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Jan 1, 1970

By A. G. Guy

In a special type of electrodiffusion experiment the entire specimen is at constant temperature. The vacancies are then created at one end of the specimen and flow to the other end where they are destroyed. The energy required to operate the corresponding sources and sinks results in a super saturation of vacancies at one end of the specimen and an under -saturation at the other end. This gradient in vacancy concentration produces a chemical-diffusion flux, J(D), of vacancies in addition to the flux, J(E), caused by the electric current. Using the experimental data of Ch. Herzig,5 it is shown that a super saturation of 1 pct can cause J(D) to be about 25 pct of J(E), and thus account for the anomalous behavior of short specimens. THERE are advantages in a phenomenological treatment as contrasted to an atomistic one. For example, there are many reactions involving the element copper that are quantitatively and usefully understood from a phenomenological viewpoint, even though electron theory is not yet able to predict whether copper should be fcc or cph.' Similarly, the lack of a complete atomic theory of vacancies need not prevent the development of a treatment based on thermodynamics and chemical kinetics. In the following discussion, models will be used for the vacancies and for the mechanisms by which they move or are created or destroyed, but the phenomenological treatments are not dependent on the details of these models. The important product of a phenomenological analysis is an equation that describes the relation among the measurable quantities determining the behavior of the system. Based on such an equation, experiments can be performed to study these quantities in detail. Eventually atomic theory will supply an adequate theoretical base for the phenomena in question. A chemical species whose chemical potential was invariant during reactions in binary and ternary systems of varying composition would indeed be an anomaly. Yet this is the role that has frequently been assigned to the vacancies in pure metals, in dilute solutions, and even in ordinary alloys. The weight of available evidence supports the view that supersatu-rations of vacancies are on the order of 1 pct in usual diffusion processes.' Although it may seem strange that such a small deviation from equilibrium could significantly affect the thermodynamic properties of the vacancies, it is well known that the driving force for an ordinary chemical reaction is the departure of the components from their equilibrium state. Similarly, the reaction of vacancies that results in the formation of pores in various types of diffusion3 can reasonably be attributed to the supersaturation of vacancies. In the present paper, it will be shown that small degrees of supersaturation can significantly affect the kinetics of the diffusion process itself. ISOTHERMAL ELECTRODIFFUSION Two different experimental techniques are convenient for studying the behavior of vacancies in a pure metal in the presence of an electric field. Gilder and Lazarus4 studied self-electrodiffusion in a gold specimen in which only the central portion was at high temperatures. In this case the significant vacancy sources operate inside the specimen in the presence of a temperature gradient. In the laboratory of Th. Heumann a method has been devised for studying self-electrodiffusion at constant temperature.5 In principle, there is then no effect of thermodiffusion. It will now be shown why in this case the significant ATungsten disks \^^ ^^ ^Gold disks^^ ^^"T>.... "TTZA ? Up Iy'7 markers ///// ////// initial plane p I y/y/y of joining \I 7//// V7//A_________I_________V//// -I 0 +I Distance from center of specimen (a) -— Direction of flow of electrons —Direction of flw of vacancies %yy} Matano I z~irkendall /%W, vy/A inlerfacej "interface ///// -} HfiK- +/ 0 Distance from center of specimen (6) Fig. 1—-Schematic illustration of the essential features of isothermal self-electrodiffusion. (a) Initial condition of specimen. (b) Condition of specimen after electrodiffusion.

Jan 1, 1970

By I. D. Shah

The Bureau of Mines investigated the sequence of principal chemical reactions taking place during the roasting of covellite (CuS). Practically all covellite is converted to digenite (Cul.SS) before oxidation to Cu20 begins. Part of the Cu2O is then converted to CuO, which in turn forms CuS04 through CuO?CuS04 as an intermediary. CuS04 and CuO'CuS04 decompose at 600° to 700° C to yield CuO and S03 (g) as final products. An overall mechanism is proposed for chemical reactions occurring at different interfaces of partially oxidized CuS pellets.

