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By Gary A. Kingston

This examination of Pacific Northwest (Idaho, Montana, Oregon, and Washington) ferrous scrap-industry operations, 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 areas 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 The best measure of the scrap supply available in an area is experience in terms of how much scrap was withdrawn at a given price.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 crap 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 E P. Graham

Orebodies occur in an infinite variety of grades, shapes and sizes, and take many millions of years to grow. When extraction starts there is only one possible end -the mine sooner or later will run out of ore and shut down. If the mineral industry is to supply the ever increasing demands of modern civilizations, more and more metals must be found and mined. This will require a never-ending search for ore, and the development of every economic body, large or small. To justify the mining of a small orebody, it first of all must pay its way. If the size of the burden imposed by the capital cost estimates is not carefully worked out, an otherwise promising situation could be killed. The very nature of mining, as a transient industry, re-leases a steady stream of good used equipment, and the trained personnel to install and operate it. All manner of plans and layouts, which can be utilized at a new property, are available. Working these and other economies into the estimates will sometimes make enough difference to give a prospect the green light.

Jan 1, 1964

By Charles Will Wright

The present struggle for economic and industrial supremacy by the Communist world is against the United States, its main target, and the other Free World nations. The basis of industrial power is minerals, so the Communist nations are building up mineral production within their borders, often regardless of costs, and are acquiring quantities of mineral products from Free World countries for future use. They are contracting for additional supplies and advancing funds for the development of these quantities. A number of the less developed mineral producing countries of the Free World are being infiltrated by Communists and Communistic influence. This situation is well known, but as yet little has been done to oppose these activities or to awaken the public to their seriousness. The Communist countries are still far behind the Free World Nations in production of many essential minerals. But, shortages are being made up from Free World nations in exchange for petroleum, manganese ore, chromite and other products. Restrictions on shipments of strategic materials to Communist countries have not been maintained.

Jan 1, 1964

By F. A. Olson, J. S. Cho, M. E. Wadworth

An infrared study of the states of hydration of MgSO4 revealed a hitherto unreported metustable dehydration state in the temperature range just below that of the stable anhydrous salt. Infrared, thermogvavimetric, and X-ray studies indicated that the state had bisulfate and hydroxide characteristics. A formula fitting all of the experimental evidence is hydrogen-bonded Mg(OH)HSO4, or possibly the chemically equivalent 1/2 Mg(HSO4)2. Mg(OH)2 Infrared spectra of the 7, 6, 1, and OH2O states of hydration are given as well as the spectra of the newly found state which is called the bisulfate state in this paper. Thermogvavimetric studies as a function of water-vapor pressure gave an enthalpy value of 16 cal per mole, and 25 eu for the conversion of the bisulfate state to that of the anhydrous salt. The free energies of the transition varied from 1.76 to 0.18 kcal per mole as the transition temperature varied from 279° to 336°C. The bisulfate state is believed to be of importance in catalytic dehydration phenomena using MgSO4 and may be of interest because of properties in sulfating reactions differing from those of the monohydrate. Also, an analogous state may exist as a hydration state of other sulfates. ANHYDROUS magnesium sulfate is a catalyst with a high degree of specificity for the dehydration of secondary alcohols.1'2 The only product obtained at the usual operating temperature range of 360" to 400°C other than the corresponding olefin is water. Thus, the bonding of water to the anhydrous salt as well as an understanding of the hydration states of MgSO4 became of interest in attempting to understand the catalytic mechanism better. In the process of this study using infrared, X-ray, and thermogravimetric analyses a dehydration state not previously reported was found. Proof of its existence, the nature of the state, and its role, if any, in the catalytic mechanism then became of interest. This paper is concerned principally with the first two aspects of this problem. Magnesium sulfate forms many hydrates, of which the monohydrate and heptahydrate (Epsom salts)3 are most important. Other hydrates4 are known with 1-1/4,5 l-1/2, 5 2, 4, 5, 6, and 12 H2O's. The hydrates with 1-1/4, 1-1/2, 2, 4, and 5 HzO's are unstable. The anhydrous salt is very stable thermally and has a strong affinity for water. It can be heated without additional decomposition to about 800°C.' At 900°C noticeable decomposition takes

Jan 1, 1964

Although Canadian bentonite is competitive in quality for most uses, it has not been accepted for the pelletizing of iron ore concentrates. In 1962, Canada consumed about 10,000 tons of imported bentonite for this use. By the end of 1965, the planned domestic consumption for this purpose alone will probably be more than 100,000 tons a year, valued at about $3 million. Consequently, a challenge exists for the establishment of a Canadian source of high-quality bentonite for pelletizing. Such a bentonite would also be suitable for the two other major applications -well drilling and foundry use. Brief mention is made of such topics as the identification, 1noperties, occurrences, exploration, applications, technology and laboratory testing of this clay. In particular, the type of bentonite in demand, the geological horizons warranting exploration, and simple preliminary test methods are discussed.

