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By Yoshinao Nakada

In many experiments involving electropolishing such as electropolishing during deformation and electrothinning of deformed metals for electron microscopy, it is usually assumed that the specimen temperature is the same as the temperature of the polishing bath. In order to test this assumption, the interior temperature of aluminum single and polycrystals was measured while they were being electropolished. Specimens were 1/4 by 1/4 by 6 in. and were of 99.99 pct purity. A small hole 1 in. deep was drilled axially at one end of the specimen so that a copper-constantan thermocouple could be inserted. The electropolishing solution was 4 parts methanol (reagent grade) and 1 part perchloric acid (70 pct). The electropolishing was performed using an apparatus shown in Fig. 1. The electropolishing solution was stirred by a motor-driven stirrer and was cooled to —5°C with a mixture of methanol and dry ice. Electrolyte temperature was measured and remained at -5°C during the electropolishing. Current density of 0.3 amp per sq. cm was used. When the current was turned on, after about a 5-sec delay, the temperature began to rise rapidly until it reached 65°C. In order to determine whether the temperature measured was localized, the thermal expansion of the specimen was meas-

Jan 1, 1965

By N. Albon, J. F. Miller, R. W. Coutant

The deposition of nickel from nickel carbonyl onto amorphous substrates has been studied, with attention being paid to the specific effects of the physical and chemical nature of the substrate and to the effect of oxygen on the crystal morphology. With substrates having microscratches or etch lines, nu-cleation was observed to occur preferentially at these surface features. Flame polishing of the substrate surfaces was found to remove any regularity in preferred nucleation sites. Nucleation was observed to occur less readily on substrates having relatively low surface energies, e.g., Teflon and carbon, than on materials having relatively high surface energies such as fused silica. At low oxygen concentrations [Ni(CO)4/O2 > 54 x 1031, apparently pure and well-formed nickel crystals were observed to nucleate and grow irrespective of the presence of oxygen. At higher concentrations of oxygen, a secondary growth process, dependent upon oxygen concentration and resulting in a gradual change in crystal morphology, was observed. It is concluded that the influence of oxygen on the nucleation and growth of nickel is determined by the relative kinetics of the various possible reactions, and that under the experimental conditions employed the 0-Ni interaction occurs at some nucleation or prenuclea-tion stage. THE purpose of the research on crystal nucleation in chemical vapor deposition as described in this paper has been twofold: 1) to examine some effects arising from the use of amorphous substrates, and 2) to study the specific effects of oxygen on the nucleation and growth of nickel in a nickel carbonyl-carbon monoxide system. The nickel-nickel carbonyl system was chosen for study for several reasons: 1) nickel films are of potential interest in electronic technology, and 2) the deposition can be carried out at moderate temperatures, thus making possible detailed study of the processes occurring and the use of a variety of substrate materials (including some which melt at relatively low temperatures). Fairly well-characterized chemical kinetics and a broad background of information are available on the py-rolysis reactions and on the mechanisms of Ni-O interactions. NUCLEATION AND GROWTH THEORY The theoretical background for the analysis of nucleation and growth by vapor deposition for a one-component system (physical vapor deposition) and the problems encountered therein have been reviewed by Hirth and pound.' More recently Mande12 has indicated the difficulties of applying such theory to chemical systems. One of the major problems involved is the possible multiplicity of chemical reactions and deposition routes. For example, those reactions which are probably of significance in a discussion of the pyrolytic deposition of nickel from nickel carbonyl under the conditions of the present experimental work are illustrated in Fig. 1. As is true with most cases of chemical deposition, many of the quantitative data necessary for a complete analysis of the system are either not available or not directly measurable. However, with the present system, sufficient data are available for a discussion of nucleation and growth on a qualitative basis. Classically, the rate of nucleation of a monatomic species being deposited from a vapor phase is given by

Jan 1, 1965

By Robert E. Barieau

In the design of plants to separate helium from natural gas, it is necessary to estimate the enthalpies of the various streams at various positions in the process. This Bureau of Mines report surveys the various methods that have been used to determine enthalpies and gives information on the organizations with such capabilities. The minimum information required for developing an enthalpy diagram is presented, and the relative merits of the various methods are discussed. It is concluded that methods that require no mass flow rate or energy measurements are to be preferred.

