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By D. K. Crampton, H. l. Burghoff, J. T. Stacy

THE effect of cold-working upon electrical conductivity of copper and of copper alloys appears not to be generally known in detail Although several papers on the subject have been presented, showing variable effects according to alloy composition, it is often assumed that the 2 to 3 per cent lowering of the conductivity of ordinary tough-pitch copper by severe cold-working is typical for copper alloys Because of this situation it was decided to carry out the present work upon several types of copper, copper-zinc alloys over the commercial range of brasses, other binary alloys, and numerous age-hardening alloys in the quenched, and quenched and aged conditions The large number of alloys investigated made it impossible to study every one in the detail it may have merited Inasmuch as several interesting points that could not be satisfactorily explained came to light, further work is contemplated by the authors It is usually considered that the normal effect of cold-work on ductile metals and unordered alloys is to decrease conductivity slightly In alloys that are in the ordered state, as annealed or otherwise heat-treated, cold-working tends to disorder the structure, resulting in very marked lowering of conductivity The random state of atomic arrangement produces lower conductivity than the ordered state for the same composition 1 PREVIOUS WORK previous work in the authors' laboratory has shown the electrical conductivity of several copper alloys to be decreased by greater amounts than might have been expected, in view of the general knowledge on the subject, when cold-worked Guillet and Ballay2 investigated the influence of cold-work upon the resistivity of several metals and alloys, including copper and some copper alloys The increase of resistivity due to severe working was less than 4 per cent for all pure metals tested, while the increases for the alloys were generally higher In the copper-zinc alloys, they found that the increase of resistance due to drawing increased with zinc content, and reported a 21 7 per cent increase of resistance for an alloy containing 67 9 per cent Cu as severely worked Masima and Sachs3 studied the change in electrical resistance of three brass crystals when stretched in the tensile test, obtaining increases in resistance of the order of 3 per cent for 30 to 40 per cent reduction of area of the specimens The resistance decreased again when the cold-worked crystals were subsequently annealed Bardenheuer and Schmidt4 found that the conductivity of copper was decreased by 3 to 4 per cent when reduced 50 per cent by working The conductivity of 72-28

Jan 1, 1941

By R. J. Wasilewski

The resistivity of single crystal and of polycrystalline metal has been determined between 77° and 1500°K. At comparable purity, the resistivity of the poly crystalline metal differs from that calculated from the axial resistivity values. The observed anisotropy is briefly discussed. A zone refined titanium rod was obtained from F. J. Darnell.1 The hardness of this material varied between 52 and 64 Bhn, indicative of its high purity. Single-crystal specimens were cut out from a few large grains, elongated predominantly along <1120>. Resistance measurements were taken with specimens immersed in liquid nitrogen, solid CO,, and acetone, and at ice point, and then recorded continuously between room temperature and 1200" to 1250°C, throughout at least one full heating and cooling cycle at a rate of l° to 3°C per min. Four probe measurements were taken using spot-welded Pt wire 0.003 in. in diam as potential terminals, and the electromotive force drop was determined poten-tiometrically. A standard resistance, in series with the specimen, served to determine the dc current (generally about 80 ma) in the circuit. In order to eliminate spurious thermal electromotive forces, the circuit polarity was automatically reversed at 5-min intervals, and the mean of the two adjacent readings taken as the true electromotive force value. The discrepancy between the readings at reversed polarities was generally of the order of a few µ v, as all the spot-welded joints were contained within a volume of some 5 mm cube. The relative resistance (R T/R 273o) variation with temperature is tabulated below, and shown in Fig. 1, as measured during the first heating run. The discontinuous drop in resistance, corresponding to the a — ß transformation, started for both initial orientations at 1170°K; i.e., some 15°K above the accepted value of 882°C (1155°K). Judging by the temperature ranse of transformation—some 30°K for the single crystal and 20°K for the polycrystal-line specimen—this difference is believed caused by the solution of the oxygen present initially on the surface of the specimens. The general trend of the resistance vs temperature shown in Fi,;. 1 is in qualitative agreement with that previously reported for polycrystalline titanium metal. 2,3 Significant anisotropy is, however, indicated by the crossing over of the curves for <1120> and <0001> orientations at 273°, 650°, and 1000°K. This difference is most startlingly shown in Fig. 2, where instantaneous temperature coefficients (l/R273 x dR /dT) are plotted for both the first heat-

Jan 1, 1962

By Walter R. Hibbard, Ming-Kao Yen

VARIOUS rationalizations of preferred orientations in cold worked polycrystalline metals have been based on the operation of at least two,1 three,2 five,4 an indefinite number,5 and all,6 slip systems of the type occurring in single crystals. Pickus and Mathewson3 suggested that the cold rolling texture in face-centered cubic metals could be rationalized on the basis of two or more operating slip directions symmetrically disposed about the direction of flow in such a manner that the resolved shear stress factor is equal for all operating slip systems and lattice rotations cancel each other. The importance of the direction of flow, † the necessity for the operation of slip systems capable of producing the required, changes in external dimensions, the maintenance of a common surface between adjacent grains and a symmetrical arrangement of the operating slip systems in order to produce an end orientation which is stable under additional deformation lead to the following rationalization of textures based on the type of slip systems operative in single crystals. The rationalization is intended to explain why certain orientations are suitable for deformational flow without a change in orientation and thus are stable end orientations or ideal texture orientations. It does not attempt to explain how the grains of a randomly oriented polycrystalline aggregate will reach this orientation. The rationalization is based on the following four postulates: I. The ideal textures for polycrystalline aggregates are the result of reorientations of individual crystals toward the same stable end orientation at which no further reorientation will occur even during additional deformation. Since, in simple slip, - the relative orientations of the stress axis and the active slip system determine the change in orientation during slip, it is considered that the orientation of the stress axis with respect to the ideal texture determines what slip systems must be active to retain the stable end orientation. Therefore the stable end orientation should be a symmetrical one around the stress axis with respect to the active slip systems such that lattice rotations resulting from slip will cancel each other and prevent a resultant change in orientation. (Rotational symmetry only-not translation, inversion, nor others-is considered here.) Thus a metal under a pure stress should develop a texture consisting of one or more of the crystallographically symmetrical directions, <100>, <110> or <111> for cubic metals or <0001>, <1010> or <1120> for hexagonal dose-packed metals, parallel to the stress axis. 2. Since the active slip direction is the direction of glide during simple slip and thus the direction of maximum shear movement, in the ideal texture the active slip

