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By Gary A. Kingston

This examination of Pacific Northwest (Idaho, Montana, Ore on, and Washington) ferrous scrap-industry opera ions, principally those in Oregon and Washington, points out factors influencing the supply and consumption of scrap materials, such as the complete dependence of steel ingot producers in these States on scrap as a metal raw material and the sizable quantity of scrap exported from Seattle and Portland to Japan. The pattern of the industry is presented as a movement of materials from their diverse sources to the consuming market. The geographic locations of the consuming industries in relation to the area generating scrap materials and the movement pattern of the supply from source to destination strongly influences the cost of the commodity. The best measure of the scrap supply available in an area is experience in terms of how much scrap was withdrawn at a given price. Scrap availability is not finite, because the return of materials as scrap is secular and influenced by constantly varying market conditions. Steel ingot producers use 75 percent of the approximate 500,000 tons of scrap consumed in Oregon and Washington; steel foundries take 15 percent of the total; and iron foundries, ferroalloy plants, and other miscellaneous consumers utilize the remainder. Also, from 1955 to 1960 an average of about 200,000 tons has been exported annually from Oregon and Washington. The foreign exports are supplemented by lesser .shipments to other steel producing States, principally in the western United States. From 1955 to 1960 the preferred and higher value heavy melting scrap grades accounted for about 60 percent of total withdrawals which varied between 600,000 and 950,000 tons annually. Total scrap withdrawals from Oregon and Washington are projected to 1.8 million tons by 1985, 60 percent (1.1 million tons) of which will be heavy melting grades. No. 1 heavy melting scrap is most attractive to scrap consumers at $35 per ton or less. Price-supply relationships compared with projected scrap requirements indicate future prices possibly over $35 per ton. High prices over a long period could motivate the Pacific Northwest scrap consumers to produce steel from iron ore. However, technologic changes taking place at integrated steel plants could reduce scrap withdrawals from the Pacific Northwest, which might keep the scrap price sufficiently attractive to obviate production of competitive iron products by the Pacific Northwest scrap consumers.

Jan 1, 1964

By D. E. Etter, J. E. Selle

HIGH-PURITY cerium metals, supplied as 99.9 pct pure, by various suppliers, vary widely in melting points and in the shapes of the differential thermal-analysis curves obtained as the samples are heated. A definite correlation is noted between the melting point, amount of premelting, and the number of inclusions present in the material. Briefly, the DTA apparatus, previously de-

Jan 1, 1964

By M. H. Pilkuhn, H. Rupprecht

The junction luminescence of GaAsxP1-x diodes containing up to 47 pct Gap was studied. Diodes were prepared by diffusing zinc into n-type material which was eithw boat- or vapor-gvown. Observations concerning the energy and the line shape of the spontaneous emission are presented and discussed; in particular the influence of inhomogeneous phosphorus distribution is considered. The role of reabsorption of the junction radiation is pointed out. With increasing current, the peak emission shifts to higher enwgy. This is alm true in cases where slow line narrowing occurs simultaneously. The length dependence of the threshold current density for lasing at 77 °K was examined for lasers made from the same material. It was found that longer lasers have lower threshold curvent densities, Estimates of the characteristic laser losses are given. Data concwning the range of Gap concentration in which stimulated emission was observed are presented. FORWARD-BIASED p-n junctions in mixed alloys of GaAsxPl-, emit light whose wave length depenfs on the composition of the alloy ranging from 8400A (x = 1) to 5350A (x = 0) at 77°K. Laser action in vapor-grown material was first reported by Holonyak and evacqua,' and in boat-grown material by Ainslie, Pilkuhn, and Rupprecht.' In both cases this was observed for low Gap concentration where GaAs,Pl-, is still a "direct" semiconductor with the lowest conductance-band minimum at k = 0 and a subsidiary minimum in the [loo] direction. As the Gap concentration is increased, the subsidiary [loo] minimum in the conduction band is lowered and finally becomes the lowest minimum for Gap concentrations above 50 pt,3 making the alloy an ''indirect" semiconductor. It is of interest to determine up to which Gap concentration stimulated emission can be observed. EXPERIMENTAL Boat-grown material was prepared by N. Ainslie of IBM by horizontal Bridgman technique. The material was n type and silicon-doped up to a concentration of 10'' cm-'. Vapor-grown material was made by E. Hull of IBM or received from Merck & Co. Diodes were fabricated in a similar manner as in the case of GaAs by zinc diffusion. Details about the diffusion can be found in a later paper.4 All diodes were of Fabry-Perot structure with two parallel sides cleaved and the other two sides sawed. Their width ranged from 50 to 150 p and their length from 50 to 700 p. RESULTS AND DISCUSSION Spectral Distributions. A typical display of the junction luminescence of a GaAsxPl-, diode is shown in Fig. 1. The liquid-nitrogen and room-temperature curves which were taken at a very low current (25 ma dc) show a relatively sharp high-energy emission which is band-edge radiation. They also show a broad low-energy emission which is due to transitions to deep impurity levels. This latter emission line may have different shapes and positions depending on the nature of the material. It can sometimes be quite near the band gap giving rise to "bumps" in the high-energy line. The results presented in this paper will be concerned only with the high-energy emission which becomes more intense relative to the low-energy emission when the current is increased and the temperature is lowered.

