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By H. C. Kenny

THE annealing or softening temperature of cold-worked copper is appreciably increased by almost unbelievably small amounts of silver. As indicated by some data in this paper, the softening temperature of high-conductivity, tough-pitch copper may be increased from 200° to 350° C. by the addition of only 15 oz. per ton (0.052 per cent) of that element. Because it has this higher annealing temperature as compared with the silver-free metal, silver-bearing copper finds considerable use in industry. For example, when hard-rolled copper is used in operations that involve soldering or tinning, silver-bearing copper insures against loss of strength, whereas silver-free copper becomes "dead soft." Yet-though several investigators, beginning with Caesar and Gerner1 in 1916, have shown that small amounts of silver do definitely raise the softening temperature of copper-data are lacking on the problem: What is the specific influence of different amounts of silver on this tem-perature? It was to help in filling this gap in the knowledge of what might be termed "alloy coppers" that the data given herein were obtained. The softening of cold-worked copper depends, of course, on a number of factors, of which the composition of the material is only one. Other highly important factors are the degree to which the material is cold-worked and the time it-is held at the annealing temperature. The method of cold working and the grain size of the metal produced are also signifi-cant. All these variables were taken into account in the investigation reported here, and the influence of silver on the electrical conductivity and on the working was also considered.

Jan 1, 1934

(The following-list contains the names of those members of the Institute of whose connection with military service we have only recently. become acquainted.) ADAIR, ARTHUR C., Corporal, 4th Co., 1st Tr. Bn., 154th D. B., Camp Meade, Md. BATCHELOR, STILLMAN, 1st Lieut., Co. 6, E. 0. T. S., Camp Humphreys, Va. BATES, BENNETT R., 1st Lieut., Engineers, Co. 3, E. 0. T. S., Camp Humphreys, Va. BJORGE, GUY N., Co. 3, E. 0. T. S., Camp Humphreys, Va. BOAS, Ross, H., U. S. A. BRADLEY, . H., JR., Capt., 408th Engineers, Camp Cody, N. M. BRINTON, OWEN F., Capt., Engineers, U. S. A. BROWN, HAROLD C., 2d Lieut., A. S. A.P.

Jan 1, 1919

By W. H. Bassett

A 10-year, sea-water, corrosion test of tubes of several copper alloys has shown that many alloys withstood attack by solution, pitting, and dezinkification; a 1-year, salt-spray test of sheet-metal specimens of the same composition showed the same results. THE late J. P. Sparrow, chief operating engineer of the New York Edison Co., carried out a series of practical tests on condenser tubes of several copper alloys and reported on the results to the Association of Edison Illuminating Companies at its meeting in' September, 1913. In the preparation of these tubes the senior author had the pleasure of cooperating. Copper-zinc alloys in the proportions of 60-40, 70-30, 80-20, 90-10, and Admiralty metal, which is in effect 70-30 with 1 per cent. of tin, were tried. Monel metal and several copper-nickel alloys, and 8, 5, and 3 per cent. aluminum bronze were also tried. At the time of this report, the aluminum bronze had been in service for 4 1/2 years and seemed to be giving especially good results but later it began to fail and showed no substantial improvement over Admiralty metal. Monel metal was unsatisfactory and the nickel alloys apparently did not give better service than the Admiralty alloy. Previous to the publication of the report, and after considerable discussion, it was agreed that a test where tubes of different kinds could be under laboratory observation would be advisable, so the apparatus described here was set up in The American Brass Co.'s Waterbury Laboratory. This was fitted with tubes of copper, brass, bronze, nickel silver, cupro-nickel and other alloys, and the test started Oct. 11, 1912. Salt water from East River, New York harbor, was barrelled and transported to the laboratory for the test. A fresh supply, completely replacing the water in service, was obtained at the end of each six months period.

Jan 1, 1925

By B. H. Bergstrom, D. D. Crabtree, C. L. Sollenberger

Experimental data is given for several natural minerals on the load required for the fracture of single specimens over a very wide size range. The experimental results are compared with published data, such as for coal specimens from 30 to 64 in. in size. Correlations of the specific energy (per unit mass) required for fracture with specimen size are given as functions of specimen shape and the experimentally observed load-size relationships. These correlations are discussed with reference to comminution theory. Comminution, through compression or impact, can result only if sufficient force, or energy, is applied to a specimen of a given size. The relation of specimen size to force requirements has not been adequately considered previously. For single particle fracture, it was previously shown 1 that the specific energy (energy, e, per unit mass, M) at fracture of single glass spheres was inversely proportional to the product size modulus, k, as indicated in the equation: e/M = C/k [1] This was found true not only for numerous glass specimens of the same nominal size but was true for all nominal sizes tested from 1/8 to 1 in. Also, it was observed that the smaller spheres required a greater specific energy at fracture than the larger spheres and consequently had a smaller product size modulus. However, the relationship giving the required fracture energy as a function of specimen size was not further elaborated upon. This paper will extend the development of the feed size effect on specific fracture energy for brittle materials. SPECIFIC ENERGY-FEED SlZE RELATIONSHIPS FROM PREVIOUS DATA For the particular glass spheres tested in the previously described experiments,' it can be shown, as on Fig. 1, that the specific energy varied inversely as the 4/3 power approximately of the feed size, F, in the span of nominal sizes ranging from 1/8 to 1 in. The load at which a 3-in. diam glass sphere (a crystal gazer's ball) was broken was within the range predicted by an extrapolation of this energy-feed size relationship. The product size distribution from this

Jan 1, 1963

By U. C. Tainton

IN reviewing progress in zinc metallurgy during the last year or so one is reminded of the premise on which H. G. Wells based his "Food. of the Gods," namely that growth does not and cannot take place smoothly and steadily, but occurs in a series of bursts and intermissions: "It is as if every living thing has to accumulate force to grow, grows with vigor only for a time, and then has to wait for a space before it can go on growing again."

