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By M. S. Abrahams

Germanium has been rolled in the temperature range of 700o to 800°C. The thickness has been decreased by as much as a factor of four, from a thickness of 0.032 in. to a thickness of 0.008 in. For deformations below 60 pet, the true strain per pass is found to be a constant; from the temperature dependence of this slope, an activation energy of about 2.5 ev is obtained. This energy agrees with that for dislocation climb in germanium . For reductions greater than 60 pet, complete rings are seen in the Lave photographs, new grains are observed in the microstructure, considerable softening occurs, and the hole mobility is very low. This evidence indicates that the recrystallization of gertnanium has occurred. GERMANIUM has been deformed in many ways1 including tension, compression, torsion, and bending since Gallagher2 first described its plastic nature at elevated temperatures. All of these studies indicate that the glide plane in germanium is (111) and that the glide direction is (110). Rolled germanium specimens were used by Kolm, Warekois, and Kulin3 in their X-ray study of deformed semiconductors, but no information is given on the rolling itself. The present experiments deal with the rolling of germanium at various temperatures and for different orientations. In all previous deformation studies, the phenomenon of recrystallization (i.e., the transformation of a single crystal into a polycrystal) in germanium has not been observed4 despite relatively large deformations at elevated temperatures. The proposed reason4 for this was that sufficient energy could not be stored in the deformed germanium lattice. In contrast to the earlier studies this work will present evidence indicating that recrystallization occurs in germanium during rolling at an elevated temperature. I) EXPERIMENTAL PROCEDURE A) Test Specimens. The samples used for rolling were in the form of rectangular parallelepipeds measuring 0.3 in. long, 0.06 in. wide, and 0.035 in. high. They were cut from an undoped single-crystal ingot of p-type germanium with a resistivity of 24.4 ohm-cm, a Hall mobility of 2300 sq cm v-' sec-l, and a hole concentration of 1.1 x 1014 cm"3 at room temperature. The surfaces of the specimens were metallographically polished prior to rolling. The initial dislocation density of the samples was about 10' cm-' as determined by etching in CP4. Two different specimen orientations were used. In the first case, the direction of rolling was parallel to (251), the surfaces in contact with the rolls were of the form (1021, and the normal to the third face was parallel to (211). The corresponding di-

Jan 1, 1964

By Howard Clarke, Cyril Stanley Smith, Clarence Zener

The importance of cold-working in the fabrication of metals is in marked contrast with our ignorance as to the nature of the accompanying internal changes. The failure of the usual methods of testing to provide a consistent picture of these internal changes has given the incentive for the present program of investigating the effect of cold-working upon the internal friction of metals measured at small strain amplitudes. It has previously been shown1,2,3, that the internal friction introduced by cold-work is removed by annealing at comparatively low temperatures. In the present paper the following additional factors are investigated: (I) frequency of measurement, (2) amount of cold-work, (3) temperature of measurement. Special care was taken to minimize the internal friction due to causes other than cold-work. The present paper is purely experimental, the authors believing that any conclusions drawn from this work as to the nature of the internal changes accompanying cold-work would be premature.'l PrEpaRations oF Specimens In this study of cold-work it was desirable to eliminate as far as possible all other sources of internal friction. One disturbing source is the lack of temperature equilibrium between adjacent crystallites of a vibrating specimen.4 Temperature equilibrium is aided by small grain size and by the use of low-frequency vibrations. Unless unduly long specimens are used, low frequencies can be obtained only in transverse vibrations. But in transverse vibrations a second source of internal friction is present, that arising from transverse thermal currents.5 The effect of these may be reduced by increasing the transverse dimensions. The grain size and transverse dimensions of the specimens were thus so chosen as to render the vibrations simultaneously nearly isothermal with respect to intercrystalline thermal currents, and nearly adiabatic with respect to transverse thermal currents. The material for this investigation was a 70-30 brass, part of the same lot of material that was used for some earlier studies on the effect of strain on proportional limit.10 It had the following composition: copper, 70.59 per cent; zinc, 29.39; lead, 0.01; iron, 0.01. This material was received from the brass mill in the form of 3/4-in. rod, cold-drawn to final size by a 65 per cent reduction of area from material that had been annealed to give a grain size of 0.060 mm, Rods of appropriate length were annealed for 2 hr. at 400°C. and cooled in air. The annealed rods (grain size, 0.012 mm.) were then stretched in a tension-testing machine, using special grips1' to ensure axial application of the load. The rate

Jan 1, 1942

By G. Mempel, D. C. Yang, D. W. Fuerstenau

This paper describes details of the design and operation of a batch tumbling mill which has been used for a number of years in the laboratories at the University of California. In order that the energy expended for grinding can be measured accurately, this specially constructed laboratory mill has sensitive torque measuring apparatus. Torque measurements are given for a variety of conditions with this particular mill. In recent years, there have been numerous and fairly extensive investigations of grinding in tumbling mills reported in the literature. Most of these investigations have been carried out in mills with widely differing dimensions. As a result, comparison of results obtained from various investigations has been virtually impossible. If similar mills were used by different investigators, a considerable step forward would be taken in grinding research. A specially constructed laboratory mill with sensitive torque measuring apparatus has been used for a number of years in the laboratories of the University of California. The purpose of this paper is to describe details of the design and operation of this batch tumbling mill so that other researchers, who might be interested in obtaining data for intercomparison, could construct a similar device for their own research. Furthermore, since torque instrumentation is quite expensive, torque measurements are given for a variety of conditions with this particular mill so that those who may not wish to duplicate torque measuring apparatus can make reasonably accurate torque estimates merely by duplicating the loading conditions. It is not intended in this paper to present theoretical derivations of energy consumption in ball mills. This has been done e1sewhere.l-3 CONSTRUCTION OF THE MILL In order to eliminate rust problems with wet grinding, the mill and grinding media are made of stainless steel. The mill shell was rolled from 1/2-in. steel plate. The inside dimensions are 10-in. diam and 11-1/2-in. length, similar to the mill used by Charles.4 It is equipped with eight lifter bars (1/4-in. in height) whose dimensions are given in Fig. 1. The lifter bars have been bolted into the shell so they can be removed for experiments without lifter bars; however, all data presented here are for the mill with lifters. One end of the mill is fitted with two 1/2-in. diam removable plugs for filling the mill with liquid for wet grinding experiments. The mill is mounted on ball bearing rollers as can be seen in Fig. 2. The pillow block bearings are single-row self-aligning sealed ball bearings with 1-1/4 in. hole diam. The bearings supporting the mill shell are single row sealed ball bearings with