Jan 1, 1964

By A. U. Seybolt, D. H. Haman

The rate of oxidation of the lowest nitride of chromium, Cr2N, was measured to be equal to the rate of oxidation of chromium metal. It was found that, while the presence of Cr2N in chromium does not affect the oxidation mechanism, a long exposure at high temperature affects the morphology of Cr2N in chromium, causing a massive internal nitriding along chromium pain boundaries. Marker expen' -ments showed that the rate of oxidation of Cr2N layers on chromium is determined by the rate of chromium diffusion through Cr,03. The rate of formation of Cr2N is determined by diffusion rate of nitrogen through Cr2N. This rate at 1000°C is around thirty times faster than the rate of oxiahtion. Evidence is presented which suggests that nitrogen from the air reaches the chromium through the Cr2O9 by migration through pores or cracks rather than by a diffusive process. IT has long been recognized that, when chromium or alloys containing substantial amounts of chromium are oxidized in air, some chromium nitride (Cr2N) is formed under the oxide scale. Although the presence of this nitride layer has often been described, there appears to have been no systematic study of the role played by the nitride during the oxidation process. Indeed, there have been conflicting re-ports'92 on the kinetics of oxidation of chromium and chromium alloys in air and in oxygen. However, it is now well-established'-5 that the rate-controlling process during the parabolic oxidation of chromium to Cr2O3 is chromium-ion diffusion through Cr2O3. Because of the importance of chromium-containing alloys as oxidation-resistant materials, it seemed desirable to investigate the behavior of chromium during oxidation with and without the presence of chromium nitride. Since a semicontinuous Cr2N layer forms relatively early during the oxidation of chromium in the air, chromium atoms must either pass out of or through the Cr2N layer to become incorporated in the growing Cr2O3 scale. Therefore, it seemed desirable to examine the oxidation behavior of the pure nitride. MATERIALS AND EXPERIMENTAL PROCEDURE The chromium used in this investigation consisted of slices of an ingot made from "five-nine" iodide chromium which had been argon-atmosphere melted in a Y2O 3-stabilized ZrO2 crucible in an induction furnace. The only impurity of any significance was 625 ppm of 0, which was usually reduced to a microscopically invisible amount by hydrogen annealing at 1400°C. However, one sample of chromium was used with the as-cast oxygen level as explained below. The samples were used after abrading through 600 Sic paper and then washing in toluene and alcohol. Both nitriding and oxidation experiments were performed in a vertical tube furnace connected to a glass vacuum system. 'This system was equipped with pressure measuring instruments for the range of 10 p to 1 atm, and a cartesian-diver pressure-control device was used in conjunction with a needle valve to allow control of pressure in the range of about 10 to 760 mm. The nitrogen or hydrogen gas was purified by passing through hot copper chips at 600°C, anhydrous calcium sulfate (Drierite), and liquid nitrogen. Oxygen gas was dried through the Drierite column and a dry-ice trap (-78°C). Changes in specimen weight were followed by a Pyrex helix used in conjunction with a cathetometer which could reproducibly be read to +0.001 cm, yielding an accuracy of about +0.2 mg. The spring was maintained in the cool upper part of the furnace tube where the temperature did not rise above about 35°C. The nitride in equilibrium with metallic chro-