Jan 1, 1948

By Elmars Ence, Harold Margolin

The partial isothermal section of the Ti-Cu-Zr system at 750°C has been studied. The crystal structure of Ti2Cu has been detevnlined as tetragonal and when expressed as face-centered tetragonal, a = 4.164, c = 3.611 A, and c/a = 0.867. TITANIUM systems in which ß-titanium decomposes eutectoidally into a and a compound rather readily are known as active eutectoid systems. Recently in active eutectoid alloys based on the Ti-Cu system, and containing additionally A1 and Zr, it has been found that zirconium may produce both moderate weakening and marked strengthening at elevated temperatures.&apos; In order to obtain some insight into the behavior of zirconium, an attempt was made to determine whether compounds of the type Tix Zr and TixZryCu exist. Only results of the Ti-Zr-Cu studies are reported here since data on Ti-Zr alloys will be presented in a separate publication. EXPERIMENTAL PROCEDURE Alloys were nonconsumably arc melted in argon atmosphere as 15-g buttons, prepared from materials of the following purities: Bureau of Mines electrolytic Ti — Bhn 63 OFHC copper Reactor Grade Zirconium Bhn .C 150 Prior to alloy preparation the electrolytic titanium was premelted to avoid excessive spattering of the charges during melting. The weight losses during melting did not exceed 1 pct of the total weight of the charge. The alloys prepared are listed in Table I together with analyzed compositions. in cases where they were determined. Specimens for heat treatment were wrapped in molybdenum sheet, annealed in argon-filled quartz capsules, and quenched by breaking the capsules under iced brine. About 1 to 2 sec are required to remove the capsule from the furnace, drop it into the iced brine and break it. Because of the insulation effect of the quartz, this delay in quenching should not produce a large drop in temperature. In many instances, no difference or little difference has been detected between the same specimen quartz capsule quenched or directly quenched in vacuum by an impinging stream of water.&apos; Ti-Cu-Zr alloys were homogenized for 48 hr at 825°C prior to annealing at 750°C. Annealing for 5 days at 750°C produced the same results as 11 days at temperature and it was therefore assumed that 5 days was sufficient to establish equilibrium. Titanium-copper alloys were homogenized for 40 hr at 900°C prior to heat treatment for 6 days at 750°C. Specimens for metallographic examination were electropolished and etched with the following solution:

Jan 1, 1962

By James K. Stanley

IRON-COBALT alloys in the range of 35-50 pct cobalt are of interest in the electrical industry because they possess the highest magnetic saturation of any magnetic material known.1,2 The magnetic saturation induction of the 35 pct alloy is 24,200 gausses, compared to 21,600 for pure iron (Fig I). This difference is significant in electrical apparatus, where weight or space is at a premium. Saturation values higher than that for iron can be attained up to about 70 pct Co but economics restrict the use to as low a cobalt content as possible without sacrifice of saturation. Fig 2 shows the iron-cobalt equilibrium diagram. Up to the present time, two factors have retarded the use of iron-cobalt alloys in the electrical industry for magnetic purposes.† One is the high cost of cobalt ($1.50 per pound) and the other is the inherent brittleness of the binary iron-cobalt alloys. Straight iron-cobalt alloys up to 25 pct cobalt are ductile and easy to process to thin sheet or strip by conventional methods of hot and cold rolling, but the alloys containing higher percentages of cobalt, including those for which the saturation magnetization is a maximum (35 to 40 pct), are increasingly brittle with increasing cobalt, at least up to 50 pct, and are consequently difficult to process, either hot or cold. Work by White and Wah13 indicated that iron-cobalt alloys could be made ductile by alloying with vanadium, and after quenching the alloys (vanadium up to about 4 pct) were found to be cold rollable to very thin gauges. With this as a background, we resumed our work on these alloys with the objective of developing methods for economical commercial production of wide strip. For this purpose we have concentrated on the 35 pct alloy in order to obtain the highest possible saturation value. Experiments were carried out on many alloy additions to the iron-cobalt alloys and on the response of these compositions to heat treatments. This work finally culminated in a commercially producible iron-cobalt alloy which has been named Hiperco. * MATERIALS STUDIED AND PROCEDURE Binary alloys of iron and cobalt in the range of 35 pct cobalt are difficult to hot work (by forging or rolling) without such additions as C, Mn, Si, V, Cr, Mo, W or perhaps others. Another beneficial effect of such additions is that they in-crease to a greater or less extent the strangely low electrical resistivity of these alloys (about 10 microohms per cm3

Jan 1, 1947

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.&apos;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 D. K. Crampton, H. I. Burghoff, J. T. Stacy