Jan 1, 1965

By R. B. Anderson

SULFUR poisoning of iron catalysts in the Fischer-Tropsch synthesis was investigated at the Bureau of Mines, because synthesis gas produced from coal contains sulfur compounds. Tests of two typical iron catalysts with synthesis gas containing known concentrations of H2S were made to determine catalyst life as a function of sulfur concentration to ascertain the type of gas purification required. Fixed beds of activated steel turnings and a fused iron oxide catalyst were investigated in sulfur poisoning tests at 21.4 atmospheres with IH2+100 gas containing 6.9, 23, or 69 mg S as H2S per cubic meter (0.3, 1.0, and 3.0 gr per 100 cu. ft.). In tests of reduced catalysts at constant temperatures, more than 80 percent of the activity was lost when 0.5 mg S/g Fe was introduced. Poisoning of nitrided or carbided fused iron oxide catalysts to a given extent required more than twice as much sulfur than for the corresponding reduced catalyst. When the synthesis temperature was increased to compensate for loss in activity, tests of the fused iron oxide catalysts at constant productivity could be continued for 19 to 98 days. The tests were terminated by clogging of the reactor, presumably caused by carbon deposition. One objective of the present work was to determine if synthesis gas, purified by the Bureau of Mines' hot-potassium carbonate process for removing H2S, OOS, and CO2, is suitable for synthesis on iron catalysts. The sulfur content of the gas purified by tills process is in the range of concentrations used in the present work. In constant-productivity tests of nitrided fused iron oxide catalysts with synthesis gas containing 6.9 mg S/m3, catalyst lives are nearly long enough for serious consideration of tills mode of operation. However, factors relating to selectivity and stability of the catalyst indicate that this type of operation is impractical for a commercial process. On this basis additional gas purification, such as iron oxide boxes following a hot potassium carbonate scrubber, is desirable.

Jan 1, 1965

By T. D. Oulton

The only known attapulgite clay deposits of any considerable extent and purity in the United States are roughly bisected by the Georgia. Florida state line between Decatur County, southwest Georgia, and Gadsden County, northwest Florida. Although attapulgite clay occurrences both farther East and South are known and have been mined to some extent in the past, at the present time it can be said that substantially: all of the commercial attapulgite clay mining and pro¬cessing is concentrated in a roughly rectangular area some 25 miles long by 15 miles wide,, in the general region of Attapulgus, Georgia, and of Quincy and Havana, Florida. Within this area are located the clay processing plants of the four major producers as well as most, if not all, of the currently active mining operations. The approximate location of the plants and of some of the open mines are shown in the local area map, Figure No. 1, for the purpose of orientation only.