Jan 1, 1968

By L. Grånäs, B. Aronsson

In a recent study of Fe-Si alloys Walter and Koch' observed pairs of dislocations in Fe-6.25 pct Si crystals rolled to reductions of 10 pct and subsequently annealed for 1 hr at 650°C. They interpreted these pairs as being due to stacking faults. From the spacing of the dislocations a stacking-fault energy of 15 to 19 ergs per sq cm was calculated. These authors did not pay any attention to the order -disorder phenomena in Fe-Si alloys. It is the purpose of this communication to report some preliminary results from a study of ordering and its influence on the plastic deformation of Fe-6.0 pct Si alloys. Our results suggest that the dislocation pairs observed by Walter and Koch may have been due to long-range order rather than to stacking faults. The alloys used in this investigation were prepared from pure electrolytic iron and silicon and were melted in argon. After hot working, strip tensile specimens were machined to a gage length of 70 mm and a thickness of 1 mm. The specimens were heat- treated for 2 hr at 1000°C, furnace-cooled, and subsequently deformed 2 pct in tension at 400°C. The strain rate was 5.6 X lo-' sec-'. Thin foils of the deformed specimens were prepared by means of the Bollman technique and examined in a Siemens Elmis-kop I at an accelerating voltage of 100 kv. In the Fe-Si system long-range ordering occurs at a silicon content of about 6 pct Si. In our alloys evidence for ordering is given by selected-area diffraction patterns which show extra reflections consistent with a super lattice of the D0 9 type. In addition, the dislocation arrangement in deformed specimens indicates that long-range order is present. A typical mi-crophotograph of a thin foil is shown in Fig. l. The dislocations are usually straight and parallel and laying in distinct directions. In the commonly observed (111) zone the projections of the dislocations are close to (113) and (oil). Observation of the image position indicates that the two dislocations in a pair have the same Burgers vector and hence constitute a superlattice dislocation.~ According to theory3 a superlattice dislocation in the DO3 structure consists of four ordinary dislocations connected by two types of antiphase boundaries as shown in Fig. 2. In our specimens only two dislocations in each pair have been observed, Fig. 1. The problem is to decide whether the area between these is a NN or a NNN antiphase boundary. Dark-field images using the (200) reflexion (the indices are defined with respect to the DO3-type superlattice) can

Jan 1, 1968

By AIME AIME

Report of Committee 24, of the International Association for Testing Materials, presented at the Brussels Congress, 1906. Republished for use at the 94th Meeting of the American Institute of Mining Engineers, New York, N. Y., February, 1908. Discussion by letter is requested by the Secretary of the Institute. The Committee appointed for the solution of Problem 24 consisted of the following members Prof. H. M. Howe, New York, N. Y. (Chairman); L. Levy, Paris, France (Vice-Chairman) ; Prof. D. Tschernoff, St. Petersburg, Russia (Vice-Chairman) ; Prof. Albert Sauveur, Cambridge, Mass. (Secretary) ; Van Drunen, Ixelles, Belgium; Lieut.-Col. H. Tusen, Copenhagen, Denmark ; E. P. Martin, Abergavenny, England ; A. Pourcel, Paris, France ; H. Brauer, Dortmund, Germany ; Dr. Prof. H. Wedding, Berlin, Germany; P. Verole, Milan, Italy ; A. Baalsrud, Christiania, Norway ; A. R. v. Dormus, Vienna, Austria ; A. Sailler, Vienna, Austria; Bureau des Forges, St. Petersburg, Russia; Prof. N. Belelub-sky, St. Petersburg, Russia ; N. Jossa, St. Petersburg, Russia ; Maj.-Gen. M. Korobkoff, St. Petersburg, Russia ; S. Smirnoff, St. Petersburg, Russia ;.Ladislaus v. Tetmajer, Budapest, Hungary ; H. H. Campbell, Steelton, Pa. Early in February, 1905, a list of species and varieties of iron and steel, with definitions, drawn by the Chairman and Secretary of Committee 24, was sent to every member of this Committee with a request for comments and suggestions. A special request was sent to the following gentlemen . for the equivalents in their several languages of these species and varieties : A. , Pourcel, Paris, France; Prof. H. Wedding, Berlin, Germany ; J. A. Brinell, Stockholm, Sweden ; Prof. H. I. Hannover, Copenhagen, Denmark; Prof. P. Kley, Delft, Holland; P. Verole, Milan, Italy; Col. Cubillo, Trubia, Spain. This present report, which is based upon our original list and definitions, and upon the replies to these requests, consists of four parts I. A polyglot, which gives the names of the chief classes of iron and steel in English, French, German, Swedish, Danish and Dutch. We .regret that we have failed to get the Italian and Spanish names. II. English definitions of principal classes of iron and steel. III. A glossary of special sizes and shapes of iron and steel. IV. A note on the boundary between steel and cast-iron. I. POLYGLOT, IN ENGLISH, FRENCH, GERMAN, SWEDISH, DANISH AND DUTCH, OF THE CHIEF CLASSES OF IRON AND STEEL, AND OF THE APPARATUS IN WHICH THEY ARE MADE. This list is not intended to be complete, but rather to include only those varieties which are of interest to the Association.