Jan 1, 1970

By Fathi Habashi

THE CHOICE of a precipitant for a certain metal ion depends, beside the economic factor. on the following factors: 1) The precipitant should be specific as far as possible so that pure precipitates can be obtained

Jan 1, 1970

By E. Miller, N. Chou, K. Komarek

The solid solubilities of the compounds PbS, PbSe, and PbTe have been determined by equilibrating single crystals with two phase alloys. The solubilities were determined by measuring the Hall coefficient of the equilibrated samples. The observed maximum deviations from stoichiometry on the lead rich and the chalcogen-rich side of the phase fields were: at. pct excess Pb at pct excess S at 850°C; PbSe--4 x 10'" at. pct excess Pb at at. pct excess at 800°C; and PbTe-2.8 x 10 4 at. pct excess Pb at 780°C, 10"1 at. pct excess Te at 720°C. The previously developed theory of retrograde solubility has been expanded to include intrinsic disorder in the compounds, and the experimental results are in agreement with the theory. THE solid solubility limits of intermetallic semiconducting compounds are of considerable interest, since many of these compounds have potential use as thermoelements in thermoelectric devices, as infrared detectors, or in semiconductor devices. The solidus curves of a significant number of these compounds have been reported to be retrograde with the maximum solid solubility occurring between the eu-tectic and the maximum melting temperatures. In a previous paper,' equations were derived which permit calculation of the maximum solid solubility of an AB compound exhibiting retrograde solubility. Derivation of these equations was based on the assumption that the compound is a nondegenerate semiconductor at the temperature under consideration, that the defects were unassociated, and that the vibrational contribution to the entropy of the compound could be evaluated by the Einstein approximation. It was shown that at the temperature of the maximum solid solubility The entropy term ASS is composed of the entropy of formation of the solid stoichiometric compound (AS$)*, and the entropy due to deviations from stoichiometric composition which is the sum of a con-figurational term (aS*), a vibrational term (AS,), and an electronic term (AS,). In the previous paper the positional entropy was evaluated considering the con- N. CHOU, Member AIME, formerly Graduate Student, New York University, N. Y., is with IBM, Yorktown Heights, N. Y. K. L. KOMAREK, Member AIME, formerly with New York University, is Professor, Department of Inorganic Chemistry, University of Vienna, Vienna, Austria. E. MI LLER, Member AIME, formerly with New York University, is Associate Professor of Mechanical Engineering, California State College at Long Beach, Calif. The paper is based on a thesis submitted by N. CHOU to the Graduate Division, School of Engineering and Science, New York University, in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Materials Science. tributions from defects arising from deviations from stoichiometric composition. The derivation is generalized in the appendix to include intrinsic disorder. The electronic entropy term is also recalculated in the appendix. Of the various semiconducting compounds, the solidus curves of Pbs,' and ~b~e,~ have been most extensively studied. The solidus of PbSe has also been determined, but the temperature of maximum solubility has not been accurately established.5129 The present investigation was undertaken to compare the experimental solid solubility data for these systems with the values predicted theoretically. Since the temperature and composition of the maximum solubility of PbSe has not been accurately determined, experimental emphasis was placed on determining the solidus curves for PbSe in the region of maximum solubility, although experiments were also performed on PbS and PbTe at several temperatures. X-ray diffraction studies were also made on carefully prepared powder samples of PbSe to determine the variation of lattice parameter with composition. EXPERIMENTAL PROCEDURE The procedure of Brebrick and Allgaier was employed for determining the solidus data. Monocrystal-

Jan 1, 1970

By M. M. Fine

Chalcocite flotation concentrates (26-34 percent Cu and 6-7 percent S) were roasted in air to determine sulfur elimination as a function of temperature, airflow rate, and residence time. Fluosolids roasting was evaluated batchwise and continuously in a 4-inch fluid-bed reactor. Kiln roasting tests were carried out in a 4-inch ID by 6-inch-long rotary drum. Pelletizing the very fine concentrates prior to roasting was essential to minimize dust losses and accretions. Concentrate pellets, sized minus 10 plus 20 mesh and bonded with 2 percent bentonite, were excellent feed for fluosol¬ids roasting and limited dust losses to 10 percent or less. One-fourth-inch pellets were best suited to kiln roasting. Both techniques were capable of producing copper calcines analyzing well under 1 percent residual sulfur when operated at 900° C with average retention times of 3 to 4 hours. Calcined pellets were strong, porous, and readily reducible.