Jan 1, 1937

By R. T. DeHoff

A general method for determining the geometric properties of structures composed of particles which are all the same shape and size is presented. The application of the method requires a knowledge of' the qualitative shape of the particles in the structure, ad a maximum of three simple counting measurenzents, which are made on a representative plane section taken through the structure. It is also shown that the number of different kinds of measurements necessary JOY the complete description of the structure can be decreased if some independent information about individual particles is available. The geometric properties that can be determined quantitatiz~ely from counting measurements for susch structures are size, shape, number, surface area, vlolume, ad such extensive properties as volume Mction and surface area per unit volume. THE simplest kinds of measurements that may be made on a metallographic section are counting measurements. There are three such simple counting measurements, which are determined by sampling the microstructure with a point, a line, and an area. The first of these, the point count, is probably the most familiar among metallographers. The second count, the number of intersections a test line makes with particle outline, is somewhat more recent in its origin and application. The third counting measurement, the number of particle sections observed in unit area of the plane of polish, has long been used in the estimation of grain sizes. The real utility of these three counting measurements lies in the fact that they are rigorously and unambiguously related to certain extensive geometric properties of the three-dimensional structure of which the metallographic section is a sample. These relationships will be reviewed briefly below. Of somewhat secondary importance to the fundamental relationships is the observation that, if some simplifying assumptions about the geometry of the three-dimensional structure are introduced, manipulation of the counting measurements gives a more complete description of the structure. Specifically, in addition to the extensive properties which these measurements rigorously estimate, the number of particles, their size, and their shape may be determined. The purpose of the present paper is to explore the consequences of introducing the assumption of constant size and shape. A later paper will deal with the estimation of geometric properties of structures which may be characterized by a two-parameter size distribution. It should be mentioned that the introduction of this simplest of assumptions, while clearly not generally justified in metallurgical structures, is not without precedent. For example, many estimates of the number of particles per unit volume of structure, based upon a single counting measurement, are scattered throughout the literature.13 Virtually all of these developments assume a constant particle shape, e.g., spherical or polyhydral, and constant size. That such an assumption is necessary is evident from the fact that, for more general structures, more than a single parameter is required to describe the three-dimensional structure, so that the determination of a single parameter on a section would be insufficient to specify the structure. Similar developments for the estimation of particle size from a single counting measurement, e.g., routine grain-size determinations, make the same very limiting assumption,435 but have nonetheless proven of practical value. The present paper embodies a generalized approach to the development of relationships among the two-dimensional counting measurements and the three-dimensional geometry of the structure, subject to the assumption of constant particle size and shape. It is the hope of the author that by presenting the relationships and the assumptions involved in dealing with this approximation, in a single, unified treatment, the reader may be impressed with the usefulness of the counting measurements, may be guided in their application to the estimation of details of the geometry in specific structures in which he may be interested, and may be moved to apply the results, with understanding, to new structural problems. Several authors6, 7 have demonstrated independently that it is possible to obtain unbiased estimates

Jan 1, 1964

By Sheldon P. Wimpfen

RESEARCH is undertaken to find out what must be done when what we are doing now is no longer adequate. To accomplish this end, researchers apply the truths of nature to industrial evolution. A survey conducted with the co-operation of 58 universities and colleges offering degrees in mineral engineering was the basis for the table accompanying this article. This survey was undertaken with the object of presenting to faculties and student bodies, as well as to industry, all available information on what action the educational institutions of the country have taken to provide the properly trained researchers so vitally needed. A hoped for result is that the great variety of opportunities available will encourage some undergraduate students to continue in their field beyond attainment of a B.S. degree.

Jan 1, 1947

By G. Ferrara

The reserves of lead and zinc ores in the metalliferous district of Iglesias in south-western Sardinia are today estimated at about 30 million tons, grading from 4 to 10% Pb + Zn. Of these reserves, about 40% are in the mines owned by AMMI Sarda S.p.A. The working of these resources goes back to ancient times. Not infrequently, traces of old Roman workings and remains of ancient implements are come upon in the higher parts of some of the ore bodies. Exploitation of these mines on larger scale, however, dates from the middle of the 18th century. Initially, the more accessible zones of the ore bodies and the richer ores were worked - the galena and the rich oxidized ores (calamine* with 25-35% Zn), which were often found in large masses, the enormous empty cavities of which still remain. The poorer grade deposits have been gradually rendered workable by the development of technology - the perfecting of the