The effect of cold-working upon electrical conductivity of copper and of copper alloys appears not to be generally known in detail. Although several papers on the subject have been presented, showing variable effects according to alloy composition, it is often assumed that the 2 to 3 per cent lowering of the conductivity of ordinary tough-pitch copper by severe cold-working is typical for copper alloys. Because of this situation it was decided to carry out the present work upon several types of copper, copper-zinc alloys over the commercial range of brasses, other binary alloys, and numerous age-hardening alloys in the quenched, and quenched and aged conditions. The large number of alloys investigated made it impossible to study every one in the detail it may have merited. Inasmuch as several interesting points that could not be satisfactorily explained came to light, further work is contemplated by the authors. It is usually considered that the normal effect of cold-work on ductile metals and unordered alloys is to decrease conductivity slightly. In alloys that are in the ordered state, as annealed or otherwise heat-treated, cold--working tends to disorder the structure, resulting in very marked lowering of conductivity. The random state of atomic arrangement produces lower con- ductivity than the ordered state for the same composition.1 Previous Work Previous work in the authors&apos; laboratory has shown the electrical conductivity of several copper alloys to be decreased by greater amounts than might have been expected, in view of the general knowledge on the subject, when cold-worked. Guillet and Ballay2 investigated the influence of cold-work upon the resistivity of several metals and alloys, including copper and some copper alloys. The increase of resistivity due to severe working w is less than 4 per cent for all pure metals tested, while the increases for the alloys were generally higher. In the copper-zinc alloys, they found that the increase of resistance due to drawing increased with zinc content, and reported a 21.7 per cent increase of resistance for an alloy contaiiiing 67.9 per cent Cu as severely worked. Masima and Sachs3 studied the change in electrical resistance of three brass crystals when stretched in the tensile test, obtaining increases in resistance of the order of 3 per cent for 30 to 40 per cent reduction of area of the specimens. The resistance decreased again when the cold-worked crystals were subsequently annealed. Bardenheuer and Schmidt4 found that the conductivity of copper was decreased by 3 to 4 per cent when reduced 50 per cent by working. The conductivity of 72-28

Jan 1, 1941

By D. K. Crampton, H. I. Burghoff, J. T. Stacy

The effect of cold-working upon electrical conductivity of copper and of copper alloys appears not to be generally known in detail. Although several papers on the subject have been presented, showing variable effects according to alloy composition, it is often assumed that the 2 to 3 per cent lowering of the conductivity of ordinary tough-pitch copper by severe cold-working is typical for copper alloys. Because of this situation it was decided to carry out the present work upon several types of copper, copper-zinc alloys over the commercial range of brasses, other binary alloys, and numerous age-hardening alloys in the quenched, and quenched and aged conditions. The large number of alloys investigated made it impossible to study every one in the detail it may have merited. Inasmuch as several interesting points that could not be satisfactorily explained came to light, further work is contemplated by the authors. It is usually considered that the normal effect of cold-work on ductile metals and unordered alloys is to decrease conductivity slightly. In alloys that are in the ordered state, as annealed or otherwise heat-treated, cold--working tends to disorder the structure, resulting in very marked lowering of conductivity. The random state of atomic arrangement produces lower con- ductivity than the ordered state for the same composition.1 Previous Work Previous work in the authors&apos; laboratory has shown the electrical conductivity of several copper alloys to be decreased by greater amounts than might have been expected, in view of the general knowledge on the subject, when cold-worked. Guillet and Ballay2 investigated the influence of cold-work upon the resistivity of several metals and alloys, including copper and some copper alloys. The increase of resistivity due to severe working w is less than 4 per cent for all pure metals tested, while the increases for the alloys were generally higher. In the copper-zinc alloys, they found that the increase of resistance due to drawing increased with zinc content, and reported a 21.7 per cent increase of resistance for an alloy contaiiiing 67.9 per cent Cu as severely worked. Masima and Sachs3 studied the change in electrical resistance of three brass crystals when stretched in the tensile test, obtaining increases in resistance of the order of 3 per cent for 30 to 40 per cent reduction of area of the specimens. The resistance decreased again when the cold-worked crystals were subsequently annealed. Bardenheuer and Schmidt4 found that the conductivity of copper was decreased by 3 to 4 per cent when reduced 50 per cent by working. The conductivity of 72-28

Jan 1, 1941

The Fifth Annual National Exposition of Chemical Industries will be held in Chicago at the Coliseum and First Regiment Armory during the week of Sept. 22. It was decided to hold the exposition in Chicago, this year, for two reasons: The U. S. Army commandeered the Grand Central Palace Exposition Building in New York, immediately on the close of the last exposition and converted it into a receiving hospital, the use for which is now, happily, nearly ceased; and it was thought that the Exposition would succeed in bringing about a greater development of chemical industries in the Chicago district and the adjoining states. The Advisory Committee of the Exposition consists of: Charles H. Herty, Chairman, Editor Journal of Industrial and Engineering Chemistry; Raymond F. Bacon, Director, Mellon Institute; L. H. Baekeland, Member Naval Consulting Board; W. D. Bancroft, President, American Electrochemical Society; Henry B. Faber, Industrial Filtration Corpn.; Ellwood Hendrick, President, The Chemists&apos; Club; Bernard C. Hesse, Chemist, General Chemical Co.; A. D. Little, President, Arthur D. Little Inc.; Wm. H. Nichols, President, American Chemical Society; R. P. Perry, Vice-president, The Barrett Co.; H. C. Parmelee, Editor Chemical &; Metallurgical Engineering, G. W. Thompson, President, American Institute of Chemical Engineers; T. B. Wagner, Vice-president, U. S. Food Products Corpn.; M. C. Whitaker, President, U. S. Industrial Chemical Co.; and Charles F. Roth and Fred W. Payne. There is also added a special Chicago committee consisting of L. V. Redman, W. D. Richardson, A. V. H. Mory, Carl S. Minor, F. W. Willard, and Wm. Hoskins; the managers, as in the past, are Charles F. Roth and Fred W. Payne.