Jan 1, 1965

By N. J. Grant, B. C. Giessen, Paul Predecki

ALLOYS of gold, silver, and aluminum with elements of the groups BII, BIII, BIV, and BV were prepared by a rapid quenching technique (splat) and were examined by X-ray diffraction. Five new intermediate phases were found and will be described briefly herein. For the gold and silver systems, the concentration ranges having an electron/atom ratio e/a of 1.4 to 1.5 ("3/2 Hume-Rothery phases") were studied primarily. Master alloys were prepared from high-purity metals (99.9+ pct or better) by melting either in evacuated fused silica capsules or by nonconsum-able-electrode arc melting in an argon atmosphere. Small pieces, 20 to 50 mg, of each alloy were blast-atomized to form a splat, by a technique similar to that described by Duwez and Willens.1 The technique used for this study is described in detail in Ref. 2; it utilizes a resistance-heated graphite crucible with a small hole at the bottom, directed toward a metal substrate or quenching plate. The prepared alloy rests over the fine hole, through which it is expelled by an explosion shock wave in the form of fine droplets (1 to 50 µ) of molten metal onto a copper or silver substrate, which is maintained at about -190°C. The resulting very high cooling rates (see Ref. 2 for quantitative measurements) can prevent the process of nuclea-tion and growth in many instances, resulting in the formation of metastable phases. The splat particles were transferred to a GE-XRD5 diffractometer and maintained at -190°C, where they were examined with CuKa radiation. The samples were then allowed to warm to room temperature or were heated to higher temperatures until the equilibrium structures formed. Of fifteen alloy systems considered, nonequi-librium structures were encountered in six; these are described below and summarized in Table I. In the system Au-Sb a metastable £ phase (A3 type, hcp, a = 2.898 + 0.002A; c = 4.731 * 0.004A; c/a = 1.633) was found in the concentration range Au + 13 to 15 at. pct Sb. This phase is isomorphous with the stable phases in the systems Au-Cd, Au-In, and Au-Sn, all at an average e/a ratio of 1.4 to 1.5. The concentration range of one-phase metastable was deduced from the small amounts of supersaturated gold solid-solution phase present in the splat product. It was found that ? could also be retained by splatting onto a substrate held at room temperature: however, decomposed into the equilibrium phases Au + AuSb2 after heating to 200°C for 1/2 hr, or on holding the powdered splatted alloy at 20°C for several months. Calorimetric measurements will be made in an attempt to decide the question whether ? is metastable at all temperatures or whether it is a stable phase at low temperatures. There is evidence that another phase, possibly also close-packed but with a different stacking sequence, can be obtained by rapid quenching of alloys with a different antimony content. Klement, Willens, and Duwez3 reported the existence of an amorphous phase on quenching Au-Si alloys (25 at. pct Si) to - 196°C. They found that on heating to room temperature another phase of unknown crystal structure was formed. This was confirmed (see Table I); however, the new crystalline phase, designated as ?, could also be formed simply by rapid quenching to room temperature, and even was found to exist already in the as-cast Au + 20 at. pct Si alloy. It was found that ? decomposed into Au + Si on the specimen surface at room temperature. This behavior, and the question whether or not there is an equilibrium-temperature region for ?, have not yet been resolved. It is probable that ? (Au + 20 to 21 at. pct Si) is cubic of the -brass type (D81-3) with a = 9.60, + 0.01A and N = 52 atoms per cell [compare 6 (CU-Sn)4]. Except for two very weak lines, the powder pattern of about thirty lines could be indexed on this basis; however, a determination of the atom positions has not yet been attempted. For Au-Ge the C phase was observed at about 21 at. pct Ge as reported by Luo et at.5 Lattice parameters a = 2.876A, c = 4.73,A, c/a = 1.64 were found. In the Au-Pb system, formation of a ? phase was not observed, but in the lead-rich region at 75 at. pct Pb, broad peaks belonging to an amorphous phase were found. The maximum diffracted intensity occurred at 28 = 32.4 deg which is about 1 deg larger than the position of the (111) line of lead (Cuka). For Ag-Pb, an amorphous phase analogous to the one found in the Au-Pb system was observed; this metastable phase exists probably at about 75 at. pct Pb. Since no lead-rich alloys were tested, all alloys consisted of silver + amorphous phase at -190°C. In A1-Ge alloys, line-rich and complex powder patterns were obtained at about 30 at. pct Ge; they bear similarities to those of aluminum and germanium, but are of lower symmetry; the existence of more than one intermediate phase is possible. The authors are grateful to the Kennecott Copper Corp. for Fellowship support, and ARPA (Contract

Jan 1, 1965

By A. J. Kauffman

This study compiles data on the zircon resources of the Pacific Northwest States, Alaska, and California, to determine the productive capability of industrial concerns to make ductile zirconium and hafnium, and to investigate markets for the nonmetallic products of zircon. West coast zircon resources are large but mostly marginal to submarginal. Development of a stable and profitable zircon mining industry on the west coast will depend upon recovery and utilization of the other associated heavy minerals needed by regional and national markets. The west coast has the only completely integrated facility for processing zircon sand to reactor-grade zirconium and hafnium and for making fabricated products from these metals. The future of the zirconium metal industry appears to be good because of increased use of the metal for nuclear propulsion and power-generating plants.