Mar 1, 1908

By A. S. Appleton, M. B. Bever, G. E. Dieter

A gold-silver alloy was deformed by explosive loading at shock pressures up to 510 kbars. The stored energy and hardness increased over the whole range of pressures; the largest rates of increase were observed between 120 and 150 kbars. In this range, markings rkavacteristic of defornation twins first appeared; higher pressures produced markings in all grains. These effects are compared with those of conventional deformation processes and are discussed in relation to probable structural changes. In recent years, increasing efforts have been devoted to the investigation of the effects produced in metals by the passage of high-intensity shock waves of explosive origin. By properly utilizing the energy released by the detonation of a high explosive, it is possible to generate pressure pulses of the order of 500 kbars and higher. (One kbar equals l0 9 dynes per sq cm or approximately 1000 atm.) The passage of a shock wave through a metal occurs at pressures which are very much greater than the yield strength. As the shock front passes a point in the metal, the pressure rises almost instantaneously, and continues to act at the point for a few microseconds. Thus, metals subjected to explosive shock loading experience a nearly instantaneous increase in pressure, and a subsequent release of pressure, which is almost as rapid. Under these conditions mechanical twinning and shear transformations occur readily. smith1 has investigated the metallurgical changes in copper and iron resulting from exposure to explosive shock waves. He found an appreciable increase in hardness in both metals. In copper, a hardness greater than that resulting from 95 pct reduction in thickness by rolling was obtained, yet in the explosive deformation, the thickness of the specimen decreased only a few percent. After explosive loading, the micro-structure of copper showed markings characteristic of mechanical twins. The amount of stored energy resulting from explosive loading is of interest. Measurements of the stored energy of cold work as a function of strain, temperature, strain rate, and composition have been made with gold-silyer alloys deforyed by rolling, orthogonal cutting,3 drilling,4 filing, wire drawing, and torsion. The investigation reported here was also carried out with a gold-silver alloy and its results can be compared with those for the deformation of this alloy by more conventional methods. EXPERIMENTAL PROCEDURES An alloy containing 82.6 wt pct Au and 17.4 pct Ag was purchased in several batches from Handy and Harman Co., New York, as annealed rod 1/4 in. dim. The rod was cold-rolled to a sheet approximately

Jan 1, 1962

By Gerald Edmunds

In a paper1 before this Institute in 1940, the writer reported that the surface orientation texture of zinc and cadmium differed from the texture existing within the casting, in that basal planes were parallel to the surface. He was unable to rationalize the , origin of this surface texture. It is conceivable that the surface orientation texture is influenced by the atomic force fields, which are different at the surface and within the body of metal. It was considered that a radical changc in the surface against which the metal is cast might alter the surface texture. In trial of this, zinc has been cast against a surface of molten lead, but the same result has been obtained—i.e., (001) parallel, ± 2oo, to the surface—as was obtained when it was cast against air, Transite or iron.' Into the bottom of an open cast-iron tray, 7 by 14 in. by 2 in. deep, preheated to about 275°C., about 1/4 in. of lead, then 1/2 in. of zinc was poured, and the whole was covered with an electric heater to enforce freezing from the bottom upward. After a lapse of time sufficient for the zinc but not the lead to solidify, the zinc slab was raised free of the molten lead. The bottom surface of the zinc casting was coated with a thin layer of lead. A specimen of the slab 136 in. square was metallographically polished to flatten it and remove the slight film of lead, and the orientation was determined by the method used before,' with the result stated above. Some determinations have also been made on other metals, as follows: Surface orientation determinations were made on the 3/8-in. diameter grip section of two 1/4-in. diameter aluminum-alloy die-cast tensile bars and on a 1/8 by 1/2-in. flat aluminum-alloy die-cast tensile bar. None of these three aluminum die castings exhibited any preferred orientation at the surface. A brass die casting (nominal composition: 60 Cu, 37.75 Zn, 1.00 Sn, 1.00 Pb, 0.10 Al, 0.15 Si) furnished by C. S. Smith was also examined. The surface showed a random orientation of alpha and beta. Summary A zinc casting solidified against a molten lead surface was found to have the same surface orientation texture, (001) parallel to the surface, as other zinc and cadmium castings. Aluminum and alpha-beta brass die castings were found to have random grain orientation textures at the surface. Acknowledgment The X-ray determinations were conducted by M. L. Fuller.