Jan 6, 1919

By W. E. Gaby

THE form of dip chart here presented for the use of the profession was devised by the author when he was confronted with a particularly heavy job of geological section making and. did not have any of the usual tables or charts at hand. This was at the property of the Teziutlan Copper Co. in Puebla, Mexico, where the orebodies are much faulted and lie conformably with a slightly inclined and. much folded schist. Because of the low dip and the folding of the orebodies, the engineering, and geological data respecting them were best represented on vertical cross-sections quite closely spaced. A less finished form of the chart was published in the Mining & Scientific Press of Aug. 6, 1921, with an explanation of its use. I have checked the new drawing for accuracy against the calculated table given, and constructed an explanatory diagram beneath. As some geologists are accustomed to using the table, I have included it, since no advantage is obtained by mere interpolations from the chart to get the required angle, except as it gives a mental picture of this angle. The chart gives a more rapid and much easier solution when cases multiply so that it becomes desirable to eliminate the tedious manipulations of a separate protractor. In fact, using the parallel ruler as des-cribed, it is not even necessary to make note of the angle sought. It is brought out graphically, leaving the mind free to note the correlations. The chart itself may be made more convenient by reproduction on celluloid with a slot running on the zero line of the protractor.

Jan 9, 1922

By S. C. Sun

This article by Spokes and Mitchell de- serves high commendation. For many years mineral dressers have been at a loss to explain the variation in magnetic susceptibility of the same mineral species obtained from different localities. In fact, they do not even have a list of accurately measured data on the specific magnetic susceptibility of weakly magnetic minerals to consult. Experience as a university teacher has firmly convinced me that the average student has more difficulty in acquiring a satisfactory knowledge of magnetism than of any other branch of mineral dressing. This is almost entirely because the subject has been treated far too much from a strict practical standpoint and far too little from a fundamental one. It is no exaggeration to state that almost all the published theoretical discussions are based on the experimental results of manufactured chemicals and alloys, but not of naturally occurring minerals. In an attempt to remedy this state of affairs, the author of this article not only set up a new magnetic balance in the Department of Mineral Preparation of The Pennsylvania State University, but also performed work of fundamental value, thus pointing the way to further research. This is evidenced by the fact that an investigation of the magnetic susceptibilities of manganese minerals was recently completed by S. G. Watt under the direction of David R. Mitchell, now acting dean of the College of Mineral Industries of the Pennsylvania State University. D. J. Cook is studying the magnetic susceptibility of titanium minerals under my supervision. It is hoped that our research program can be continued for several years and that similar investigations will be Initiated at other universities and research institutions.

Jan 4, 1958

By W. J. McKenna

THE International Smelting Co. concentrator at Tooele, Utah, first operated on a custom basis for the treatment of lead-zinc-iron ores on Nov.&apos; 1, 1924, with a capacity of 500 tons per day. On May 1, 1925, the capacity was increased to 1000 tons per day by the addition of another 500-ton section. The concentrator has since operated on the two-section basis, each treating 500 tons per day entirely by flotation. LABORATORY AND TEST MILL In connection with the concentrator, a well-equipped laboratory and small continuous testing plant are maintained. The flotation equipment in the test plant is of both the Callow and Mineral Separations Sub-"A" types, so that actual concentrator conditions may be duplicated as closely as possible. PURCHASING OF ORE A new shipper usually sends to the plant a 25 to 50-lb. sample, representative of the ore to be shipped. Batch flotation tests are made on this sample to determine its amenability to the concentrator treatment flowsheet and reagent combinations. The results of these tests, which are accurately correlated with those obtained at the concentrator, both as to grades of products and recoveries, determine the actual value of the ore as submitted in the ore purchasing department&apos;s treatment schedule. Hearty cooperation has existed at all times between the ore purchasing and operating departments in the selection of ores as concentrator feed. ORE TREATED The basic tonnages for mixtures on the two sections come from the Park City and Bingham mining districts. The Park City tonnages are received by rail and consist of crude ores and gravity mill products. Those from the Bingham district are received by rail and aerial tramway,