Jan 1, 1965

By Noel Brien, O&apos

General: National Asbestos Mines Limited has operated an asbestos mine and mill near Thetford Mines, Quebec, since 1958. As a result of additional exploration of the orebody in 1962-63, it became apparent that long-range mining plans would have to be revised to allow for a large increase in both ore and waste tonnages. It was decided that the task of checking out possible mine designs could best be analyzed by a computer to obtain data from which an optimum open-pit configuration could be plotted. Object: It was desired to arrive at an optimum open-pit configuration with an over-all pit slope of 45 degrees and a minimum operational width of 200 ft. at the bottom. Calculations were based on assay values from diamond drill holes in cross sections of the mine. The computer's assignment was to select and describe, by coordinates, the optimum cross section for the mine. Mine engineers then assembled the various optimum sections to produce the pit outline. As this would not necessarily result in a practical mining arrangement, the computer also provided alternate solutions,

Jan 1, 1965

Jan 1, 1965

By D. C. Shelton, C. S. Ek

Corneille S. Ek (Assistant Professor in Ore Dressing, University of Liege, Liege, Belgium) — This is a very valuable paper, in that it shows how it is possible to take care of a multitude of laboratory routine tests, and derive from them successful modifications of flowsheets or of operating methods. The author and the Company appear to be test-minded and this is best seen through the case histories described. There are however some corrections to be made, and questions arise when one studies the paper. If all the equations are to be homogenous, one obviously has to write Eq. 4 On the other hand, it is difficult to accept the definition put on Eq. 7, for that equation, which represents the factor of transformation from tpd of solids to cu ft per min of pulp in Eq. 6, has nothing to do with conditioning. It is evidently assumed here that conditioning means, as Gaudin calls it,' modulation of collection. One would prefer, for Eq. 7, the appel-ation "pulp conversion factor". Eq. 8 and 9, giving the amount of reagent to be fed

Jan 1, 1965

Jan 1, 1965

To enable ammonium nitrate-fuel oil (AN-FO) to be used on an equal weight basis with nitroglycerine explosives, smaller diameter bore holes became necessary with consequent modifications to drill steel and burden on holes. Detonation of AN-FO in small diameter holes proved successful both with and without primer charges but some alterations were required to adapt anoloders to the smaller holes.Important factors in training all operators in the new charging method were the retention of improved fragmentation, avoidance of excessive overbreak and keeping wall rock dilution to an absolute minimum. The successful storage of ammonium nitrate in climatic conditions with daily temperature fluctuations above and below the critical 90°F has been achieved.INTRODUCTIONTechnical aspects of ammonium nitrate-fuel oil (AN-Fa) blasting agent are well covered in recent literature. This paper deals primarily with the manner of its introduction as the principal explosive underground at Great Boulder Gold Mines Ltd. and with the many problems encountered in the process. Following reasonably successful experimental firings in June 1962', using granular ammonium nitrate and an anoloder, permission was granted by theWestern Australian Mines Department to carry out test work in selected areas of the mine. The permit allowed for fuse firing only, and for a mixture of AN-Fa containing between 5t and 6 per cent fuel oil, with an adequate primer.The use of AN-Fa on an equal weight basis with nitroglycerine explosives, involved smaller diameter holes with alteration to ground burden and modification to drill steel.Initial tests indicated that it was apparent that AN-Fa could not replace gelignite on an equal weight basis if the...

Jan 1, 1965

By Elmer R. Drevdahl

During the last few years there has been a rapid increase in the development of the community or junior college throughout the United States, Some factors behind this development include the need for more college facilities to service the growing number of high school graduates, the desire of the public to provide some post high school education at reasonable costs, and the need to provide post high school educational opportunities not now provided by most of the universities and colleges. Many of the new community colleges provide at least three educational services including local opportunity to provide the first two years of a four year college program, two year technical-vocational programs of a terminal nature, and adult educational opportunities. The community college has the advantage of not being saddled with years of academic tradition which prevent it from changing to suit the educational needs of the community It serves. The flexibility of the community college in developing new programs, particularly in the technical areas, is going to provide industry with many of the badly needed technicians it is now unable to secure.