Jan 1, 1970

Jan 1, 1970

By Sadao Maruyama

INTRODUCTION Since the big discovery of Kuroko deposits in Kosaka mine, Akita Pref., northeastern Japan in 1959, major Japanese mining companies have been engaged in extensive exploration for the deposits expending large amounts of money. Above all their exploration activities have been particularly fruitful in discovering new deposits in northern Akita Pref. It is estimated that the total ore reserves newly found in the area are at least 50 million tons. Kuroko deposits are the most important ore source of copper, lead and zinc in Japan and have been mined since last century in the said area. Kuroko (black ore) is fine, compact aggregates with sphalerite , glena and barite as principal constituents and chalco- pyrite, pyrite and tetrahedrite as subsequent constituents. The name Kuroko comes from its appearance. It is not rare that total grade of copper, lead and zinc reaches 20 - 30% and the gold and silver content is also fairly good. Accordingly the unit value of the ore is much higher than the ore from other types of deposits. Besides the Kuroko ore, the Kuroko deposits consists of Ohko (yellow ore, massive cupriferous pyritic ore), Keikoh (silicious ore, cupriferous network ore) and gypsum ore. This type of deposit is considered to be not only an important source of base metal but also a source of gypsum and barite. Although the importance of this type of deposit had been commonly recognized, sub-surface nature of the occurrence hampered exploration work. In recent years the improved exploration techniques and increased knowledge of the Kuroko deposits have met with remarkable success in the location of new deposits. This outburst of exploration and dis-

Jan 1, 1970

By Manuel Gomez

The purpose of this study was to evaluate the feasibility of using statistical response surface regression analysis to predict the sulfur and ash distributions and the washability characteristics of coal along a seam in advance of mining. Prediction equations were developed with experimental data from channel, bench, and core samples from the Pittsburgh coal seam in Greene County, Pa. It was not possible, with the available experimental data, to construct mathematical models to predict ash and sulfur concentrations between sample points. In the authors' opinion, however, the good agreement between experimentally determined and predicted values at given sample points demonstrates the usefulness of the method. More input data, such as geologic information, seam characteristics (rock-to-coal ratio), petrographic analysis, and chemical data, would perhaps make it possible to predict sulfur and ash concentrations and washability characteristics between sample points.