Jan 1, 1928

By R. C. Himes, K. Zanio, J. B. Wagner, J. W. Moody, J. F. Miller, W. Johnson

The recent research with which this paper deals has been concerned with the preparation of pure PbTe crystals suitable for control of radiative processes and othe.v electronic applications. The research has been directed toward the developrnent of methods for the preparation of puve, homogeneous, loul-ca,wier-density PbTe crystals suitable for use in the fabrication of optically pumped and electrically pumped diode lasers. Steps in the preparation of the crystals include 1) purification of the starting materials, 2) synthesis and purification of the PbTe, 3) growoth of PbTe crystals, and 4) adjustt~zertt of composition of the crystals This Paper describes the general preparation procedure employed and discusses some investigntiotzs of purification processes. THE as-received lead and tellurium are nominally 99.999 to 99.9999 pct pure. Assays furnished by the suppliers, obtained by emission spectrographic analysis, show only the presence of about 2 ppm Mg in the tellurium. Such analyses are not very informative, however, since they give no information on the concentrations of normally gaseous impurity elements such as oxygen. Both the lead and the tellurium in the as-received state usually contain appreciable concentrations of oxygen—primarily in the form of oxides on the surfaces of the material. To reduce the oxygen content, the lead is held in the molten state in hydrogen at -700°C for several hours. For this treatment, the lead is contained in a graphite boat which is rf-heated, and the hydrogen is passed through a liquid-nitrogen trap prior to use. Tellurium is subjected to multiple distillation in hydrogen to remove oxygen and other foreign impurities. If, in conducting the distillation, approximately the last 10 pct of the charge at each "stage" is left as the discard cut, purification of the tellurium proceeds as indicated in Fig. 1.l Tellurium used in this work has been distilled two or three times to reduce carrier concentration to about 10" per cu cm. The PbTe is prepared from the purified elements by reacting them in the molten state in sealed, evacuated, or hydrogen-filled silica ampoules. The charge is usually held above the melting point of PbTe (923°C) at 1000 C for 24 hr to ensure that it has been homogenized. Two methods have been employed for the growth of the required single crystals of PbTe: growth from the melt, which will be discussed first, and growth from the vapor phase. Large single crystals of p-type PbTe can be grown readily from the melt by the Bridgman method. For this method of crystal growth, the PbTe is synthesized in situ from proper proportions of the purified elements. Growth (dropping) rates in the range 1.3 to 6.5 mm per hr are employed. Material near the maximum melting composition (about 50.012 at. pct Te) is utilized to avoid composition change on freezing, and thus to obtain crystals of nearly uniform composition. Crystals prepared by use of procedures described up to this point were sufficiently pure and perfect that they could be used for the preparation of laser crystals in studies at Lincoln Laboratory.2-5 ADJUSTMENT OF COMPOSITION Good n-type crystals of PbTe cannot readily be grown from the melt. Further, growth from the melt of crystals of any compositions (n or p type) other than those near the maximum melting composition is difficult because of the large composition changes that must occur on freezing.&apos;" However, melt-grown crystals can rapidly be brought to other desired compositions by isothermal equilibration through the vapor phase with a two-phase Pb-Te stock material, essentially as described by Brebrick and Allgaier.1 The work to be discussed has been concerned with the preparation of n-type crystals; thus, the two-phase stock which was employed contained excess lead, and all ensuing discussion is of the preparation and properties of n-type crystals. The equilibration was designed to the shift composition to the lead-rich limit of stability at the selected temperature. Initial treatment of the crystals at high temperature was employed to minimize the total time required for the equilibration. Final adjustments of the composition and state of the crystals were made by use of low-temperature heat treatment at temperatures in the range 200" to

Jan 1, 1968

By G. Purcell, S. C. Sun

In an attempt to determine the relative collecting ability of 18-carbon fatty acids, studies were performed on rutile in aqueous solutions of the fatty acid soaps. The preceding article reported the electro-kinetic properties; this article outlines the flotation behavior. Results of these flotation experiments are described and correlated with the electrokinetic results. Recent studies of the electrokinetic1-4 and the electrochemical5,6 properties of a few solid-liquid interfaces have provided a better understanding of the flotation process. A number of investigators have attempted to determine the relative collecting ability of 18-carbon fatty acids, but their published results (even for the same mineral) vary widely. Such lack of agreement indicated a need for further investigation. In an effort, therefore, to resolve the problem, electro-kinetic studies were made on rutile in aqueous solutions of the fatty acid soaps. Following the determination of the electrokinetic properties, the flotation behavior of rutile was studied. Results of these flotation experiments are described in this paper and are correlated with the electrokinetic results. MATERIALS AND EXPERIMENTAL PROCEDURE Materials: Pure -28, + 35-mesh rutile crystals were used for all flotation tests, and nitrogen-saturated conductivity water was used throughout. Sodium hydroxide and hydrochloric acid were added for pH regulation. The methods of purification for these materials and the preparation of the soaps have been described elsewhere. 7 Equipment: A Hallimond cell, constructed in a manner similar to that described by Fuerstenau, Metzger and Seele,8 was used for the flotation of mineral particles; however, a coarse pyrex frit was substituted for the capillary. Procedure: Purified nitrogen was led through a two- way stopcock into a graduated cylinder partly filled with water. The gas forced water from the cylinder back into a header tank until the water level in the cylinder coincided with a predetermined mark. Reversal of the stopcock then allowed water in the tank to force nitrogen into the cell until the water in the graduated cylinder rose to a second predetermined mark. In this way a constant volume of nitrogen under practically constant pressure was used for each flotation test. However, the flotation time varied, depending upon the amount of mineral floated and the pH of the solution. Rutile crystals were transferred under water from a storage bottle by a glass scoop holding 1.7 g. Consistency of the scoop samples was good, varying from a low value of 1.67 to a high of 1.74 g. The water added to the conditioning bottle during mineral transfer was drained off, and then 2 cu cm of either hydrochloric acid or sodium hydroxide were added. The concentration of pH regulator was adjusted to give approximately the final soap solution pH that was required. The order of addition of reagents did not affect the results within the limits of experimental error. Soap solution of the required concentration was added under nitrogen pressure to fill the bottles completely. Conditioning for 1 hr was carried out on rolls rotating at 35 rpm. After conditioning, 2.5 cu cm of solution were run off into the container of a Beckman (model G) glass electrode pH meter. The electrodes were rinsed in this solution, which was then discarded, and 2.5 cu cm more were added for pH determination. The remaining solution and the mineral were transferred to the cell; care was taken to ensure that all mineral was washed out of the bottle by the conditioning solution. With the cell back in its flotation position the liquid just reached the desired level, and the test was started immediately. The amount of agitation in the cell was kept constant, and flotation was carried out without the use of a frother. In each series of ten tests one was run with no collector added to ensure that the mineral had not become contaminated, and two were conditioned at the same pH to check reproducibility. After each test the cell was dismounted, soaked in cleaning solution, washed in hot water and then rinsed with distilled water.