Jan 1, 1965

By Larry A. Haas

The Bureau of Mines constructed a torsion effusion apparatus to measure the equilibrium vapor pressure of pure metals, alloys, and compounds at temperatures up to 1,500° K. The reliability of the apparatus was established by determining the vapor pressure of silver. The data obtained on solid and liquid silver in the temperature range 1,200° to 1,500° K can be expressed by the following equations:

Jan 1, 1965

By W A. Bardswich

The numerous factors associated with the prov1s1on of satisfactory air conditions in hot and humid Canadian mines are described. The main heat sources are auto-compression and the actual flow of heat from the rock. Temperatures reach 97°F at a depth of 8,100 feet. Various methods used in coping with high temperatures are described, including the use of ice stopes and heat exchangers. Moisture control, desirable air volumes and velocities, sizes of airways and methods of distribution are important considerations. A comparison of the temperatures, humidities and types of airways of two deep mines should prove useful in the design of future ventilation systems. Introduction OUTDOOR temperatures in northern Ontario vary from a low of around -40°F in winter to a high of about +90°F in summer. The average annual mean temperature over a 12-year period was +35°F, with a summer mean of 54 o and a winter mean of 16°. Because of low outdoor temperatures, a number of northern mines must heat fresh air for underground ventilation in winter; others, with high rock temperatures, are faced with a year-round cooling problem.

Jan 1, 1965

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

HE high vapor pressures of metals such as lead, calcium, lithium, bismuth, and magnesium at steel-making temperatures present experimental problems which have thus far rendered it almost impossible to obtain really reliable data for their solubilities in liquid iron. Many investigators have attempted to equilibrate liquid iron in the same crucible with the undissolved liquid phase of such volatile metals. The published results,l-6 although useful, are often questionable on the grounds of not being obtained under true equilibrium conditions. Such information is not always of practical value in any case since the equilibrium vapor pressure is often several atmospheres and steel is not currently made at these pressures. Solubility measurements at lower partial pressures (< 1 atm) appeared to be more practical and easier to make. These data could be used to calculate solubilities at other pressures where Henry&apos;s Law is obeyed, and to estimate solubilities under other conditions of temperature and pressure with useful accuracy. This note outlines the development of a general technique for the measurement of solubilities in systems of this kind. The method involves equilibration of the high-boiling metal at known temperatures with the vapors of a low-boiling metal at known partial pressures. Analyses of quenched samples provide vapor pressure-solubility data and make calculations of alloy thermodynamics possible. The principle involved is similar to the closed-system diffusion-transport method which is difficult to apply with most high-melting liquid metals like iron, due to closure problems. A two-zone horizontal (molybdenum wire element) tube furnace, Fig. 1, provides two constant-temperature zones in a reaction tuve (3/4 in. ID by 1 in. OD by 36 in.). A high-boiling metal sample, 9, introduced in the higher-temperature zone, is maintained at temperature T1, and a volatile metal sample, 7, in the lower-temperature zone, is held at T2. A stream of argon with 10 pct hydrogen is passed via flowmeters, 1, and mixing-drying towers, 2 and 3. through the reaction tube at a favorable flowrate and acts as a carrier gas which entrains vapor from the volatile liquid metal at a specific constant partial pressure. The gas mixture passes through a system of constrictions, 6 and 8, to the higher-temperature zone, establishes intimate contact with the high-boiling liquid sample, 9, and exits through a small condenser tube. The entire system is at (nearly) atmospheric pressure and the volume of carrier gas passed is measured with a wet gas meter. When the high-boiling sample attains equilibrium with the vapor phase, both samples are removed and quenched. Analysis of the high-boiling sample for solute content reveals its solubility for the low-boiling metal at a vapor pressure calculated from carrier-gas volume and either a) weight loss of volatile metal or 6) weight gain of high-boiling sample plus condenser (which collects the undissolved vapors). To test the capabilities of the method, liquid silver at 1403&apos;C was equilibrated with lead vapor at various partial pressures. The relatively simple Pb-Ag system was particularly suitable for uncovering experimental problems and providing the first step toward investigations with more volatile metals and more difficult combinations.