Jan 1, 1945

By Henry J. Joesting

During the past year and a half, the Territorial Department of Mines in Alaska has conducted a modest experimental program for the purpose of determining the extent to which magnetic and resistivity methods can be used in interior Alaska in connection with prospecting, mining and geological studies. Since little information is available concerning previous work,l,2 and since conditions differ considerably from those in most other regions, it was considered advisable to make a general study of the possibilities and limitations of the two methods, rather than a detailed study of any single problem. Problems One of the most serious handicaps to prospecting and geological study in interior Alaska, especially in the mature regions, is a cover of unconsolidated deposits ranging in thickness from a few feet to several hundred feet. These deposits, some of which are permanently frozen, consist of silt with varying proportions of vegetation and windblown material in the valleys and of residual deposits on the hills.3'4 The problems treated here are caused by the existence of this overburden: I. Location of buried placers. 2. Determination of depth and areal distribution of permanently frozen and of thawed unconsolidated deposits. 3. Location of water-bearing beds under unconsolidated deposits. Instruments and Methods Magnetic and direct-current resistivity methods were used because they are relatively simple, rapid and inexpensive and because generally they are well suited to the study of the problems indicated. The instruments used were a vertical Schmidt-type magnetometer and a direct-current resistivity instrument similar to those used by the Geophysical Branch of the U. S. Geological Survey. For placer surveys with the magnetometer, a sensitivity of about 25 gammas per scale division was found suitable. For resistivity studies of frozen and thawed overburden and of underground water, the Lee partitioning method6 was found to be most generally suitable. In the Lee method a central potential electrode is placed midway between the two potential electrodes of the Wenner four-electrode configuration.7 Nonpolarizable electrodes were made from unglazed porcelain pots about 10 cm. high and 5 cm. in diameter. In order to retard evaporation of the electrolyte the sides of the pots were glazed, inside and out, with clear Duco lacquer. For resistivity work in cold weather, a nonfreezing electrolyte consisting of equal parts of ethylene glycol and a saturated water solution of copper sulphate proved satisfactory. Stainless steel rods of 3/4-in. diameter made excellent current electrodes because their bright finish enabled good ground contacts to be made.

Jan 1, 1946

By Henry J. Joesting

During the past year and a half, the Territorial Department of Mines in Alaska has conducted a modest experimental program for the purpose of determining the extent to which magnetic and resistivity methods can be used in interior Alaska in connection with prospecting, mining and geological studies. Since little information is available concerning previous work,l,2 and since conditions differ considerably from those in most other regions, it was considered advisable to make a general study of the possibilities and limitations of the two methods, rather than a detailed study of any single problem. Problems One of the most serious handicaps to prospecting and geological study in interior Alaska, especially in the mature regions, is a cover of unconsolidated deposits ranging in thickness from a few feet to several hundred feet. These deposits, some of which are permanently frozen, consist of silt with varying proportions of vegetation and windblown material in the valleys and of residual deposits on the hills.3'4 The problems treated here are caused by the existence of this overburden: I. Location of buried placers. 2. Determination of depth and areal distribution of permanently frozen and of thawed unconsolidated deposits. 3. Location of water-bearing beds under unconsolidated deposits. Instruments and Methods Magnetic and direct-current resistivity methods were used because they are relatively simple, rapid and inexpensive and because generally they are well suited to the study of the problems indicated. The instruments used were a vertical Schmidt-type magnetometer and a direct-current resistivity instrument similar to those used by the Geophysical Branch of the U. S. Geological Survey. For placer surveys with the magnetometer, a sensitivity of about 25 gammas per scale division was found suitable. For resistivity studies of frozen and thawed overburden and of underground water, the Lee partitioning method6 was found to be most generally suitable. In the Lee method a central potential electrode is placed midway between the two potential electrodes of the Wenner four-electrode configuration.7 Nonpolarizable electrodes were made from unglazed porcelain pots about 10 cm. high and 5 cm. in diameter. In order to retard evaporation of the electrolyte the sides of the pots were glazed, inside and out, with clear Duco lacquer. For resistivity work in cold weather, a nonfreezing electrolyte consisting of equal parts of ethylene glycol and a saturated water solution of copper sulphate proved satisfactory. Stainless steel rods of 3/4-in. diameter made excellent current electrodes because their bright finish enabled good ground contacts to be made.

Jan 1, 1946

By G. W. Jones, G. S. Scott

Economic waste caused by mine fires may become considerable,l5 especially if a fire is allowed to spread or temporarily to get beyond control. It is important, therefore, to act promptly whenever a fire is suspected and to make every action count. To contribute toward its extinction effectively it is necessary to know at the earliest possible moment, and continuously thereafter, what is happening at the seat of the fire, which may be in a remote or inaccessible area, and also to recognize what may be expected as a result of any proposed combative measure. In combatting a fire the mining engineer and the chemist should cooperate, first deciding upon the course of action to be taken and then drawing upon the mining engineer's intimate knowledge of the physical structure of the fire area, the cost and time required to carry out proposed operations, and the probable efficiency with which these operations could be performed, and upon the chemist's knowledge for the results to be expected therefrom. After the initial steps to be taken have been decided, it devolves upon the mining engineer to see that they are carried out and upon the chemist to evaluate the results and to keep the mining engineer continuously informed in regard to a variety of matters—such as the composition and toxic or asphyxiating properties of the atmosphere in which the men may be working, whether the fire is increasing or decreasing in intensity and its probable temperature, the quantity of air leakage and the explosion hazards of the fire area. The purpose of this paper is to discuss what the chemist can and cannot contribute as a member of the fire-fighting personnel. The technical literature contains several hundred papers relating directly and indirectly to mine fires, and this fact alone is testimony to the complex nature of the phenomena involved in the birth, life, and final demise of a fire. A fire may be stopped (I) by preventing oxygen from reaching the coal or (2) by removing the conditions necessary for the rapid reaction of coal with oxygen; i.e., decreasing the temperature. All methods of prevention or control necessarily must be based upon one or the other, or both, of these two principles. The chemistry of a fire may be understood readily if the low-temperature oxidation of coal is considered as a starting point; then oxidation at higher temperatures (or combustion); and with these, the composition of the solid and gaseous products resulting from the oxidation or from the effects of the heat liberated. This discussion refers particularly to Pennsylvania anthracite, although much of the material applies equally well to coals of lower rank. Oxidation of Coal Oxidation of coal fundamentally is confined to the surface; that is, the rate at which oxygen penetrates into the interior of a solid block of coal is so slow that it may be ignored."16 Oxidation starts when a fresh surface is exposed, and the rate is