Jan 1, 1963

By B. C. Raynes

IN the early part of 1952, under the auspices of the U. S. Atomic Energy Commission, Horizons Inc. undertook an investigation dealing with the preparation of high purity thorium metal in order to develop an economically competitive production process for this metal based on a recovery of the metal by a fused salt electrolysis, since a survey of the literature of thorium chemistry indicated that electrolytic methods had not received much attention, despite the consideration that electrochemical production methods often offer attractive commercial potentialities. Thorium metal has been prepared by methods which fall into four general categories: 1) reduction of halides or double halides; 2) reduction of the oxide; 3) thermal decomposition of halides; and 4) electrolytic methods. Some of the important results obtained by various investigators since about 1900 in recorded attempts to prepare pure thorium metal are summarized in Table I. A bibliography of pertinent literature is included in this paper. Thorium is strongly electropositive and possesses a great affinity for oxygen and nitrogen. As a result the prospects for the production of high purity thorium from aqueous media or oxygen bearing compounds are remote. The most promising and profitable area of investigation for production of thorium metal lies in fused salt electrolysis. Thorium has been produced previously by this technique from halide salts in fused alkali chloride eutectic mixtures. Until recently, however, the lack of known large uses for thorium has inhibited the investigation of these methods. The basic problem in an investigation into fused salt production methods for thorium is to develop a suitable fused salt system for the economic preparation of thorium. The first portion of the work in these laboratories was a small scale investigation of the electrolysis of potassium thorium fluoride, KThF5, under a variety of conditions. High purity thorium was prepared in this manner, but the process did not appear to offer the simplest and most attractive continuous commercial operation. The work reported here relates to an all-chloride system employing thorium chloride as the cell feed. ThCL4 was produced as an anhydrous material stabilized in molten sodium chloride. This product, further diluted in NaCl, was subjected to electrolysis. The electrolytic process has been studied in cells capable of holding up to 50 lb total salt charge. Ductile, pure thorium metal has been reproducibly obtained in this operation. Considerable experimentation was carried out in the preparation of ThCL as a cell feed free from moisture, oxides, and other impurities. Thorium was cathodically deposited as a coarsely crystalline powder interspersed with residual bath salts. Aqueous procedures for separating and recovering the metal were developed. The thorium metal powder obtained has been evaluated with respect to its hardness, chemical purity, and certain other physical properties. Preparation of ThC1,—Thorium chloride, and the chlorides of some other metals (aluminum, beryllium, tantalum, zirconium, etc.) cannot be obtained from aqueous solution by direct heating and evaporation. Evaporation and heating of a solution of thorium chloride yields a hydrated salt or partially hydrated salt, and finally Tho,. Anhydrous thorium chloride is obtained by forming a hydrated ammonium chloride complex salt in acidified water solution, dehydrating this compound, and finally decomposing the double salt and subliming the ammonium chloride component. Various methods for the preparation of anhydrous thorium chloride, in accordance with this concept, were investigated as indicated in Table I1 from hydrated thorium chloride (ThCl, . 3H2O), and from thorium oxycarbonate (ThOCO,). In the method found most satisfactory for this work, thorium oxycarbonate was dissolved in an excess of concentrated HC1 to give a clear yellow solution. At least 2 mol NH,Cl were added to the solution per mol of contained thorium. Ammonium thorium chloride hydrate was crystallized from solution by cooling and saturation with HC1. The resultant complex, (NH,Cl),ThCl;xH,O, was dehydrated by evaporation at 130° to 150°C and thoroughly dried at about 250°C. The dried ammanium thorium chloride was then mixed with sodium chloride in proportions to form NaThCL or to produce a ThCL4-NaCl mixture with a given thorium content. The ammonium chloride was sublimed off at temperatures above 500°C in an inert atmosphere furnace to give an anhydrous chloride source electrolyte, essentially free of Tho, and of NKC1.