Jan 1, 1964

By A. O. Drysdale

From a mining point of view the Portland Cement Industry falls logically into the Industrial Minerals Division. Portland Cement manufacture requires four principal materials, lime, silica, alumina and iron. The usual source of lime is limestone. Silica sources include clay, shale, quartz, sandstone and sand. Alumina is usually provided by selecting a silica source with a suitable alumina content such as clay and shale. "Cement Rock" is occasionally found in which all four ingredients are found in natural combination or sufficiently close that only minor adjustments are required. In the absence of iron oxides a white cement can be produced. All raw materials used in Canada contain some iron and in most plants further minor quantities of iron are added to promote fluxing, hence the typical grey colour of Portland cement. The modern period in cement manufacturing started in 1824 when Joseph Aspdin of England patented a process for the manufacture of a modified hydraulic cement which he called "Portland Cement". Hydraulic cements are cements that harden under water. Although natural cements, made by calcining and grinding natural argillaceous limestone were produced in Canada as early as the 1830's, Portland cement was not produced in Canada until 1890, about 18 years after it was first made in the United States.

Jan 1, 1964

By Gill Montgomery

The problems of the domestic merchant fluorspar producers are more or less common with those of many other producers of metallic and non-metallic minerals. For more than ten years the American fluorspar producers have seen an ever lowering price in the market-place for the fluorspar product, while their labor and material costs-continue to mount steadily. This cost-price squeeze has forced out of business all but a few of the merchant producers, and only two captive producers continue to operate, and one of them has announced early curtailment. The prices of domestic fluorspar, of all grades, have declined because of the competition from cheaper foreign imports, principally from Mexico, Spain and Italy. Tariff protection on fluorspar, particularly on the highest or acid grade, has never been sufficient to cover the production cost differential between foreign and domestic fluorspars. Low ocean and barge freight rates have also contributed to the barring of the product of domestic mines from, the major consuming centers along the Gulf and East Coast. Because of the freight disadvantage, all but one or two fluorspar producers in the western states have had to suspend business. More than 80% of the domestic fluorspar is being produced in Illinois and Kentucky fluorspar districts which adjoin on both sides of the Ohio River.

Jan 1, 1964

By S. T. Wlodek

The scale md subscale reaction products were identified and their rates of formation were studied in air over the range 1600" to 2000°F (871 " to 1149°C) for periods of up to 400 hr and for hoth the solution-annealed and aged conditions. The effect of prior sltrface preparation on suhscale oxidation was also studied The general oxidation behavior of both Ni-Cr-Mo-Al-Ti type alloys was similar. A surface film of a, Al2O3, forms immediately on exposure Subsequent oxidation continued at a linear rate (QL = 55 * 5 kcal per mole) as colonies of Cr2O3 nucleated at the A12O3/gas interface Further oxidation proceeded at a paraholic rate zvhiclz could he fitted to two successive rate constants. During paraholic oxidation, and depending on temperature, the scale consisted of Cr2O3, NiCr2O4 , and TiO2 with traces of NiO. In the case of Rene 41, the activation energy of both paraholic processes was 66 * 3 kcal per mole suggesting that diffusion of cations tlzrozrgh Cr2O3 was the rate -determining process. An unusual decrease in the oxidation of Udimet 700 at 1900°F where a spinel of Ni(A1,Crh0, zuas the predominant reaction product prevented the accurate assignment of activation energies for this composition. In both alloys internal oxidation of Al2O3 commenced shortly after parabolic scaling was observed. Prolonged exposure prod7tced intemal oxidation of TiN, and in Udimet 700 a complex Mo-Ni nitride was also found. At 1900oF, the subscale reactions in Udimet 700 undergo an inversion which parallels the decrease in surface oxidation; internal oxidation ceases hut is replaced by the formation of "spherodized" 3.' colonies. Surface-preparation techniqtles which introduce appreciable working, such as coarse surface grinding or grit blasting. increase the amount of alloy depletion and internal oxidation in Reni 41. The reverse is true of Udimet 700 for which electropolished or mechanically polished specimens show much more subscale oxidation than strongly worked stirfaces. The strongest commercial nickel-base alloys presently available are generic to the Ni-Cr-Mo-A1-Ti base which exploits the precipitation of Ni3(A1,Ti) as the main strengthening mechanism, while relying on solid-solution strengthening by molybdenum and chromium reinforced by the pre- cipitation of carbides to attain maximum properties. This study characterizes the oxidation behavior of Rene 41, the strongest alloy of the Ni-Cr-A1-Ti type commercially available in sheet form, and Udimet 700, whose higher aluminum and titanium content allows it to exhibit one of the more attractive combinations of high-temperature properties available in a wrought product. The scaling processes of complex, type nickel-base alloys have received relatively little attention. Malamand and vidal as well as Poulignier et al.2'3 have determined the composition gradients across the metal/oxide interface produced by high-temperature oxidation and considered the effect of surface perature, Limited weight-gain data has also been published by Fere 5 for alloys of this type and Radavich6 has identified the reaction products on Udimet 500 and Inco 702 after oxidation at 1832°F. Reference can, of course, be made to the excellent reviews of Kubaschewski and Hopkins7 or Ignatov and Shamgunova8 for a summary of the data available on the oxidation of binary and ternary alloy systems which are related to the more complex alloys considered here. EXPERIMENTAL The analyses of the different commercial heats studied are given in Table I. Using the experimental procedures previously established,9 continuous weight-gain data were obtained on both heats of Rene 41 sheet (A and B) and 150-mil-thick slices of cast Udimet 700. Subscale oxidation reactions were followed by static exposure of cylindrical specimens obtained from swaged Rene 41 (Heat C) and Udimet 700 (Heats E and F). In brief, continuous weight-gain tests were performed on specimens with a surface area of 10 to 12 sq cm. These were abraded through 600 grit Sic paper, electropolished to 2p rms in an electrolyte of 10 pct H2So4 in ethanol, and lightly etched in 10 pct HCl in ethanol before final washing and rinsing in ethanol. All continuous weight-gain data were obtained in dried (-70°F dew point) flowing (1 liter per min) air to an accuracy of +0.1 mg. Subscale oxidation processes were followed by the metallographic examination of 0.5-in-diam by 1.0-in.-long specimens. After an initial center-less grinding, various additional surface treatments were employed to determine the effect of surface preparation on subscale oxidation processes. Before exposure in zirconia crucibles, all samples were lightly etched in 10 pct HCl-ethanol, washed in ethanol, and dried. The depth of internal oxidation was measured to ±0.00025 in. on unetched specimens mounted so as to provide a taper mag-