Jan 1, 1970

By L. H. Van Vlack, T. Y. Tien, R. J. Martin

The phase relationships of the MnTe-MnS system were studied by DTA procedures. There is an eutectic at 810°C with about 10 mole pct MnS-90 mole pct MnTe. An eutectoid occurs at about 710°C with approximately 7 mole pct MnS where the MnTe(NaCl) solid solution dissociates on cooling to MnTe(NiAs) and MnS. There is very little solid solubility of MnTe in MnS. ALTHOUGH MnS may exist in three different crystal forms,' only the NaC1-type phase is stable.2 Above 1040°C, MnTe also has the cubic NaC1-type structure. Below that temperature, MnTe changes to the NiAs-type structure.3 This phase transition is rapid for both heating and cooling. As a result the high-temperature crystal form of MnTe cannot be retained at room temperature. Because MnO, MnS, and MnSe are all stable with the NaC1-type structure, and MnTe has this structure at high temperatures,4 solid solution formation could be expected among these compounds. It is interesting to note, however, that a complete series of solid solutions exist only in the MnS-MnSe system,' and that the solid solution is quite limited in the MnO-MnS system.' The MnSe-MnTe system possesses a complete series of solid solutions at high temperatures with separation at lower temperatures.7 Although ion size may be critical in the miscibility of MnO-MnS, it is quite possible that the bond type plays a more important role with the miscibility of MnSe-MnTe. This would permit us to speculate that the miscibility gap would be extensive in the MnTe-MnS system. EXPERIMENTAL Preparation. The samples were prepared by mixing and compacting MnTe and MnS powders. The MnS was previously prepared through the sulfur reduction of Mnso4.8 The MnTe had been prepared by mixing and compacting double vacuum distilled metallic manganese and high-purity tellurium in stoichiometric ratio modified with 1 wt pct excess tellurium. The compacted powders were put in a graphite crucible which was sealed in an evacuated vycor tube. The free space in the vycor tube was made minimal to reduce the loss of tellurium. The sealed assembly was then heated slowly to about 500° C where the free manganese and tellurium reacted vigorously, melting the MnTe which formed. Only one phase, MnTe, was detected by X-ray powder patterns and metallographic techniques. Each compact of MnTe-MnS was placed in a graphite crucible and then sealed in an evacuated vycor tube. The samples were heated at 1250°C for 4 hr and furnace-cooled. Microscopic examination revealed no third phase beyond MnS and MnTe. A typical microstructure is presented in Fig. 1. Identification. X-ray powder patterns were obtained using 114.6 mm Debye-Scherrer camera and Fe-Ka radiation. Mixtures of cubic MnS and hexagonal MnTe were observed in all of the compositions prepared. No lattice parameter change was noticed among different compositions, indicating no solid solution could be retained at room temperatures between these two end-members. A lattice parameter of 5.244Å for MnS was obtained by the Nelson and Riley9 extrapolation method using the diffraction lines of (h2 + k2 + 12) equal 12, 16, 20, and 24. The values, a = 4.145Å and c = 6.708Å, for hexagonal MnTe were obtained from the (006) and (220) lines in the back-reflection region. These values agree well with the values reported by Taylor and Kag1e.10 Differential Thermal Analysis. A differential thermal analysis procedure was used to determine phase relationships since the high-temperature equilibrium conditions could not be retained for examination at room temperature, even when the sealed samples (~0.5 g) were quenched in water. The samples were sealed in an evacuated 4 mm vycor tube with a recess in the bottom to accept a thermocouple. An Al2O3 reference was similarly prepared and the two placed within a piece of insulating fire brick to dampen spurious temperature changes within the furnace. The furnace was controlled by a mechanically driven rheostat which increased the temperature at a rate of about 15°C per min. Known phase changes in the Pb-Sn system1' and the a-to-ß quartz inversion12 were used for calibration

Jan 1, 1969

By W. B. Lilienthal, J. C. Melrose

The application of Bingham's law to the behavior of drilling fluids in a rotational viscometer permits the expression of viscometric data in terms of plastic viscosity and yield value, the flow properties of a plastic fluid. A commercially available rotational viscometer is described, and when modified to a multispeed type viscometer, is shown to provide a simple and convenient instrument for the measurement of these properties both in the laboratory and in the field. The data obtained are shown to be useful in defining and understanding mud control problems relating to chemical treatment and to the hydro-dynamic behavior of muds. INTRODUCTION The highly complex drilling fluids which are required for deep drilling often give rise to new and unusual mud control problems. Rapid and economic solutions to these problems may require, on the one hand, better understanding of the changes which contaminants and chemical treating agents produce in the colloidal and inert solids of the mud, or, on the other hand, closer control of the hydrodynamic behavior of the mud. The latter objective obviously can be achieved only if a correct rheological analysis of the flow behavior of drilling muds is available and if this is accompanied by the appropriate rheological measurements. The purpose of this paper is to describe such measurements in the field, and to show how the resulting data can be of value in solving difficult mud control problems. It is now generally recognized that Bingham's law of plastic flow can be utilized in describing the hydrodynamic behavior of drilling fluids in the non-turbulent flow range. Beck, Nuss, and Dunn' have recently applied this law to the flow of mud in small pipes, and Rogers2 has reviewed the rather extensive literature on this subject. So far, however, the use of Bingham's law has been restricted to the analysis of mud flow in pipes or capillary tubes, and it has not been directly applied to the flow in rotational viscometers. In the work to be reprted, the Reiner-Riwlin3 equation for the flow of a plastic fluid in a rotational viscometer has been utilized to permit the expression of multispeed viscometric data in terms of plastic viscosity and yield value. the two absolute flow properties of a plastic fluid. With regard to the application of these measurements, the calculation of the relationship between pumping rate and pressure drop, both in the drill pipe and annular space, has long been a subject of interest. Beck, Nuss, and Dunn,' following Caldwell and Babbitt: base their calculations for non-turbulent flow on Buckingham's integration of Bingham's law for pipe flow and measurements of the plastic viscosity (rigidity in their terminology) and yield value. In the case of turbulent flow, Fanning's equation is employed, and the pressure drop is relatively insensitive to the flow properties of the mud. Since flow in the drill pipe is likely to be turbulent at usual circulation rates, the plastic flow properties will chiefly influence the pressure drop in the annular space. As pointed out by Beck,' the control of this component of the total pressure drop may be of special importance where lost circulation problems are encountered. Other hydrodynamic problems to which it should be possible to apply measurements of the plastic flow properties include predictions of the velocity distribution in non-turbulent flow and the critical velocity for transition to turbulence. Plastic viscosity and yield value. as abmlute flow propertie.;, will reflect the colloidal or surface-active behavior of the solids present in drilling fluids. Measurements of these properties should therefore find application in developing a better understanding of such behavior and in characterizing the type and condition of these solids. Garrison and ten Brink have utilized multispeed viscometric data in this manner. although their measurements were not expressed in terms of the absolute flow properties. In connection with the application of these measurements, it should be recognized that the presently used one-point viscosity measurements are relative in nature. The API Stormer 600-rpm measurement, for example. is a function of both plastic viscosity and yield value, as well as mud weight, and will often be misleading when its application to mud control problems is attempted. NOMENCLATURE, UNITS, AND DEFINITIONS In Fig. 1 an idealized plot is given of the flow variables involved in any viscometric measurement. It is seen that the flow behavior of plastic fluids is characterized by two constants — plastic viscosity, µp, and yield value, F. Other workers hate used the term rigidity for plastic viscosity or the term mobility for its reciprocal. The term plastic viscosity, however, emphasizes the close relation this property bears to the viscosity of a true fluid and is expressed in the familiar viscosity units of centipoises. The yield value is expressed in lbs/100 sq ft, the units adopted for gel strength measurements with the APT shearometer. Definitions of these properties based on rheological or macrc)scopic flow considerations follow from Fig. 1. The plastic viscosity of a substance obeying Bingham's equation is defined

