferrous alloys, made with electrolytic manganese. A broad general program instituted after commercial quantities of electrolytic manganese became available was necessary in order to compare the effects of electrolytic manganese with those of the ordinary commercial grades. Representative analyses of these two materials show the commercial manganese metal to contain up to 2 per cent iron, a maximum of I per cent silicon and 0.06 per cent carbon, while the electrolytic manganese rarely exceeds 0.01 iron, 0.02 sulphur, with no silicon or aluminum. In the literature, the emphasis has been largely on high-strength casting alloys containing up to 5 per cent manganese, and few data are available on wrought manganese alloys. These factors, coupled with the strategic position of copper and zinc, have given impetus to the Bureau's War Research Program for the development of alloys containing nonstrategic manganese for the purpose of supplementing or providing alternates for the more strategic metals. The alloy reported here was studied, along with several other ferrous and nonferrous alloys, as possible cartridge-case material, and was chosen after a review of the properties of the ternary alloys of copper-manganese-zinc. PRELIMINARY WORK In a cursory survey of this system, alloys ranging from 60 to 95 per cent copper, 0 to 50 per cent manganese, and 5 to 40 per cent zinc were investigated. The alloys containing 60 per cent copper were found to fall into the two-phase alpha plus beta region of the system, and since those containing 70 per cent would not permit a saving, only alloys containing 65 per cent copper were considered. The tensile properties of these 65 per cent alloys are plotted in Fig. I as a function of manganese content for annealed material and for four conditions of cold-work In the annealed condition the increases in strength and decreases in elongation are minor up to 15 per cent manganese; beyond this, the changes become more significant. In the cold-worked condition, the first 5 to 10 per cent of manganese appears to have the greatest strengthening, effect, the rate of increase dropping off as the manganese increases beyond this amount. These effects are more pronounced with moderate than with severe cold reduction. It is also interesting to note that while the elongation of annealed material drops regularly with increasing manganese, the elongation in the cold-worked state is relatively little affected by increasing manganese content, particu-

Jan 1, 1944

By H. S. Kalish, F. J. Dunkerley

INTRODUCTION AND PREVIOUS WORK THE determination of the low temperature tensile properties of tin and tin-lead alloys was initiated as part of an extensive research program on the phasial equilibria of tin binary systems below 13.2°C and the property changes associated therewith. A survey of the literature revealed that, although some room temperature tensile data were available for tin and a few tin-lead alloys, there existed no survey report of the low temperature tensile properties of these alloys. Accordingly, the tensile data for tin and a series of pure tin alloys containing from 0.01 to 50 pct lead were measured at eleven temperatures from -196 to +20°C and are presented here in survey form. In addition to the importance of these tensile data as a preliminary to certain fundamental research, this information promises also to be of commercial importance because of the 'extensive use now being made of tin-lead solders in refrigeration and gas liquefaction equipment. Occasional failures of the solders in low temperature service have been attributed by some metallurgists to low temperature mbrittlement, while others hold that failure results from the transformation of the tin-rich phase of the solder from the solid white (beta) to the powdered gray (alpha) form. From the data previously available in the literature, neither of these explanations can be completely corroborated. Cohen and van Lieshout1 have established the beta to alpha tin transformation at 13.2°C and have shown that strain accelerates the transformation. Further, they showed that although I pct lead retarded the transformation, it was not eliminated. It will be pertinent, then, to note whether the beta to alpha transformation of the tin-rich phase will occur in a short-time tensile test. Polanyi and Schmid2 studied the tensile . properties of tin single crystals at -185°C and report that tin is brittle at-this temperature. In 1946, Kostenets3 reported that pure tin was brittle at -196 and -253°C, while lead remained ductile at both these temperatures. He also studied the tensile properties of tin-lead alloys containing from 10 to 75 pct lead at -253, -196 and +17°C. The ultimate tensile strength increased more than two times in going from room temperature to -196°C and about three times that value on further cooling to -253°C. All the alloys were brittle at -6°C except those containing more than 75 pct lead. Even at -253°C, the 75 pct lead alloy retained 36 pct elonga¬tion in a 30 mm-ga. length. Creep is also an important phenomenon

Jan 1, 1948

By T. W. Bossert

MELTING is the initial step in the fabricating of all aluminum and aluminum-alloy products. Its function may be considered as threefold: to improve the metal quality, to adjust the composition, and to change the form to that required for subsequent fabrication. Because the melting operation is generally somewhat removed from the final product fabrication, its importance is frequently overlooked. Melting equipment and melting procedures can reflect materially on fabricating procedures as well as on quality and cost of final product. The selection of equipment and the establishment and control of melting procedures, therefore, should be given careful consideration. It is the purpose of this paper to present the various factors that should be considered in establishing melting procedures and in selecting melting equipment. Certain of these are the result of the inherent characteristics of aluminum and can be treated rather specifically. Others depend on the particular production requirements and hence will have to be considered more generally. This paper is intended to cover only the melting of solids, as differentiated from fines, such as borings, turnings, and sawdust. The melting of fines, in many respects, is a subject that should be treated by itself, and practices for melting fines are by no means as standardized as are those for melting solids. The melting of fines is today the subject of considerable developmental interest; hence practices discussed today may soon be replaced by new or improved ones. CHARACTERISTICS OF THE METAL THAT AFFECT MELTING Aluminum and aluminum alloys possess several inherent characteristics that affect the melting problem. Of the physical properties, density, heat content, thermal conductivity, emissivity, and melting temperatures are important because of their effect on equipment design. A list of such properties for commercially pure aluminum is given in Table r, compared with similar properties for iron and copper. The low density of aluminum as well as of the aluminum alloys is of material advantage in the design of melting equipment, in that such equipment can be considerably lighter than similar equipment for handling the heavier metals. The density, however, particularly of the molten metal, is not greatly different from that of the oxides and other nonmetallic materials that develop or become part of the melt during the melting process. Separation of such nonmetallics is not as rapid a process as with some of the other metals, and consideration of this must be made in establishing melting procedures. Sufficient holding time to permit such materials to separate out and, in some cases, fluxing treatments to aid the separation, are required. Since some of these nonmetallics settle to the bottom of the melt, provision should also be

Jan 1, 1946

By C. A. Stetefeldt

In my paper on "The Refining of Sulphides Obtained in the Lixiviation-Process with Hyposulphite Solutions," read at Cleveland, June, 1891 (Trans., xx., 37), I recommended the Roessler converter

Jan 1, 1893

Most of the production of germanium in the U. S. is from byproducts of smelting Tri-state zinc ore. Only in England has commercial manufacture been reported from coal.

Jan 1, 1953