Jan 1, 1964

By Robert B. Johnson

The refraction seismic method has been used as an indirect means of exploring for fluorspar in southern Illinois by the Illinois State Geological Survey. Use of the method has been restricted to those areas where mineralization is associated with faults, a restriction necessitated by the operating principles of the refraction method. The seismic data enable the interpreter to locate fault zones in the subsurface and, under ideal circumstances, to make estimates of dip direction and magnitude and vertical displacement provided the local stratigraphic units are known and are geophysically recognizable. In this instance, refraction seismic exploration has been successful in the surface mapping of well-developed faults, both simple and complex with which fluorspar may or may not be associated. However, less clear results have been obtained where faulting has been less severe and where there are numerous accompanying mineralized joints.

Jan 1, 1964

By C. O. Ensign

Results of the application of geo1ogic knowledge to grade control have been remarkable. Grade reduction from dilution has been diminished from greater than 9% at the time of the program's beginning to about 2% at present. This has resulted in an increase of about 1.8 lb of copper per ton of ore mined and has made a substantial contribution to earnings at White Pine during the past two years. Even more improvement is expected in the future. The White Pine orebody, situated in the southwestern portion of the Keweenaw peninsula of upper Michigan, is a gently dipping stratiform or bedded deposit. Copper distribution is stratigraphi-cally controlled with higher values being confined to specific beds in the ore column. Room-and-pillar mining is practiced. Mining technique and geologic characteristics present a special array of problems in controlling the grade of ore. A routine program of grade control was started in the White Pine mine in August 1961. The program is based upon development and application of geologic knowledge to assist mine operating personnel to increase the grade of ore, primarily by accurate stratigraphic control and selection of areas for development on the basis of grade distribution trends. Geologists work closely with mine supervisors to offer the necessary geologic guidance. STRATIGRAPHIC POSITION OF COPPER The important rock series in the White Pine area is comprised of three formations of late Precambrian age. In descending order they are the Freda sandstone, Nonesuch shale, and Copper Harbor conglomerate. The Nonesuch shale is about 600 ft thick. Economic copper concentration occurs only in the lowermost 20 to 25 ft of the formation; however, within a restricted area along the southwest side of the mine the uppermost 1 to 7 ft of the Copper Harbor conglomerate (lower sandstone) contain sufficient quantities of copper to be included in the ore column. The ore consists primarily of chalcocite with subordinate native copper disseminated in shales, siltstones, and sandstones. MINE BOUNDARIES AND STRUCTURE The mine area is bounded on the west by the sub-outcrop of basal Nonesuch at bed rock surface and on the southwest by the White Pine fault (Fig. 1). The south and southeast limit of the orebody is reasonably well delineated by thinning or pinch-out of favorable host beds. Northern, northeastern, and eastern limits have not been established. The White Pine fault is actually a wide zone of shearing which strikes approximately N 40° W. It is downthrown on the southwest side and dips steeply to the northeast. Maximum vertical displacement is about 1500 ft.