Jan 1, 1951

By J. C. Melrose, W. B. Lilienthal

The application of Bingham's law to the behavior of drilling fluids in a rotational viscometer permits the expression of viscometric data in terms of plastic viscosity and yield value, the flow properties of a plastic fluid. A commercially available rotational viscometer is described, and when modified to a multispeed type viscometer, is shown to provide a simple and convenient instrument for the measurement of these properties both in the laboratory and in the field. The data obtained are shown to be useful in defining and understanding mud control problems relating to chemical treatment and to the hydro-dynamic behavior of muds. INTRODUCTION The highly complex drilling fluids which are required for deep drilling often give rise to new and unusual mud control problems. Rapid and economic solutions to these problems may require, on the one hand, better understanding of the changes which contaminants and chemical treating agents produce in the colloidal and inert solids of the mud, or, on the other hand, closer control of the hydrodynamic behavior of the mud. The latter objective obviously can be achieved only if a correct rheological analysis of the flow behavior of drilling muds is available and if this is accompanied by the appropriate rheological measurements. The purpose of this paper is to describe such measurements in the field, and to show how the resulting data can be of value in solving difficult mud control problems. It is now generally recognized that Bingham's law of plastic flow can be utilized in describing the hydrodynamic behavior of drilling fluids in the non-turbulent flow range. Beck, Nuss, and Dunn' have recently applied this law to the flow of mud in small pipes, and Rogers2 has reviewed the rather extensive literature on this subject. So far, however, the use of Bingham's law has been restricted to the analysis of mud flow in pipes or capillary tubes, and it has not been directly applied to the flow in rotational viscometers. In the work to be reprted, the Reiner-Riwlin3 equation for the flow of a plastic fluid in a rotational viscometer has been utilized to permit the expression of multispeed viscometric data in terms of plastic viscosity and yield value. the two absolute flow properties of a plastic fluid. With regard to the application of these measurements, the calculation of the relationship between pumping rate and pressure drop, both in the drill pipe and annular space, has long been a subject of interest. Beck, Nuss, and Dunn,' following Caldwell and Babbitt: base their calculations for non-turbulent flow on Buckingham's integration of Bingham's law for pipe flow and measurements of the plastic viscosity (rigidity in their terminology) and yield value. In the case of turbulent flow, Fanning's equation is employed, and the pressure drop is relatively insensitive to the flow properties of the mud. Since flow in the drill pipe is likely to be turbulent at usual circulation rates, the plastic flow properties will chiefly influence the pressure drop in the annular space. As pointed out by Beck,' the control of this component of the total pressure drop may be of special importance where lost circulation problems are encountered. Other hydrodynamic problems to which it should be possible to apply measurements of the plastic flow properties include predictions of the velocity distribution in non-turbulent flow and the critical velocity for transition to turbulence. Plastic viscosity and yield value. as abmlute flow propertie.;, will reflect the colloidal or surface-active behavior of the solids present in drilling fluids. Measurements of these properties should therefore find application in developing a better understanding of such behavior and in characterizing the type and condition of these solids. Garrison and ten Brink have utilized multispeed viscometric data in this manner. although their measurements were not expressed in terms of the absolute flow properties. In connection with the application of these measurements, it should be recognized that the presently used one-point viscosity measurements are relative in nature. The API Stormer 600-rpm measurement, for example. is a function of both plastic viscosity and yield value, as well as mud weight, and will often be misleading when its application to mud control problems is attempted. NOMENCLATURE, UNITS, AND DEFINITIONS In Fig. 1 an idealized plot is given of the flow variables involved in any viscometric measurement. It is seen that the flow behavior of plastic fluids is characterized by two constants — plastic viscosity, µp, and yield value, F. Other workers hate used the term rigidity for plastic viscosity or the term mobility for its reciprocal. The term plastic viscosity, however, emphasizes the close relation this property bears to the viscosity of a true fluid and is expressed in the familiar viscosity units of centipoises. The yield value is expressed in lbs/100 sq ft, the units adopted for gel strength measurements with the APT shearometer. Definitions of these properties based on rheological or macrc)scopic flow considerations follow from Fig. 1. The plastic viscosity of a substance obeying Bingham's equation is defined