Jan 1, 1970

By Morris Cohen, Robert C. Ruhl

The phases in Fe-C alloys over a wide composition range have been studied after splal quenching from the liquid state. Binary alloys containing 0 to 5.1 wt pel C as /cell as a large number of ternary Fe-C-Si alloys with 2.5 to 5.0 wt pct C and 0.3 to 5.1 wt pct Si were attlong those sludied. Olher Fe-C-X alloys, zcilh X being Co, Cr, ,Wn, Ni, and Ru , were also inrestigated after splat quenching. At high carbon contents, a new hcp phase (designaled 6 phase, but different from e carbide) is retained upon splat quenching. The .fraction of this phase varies up lo 97 pcl for a Fe-4.K-1.9% alloy. The composition of the E phase ranges from about 3.8 10 4.8 wt pet C, and the corresponding laltice parameters increase linearly ulith carbon content, while the c/a ratio remains essentially conslc~nl. The E phrtse appears to he a solulion of carbon in E iron, the latler being nornially found only at high pressures. It is deduced that the unit cell of the E phase corresponds to the formula Fe12C3, and llzal il is relaled to tlie ordered slruclures 0.f 6 iron carbide and c iron nilride. The E phase is compared and contrasted to the olher known carbides and nitrides of iron and nickel. An exlrapolaTion of the atomic volume 1,s carhon conlent of /he E pllase lzcts giz.en a neu7 estitnale jor /he alomic volume of E iron, 11.30 cu A, a1 atmospheric pressure and temperature. Other alomic volume relalionships lead to /he co~zpositioti Fe2.iC tor E iron carbide, /he unit cell fortr~ula being -Fe2rClo The E phase undergoes a lulo-slage decomposition upon healing, .forrning firsl rnarlensile plus E carhide, a/ler 1 hr at 140" lo 200°C, slid then ferr ite Plus cementile, after 1 lir a1 330" to 460°C. A1 carbo,l contents between 1.5 and 3.0 LC/ pcl, (he predo.wirzar/t plzase alley quenching is fcc austenite. The retained carbon content of this phase increases with itlcreasing silicon in certain concentration ranges, reaching a maximum of 2.37 wt pct C itz a Fe-2.6C-4.OSi alloy. This is the highest carbon conten1 reLaitled in austenite to date. These high-carbon aus-tenites can be partially tm?zsforttled lo tnartensile hy severe deformation in the temperature range of — 190 to -50°C. TECHNIQUES for splat quenching from the liquid state have been utilized in numerous recent investigations to produce metastable phases in a variety of alloy systems. Among the several ways of splat quenching, the shock-tube method appears to yield the highest cooling rates1-3, 7, 8 and was adopted here. Estimated cooling rates attained in the present experiments ranged from 10' to 10 80Cper sec.' As a part of a research program on interstitial al- loy phases, the Fe-C system was selected for splat-quenching studies. It was hoped that splat quenching would allow high metastable supersaturations of carbon to be retained in solution. Also of considerable interest were the conditions governing the occurrence of the various intermediate phases upon solidification. The alloys investigated included both binary Fe-C compositions as well as six ternary Fe-C-X alloy systems. The known phases in the Fe-C system are summarized in Table I.* Only the ferrite and graphite are ent investigation.14 and is described in detail herein Table II summarizes corresponding data on Fe-N phases, which are also of interest here because of their similarity to the Fe-C phases. EXPERIMENTAL PROCEDURES Alloys were prepared by melting the elements. 99.9 pct purity, in an inert gas nonconsumable electrode arc furnace. The buttons. weighing about 5 g. were remelted twice. were then fragmented. and their interior surfaces were examined for uniformity: if any doubt existed. they were remelted again. Chemical analyses were performed on all the alloys. the accuracy being about k0.05 wt pct. At high temperatures, carbon-containing alloys react with alumina crucibles as follows: If the atmosphere in the splat-quenching furnace does not contain sufficient carbon monoxide the alloy can be depleted of carbon and contaminated with aluminum. Calculations and experimental observations showed that 50 to 100 torr CO partial pressure effectively blocked the above reaction in all the alloys investigated. The splat-quenching equipment in Figs. 1 and 2 provides for evacuation and back-filling with CO-Ar mixtures. The furnace is capable of operation up to 1650°C. and the gettering action of the graphite heating element reduces the oxygen partial pressure in the furnace atmosphere to below 10-5 torr, thus preventing oxidation of the specimens.

Jan 1, 1970

By Willaim A. Berg

Vegetative stabilization can help meet the esthetic objections and pollution problems posed by mine wastes. However, mine wastes are often unfavorable growth media and special treatments and techniques are needed for plant establishment and continued growth. The establishment of vegetation on mine wastes was the subject of many papers presented at the International Symposium on Ecology and Revegetation of Drastically Disturbed Areas held at Pennsylvania State University on August 3-16, 1969. This paper is a summary of those papers presented at the symposium that dealt with the nutritional and physical aspects of plant establishment on a variety of mine wastes. The synopsis presented is a combination of excerpts from the abstracts, notes on the oral presentations, and rough drafts of some of the papers. The papers will eventually be published in the symposium proceedings.

Jan 1, 1970

By C. J. Chindgren

A refractory-lined, garage-type automobile incinerator with a natural gas afterburner for air pollution control was cooperatively constructed and tested by the Bureau of Mines and the Wasatch Metal & Salvage Co. in Salt Lake City, Utah. The incinerator is capable of relatively smokeless burning of 32 to 60 cars per day, dependent on the degree to which the cars are stripped prior to incineration. Preliminary burning campaigns indicate the cost of incineration to be approximately $2.75 per car.

Jan 1, 1970

By Paul G. Mahoney

The original Radum aggregate plant, built by Henry Kaiser in 1931, is the oldest of the nearly 200 individual operations established by the Kaiser companies. Since that time it has been producing aggregate products primarily for the San Francisco Bay Area. Currently, and for many years, this plant has been listed as the Nation's No. One aggregate producer. Early this year a new $10,000,000 facility went on line replacing the old plant. Construction of the facilities was performed under the direction of Kaiser Engineers construction management teams. The existing plant continued to operate without interruption during the entire construction period.