Jan 1, 1964

The C.S.I.R.O. acid alumina process employs the essential steps of digestion, hydrolysis and calcination to produce pure alumina from ores too high in silica or too low in grade for the Bayer process. The two latter stages have been described in some detail previously but the digestion stage requires separate discussion since ores vary widely in composition and reactivity. Kaolinitic clays require roasting to 800°C to render the alumina soluble in the 11 per cent sulphuric acid used in the process while some ferruginous laterites require roasting to reduce the reactivity of iron minerals.The iron content of pregnant solutions is kept at a low figure by digesting at temperatures where the solubilities of ferric oxide or basic ferric sulphates are small. A two-stage, counter-current digestion is necessary to extract a high percentage of alumina from the ores and to produce a basic pregnant liquor with an SO3 : AI 203 ratio of 1'\1 suitable for high temperature hydrolysis. The second stage of digestion, called the modification stage, treats slightly acid liquors with excess of ore in the temperature range 1200-1400C.The first stage operates at 170°-1900C to extract further alumina from modification residues, using recycled acid obtained from later steps of the process. Both temperature ranges are critical for economic operation and for proper control of the iron content of solutions. In batch experiments, 30 min is regarded as a suitable retention time for digestion and modification; ores which require much longer than this are less suitable for the process. Impurities such as silica, and titanium and vanadium oxides are discarded in the residue along with iron oxide, and do not contaminate the final product. Bivalent metallic sulphates such as MgSO4, can build up in the circuit to a very considerable degree without affecting product purity.Comparison with other processes shows that the C.S.I.R.O. process is superior for control of contamination by iron, which is the major problem in acid processes. The pure intermediate product (3Al203.4S03.9H20) is also more convenient for calcination to alumina than the hydrated aluminium sulphate usually recovered in other processes. Detailed cost comparisons must await pilot-plant evaluation of the C.S.LR.O process.

Jan 1, 1964

By F. R. Lee

[WHEN the Bureau of Mines was established in July 1910, one of the problems immediately attacked by the new organization was the development of standard, for the design and testing of electrical equipment that could be used without fear of initiating fires and explosions in underground coal mules. Research and investigation by Bureau personnel, supplemented by the published results of similar work by European mining authorities, led to the establishment of standards or "schedules." which guide manufacturers in the design of many types of electrically operated machines and devices used in. underground coal Mining. By issuing these standards, Bureau personnel establish the requirements to be met by such equipment before it tan be approved by the Bureau of Mines as permissible for use in gassy coal mines. Every 2 years the Bureau of Mines publishes a list of equipment that leas been accepted as approved or permissible during the preceding 2 calendar years. This is done to inform the mining industry of the availability of the latest equipment for safe use underground.]

Jan 1, 1964

By Chester O. Ensign

The White Pine Mine is situated in the southwestern portion of the Keweenaw Peninsula of Upper Michigan approximately 6 miles south of Lake Superior (Fig. 1). It is east of the Porcupine Mountains in Ontonagon County. The ore deposit is about 70 miles southwest of the famous native copper deposits of the "Copper Country" lying northeast of Houghton. Geological conditions are different at every mine and create a special set of problems in dilution control. This paper is largely intended to describe the techniques applied in mine dilution control (grade control) at White Pine, and present results of the program. For necessary background information major geologic characteristics of the deposit, particularly those that exert control over the distribution of ore, are briefly discussed. Mining methods are described in considerable detail since applied grade control techniques are adapted to these.