Jan 1, 1942

By G. S. Scott, G. W. Jones

Economic waste caused by mine fires may become considerable,l5 especially if a fire is allowed to spread or temporarily to get beyond control. It is important, therefore, to act promptly whenever a fire is suspected and to make every action count. To contribute toward its extinction effectively it is necessary to know at the earliest possible moment, and continuously thereafter, what is happening at the seat of the fire, which may be in a remote or inaccessible area, and also to recognize what may be expected as a result of any proposed combative measure. In combatting a fire the mining engineer and the chemist should cooperate, first deciding upon the course of action to be taken and then drawing upon the mining engineer's intimate knowledge of the physical structure of the fire area, the cost and time required to carry out proposed operations, and the probable efficiency with which these operations could be performed, and upon the chemist's knowledge for the results to be expected therefrom. After the initial steps to be taken have been decided, it devolves upon the mining engineer to see that they are carried out and upon the chemist to evaluate the results and to keep the mining engineer continuously informed in regard to a variety of matters—such as the composition and toxic or asphyxiating properties of the atmosphere in which the men may be working, whether the fire is increasing or decreasing in intensity and its probable temperature, the quantity of air leakage and the explosion hazards of the fire area. The purpose of this paper is to discuss what the chemist can and cannot contribute as a member of the fire-fighting personnel. The technical literature contains several hundred papers relating directly and indirectly to mine fires, and this fact alone is testimony to the complex nature of the phenomena involved in the birth, life, and final demise of a fire. A fire may be stopped (I) by preventing oxygen from reaching the coal or (2) by removing the conditions necessary for the rapid reaction of coal with oxygen; i.e., decreasing the temperature. All methods of prevention or control necessarily must be based upon one or the other, or both, of these two principles. The chemistry of a fire may be understood readily if the low-temperature oxidation of coal is considered as a starting point; then oxidation at higher temperatures (or combustion); and with these, the composition of the solid and gaseous products resulting from the oxidation or from the effects of the heat liberated. This discussion refers particularly to Pennsylvania anthracite, although much of the material applies equally well to coals of lower rank. Oxidation of Coal Oxidation of coal fundamentally is confined to the surface; that is, the rate at which oxygen penetrates into the interior of a solid block of coal is so slow that it may be ignored."16 Oxidation starts when a fresh surface is exposed, and the rate is

Jan 1, 1942

By R. H. Dourson, B. H. Sage, W. N. Lacey

The compositions of coexisting phases in the methane-propane-n-pentane system were determined at 160° and -2 20°F. throughout the two-phase region, at pressures above 500 lb. per sq. in. The experimental results permitted the calculation of gas-liquid equilibrium constants as well as the establishment of the critical behavior of this ternary system. Although many binary paraffin hydrocarbon systems have been investigated, the experimental work relating to the phase behavior of ternary paraffin hydrocarbon mixtures at elevated pressures is relatively scarce, being limited to a study of the meth-ane-propane-PL-pentane system at 100°F.l,2 However, Guter and co-workers have studied the phase behavior of the methane-ethane-ethylene system at relatively low temperatures. Information concerning the phase behavior of ternary systems is of value in predicting the behavior of the components in multicomponent systems, since the influence of pressure, temperature, and concentration may be individually ascertained. In the light of the importance of such information, the study of this ternary system was extended to higher temperatures in order to increase the field of temperature in which the data could be applied. Since all states encountered in this investigation are above the critical temperature of methane, the details of its phase behavior are not of direct significance. The properties of propane in the heterogeneous region were taken from a correlation3 based upon recently published data. The corresponding information for n-pentane was taken from experimentally measured vapor pressures and volumetric data.4 The rnethane-propane system has been studied throughout the two-phase region at temperatures above 70°F.,5 while the phase behavior of the propane-n-pentane system has been established for temperatures above 160°F.6 The volumetric and phase behavior of the methane-72-pentane system has been studied in detai1.7,8 The experimental measurements serve to establish with adequate accuracy the phase behavior of the components and of the constituent binary systems for this ternary system. It is believed that, with the exception of the measurements for the methane-propane system, the uncertainties in the earlier data relating to the pure substances and the binary mixtures are probably less than those associated with the values reported here. Method The methods and apparatus employed in this investigation have been described.137 In principle, the method involved the withdrawal of samples of the coexisting gas and liquid phases from a vessel containing a heterogeneous mixture of methane, propane and n-pentane. Provision was made so that