Jan 1, 1970

Average annual growth in consumption of primary energy in Australia over the past ten years has been 5.5% compared to a world average of 4.1%. Over the next ten years growth rate is expected to increase to 6% per annum due largely to the rapid development in the mineral processing industry. By the end of the 1970's natural gas is expected to supply more than 9% of Australia's, primary energy market. Coal will supply 40% and petroleum products 47%. Nuclear energy will make its appearance but-will only make a small contribution in the period. Australia has adequate reserves of natural gas and coal to supply its needs in the 1970's and beyond. However the newly developed reserves of crude, while supplying 60-70% of requirements-in the initial years; will need regular and sizable additions if they are to .keep pace with the expanding consumption. For Australia to become self sufficient in the period 1970-1990 it is estimated *that new discoveries-will need to approximate. ten times the volume of recoverable reserves found in Australia to date. .

Jan 1, 1970

By P. Dosmond

In ore mining technology, the loading and hauling operations are undoubtedly the area where the most spectacular progress has been made during the last twenty years. In the iron ore mines of Eastern France production of 62 million tons for 1962 and 19863 constitute a worthwhile experience worldwide. These deposits which are located in Lorraine are of sedimentary origin and they contain many mineralized horizons with workable seams varying in depth from 330 to 830 ft.

Jan 1, 1970

By L. B. Pankratz

Enthalpies above 298° K were determined for AgCl to 1,400° K and for AgBr to 1,200° K by copper-block calorimetry. Before melting, both compounds showed an anomalous increase in enthalpy, an effect associated with lattice defect formation. Melting points and heats of fusion were determined to be AgCl, 730° K and 2,945 cal/mole; AgBr, 700° K and 2,030 cal/mole. The heat capacity of both melted substances decreased with increasing temperature over the entire liquid ranges investigated. Enthalpies above 298° K were tabulated at even temperatures along with derived entropy increments and heat capacity values. The results were combined with the known heats of formation and entropies at 29.8.15° K to obtain values of the heats and free energies of formation over the range 298.15° to 1,400° K for AgC1 and 298.15° to 1,200° K for AgBr.