Jan 1, 1964

In 1961, West Australian Petroleum's Eneabba No. 1 bore encountered 22 seams of coal totalling 40 ft in thickness between the depths of 6373 ft and 6441 ft. On analysis, this coal had a similar calorific value (8000-HOOO B.T.U./lb, assuming 20 per cent water) to the coal from the Collie Coalfield, Western Australia's only known area of commercially exploitable coal. Being buried to depths in excess of 6000 ft, the coal at Eneabba had developed weakly-coking properties, and thus, although much younger than the Permian coals of Collie, gave promise of being a major potential source of power for Western Australia.West Australian Petroleum undertook a programme of stratigraphic drilling and shallow test drilling to determine whether this coalhorizon persisted into the outcrop of the Lower Jurassic sediments in the Hill River district, 140 miles NNW. of Perth, and, if it was present, if the quality and quantity of the coal would warrant development of the deposits by open cutting. The coal horizon was identified in the near surface, but the poor quality of the coal and the complexity of the structure made development (in the area examined) uneconomic at the time.A strong seismic reflection in the Eneabba area occurs at the same depth as the Jurassic coals. This event originates within the upper beds of the Lower Jurassic and it is probable that the velocity contrast between the higher velocity siltstones and the very low velocity coals enhances this very strong, distinctive seismic reflection.This event can be followed on continuous seismic data over a large area of the northern Perth Basin, from 13 miles SE. of Dongara to 20 miles SW. of Coorow. It can be followed from a depth of 4000 ftnear Dongara to over 17,000 ft to the SE., so development of thisvast potential source of power will depend on the economics ofprocesses being developed for the production of power from theburning of coal seams in situ.INTRODUCTIONThe discovery of 22 seams of economically useable coaltotalling 40 ft in thickness in the Lower J urassic sedimentsof the Eneabba No. 1 bore (Fig. 1) led to the search forthese seams at economically workable depths. The Ministerfor Mines in Western Australia granted to West Australian1. Supervising Geologist, West Australian Petroleum Pty. Ltd.Manuscript received at The Institute, 25th May, 1964. and presented to the 1964Annual Conference.

Jan 1, 1964

Some important mineral fields are referred to in discussing the formation of placer deposits in Australia. Testing methods include boring hand, with percussion rigs; with auger and pit digging drills; and l by vibro drilling. Sampling errors are minimized by the use of correct techniques and equipment for boring, sampling, and sample dressing, A hypothetical set of data is used to demonstrate the final process of evaluation, and some relevant taxation provisions are discussed.

Jan 1, 1964

By R. L. Bleifuss

The object of this study was to evaluate the oxidized taconites of the western Mesabi iron range and to establish a correlation between the various basic taconite types and their concentratability. This study was made at the Mines Experiment Station of the University of Minnesota under the sponsorship of the Great Northern Railway Company. The initial work included a study of the original mineralogical and stratigraphic facies of the fresh taconite and traced the oxidation and leaching patterns developed during the conversion of this material to oxidized taconite. Subsequent studies have extended this work to include the semi- taconites and also the wash and heavy media ore types widely developed in the area. Each basic, original mineralogical facies or taconite type produces during alteration an equivalent secondary oxidized facies which has a unique mineralogical composition and texture. These control the concentratability of the oxidized taconites. Actually the influence of the original mineralogical composition of the iron formation extends even further and determines whether the most likely product of oxidation and leaching will be a wash ore or a heavy media ore and even to the direct shipping ores where the ratio of hematite to goethite is largely determined by the original taconite type.