Jan 1, 1958

By Carl Altstetter, Roy Adams

Measurements of enthalpy changes and transformation temperatures me reported for the fcc -hcp marten-sitic transformation in pure cobalt single and multi-variant crystals andpolycrystalline specimens. From these measurements the free-energy difference between the two phases was calculated for both heating and cooling and for repeated cycles through the transformation. For heating of single crystals the average value of enthalpy change was 113 cal per mole but on cooling it was 84 cal per mole. This difference is interpreted in terms of lattice imperfections which are introduced during transformation. A calorimeter suitable for measurement of enthalpy changes of athertnal transformations is described. COBALT exhibits an allotropic phase transformation at around 417°C&apos; where an hcp phase (a = 2.507, c = 4.0686, c/a = 1.6228)~ stable at low temperatures transforms to an fcc phase stable up to 1495°C. The transformation has a hysteresis of about 30°C— the exact magnitude of the hysteresis depending on the number of transformation cycles, grain size, impurity content, and prior treatment.&apos;-6 The athermal character of the transformation and surface relief due to transformation shear indicate that the transformation is martensitic. Pole mechanisms for the transformation have been discussed by Sebilleau and Bibrin, Bilby, Seeger,&apos; and Basinski and Christian. These authors have proposed that the cooling transformation is effected by rotation of a Shockley partial dislocation around a pole dislocation with a screw component of 2a/3(111). Such a rotation would change the stacking of close-packed planes from the abcabc fcc stacking to the ababab hcp stacking sequence. This mechanism would predict a lattice correspondence of {111}fcc~~(0002~cp, have been observed. One would expect the heating transformation to occur similarly, involving dislocation movements on the (0002)hcp. However, a high density of pole dislocations and high dislocation ve- locity are required to account for microscopic observations. Furthermore, the high back stress developed on the Shockley partial dislocation as it rotates toward the sessile dislocation associated with it makes it doubtful that this is in fact the transformation mechanism. A mechanism for spontaneous nucleation of partial dislocations1*l2 seems more reasonable. If a single crystal of cobalt is cycled through the transformation but never heated above 600°C, it will remain single."13 However, if the specimen is heated through the transformation and held for a short time at or above 1000°C before cooling, the cooling transformation usually involves all four {lll}fcc habits, resulting in neighboring orientations of hcp differing by 70.5 deg. This condition is termed multivariance and has been observed by Bibring and sebilleau5 and Nelson and ~ltstetter.&apos; The latter authors used single crystals of cobalt grown in an electron beam zone refiner. They proposed that the strongly directional cooling caused the initial cooling transformation to occur on the {lll)fcc most nearly perpendicular to the temperature gradient. Transformation shear on one set of {lll}fcc planes immobilized dislocations on the other {lll}fcc planes involved in the initial transformation. Since there is only one (0002)hcp plane orientation, the product of subsequent heating transformations could have no more than two variants—the original fcc orientation or its twin. If, however, the specimen was annealed at a high temperature, such as 1000°C, there would be relaxation of dislocations into low-energy configurations, and in the absence of a sharp temperature gradient transformation on all four (111 Ifcc planes could occur. If a dislocation mechanism is responsible for the transformation, the perfection of the lattice should affect the reversibility of the transformation. Mutual constraints of neighboring grains in polycrystalline material would inhibit dislocation movement resulting in increasingly sluggish transformation. Indeed, Nelson and Altstetter found the M, to decrease and the A, to increase in going from single crystals to multi-variant specimens to polycrystals. The effect is enhanced by decreasing the grain size of a solid specimen or a powder.6&apos;14 Data on the free-energy difference necessary to initiate the transformation gives information about the driving force of the transformation. This is an important consideration in the understanding of the transformation mechanism. The free-energy change associated with the transformation of the hcp phase to the fcc phase at some temperature T different from the equi-

Jan 1, 1969

By T. Seldenrath

In the development of a fluid -operated hammer drill&apos; for accelerated penetration of hard rock formations in oil wells, a research investigation was conducted to evaluate the percussion effects obtained with different design characteristics and to determine the possibilities of percussion in the low frequency range. Tests were conducted on granite blocks and comparable impact forces were measured with a load cell under selected test conditions. These full-scale laboratory tests provided an evaluation of the effectiveness of percussion which was further supported by actual downhole field performance. While much pertinent data have been presented by other investigators the method of evaluation described in this article resulted in good correlation between laboratory and field performance and may be applicable in other low frequency percussion developments. EXPERIMENTAL METHOD For these tests the bit was held stationary and the test block was rotated and forced upward against the bit by a hydraulically-lifted rotary table. "Weight on bit" was calculated from pressure readings on the fluid system of the lifting cylinders—corrected for tare and friction. Percussion was obtained with several tubular hammers of different weights up to 320 lb. These were lifted mechanically and allowed to drop by gravity from various heights onto a slidably-mounted bit sub or "floating anvil" for calibration of the load cell response with known kinetic energy of the hammers. During evaluation of percussion effects, the hammers were hydraulically operated to provide a range of percussion frequencies up to 1,020 blows per minute delivered to the anvil. To obtain comparable test readings, the load cell of the strain gauge type, was attached to the bottom of the anvil or bit sub in place of the bit. The load cell rested on a typical granite test block mounted on the drilling table. The latter was hydraulically supported as in the actual drilling operation. The effect of support resistance was the same for all tools when calibrating. Impact forces so determined werethusdirectly comparable with one another for the purposes of this investigation. When a roller bit was substituted for the load cell for actual drilling, the impact force would probably be reduced due to the resiliency of the bit body, legs. cones and teeth and the penetration of the teeth into the rock. However, since the bits and rock specimens were uniform in these tests, an evaluation of actual tool performance, in terms of parameters previously determined with the load cell at the selected standard conditions of calibration, proved satisfactory. Throughout these tests, 8¾-in. standard tricone, hard rock toothed roller bits and carbide-insert roller bits were used. Rotary speeds were 50 and 100 rpm; static weight on bit was applied up to 40,000 Ib, and percussion frequencies up to 1,020 blows per minute were available. During this investigation it was found that toothed bits on which the teeth had developed flat ends about 3/16 in. wide did not change appreciably for the duration of a test. Hence, all toothed bits used in this study were in this condition. Conventional reference curves obtained in these tests show that increasing weight on hit by 2:1 yielded an increased penetration rate of approximately 2.7:1, while an increase in rotary speed of 2:1 netted an increased penetration rate of roughly 1.7:l. Results are thus of the same order as those reported for hard rock drilling by other investigators." CALIBRATION Under the selected standard test conditions previously described, with the lifting table hydraulically supported, and the anvil interposed between hammer and load cell, the hammers were dropped from known heights. Thus, with the kinetic energy of the hammer known, the corresponding maximum impact force shown by the cell was determined. (It may be of passing interest to note here that special drop tests with the hammers showed that no appreciable reduction in impact force resulted from introduction of the anvil or hit sub.) From these calibrations, it was possible to determine the theoretical kinetic energy available in the hammer from the maximum impact force shown by the load cell while operat-