Jan 1, 1951

By Jacques Steininger, Robert E. England

Single crystals of ZnTe and ZnTe1-,Sex with x up to 0.13 have been grown from the elements by temperature gradient solution zoning using excess tellurium as a solvent. Best results have been obtained with charges with the compositions 45/55 at. pct Zn, Te, for ZnTe and increasing amounts of selenium for ZnTe1-xSex. The temperature in the molten zone was maintained at about 1070°C with a gradient of about 10°C per cm. Chemical analyses of quenched ZnTe ingots show tellurium concentrations in the molten zone as high as 70 pct with concentration differences across the zone of 1 to 2 at. pct Dark dots which are observed by transmitted light microscopy in as-grown crystals can be removed by annealing in zinc vapor at 900 C. INTEREST in wide band gap semiconductors has led to a new study of ZnTe and ZnTel-xSex crystal growth. ZnTe is the only II-VI compound with a wide band gap (2.3 ev) that can be made p type with low resistivity. Attempts to make it n type with low enough resistivity to be useful for p-n junctions have so far been unsuccessful.1 ZnSe has a band gap of 2.65 ev but can be made n type only. However, ZnTel-xSex solid solutions with x as low as 0.36 have been made both highly n and p type2 with a minimum band gap around 2.12 ev3 at room temperature and appear to hold the best promise for efficient injection electroluminescence in the visible. ZnTe has the lowest melting point of the zinc chal-cogenides (1295°C) and consequently attempts have been made to grow crystals from both the liquid and the vapor phase.4 Complicated apparatus is required for growth from stoichiometric melts because of the high vapor pressures of the elements at the melting point of ZnTe and because of the problem of quartz devitrification. Small crystals have thus been grown in high-pressure equipment by Fischer5 and by Narita et a1.6 with pressures of the order of 50 atm of argon to prevent excessive evaporation from the melt. Large crystals of ZnTe can be obtained by growth from the vapor phase4 but they often present numerous dislocations and inclusions. An improvement in the quality of vapor- grown ZnTe crystals was reported by Albers and Aten7 by equilibration of mixtures of small crystals with compositions lying on either side of the solid single-phase field at fixed temperature. The same technique was later applied by Aten8 to the growth of ZnTe1-xSex crystals with less than 1 pct inhomo-geneity. Because of the higher liquidus temperatures of the solid solutions and the high vapor pressure of selenium, previous attempts to grow ZnTel-xSex from the melt have been limited and unsuccessful.9 The phase diagram of the Zn- Te system is reproduced in Fig. 1, based on data from Kobayashi10 and Kulwicki.11 Carides and Fishher12 have reported lower liquidus temperatures on the tellurium-rich side, but their data would require confirmation. The liquidus temperature on the tellurium-rich side decreases rapidly with increasing tellurium concentration and the Te2 vapor pressure over the liquidus also decreases accordingly.'3 The decrease in liquidus temperature and vapor pressure therefore makes it possible to use conventional apparatus if there is a sufficient excess of tellurium in the melt. Single crystals of ZnTe have thus been grown by Kucza,14 in a modified Bridgman technique, from solutions containing up to 60 at. pct of Te by lowering unsupported quartz ampoules through a temperature gradient at about 1200°C. Under these conditions, the phase diagram indicates that the entire charge is initially molten. Crystal growth can therefore proceed by normal freezing and rejection of excess tellurium into the melt. The modified Bridgman technique has several major limitations. Because of the rejection of excess tellurium into the melt during freezing, the melt composition and the temperature at the growth interface vary continuously. They tend to follow the liquidus until the eutectic which is very close to pure tellurium (447°C, >99 pct Te). Since the solidus composition also varies with temperature,15 crystals grown by this method are inhomogeneous. They present small variations from stoichiometry which may affect their structure and physical properties. The simultaneous increase in tellurium content and decrease in melt temperature also combine to reduce the rate of diffusion of tellurium away from the growth interface, thereby causing constitutional supercooling and possibly dendritic growth. To minimize these effects, the initial melt composition is in practice kept relatively close to stoichiometry (less than 60 pct Te). This however limits the possibilities of operating at low temperatures and pressures. This paper describes a modified method of crystal growth by temperature gradient solution zoning (TGSZ) which is an adaptation of the temperature gradient zone-melting technique developed by pfann16 and of the traveling solvent method of Mlavsky and weinstein.I7 The TGSZ method now applied to the growth of ZnTe and ZnTel-xSex crystals is characterized by its very simple experimental arrangement and sample preparation technique. Unlike the modified Bridgman technique, there is no increase in the tellurium concentration in the melt and therefore it is possible to operate at lower temperatures and pressures. This method is also suitable for maintaining a constant temperature at the growth interface.

Jan 1, 1969

By Malcolm V. Lowry

At Balmat in northern New York State, the St. Joseph Lead Co.'s 2100-tpd zinc mining and milling operation is utilizing a unique thickener in conjunction with conventional crushing, grinding and flotation methods. From 1930 through 1962, zinc concentrates went directly from flotation to the filtering, drying and loading facilities, all of which had to operate 24 hr per day. Wide fluctuations in tonnage also had to be accommodated due to variations in the grade of ore. Many problems were thus encountered in filtering and drying, but the cost of installing a conventional, large diameter thickener could never be justified. In 1963, after thorough investigation, an unconventional thickener that is unusual in several respects was installed at Balmat. The tank depth is 16 ft instead of the normal 8 ft. The rakes are raised and lowered by having the main drive gear located on a movable platform. Automatic controls are programmed to raise the drive platform and rakes during one shift of storage. During the next two shifts of withdrawal, the controls are programmed to lower the drive platform and rakes.