Jan 1, 1964

By H. I. Aaronson, H. A. Domian

The self-diffusivity of Ag10 has been measured as a function of temperature and composition in AgMg. a CsCl-type intermetallic compound with a substitutional defect structure on both sides of the stoichiometric (50 at. pct Mg) composition. These measurements show that In D increases linearly, and both In Do and Q decrease linearly with deviation from stoichiometry. The slopes of these lines are significantly steeper in magnesium-rich alloys. Equations for the variation of Q with composition have been derived by application of the theory of random walk processes on the assumption that diffusion in compounds of this type takes place by the six-jump cycle mechanism of Huntington, Elcock, and McCombie. The favorable agreement obtained with experiment furnishes fresh support for the correctness of this assumption. A principal result of this treatment is that. although the concentration of vacancies is considerably higher in the silver sublattice than in the magnesium sublattice, the acfivation energies for movement of the magnesium sublattice vacancies are so much lower that these vacancies are responsible for effectively all diffusion of silver in this compound. A tendency for vacancies of both types to be kinetically bound to wrong atoms is also noted. THIS study was undertaken to examine the influence of substitutional defects upon self-diffusion in an intermetallic compound, AgMg, with a CsCl-type crystal structure. The CsCl structure is exception- ally simple. At the equiatomic or stoichiometric composition in a binary alloy, it consists of two interpenetrating simple cubic sublattices, each of which is exclusively populated by the atoms of one species. When atomic size and other factors are favorable, deviations from stoichiometry can be entirely accommodated by the substitution of atoms of the species present in excess of 50 at. pct on the sublattice of the other species on a one-for-one basis. Under this condition, the only vacancies present are those formed by thermal activation. The excess atoms thus incorporated into the sublattice of the minority species may be considered as substitutional defects in this sublattice. Several X-ray studies have shown that the defect structure of AgMg is entirely of the substitutional type on both sides of the stoichiometric composition.1"3 The thermodynamic investigation of Kachi indicates that, aside from a low level of thermal disorder and these constitutional defects, order is maintained to the solidus temperature. This compound is therefore a particularly useful vehicle for a study of the influence of substitutional defects upon diffusion kinetics. Other advantages of AgMg for this purpose include: the broad composition region, as much as approximately 10 at. pct on either side of the stoichiometric (50 at. pct Mg), in which the compound is stable; the comparatively low temperature range of the solidus (820°C and below),5 making diffusion anneals near this range experimentally convenient; the reasonably good machinability of the compound, permitting utilization of the standard sectioning method of radiotracer analysis; and the availability of a good tracer, A for one of the constituent species. While this investigation was in progress, Hagel and westbrooks reported data on the self-diffusion

Jan 1, 1964

By R. B. Anderson

As a part of a Bureau of Mines program on the conversion of coal to liquid and gaseous fuels, the kinetics of the Fischer-Tropsch synthesis on iron catalysts was investigated. Nitrided catalysts were studied at 21.4 atmospheres using feed gases ranging from 2H2+1CO to 0.25H2+1CO, and at 7.8 to 21.4 atmospheres using 1H2+1CO gas. The overall apparent activation energy increased with increasing carbon monoxide content of the feed gas from 19.5 kcal/mole for 2H2+1CO to 23.7 for 0.7H2+1CO. The rate of synthesis with 1H2+1CO feed increased linearly with operating pressure from 7.8 to 21.4 atmospheres. A semifundamental rate equation of the form [r=a'PH2 0.6pco 0.4- ?r0.5PH200.5] was shown to fit the data satisfactorily. The relative usage of hydrogen to carbon monoxide decreased with increasing conversion, passed a minimum, and then increased. Apparently water is the principal primary product and carbon dioxide is produced by subsequent water-gas shift reaction. In another group of experiments water, carbon dioxide, argon, and methane were added to 1H2+1CO feed to a nitrided iron catalyst. Argon and methane were only diluents. Carbon dioxide was a slight inhibitor and water vapor was a strong inhibitor to the rate of synthesis. Water accelerated the water-gas shift and usually increased methane production. Important factors of catalyst geometry in determining rate were found to be particle size and extent of reduction. Apparently the active portion of the catalyst is confined to a layer of 0.01 to 0.02 cm from the external surface of particles. A special solution was made of differential equations relating re¬action at the catalyst surface to diffusion in pores of the catalyst for spherical particles with an active layer surrounding an inert core. The equation derived expressed the experimental data reasonably well. Diffusivities determined by this equation varied from 3 to 24X10-6 cm2/sec; these values are of the same magnitude as observed for the diffusion of gases in liquid. The appendix presents a group of synthesis experiments at pressures of 21.4 to 103 atmospheres. In this range the rate of synthesis on nitrided iron catalysts increased with pressure to the 0.74 to 0.84 power.