Jan 1, 1965

By C. H. Schack

Extractive metallurgy techniques currently employed to recover silver from primary ores and secondary scrap were reviewed and evaluated to identify and delineate metallurgical problems whose resolution would increase the supply of silver from domestic materials. The survey revealed that practically all primary silver is recovered by froth flotation concentration of various types of ores, followed by smelting and refining of the separate lead, copper, and zinc concentrates. Silver losses during the complex processing are, with rare exception, inconsequential. Furthermore, any silver production gain from base metal ores, which contribute about two-thirds of the total primary silver, is directly dependent in improvement in the market for the base metals. Statistical data on new and old silver scrap are wholly inadequate to make reliable conclusions about scrap processing problems and the possibility of increasing the recovery of silver from the many forms of secondary silver- bearing materials. The available information indicates (1) that efficient silver reclamation practices are employed by the larger users of silver, and (2) that recovery of additional secondary silver involves solution of problems of collection rather than of processing. Several possibilities exist for limited increases in silver production from primary ores by improvement in metallurgical practices. Specifically, research is needed to (1) solve the problem of recovering silver from the copper ores of the Copper Range district, Michigan; and (2) devise economically feasible methods for recovery of silver from presently marginal or submarginal ores that because of grade, location, and frequently complex nature cannot presently be exploited by conventional techniques.

Jan 1, 1965

By L H. Warren

The types of equipment available for generating a plasma have been reviewed. The efficiency and potential of the plasma generating equipment used in performing extractive metallurgical reactions have been determined. A general classification of the reactions that might be per-formed in a plasma has been proposed. Experimental work done on extractive metallurgical plasma reactions, heat transfer between the plasma and solids, and the quench of the products of plasma reaction has been summarized. From the preliminary results it appears that the high-intensity are or the transpiration-cooled anode plasma torch offer the most promising areas for further research. C ONSIDERABLE world-wide research effort is currently being devoted to the development of processing technologies which employ the new high-temperature generating devices that have appeared over the past few years. The plasma flames produced by these devices offer the potential for subjecting materials to any single gas or mixture of gases at temperatures up to 20,000°K. With these conditions available, many reactions in extractive metallurgy,

Jan 1, 1965

By T. C. Davis

Nine organic derivatives of fluorine, silicon, boron, and aluminum were purified for thermodynamic studies using distillation, zone melting, and gas liquid chromatography, The unusual properties of these compounds required the development of special techniques for handling and purification. To determine purities of purified samples, new techniques for analyzing spectral data were developed.

Jan 1, 1965

By J A. Gilliand

Mineralogical cross sections of orebodies on the 300-,600- and 900-foot levels of the Coronation mine have been interpreted in terms of centers of mineralization. The maximum concentration of chalcopyrite occurs closest to these centers, with pyrite and pyrrhotite concentrated some distance away. The magnetite concentrations are farthest removed from the centers. A hydrous halide fluid model is established. Attempts to explain the observed mineralogy by the action of temperature gradients on the fluid model were unsuccessful. Likewise, the action of diffusion alone on the fluid model cannot explain the observed mineral distribution. The concept of attenuation is introduced-i.e., the rate of diffusion of a particle species is related to the product r2 I/ M, the attenuation coefficient, where r is the particle radius and M its molecular weight. Attenuation, acting on the fluid model alone, will not produce the observed mineral distribution, but, when considered together with the action of temperature gradients, the observed mineralogy can be well explained by the combined effects of these two processes on the assumed fluid model.

Jan 1, 1965