By I. R. Kramer

In his technical note entitled "Specimen Temperature During Electropolishing of Aluminum Crystals" Dr. Nakada 1 reported that the temperature of his aluminum specimen increased 65°C when it was polished electrolytically; he therefore concluded that the temperature of the specimens used in our work (Nakada&apos;s Refs. 4 and 5) similarly increased by this amount. From this he further concluded that the change in plastic-flow characteristics associated with the removal of the surface by electropolishing during deformation were due solely to a temperature effect. We believe that these conclusions are not justified. It is, of course, realized that the amount of the temperature increase is associated with the total heat transfer of the entire system, including the efficiency of the stirring action, heat flow through the grip on the specimen, and so forth. Of great importance is the type of electrolyte used for polishing. For example, in Dr. Nakada&apos;s experiment a methanol-perchloric acid solution was used. This solution has a relatively low conductivity and for the current densities of 0.3 amp per sq cm the electrical input appears to be 30 to 40 w. In our research a methanol-nitric acid solution was employed and for the size of specimen employed by Dr. Nakada the power never exceeded 7 w. There are major differences in his test apparatus which also appear to affect the temperature rise. In our case a steel specimen holder was used in order to provide a good heat sink and conduction path. The cathode was a coiled aluminum tube through which a coolant was passed to provide additional cooling capacity near the specimen. The stirrer was placed in a position to obtain maximum cooling efficiency. On the other hand Dr. Nakada used a teflon grip to support the specimen at one end only and a flat copper cathode, thus providing a much less efficient heat sink as compared with the metal grips used in our studies. The relationship between current density and the temperature increase for two sizes of aluminum crystals tested in our tensile apparatus is shown in Fig. 1. The temperature measurements were determined from a thermocouple spot-welded to the surface of the specimen. The thermocouple was protected from the acid by means of a thin film of stop-off lacquer which covered just the outer surface of the thermocouple junction. Whereas Dr. Nakada reported a time delay of 8 min to obtain thermal equilibrium, our temperature change occurred in less than 15 sec. This emphasizes the importance of the heat transfer in the entire system. However, readings were taken over a period in excess of 5 min to assure thermal equilibrium. The data given in Fig. 1 were also confirmed by determining the thermal expansion of the specimen in a sensitive creep apparatus. As may be seen, for the smaller specimen the increase in temperature is 8°C for a current density of 1.5 amp per sq in. The majority of our data on the effects of surface removal on the plastic behavior of aluminum were obtained at current-density values at or below this value. Above 1.5 amp per sq in. the temperature rise is uncertain; for under certain conditions, especially in the vicinity of 2 amp per sq in., the anode can become polarized and the current flow is erratic. This condition is easily recognized because wide fluctuations in the creep and stress-strain data make it virtually impossible to obtain reliable results, a condition which was always avoided in our work. The temperature increase for the larger specimen is less than that of the smaller specimens below a current density of 1.5 amp per sq in. At a current density of 2 amp per sq in. the temperature increased 13°C. The above temperature data are in accord with observations made during creep experiments. Using a transducer capable of detecting strain in the order of 10 -6, temperature changes in excess of 8°C were not detected when the current density was increased to as high a value as 1.5 amp per sq in. Finally we wish to point out that our experimental data cannot be explained solely in terms of a heat effect. For example in Fig. 1 of Ref. 2, the change in slope of Stage II as a function of the rate of re-

Jan 1, 1965

By John T. Galey

Oil and gas development in southern Pennsylvania during 1937 was marked by considerably increased activity in deep-sand drilling. Nine tests were completed to the Oriskany sand: one in Independence and three in South Beaver townships, Beaver County; one in Franklin township, Butler County, two in Slippery Rock township, Lawrence County; one in Mt. Pleasant township, Washington County, which is drilling below the Oriskany, and one in Fairfield township, Westmoreland County. Two of these wells, both of which were in the Blackhawk pool, South Beaver township, Beaver County, obtained wet gas with open-flow volumes of 1.5 million cu. ft. and 3.1 million cu. ft. and closed-in pressures of 1900 Ib. The remaining seven were unproductive in the Oriskany. Two wells, one in Hampton township, Allegheny County, which is shut down temporarily as a result of a gas pocket, and one in South Beaver township, Beaver County, are drilling to the Oriskany. One deep test on the Chestnut Ridge anticline, South Union township, Fayette County, was completed after considerable difficulty as a dry gas well in the Onondaga limestone. At this locality the cherty limestone is porous as a result of fracturing. Three additional tests are under way in the area, one in South Union township, a second in North Union township, and a third in Wharton township. Completions Oil.—Despite price cuts and production curtailment of Pennsylvania Grade crude, caused largely by a decreasing demand from export markets, operation in the shallow oil areas continued at a fairly high rate and a number of good wells were completed. Some of these were new wells in close proximity to old production and others were old wells drilled into deeper pays. One new well of a number of producers drilled to the Nineveh Thirty-foot sand in the Harvey pool, Center township, Green County, made 400 bbl. of oil and 500 million cu ft. of gas the first 24 hr. The Chambers dam pool of Amwell and South Franklin townships, Washington County, yielded a number of Fifth Sand producers with initials as high as 200 bbl. Several wells in the old Mars-Butler field

Jan 1, 1938

By Frank V. Hicks

THE following paper-in no sense a technical paper-is a summary of a safety campaign instituted by a coal-mining company to improve an unfortunate safety record. The experience should be suggestive equally to coal and metal-mining companies. With few precedents to follow in the beginning, the course was charted by trial and error. The endeavor, often disheartening, finally resulted in the capture of the most coveted safety trophy in the mining industry, "The Sentinels of Safety," awarded by the Hercules Powder Co. of Wilmington, Del., through the U. S. Bureau of Mines. The period described covers the 10-year interval, 1924 to 1933, the year 1933 being that for which the award was made. The coal company considered has produced annually for a number of years an average of 2,750,000 tons of coal, employing at various times from 1.800 to 3000 men. Prior to 1924, the

Jan 1, 1935