Jan 1, 1964

By G. W. Form, W. A. Spitzig

The effects of hydrogen and vacuum shtering treatments on the physical and mechanical properties of arc plasma-sprayed tungsten were inuestigated. Temperatures examined ranged from 3000" to 4000°F in vacuum and 2000" to 3000°F in hydrogen for both single and duplex sintering cycles. Densities of 92 pct of theoretical density were obtained when a long-time hydrogen treatment at 2000°Fpreceded sintering in vacuum at 4000°F for 4 hr. This cycle also produced the highest ualues for modulus of rupture and bend angle. The results of this investigation point out the desirability of using a low-temperature long-time hydrogen treatment prior to a high-temperature vacuum sinter for arc plasma-sprayed tungsten. ADVANCES in the development of arc plasma-generating equipment have provided a high-temperature heat source that makes the fabrication of tungsten shapes possible by a metallizing process. Tungsten in the as-sprayed condition is very brittle. It has a density between 80 and 85 pct of theoretical density, a lamellar structure with elongated pores, and a high interstitial impurity content. To improve these properties, sintering treatments can be applied to the as-sprayed material, similar to those used for the densification of compacted tungsten powder. However, in view of the differences in the density and microstructure of as-sprayed tungsten as compared with compacted tungsten, responses to sintering were expected to be different. EXPERIMENTAL PROCEDURES The tungsten powder used in this investigation had a particle size varying from 3 to 13 p with an average diameter of 8p. The impurity level was less than 0.1 pct. The arc plasma spraying was done with an F-40 Thermal Dynamics Corp. plasma jet. Spraying was performed in air and thus required cooling of the substrate by an air blast in order to minimize oxidation. The spraying parameters employed in the fabrication of all specimens are listed below: Power input, kw 12 Arc-gas flow, cfh 95N2 + 5H2 Powder feed rate, g per min 33 Powder carrier gas flow, cfh ION, Spray distance, in. 3 Traverse rate, in. per min 30 Mandrel speed, rpm 100 Nozzle orifice, in. 7/32 These values of the spraying parameters correspond to optimum conditions ascertained in a previous study. Sintering was conducted at 3000°, 3500, and 4000°F in vacuum (< 0.1 Hg), and at 2000 and 3000°F in hydrogen. Duplex sintering treatments investigated are listed in Table I together with the designations that will be used for reference throughout this paper. The samples were fabricated by spraying onto a copper mandrel which was removed prior to sintering. The specimens used for the sintering analyses had the shape of small hollow truncated cones 1 in. high with an inside diameter varying from 0.500 to 0.125 in. and a wall thickness of 1/8 in. Specimens for bend testing were taken from hollow hexagonal prisms 1-1/2 in. high with a 1-in. diam across the flats and a wall thickness of 1/8 in. The bend-test specimens were ground to the dimensions 0.085 by 0.350 by 1-1/2 in. Prior to bend testing 0.0025 in. of stock was removed from each surface by electro-polishing. Density measurements were made by the water-displacement method. In addition, a porosimeter was used to determine the amount of interconnected porosity for representative samples. Strength and ductility were determined from recorded values in transverse bending using a cross head speed of 0.020 in. per min. The load was applied at the midpoint of a 1-in. span. The deflection data reported herein refer only to the plastic portion of the total deflection. RESULTS AND DISCUSSION The as-sprayed samples had a density corresponding to 83 pct (l pct) of the theoretical density of tungsten. Fig. 1 shows a representative as-sprayed tungsten structure.

Jan 1, 1964

CESIUM metal production increased sharply in 1963. Domestic Production.--Cesium metal was produced by The Dow Chemical Co., Midland, Mich., MSA. Research Corp., Callery, Pa., and by Penn Rare Metals, Inc., Revere, Pa. American Potash & Chemical Corp., Trona, Calif., produced some combined cesium and rubidium. This company, Penn Rare Metals, Inc., and Rocky Mountain Research, Inc., Denver, Colo., produced various cesium compounds. Complete production data on cesium and rubidium and their compounds were not available for publication. Consumption and Uses.-Substantially more pollucite was consumed to produce cesium metal and compounds in 1963 than in 1962 but the overall consumption of pollucite continued to be small.

Jan 1, 1964

By John A. Dunn

The history of underground coal mining has developed through the years from a manual digging and loading process to the highly mechanized pro- cess that it is today through the use of electric power. Mine power systems have closely followed the continued pattern of improvement and mechanization, through necessity and the application of technological advances, At the beginning electric power used in coal mines was confined to haulage. Since d-c power was better suited to traction drives, mine power systems naturally developed using direct current. During this development, a number of street railway systems were in service, using 550 volts, and it was natural that mine trolley systems went in at 550 volts. As machines for mining operations developed and the number of operating mines increased, a safety hazard developed through the use of 550 volts. Most regulating agencies opposed the use of 550 volts, and after a time the maximum voltage permitted was limited to 300 volts hot line to ground. Up until this time most mines had operated with one central generating station, which served utilization power to the whole mine. Power demands were not very great and transmission losses were within reasonable limits.

Jan 1, 1964