Jan 1, 1970

By M. Metzger, J. C. Bilello

Microyielding in 99.999 pct Cu occuwed in two distinct parabolic microstages and was substantially indeoendent of grain size at the relatiz~ely large grain sizes stzcdied. The strain recouered on unloading was a significant fraction of the forward strain and was initially higher in a copper-coated single crystal than in poly crystals. Results were interpreted in terms of cooperative yielding and short-range dislocation motion activated otter a range of stresses, and a formalism was given for the first microstage. It was suggested that models involving long-range dislocation motion are more appropriate for impure or alloyed fcc metals. THERE are still many unanswered questions concerning the degree and origin of the grain size dependence of plastic properties. In the microstrain region, a theory of the stress-strain curve proposed by Brown and Lukens,' based on an exhaustion hardening model in which the grain boundaries limit the amount of slip per source, accounted for the variation with grain size of microyielding in iron, zinc, and copper.' This theory assumes N dislocation sources per unit volume whose activation stress varies only with grain orientation. Dislocations pile-up against grain boundaries until the back stress deactivates the source, which leads to a relationship between the axial stress and the strain in the microstrain region given by: where G is the shear modulus, D the grain diameter, a the flow stress, and a, is the stress required to activate a source in the most favorably oriented grain.3 If this or other grain-boundary pile-up models are correct, then the reverse strain on unloading would be much larger for a polycrystalline specimen than for a single crystal. Also, the microplasticity would become insensitive to grain size if this could be made larger than the mean dislocation glide path for a single crystal in the microregion. These questions are examined in the present work on polycrys-talline copper and a single crystal coated to provide a synthetic polycrystal. EXPERIMENTAL PROCEDURE Tensile specimens 3 mm sq were prepared from 99.999 pct Cu after a sequence of rolling and vacuum annealing treatments similar to those recommended by Cook and Richards4-6 to minimize preferred orientation. Grain size variation from 0.05 to 0.38 mm was obtained by a final anneal at temperatures from 310" to 700°C. Dislocation etching7 revealed pits on those few grains within 3 deg of (111). For all grain sizes dislocation densities could be estimated as -107 cm per cu cm with no prominent subboundaries. The single crystals, of the same cross section, were grown by the Bridgman technique with axes 8 deg from [Oll] and one face 2 deg from (111). An anneal at 1050°C produced dislocation densities of 2 x 106 cm per cu cm and subboundaries -1 mm apart in these single crystals. A Pb-Sn-Ag creep resistant solder was used to mount the specimens, with a 19 mm effective gage length, into aligned sleeve grips fitted to receive the strain gages. All specimens were chemically polished and rinsed8 to remove surface films just prior to testing. The synthetic polycrystal was made by electroplating a single crystal with 1 µ of polycrystalline copper from a cyanide bath. Mechanical testing was carried out on an Instron machine using two matched LVDT tranducers to measure specimen displacement, the temperature and the measuring circuit being sufficiently stable to yield a strain sensitivity of 5 x 107. At the crosshead speeds employed, plastic strain rates were, above strains of 10¯4, about 10¯5 per sec for polycrystalline specimens and 10-4 per sec for the single crystals. Plastic strain rates were an order of magnitude lower at strains near l0- '. A few checks at strain rates tenfold higher were made for reassurance that the initial yielding of polycrystalline copper was not strongly strain-rate dependent. Test procedures followed the general framework outlined by Roberts and Brown.9,10 An alignment preload of 8 g per sq mm for polycrystals, and 2 to 4 g per sq mm for single crystals, was used for all tests. These gave no detectable permanent strain within the sensitivity of the present experiments; although at these stress levels, small permanent strains are detectable in copper with methods of higher sensitivity.11 12 stress and strain data are reported in terms of axial components. RESULTS General. The initial yielding is shown in the stress vs strain data of Fig. 1. For polycrystals, cycle lc, the loading line bent over gradually without a well-defined proportional limit, and almost all of the plastic prestrain appeared as permanent strain at the end of the cycle. The unloading curve was accurately linear over most of its length with a distinct break indicating the onset of a significant nonelastic reverse strain at the stress o u, indicated by the arrows. The yielding in subsequent cycles, Id and le, had the same general character. The single crystal behavior, shown to a different scale at the right of Fig. 1, was different in that initially the nonlinear reverse strain was unexpectedly much greater than for polycrystals. It should be noted that these soft crystals had a small elastic

Jan 1, 1970

By H. V. Fairbanks

This report covers a study of three different methods for drying ultrafine coals by sound waves. Ultrafine material is classified as coal which passes through a 100-mesh sieve. During the investigations, it was found that the addition of acoustic radiation to the drying of ultrafine coal is effective in increasing the rate of drying; the effect of acoustic radiation to improve drying decreases with an increase in the temperature of the system; the drying rate increased 10-40% when acoustic radiation was introduced into a rotary kiln but was dependent upon the environmental conditions; the application of vertical vibrations to multi-tiered drying screens increased the rate of moisture removal ten times over that obtained in the rotary kiln; the formation of coal balls in any of the drier systems retards the rate of drying; the higher the initial moisture content of the coal the greater the amount of coal balls formed.

Jan 1, 1970

Jan 1, 1970

By John V. Beall

If there is one thing that makes a fellow feel like the years are catching up with him, it is to go through a second cycle in which the adequacy of mineral resources is being "viewed with alarm." The first time we experienced such a flap was in 1951. At that time, the United Nations convened a meeting at Lake Success to study ways and means of averting a crisis in minerals. Presently there is some sentiment being expressed about the mineral scarcities that will occur in the decades ahead, in view of world population trends and increasing per capita consumption of metals. To be greatly concerned about the adequacy of metal supplies is to be highly pessimistic about the capabilities of technology. As in the past, shortages will be of temporary duration for as far ahead as the most ambitious prognosticators are projecting. The study of mineral economics is a fascinating and surprising subject. The law of supply and demand is but a starting point. The iron ore market for the steel industry is an example which comes to mind because of our receipt this week of the United Nations report "Survey of World Iron Ore Resources."

Jan 1, 1970