Jan 1, 1943

By W. N. Lacey, R. H. Dourson, B. H. Sage

The compositions of coexisting phases in the methane-propane-n-pentane system were determined at 160° and -2 20°F. throughout the two-phase region, at pressures above 500 lb. per sq. in. The experimental results permitted the calculation of gas-liquid equilibrium constants as well as the establishment of the critical behavior of this ternary system. Although many binary paraffin hydrocarbon systems have been investigated, the experimental work relating to the phase behavior of ternary paraffin hydrocarbon mixtures at elevated pressures is relatively scarce, being limited to a study of the meth-ane-propane-PL-pentane system at 100°F.l,2 However, Guter and co-workers have studied the phase behavior of the methane-ethane-ethylene system at relatively low temperatures. Information concerning the phase behavior of ternary systems is of value in predicting the behavior of the components in multicomponent systems, since the influence of pressure, temperature, and concentration may be individually ascertained. In the light of the importance of such information, the study of this ternary system was extended to higher temperatures in order to increase the field of temperature in which the data could be applied. Since all states encountered in this investigation are above the critical temperature of methane, the details of its phase behavior are not of direct significance. The properties of propane in the heterogeneous region were taken from a correlation3 based upon recently published data. The corresponding information for n-pentane was taken from experimentally measured vapor pressures and volumetric data.4 The rnethane-propane system has been studied throughout the two-phase region at temperatures above 70°F.,5 while the phase behavior of the propane-n-pentane system has been established for temperatures above 160°F.6 The volumetric and phase behavior of the methane-72-pentane system has been studied in detai1.7,8 The experimental measurements serve to establish with adequate accuracy the phase behavior of the components and of the constituent binary systems for this ternary system. It is believed that, with the exception of the measurements for the methane-propane system, the uncertainties in the earlier data relating to the pure substances and the binary mixtures are probably less than those associated with the values reported here. Method The methods and apparatus employed in this investigation have been described.137 In principle, the method involved the withdrawal of samples of the coexisting gas and liquid phases from a vessel containing a heterogeneous mixture of methane, propane and n-pentane. Provision was made so that

Jan 1, 1943

By J. B. Darby

In an investigation of various equiatomic alloys of transition elements, Dwightl did not find evidence for the CsC1-type ordered structure in VMn. More recently waterstrat2 has reported the occurrence of this structure in the alloy his sample had been homogenized at 1150°C and subsequently reannealed at 725°C after crushing to powder. The purpose of this note is to confirm the existence of the CsC1-type ordered structure in VMn and to report a lattice parameter. An equiatomic alloy was prepared by arc-melting under an argon atmosphere vanadium and electrolytic manganese having a purity of at least 99.9 pet. The composition was obtained by charging an excess of manganese and monitoring the weight loss until the stoichiometric composition was achieved; the assumption that the loss during melting was due to the vaporization of manganese appears to be a valid one.' The calculated composition of the sample prepared was 49.85 at. pct V and 50.15 at. pct Mn. Specimens taken from the fractured as-cast buttons were wrapped in molybdenum foil and encapsulated in quartz capsules under vacuum; there was no evidence of a reaction between the alloy and foil. The X-ray patterns were obtained using filtered copper or chromium radiation with a Straumanis-type Debye-Scherrer camera having a diameter of 114.6 mm. The CrKa radiation is best suited for detecting the superlattice lines since it overcomes the slight difference in scattering powers of the components by making use of the anomalies in atomic scattering factor which occur when the frequency of the radiation is close to the characteristic absorption frequency of one of the elements.394 A specimen in the as-cast condition, as well as one which had been annealed for 1 week at 900°C and water-quenched, gave a diffraction pattern for the disordered bcc solid solution. However, when samples were homogenized at 900°C for 3 weeks followed by a subsequent anneal at 700°C for 6 to 7 weeks and then water-quenched or furnace-cooled, the (loo), (1111, and (210) Ka superlattice lines were observed in films taken with chromium radiation. An ao = 2.904 * 0.001 was determined by a Nelson-Riley extrapolation from a film taken with CuKa radiation. The author wishes to thank Mr. J. W. Downey and Mr. L. J. Norton for carrying out the experimental portion of this investigation. This work was performed at the Argonne National Laboratory under the auspices of the U.S. Atomic Energy Commission.

Jan 1, 1963

By E. S. Wheeler

The conversion plant of the Clirnax Molybdenum Co. is at Langeloth, Washington . County, Pennsylvania, approximately 30 miles west of Pittsburgh. The molybdenite concentrates converted originate in the company's mine and mill at Climax, Co1orado.l They are delivered to the Langeloth plant by rail packed in 175-lb. bags. War production of concentrates at the mill started in 1918 but it was not until about 1920 that any peacetime uses of the metal began to develop. Early conversion of Climax concentrates was mainly into ferromolybden um, produced for the company by a custom smelter. Chronology of Plant Development In 1924 a small hand-rabbled roaster was built at Langeloth, the roasted concentrates being used principally in the production of calcium molybdate by a conventional wet method. The size of the original plant is indicated by the fact that during 1925 about 400,000 lb. of molybdenum was converted. In 1925-1926, a multiple-hearth roaster was erected (12-ft. 0.d. 8-hearth Nichols-Herreshoff); also the first experimental ferromolybdenum was produced at Langeloth. At this time sa.1cium molybdate was produced in the furnace by a process to be described. With continued interest in and increased use of molybdenum, it was necessary to arrange for enlargement of plant facilities. Although only one 12-hearth 16-ft. 0.d. roaster was erected at this time (1929), plans were prepared for a duplicate unit, which was completed in 193 5, giving a potential roasting capacity of some 16,000 lb. Mo per day under the then prevailing roasting practice. Shortly after this second unit had gone into production, increased demand overtaxed the plant, and as a result two 12-hearth 18-ft. 0.d. roasters were placed in operation in 1936 and 1937. This gave the plant a potential roasting capacity of 40,000 to 50,000 lb. Mo per day, and necessitated major changes in auxiliary handling equipment as well as improved facilities for producing ferromolybdenum. Following the introduction (1938) of a new product—molybdic oxide briquets— and because of the constantly growing demand for molybdenum, plant facilities were again enlarged in 1940 and 1941 by the erection of two 16-hearth 18-ft. 0.d. roasters. These two new units, along with a change in roasting practice, brought the potential roasting capacity to 150,ooo to 190,000 Ib. Mo per day, based on about 15 lb. per sq. ft. of hearth area. Other departments of the plant have necessarily grown, until today the plant is modern throughout and completely mechanized, with equipment geared to produce marketable products as follows:

Jan 1, 1944

By D. Weinstein, F. C. Holtz

AS a possible method of improving the elevated temperature strength properties of zirconium, an investigation was initiated on the feasibility of producing a dispersion-strengthened material. Because of the high reactivity of zirconium, its high solubility for oxygen, and the stability of the Zr-0 solid solution, the major problem in such a development is choice of a suitable dispersant. Thus, in the present investigation we were concerned primarily with the stability of various dispersants in the zirconium matrix. The experimental procedure consisted of blending powders of zirconium and a dispersant, followed by cold compaction and extrusion. The best available source of -325 mesh zirconium powder contained between 1500 and 3500 ppm Oz; to this material, powders of zirconium carbide (5 p max), vanadium carbide (5 p max), alumina (0.03 p average), lan-thana (0.8 to 2 p), ceria (0.8 to 2 p), yttria (0.8 to 2 p), calcia (44 p rnax), or thoria (0.6 to 0.8 p) were added in amounts of 7 vol pct and compacted at 65 tsi. A cylindrical compact having a density between 70 and 80 pct of theoretical and dimensions of 1 in. diam by 1-114 in. high was thus produced. After canning in copper, these billets could be extruded (5: 1) on a 54-ton capacity, slow-traverse hydraulic press with the billet temperature at 1550°F and the extrusion die at 900°F. However, lack of densifica-tion of some of the extruded billets necessitated ratios of at least 23 :1. Ultimately, all billets were successfully extruded at 1500°F to 0.190 in. diam (32 :I), fully dense rods using a 200-ton capacity press and a ram speed of 90 ipm. The microstructures of as-extruded Zr-7 vol pct LazOS and Zr-7 vol pct Y2Os are shown in Fig. l(a) and (c), respectively. These structures are similar to all the as-extruded materials and consist of an elongated, single-phase zirconium matrix dispersed with oxide or carbide particles. Very little porosity is observed, and the interface between matrix and particles appears satisfactory. The size and distribution of particles, however, are not ideally of the type desired for dispersion strengthening. Since the primary study was of particle stability with respect to zirconium, no attempt was made to overcome agglomeration during powder blending and fabrication. Some areas exhibit fine, well-distributed particles; undoubtedly, a small proportion is submicroscopic and has the

Jan 1, 1963

By R. J. Allio, C. H. Randall

An automatic system for the quantitative analysis of microstrulcture has been developed. The method is based upon a statistical model of microstructure and employs phase intercept fractions as fundamental random variables. Structure-sensitive properties can be related explicitly to parameters derived from the distribution of phase intercept fractions in a matevial. THE properties of mechanical dispersions and of multiphase alloys art: intimately related to the amount, distribution, and intrinsic properties of the dispersed material. In many instances, the amount and distribution of the dispersed substances have greater influence on the over-all system properties than do the properties of the dispersed substance-Such properties as average particle size, particle size distribution, homogeneity of dispersion, volume per cent of dispersed phase, and mean free path between dispersed particles thus become critical in any evaluation of the properties of a dispersion. Unfortunately, techniques for evaluating quantitatively the microstructural characteristics of dis~ersions rapidly and accurately have not been available. If necessary, qualitative or semiquantitative devices can be utilized. Some such devices are based merely upon comparison of the specimens in question with arbitrary standards. Other techniques involve superposition of grids and tabulation of particles observed in different portions of the grid. Still other methods based upon lineal analysis entail counting lines or points at random upon the specimen to be examined; the number of intersections of the line with a given phase, the proportion of line or number of points which are covered by given phase are variously recorded. The mathematical basis for most of the techniques of quantitative metallography have been amply reviewed in the literature.'l2 without exctption, however, the standard techniques for quantitative metallography are either imprecise or are exceedingly tedious to apply. For example, tranverse integrating stage for rapid manual areal fraction measurement has been designed by Smith.3 Howerer, as in the case of any device based upon visual eslimation, operator bias may cause appreciable error. Various flying spot devices, on the other hand register particle size distributions in 2-dimensions, from which it is difficult to derive other properties of the dispersion. Thus, e.g., the 3-dimensional distribution cannot be inferred unless certain rather broad assumptions are made concerning the randomness of distribution and geometrical configuration of dispersed phase. Many limitations to the application of quantitative structural analysis can be overcome by the use of the microdensitometer, which is essentially an automated areal analysis device. Data obtained in the form of a distribution of phase intercept values are

Jan 1, 1962

By Nathaniel Arbiter

T. M. Morris (School of Mines and Metallurgy, Rolla, Mo.)—Rate studies promise to help quantify flotation operations. The author's exposition of rate studies is therefore laudable. However his exposition of a second order rate equation rather than a first order rate equation is not convincing. It is important to use the correct equation, otherwise erroneous conclusions may be drawn. The data assembled by the author and plotted according to a second order rate equation can be plotted according to a first order rate equation. As a matter of fact much of the data used reveals that a second order rate equation is not applicable. According to the method used by the author for plotting data, the reciprocal of the slope of the line is the maximum possible recovery. Physically this cannot exceed 100 pct, yet several graphs yield maximum recoveries greater than 100 pct. For example: l—Curve 2, Fig. 1 yields a value of 120 pct; 2—Curve 2, Fig. 2 yields a value of 115 pct; 3—Fig. 7 yields a value of 110 pct. The real test of the graphical method is, as the author points out, whether or not the earliest points agree with a straight line. The second order rate plot does not fulfill this requirement. Fig. 10 shows the data used by the author to obtain Curve 2 in Fig. 1, plotted according to both a second and first order rate equation. Fig. 11 shows the two rate plots made from data published by Ludt and DeWitt.19 In Fig. 10 the first order rate plot gives a very good fit and obeys the boundary condition of passing through the origin. For the second order rate plot a straight line can be drawn through the last three points but the earliest points are not in agreement with this line. The reciprocal of the slope of the straight line gives a value of maximum possible recovery of 112 pct. The maximum possible recovery according to the first order rate plot is 78 pct. In Fig. 11 the first order rate plot again fits all of the points very well and passes through the origin. The second order rate plot shows wide deviation of the earliest point, indicating that the second order rate equation is not applicable. The reason for the fit of data to the second order rate equation during longer flotation times is that R, the cumulative percent recovery, changes slowly toward the end of the flotation operation, so that when t/R is plotted against time, one is, in effect plotting t against t and one would certainly expect a straight line. The author attempts to show that the second order rate equation is correct by citing evidence which shows that recovery is a function of initial concentration. This is a debatable point especially since, in the author's original presentation of this paper at the St. Louis