Jan 5, 1966

By Gerald A. Munson, Fremont F. Clarke

DURING recent years the use of lithium has expanded greatly in industrial, chemical, and metallurgical fields, while at the same time modernized methods of mining and refining lithium have increased production. Technical literature includes many papers describing the geology and mineralogy of lithium deposits. Mining and beneficiating problems, however, have not been thoroughly described. Published reports have failed to emphasize that one of the chief reasons lithium minerals were not extensively mined until recently is the difficulty of beneficiation. Four lithium minerals of pegmatites and the lithium-sodium-phosphate byproduct from the brines at Searles Lake, Calif., have been sources of lithium. Among the pegmatite minerals, only spodu-mene and petaline are known to occur in deposits large enough to support large tonnage operations. Spodumene, a lithium-aluminum-silicate, is the principal lithium mineral mined in the U. S. Lithium Corp. of America, during its rapid development and growth, has successfully employed three different methods of concentration: 1) hand sorting, 2) Heavy Media separation, and 3) froth flotation. Each method, though economic in its sphere, is becoming outdated as extractive techniques improve. The most recent development has taken place at Lithium Corp.'s new operation in North Carolina, where the extractive process yields lithium compounds directly from mined rock without an intervening concentrating step. Until 1954 Lithium Corp. mined only in the southern part of the Black Hills of South Dakota, where the various types of lithium-bearing pegmatite could be used to develop untried processes of beneficiation. Concentrates from these operations are shipped to the corporation's chemical plant in St. Louis Park, Minn., where actual extraction of lithium and production of commercial compounds takes place. Nature of Deposits The geology of the southern Black Hills pegmatite deposits is admirably presented by a U. S. Geological Survey publication.' Only the factors pertinent to exploitation need be mentioned here. Lithium Corp. has been interested primarily in three deposits, the Edison, the Mateen, and the Longview-Beecher No. 2. The history of these deposits dates back to the mining boom of 1880 to 1900 in the Black Hills, when most of the deposits were prospected for tin by the ill-fated Harney Peak Tin Mining Co. The three deposits described here, however, lay idle and unwanted until Lithium Corp. opened the Edison mine in 1943 and the Mateen and Longview-Beecher No. 2 in 1951. Edison Deposit: The Edison deposit is about a mile southeast of Keystone, S. D., on the northeastern flank of the Harney Peak uplift. The deposit consists of no less than four and probably at least six separate pegmatites that coalesce in a central mass from which the individual pegmatites finger outward and downward in complexly folded schist and gneiss beds of the country rock.

Jan 1, 1956

By Carl Tolman, LeRoy Scharon, Harold Powers

THIS paper presents geophysical and subsurface data observed in the vicinity of Shafts No. 1 and and 5 of the National Lead Co. lead mines at Fred-ericktown, Madison County, Missouri, see Fig. 1. The area selected is an excellent example to illustrate the close correlation between geophysical data and geological facts as revealed by drilling and mining. Such close correlations make geophysical applications appropriate to the development of known ore-bodies as well as the exploration for new orebodies. In the past, magnetic and shallow electrical resistivity observations were made over limited areas in the Fredericktown lead district by the Missouri Geological Survey, with favorable results. The first extensive magnetic and electrical resistivity surveys were started by the U. S. Bureau of Mines in May 1945 in two areas located northwest and southwest of Fredericktown, as shown in Fig. 1. The results of these surveys were reported in April 1948 at Denver, spontaneous-polarization surveys were made over the property of the St. Louis Smelting and Refining Co. at Fredericktown by Sherwin F. Kelly Geophysical Services, Inc. Aeromagnetic surveys were completed in 1948 over the Fredericktown quadrangle by the U. S. Geological Survey. Since 1945 geophysical surveys have been an important part of exploration programs in the Fred- ericktown district. Such methods, magnetic and electrical resistivity, are now serving as guides in the further development of known orebodies. On an irregular pre-Cambrian igneous erosion surface Lamotte sandstone of upper Cambrian age was deposited, partially filling the topographic basins, see Fig. 2. Above and conformable with the Lamotte sandstone lies the Bonneterre formation, a dolomite with locally interbedded thin dolomitic limestones and shales at its base. This formation also only partially filled the topographic basins. The Bonneterre was overlain by the Davis, Derby, Doe Run, and Potosi formations, which are principally dolomite. Uplift, tilt, and slight warping has allowed erosion and weathering to remove most of the sediments overlying the Bonneterre, and in many places, not far from the mine, the Lamotte sandstone is exposed. This erosion has also exposed areas of pre-Cambrian igneous rock. The Lamotte sandstone, having been deposited on an irregular pre-Cambrian surface, is extremely variable in thickness and ranges from zero where it laps the pre-Cambrian rocks to 250 ft thick in the deeper basins. In the vicinity of the mines the Bonneterre dolomite ranges from zero where it wedges out against the pre-Cambrian igneous rocks to 400 ft thick. The ore deposits occur as a bedded disseminated type1 and are chiefly composed of galena and pyrite with minor amounts of chalcopyrite and siegenite. Heavy pyrite and marcasite mineralization may be found throughout the Bonneterre formation. However, there is little or no apparent association of these iron sulphide bodies lying above the ore hori-