Jan 1, 1952

By Gerald Edmunds

IN a paper1 before this Institute in 1940, the writer reported that the surface orientation texture of zinc and cadmium differed from the texture existing within the casting, in that basal planes were parallel to the surface. He was unable to rationalize the origin of this surface texture. It is conceivable that the surface orientation texture is influenced by the atomic force fields, which are different at the surface and within the body of metal. It was considered that a radical change in the surface against which the metal is cast might alter the surface texture. In trial of this, zinc has been cast against a surface of molten lead, but the same result has been obtained-i.e., (001) parallel, ±20°, to the surface-as was obtained when it was cast against air, Transite or iron.1 Into the bottom of an open cast-iron tray, 7 by 14 in. by 2 in. deep, preheated to about 275°C., about ¼ in. of lead, then) ½ in. of zinc was poured, and the whole was covered with an electric heater to enforce freezing from the bottom upward. After a lapse of time sufficient for the zinc but not the lead to solidify, the zinc slab was raised free of the molten lead. The bottom surface of the zinc casting was coated with a thin layer of lead. A specimen of the slab 1 ½ in. square was metallographically polished to flatten it and remove the slight film of lead, and the orientation was determined by the method used before,1 with the result stated above. Some determinations have also been made on other metals, as follows: Surface orientation determinations were made on the 3/8-in. diameter grip section of two ¼ -in, diameter aluminum-alloy die-cast tensile bars and on a 1/8 by ½ -in. flat aluminum-alloy die-cast tensile bar. None of these three aluminum die castings exhibited any preferred orientation at-the surface. A brass die casting (nominal composition: 60 Cu, 37.75 Zn, 1.00 Sn, 1.00 Pb, 0.10 Al, 0.15 Si) furnished by C. S. Smith was also examined. The surface showed a random orientation of alpha and beta. SUMMARY A zinc casting solidified against a molten lead surface was found to have the same surface orientation texture, (001) parallel to the surface, as other zinc and cadmium castings. Aluminum and alpha-beta brass die castings were found to have random grain orientation textures at the surface. ACKNOWLEDGMENT The X-ray determinations were conduced by M. L. Fuller.

Jan 1, 1945

By A. Mitchell, T. Bagshaw

A recent paper by Thomas1 has presented new data on the solubility of hydrogen in solid silver at 1 atm pressure in the temperature range 600° to 963°C. However, no data is reported in the literature on hydrogen solubility in liquid silver. The Sieverts technique which has been described previously2,3 was used in the present work. Charges of approximately 160 g were melted in Morgan "purox" recrystallized alumina crucibles and purified helium was used for the determination of the "hot volume" during each experiment. A chemical analysis of the silver indicates that the impurity content (Cu + Al) is less than 0.02 wt pct. Hydrogen solubility in the temperature range 963° to 1200°C was investigated. The results of three experiments are shown in Table I. Fig. 1 shows an Arrhenius plot of the present work together with the solid-state data of Thomas, Steacie, and johnson,4 Eichenauer et al.,5 and Siegelin et al.6 The following expression has been derived from the Arrhenius plot of the present data: log (solubility of hydrogen, cm3 per 100 g) = 2.154-3512.0/ToK The heat of solution derived from Fig. 1 is 31,150 cal per g mole H2 compared with the value of 33,020 cal per g mole H2 obtained by Thomas and 12,000 cal per g mole H2 obtained from the data of Steacie. It was observed that hydrogen evolution took place when the silver melts were solidified under 1 atm of hydrogen, which would not be expected from an extrapolation of the results of Steacie. Schenck and Lange7 have observed that, for several transition metals at their melting points, the ratio of the hydrogen solubility in the liquid to that in the solid lies in the range 2.1 to 3.1. The present results and those of Thomas are in accord in this respect having a ratio of 2.8. 'C. L. Thomas: Trans. TMS-AIME, 1967 vol. 239, pp. 485-96. 2T. Bagshaw and A. Mitchell: I. Iron Steel Inst., 1966, vol. 204, p. 87. 'M. Weinstein and J. F. Elliott: Trans. TWS-AIME, 1963, vol. 227, p. 382. 'E. W. R. Steacie and F. M. G. Johnson: Proc. Roy. Soc. (London), Ser. A, 1928, vol. 117, pp. 662-79. 'W. Eichenauer et al.: Z. Metallk., 1958, vol. 49, pp. 220-25. 6W. Siegelin et al.: Z. Elektrochem., 1957, vol. 61, pp. 359-66. 'H. Schenck and K. W. Lange: Arch Eisenhuettenw., 1966, vol. 37, no. 9, pp. 739-48.

Jan 1, 1969