Jan 1, 1954

By R. T. O’Brien, J. M. W. Mackenzie

A microelectrophoresis technique has been used to measure the zeta potential of quartz over a range of pH and Ni (11) and Co (Ilj concentrations. Results have been discussed in terms of adsorption of Ni (11) and Co (11) cations and hydroxide precipitates. Possible relationships between the experimental results and the formation of lateritic nickel deposits have been discussed. The adsorption of metallic cations to the surface of silicate minerals is of significance in many industrial and natural processes. In an earlier publication,' the adsorption of Fe (111) to the quartz surface, a phenomenon of importance in flotation, was studied qualitatively using microelectrophoresis techniques. This paper reports the extension of this work to an investigation of the adsorption from aqueous solution of Co (11) and Ni (11) to the quartz surface. The adsorption of these metals was of interest for two reasons; firstly, the importance of such an adsorption process in the formation of nickel deposits by the lateritization of nickeliferous rocks, and secondly, the comparison of electrophoresis data for these metals, whose hydroxides precipitate in the pH range 7-8, with similar data for Fe (111) where the hydroxide first precipitates at pH 2.8. The development of laterites is essentially a near-surface geological process involving vertical and, in part, horizontal redistribution of elements derived from rock-forming minerals. This redistribution of elements leads to the formation of layers within the lateritic profile which are enriched in one or more of these elements and, depending on the nature of the original rocks, continued lateritization may give rise to iron ores, bauxites or nickeliferous laterites. The mechanisms discussed in this paper deal with the last mentioned type of deposit although the considered factors are applicable to laterites in general. Nickeliferous laterites are derived from basic and ultrabasic rocks containing ferro-magnesian silicates. These rocks may be partly or wholly converted to serpentinites. Besides their high Mg, Si and Fe contents, they also contain small amounts of Mn, Al, Cr, Ni, Co, Cu and Zn. The nickel content is usually near to 0.2-0.3%, but for economic use this must be increased during lateritization to over 1% and preferably over 2%. The zone of nickel enrichment is usually at some depth within the lateritic profile. Unpublished work by Mr. O'Brien on nickel-bearing laterites in eastern Australia indicated four visually different types of material which were separated from crushed samples under a stereo-microscope. Although chemical analyses indicated that all four types of fragments contained 2-4% nickel and smaller amounts of cobalt, X-ray diffraction and optical studies revealed only quartz, hematite and chromite as well as, in one of the types, a serpentine mineral. No distinct, nickeliferous minerals were detected. Furthermore, it was possible to extract some 60% of the nickel content of the laterites with cold 0.5N hydrochloric acid. It was therefore postulated that much of the contained nickel was present as amorphous, adsorbed material. In considering this fact, as well as the problem of the actual method of transfer and fixation of elements within the lateritic profile, it was further postulated that the transfer of these elements probably took place partly as solutions and partly as colloids and that the fixation of these was caused by adsorption and flocculation. The existence of nickel in solution in water draining from serpentinites has been confirmed by Smurov.2 Although we have no evidence for the transportation of nickel in the colloidal state, it is well accepted that colloids are important in the formation of laterites. Previous work by Mr. Mackenzie' has already indicated that iron may be adsorbed on quartz under conditions which could be expected in a lateritic profile, but no information was available for nickel or cobalt. Although adsorption possibly also takes place on minerals other than quartz, the latter is significant because silica is an important constituent of the silicate parent rocks. During lateritization, it is released to form free quartz and it is likely that it is initially extremely fine-grained. This would provide abundant opportunities for adsorption and it was de-

Jan 1, 1970

By Ravindra M. Nadkarni, Milton E. Wadsworth

The kinetics of cetnentation of copper with iron were observed to follow first-order kinetics and increase with speed of agitation to a limiting value. Maximum rates agree closely with theoretical values based upon a model of aqueous solution diffusion through a litniting boundary film. Back reaction kinetics are shown both theoretically and experimentally to be independent of ferrous iron concentration in solution. The inlportance of attnospheres of air, oxygen, nitrogen, and hydrogen was studied and the results have been correlated with several impovtant oxidation processes involving metallic iron and copper. The kinetics of the reaction of ferric ion with metallic iron were found to be slow in the absence of metallic copper and essentially proportional to the surface area of metallic copper present in the system. THE precipitation of copper on iron is classic as an example of a relatively ancient art applied successfully for centuries with little fundamental understanding of the important parameters involved. There is some indication that the process has been a commercial means to produce copper since the sixteenth century.' The amount of fundamental work on the cementation of copper with iron is not great. Wartman and Roberson2 carried out a series of detailed copper cementation experiments using natural and synthetic mine water. The following were presented as the three principal reactions: Reaction [I] is the desired cementation reaction and accordingly 0.88 lb of iron would produce 1 lb of copper. In actual practice iron consumption would more normally fall in the range of 1.5 to 2.5 lb per lb of copper. Wartman and Roberson attributed the excess consumption of iron to Reactions [2] and [3]. They found that Reactions [I] and [2] proceeded at approximately the same velocity while Reaction [3] was much slower and would be diminished by controlling the contact time. It was also pointed out that increased agitation is beneficial in removing hydrogen bubbles and barren layers of solution at the iron surface as well as removing contaminants resulting from the hydrolysis of iron. Episkoposyan3 and Episkoposyan and Kakovskii4 studied copper and silver cementation on rotating iron disks in chloride solutions. The kinetics based upon a diffusion model were first order and varied linearly with surface area and with angular velocity raised to the one-half power according to the Levich equation. The experimental activation energy for both copper and silver was approximately 3 kcal per per mole. Excess iron consumption was found to increase with temperature. The rate of cementation first increased with increasing acidity and then diminished at high acid concentrations. sutolov5 has presented an excellent review of the Leach-Precipitation-Flotation (LPF) process including a discussion of copper cementation from an electrochemical point of view although few experimental results were presented. From voltage considerations he predicted that cementation should not be influenced by the concentration of ferrous iron in solution. He considered several secondary reactions including Reactions [2] and [3] and pointed out the importance of oxidation of ferrous iron to ferric with oxygen. In addition it was suggested that Reaction [2] was enhanced by the dissolution of metallic copper by ferric iron which in turn consumed excess iron by the cementation reaction, Eq.[1]. Cementation of copper on metals other than iron has been studied by several investigators but, as in the case of iron, the amount of fundamental work is not extensive. Bashkova and kovalenko6 and Bashkova7 studied the cementation of copper on indium from copper and indium sulfate solutions. The rate was found to be first order and to increase with acidity. This was associated with a decrease in potential (EIn — ECu) and the simultaneous reduction of hydrogen ions at low pH. The rate of cementation also decreased with increasing indium concentrations which was postulated to be due to the decrease in the rate of diffusion of the ions in solution. Below 97°C the experimental activation energy was found to have the unusually low value of 2 kcal per mole and was attributed to diffusional control. Above 97°C the rate increased suddenly and was explained as a change in the rate-controlling step to a chemical reaction. In Part I of this study Nadkarni et a1 .1 have reported on preliminary results obtained in a laboratory study of the kinetics of the cementation process. The rate was found to be first order, proportional to the surface area of the iron, and to increase with speed of stirring until a maximum rate was observed. At low stirring speeds the deposit was spongy and adherent. At medium speeds the copper peeled off in bright strips and at high speeds finely divided copper was produced and continually removed from the surface. The amount of excess iron consumed increased with speed of stirring and with temperature. The average experimental activation energy combining results from several types of iron was 5.8 + 1.6 kcal per mole suggesting diffusional control through a limiting boundary film. Traditionally copper cementation has been carried out over the centuries in gravity-fed launders of various design containing scrap iron. More recently rotating drum precipitators and activated launders8'10 have been used. In the latter, copper-bearing solutions are

Jan 1, 1968

By W. W. West

MACHINERY used for size reduction of materials may be divided into three classes-depending upon the manner in which the crushing force is applied. In the first class could be listed the primary crushing units, such as the jaw crusher and gyratory crusher-which crush to coarse sizes by applying pressure intermittently between converging surfaces. In the second class may be listed crushing units, such as the hammer mill, roller mill, and ball mill, which crush principally by grinding or attrition. In the third class is the impact mill which, as the name infers, crushes by impact. The second and third classes generally include machinery used as secondary units for intermediate or fine crushing and grinding. Theory of Crushing by Impact Throw a stone into the air and give it a severe blow while it is momentarily suspended, and it shatters into several pieces. The impact crusher uses this "batting" principle, but carries it one step further. As the material to be reduced enters the crushing chamber, it receives a severe free-air impact blow by hard-hitting beaters suspended from rotor discs. The shattered particles formed are then driven at high velocity against impact blocks, where a further reduction in particle size takes place. The rebounding particles from the impact blocks are again caught by the beaters, and the process repeated until the material is swept out of the open bottom of the crusher. Impact Crushing Versus Attrition Crushing Fig. 1 shows a Hammermill type of attrition crusher. This particular mill has central feed and is reversible. Because of the central feed, an impact section can be designed into it at the feed entrance for preliminary crushing, followed by the cage bar attrition area for final sizing. The material is caught and held in a crushing chamber enclosed by grate bars or perforated plate. It remains in this chamber until it is reduced to particle size small enough to pass through the openings between the bars or in the plate. In this manner the top particle size discharged from the mill is closely controlled. As the swinging hammers pass through the bed of material, the material is broken down by a scrubbing action between hammers and material, material and grate bars, and material against material. This attrition produces a rounded particle shape, accompanied by slivers and a comparatively high percentage of fines. The crusher is especially useful in industries where the material treated is not too abrasive, such as limestone, cement or coal plants. It can be readily understood that from the maintenance standpoint, it is not suitable for hard abrasive materials such as refractories and aluminum oxides. One common type of impactor is shown in Fig. 2. The bottom of this type crusher is entirely open and the passage of the material through the crushing chamber is almost instantaneous. Liberal clearances are maintained between the impact hammers and the anvil type breaker blocks. This eliminates practically all attrition. It is the elimination of attrition that makes the impactor particularly adaptable for reducing hard, abrasive materials. The impactor is also well suited for the reduction of wet or frozen materials, which clog an ordinary Hammermill. Particles broken by impact, when examined under the microscope, show a distinct tendency toward rough, cubical shape, with a minimum of fines. Another important factor in impact crushing is that crushing is accomplished along natural cleavage lines, thus freeing foreign ores or materials.

Jan 1, 1952

ARIZONA Tucson University of Arizona, Mining Engineering Society. B CALIFORNIA Berkeley University of California, Mining Asso. B University of California, Library. T Los Angeles Chamber of Mines and Oil. B Southern California Local Section. T Public Library. T Oakland Oakland Free Library. T San Francisco California State Mining Bureau. T Mining and Scientific Press. B Stanford University Stanford University Geological and Mining Society. B

Jan 1, 1917

By W. D. MOTTER

THE following brief description of the status of operations of the Chile Exploration Co. at Chuquicamata, Chile; and of the plant as it exists today, points out the-great progress that has been made since the initiation of prospect drilling in 1912. During the 11 years which have elapsed since then, a group of small mines, eking out a 'precarious existence, has been consolidated into one large operating property,, taking high rank among the world's producers of copper. After a drilling campaign followed by a construction period, the plant first started operations in 1915. Since then production has been gradually increased, as world conditions permitted, until the present status has been reached.

Jan 1, 1924