Jan 1, 1964

By Alvin Kaufman

Geothermal plants are competitive with conventional units. A geothermal plant can produce electric energy for 6.70 mills per kwhr, compared with 6.96 mills for coal, 6.74 mills for oil, and 7.04 mills for gas. These costs include fixed and variable charges. Potential for geothermal power exists in the Western United States, Alaska, and possibly Hawaii. Assuming that the current downward trend in cost per kilowatt of coal will cease and that the relative cost of gas and oil, already trending upward, may rise considerably more, geothermal energy will be utilized where available, in producing electric energy. It will be used in California first because it is directly competitive with gas-and oil-fired installations there. A long-term appraisal is difficult because little is known about the sources of geothermal power and the electric generating capacity which the steam fields will support. However, a market for geothermal steam-generated electricity exists within the Western States.

Jan 1, 1964

By H. M. Thorne

Oil shale, a potential source of products presently obtained from petroleum, is found in many countries. The most extensive known deposits from the standpoint of potential shale oil in place are those in Brazil and the United States of America. Mining methods used for oil shale range from open-pit operations for shallow deposits to room-and-pillar and longwall techniques for deposits with thick overburdens. Oil shales from different sources vary greatly in the amounts and types of organic and inorganic constituents. By retorting, the organic material is converted to oil, gas, and coke. The largest percentages of oil are obtained from materials having the highest hydrogen content. Over 2,000 retorting systems have been patented, but only a few have been used industrially, and no single process seems best for all types of shales or economic conditions. Shale oils have different characteristics, depending on the source rock and method of retorting. They contain large quantities of olefinic hydrocarbons and more oxygen, nitrogen, and sulfur derivatives of hydrocarbons than most petroleums. Consequently, petroleum refining methods usually must be modified for shale oil. This is particularly true in catalytic processing. Hydrogenation, even under mild conditions, improves shale-oil refinability. Several byproducts may be obtained from both the retorting and refining steps.

Jan 1, 1964

By W. A. Backofen, G. Y. Chin, W. F. Hosford

The ductile fracturing process was studied in single-crystal and poly cvystalline aluminum deformed in tension over a temperature range from 295° to 4.2°K. At temperatures as low as 77°K, the fracture of "inclusion-free" material, including zone-refined aluminum, was by rupture (-100 pct RA). At 4.2 OK, fracture was brought on by adia-batic shear. Metallographic examination did not disclose any voids or slip-band microcracks, thus negating for inherently ductile metals any mechanism of void nucleation by vacancy condensation or of cracking due to dislocation pile-ups. In Izigh-purity aluminum not treated to be inclusion-free, fracture at temperatures as low as 45°K was of the double-cup type and a result of void formation. The reduction-of-area decreased as temperature was lowered, corresponding to the earlier appearance of voids. Such behavior was rationalized in terms of a larger increase, with decreasing temperature, in the .flow stress relative to the strength of the inclusion-matrix interface. Evidence for low-temperature adiabatic shear was found in discontinuous flow at 4.2"K, in the transition to a localized shear fracture at low temperatures, and in the suppression of shear fracture with an elastically hard pulling device. A simple analysis for the initiation of adiabatic shew permitted a general correlation of the various contributing factors. It has been pointed out that the duration of shear depends upon effective mass and elastic stiffness of the deformation system. IT has long been recognized that fracture* may Throughout this paper, the term "fracture" is taken to mean any process that results in the separation of a material into two (or more) parts. Thus rupture as it may be encountered in a tension test leading to 100 pct reduction-of-area is included in this category. occur in a ductile mode, and that the process can be of great practical as well as general interest. Much information about ductile fracture has also been accumulated over this period, but only recently has an understanding of mechanism begun to appear. Ludwik,' in 1926, first reported fracture in a tensile specimen starting with a central crack in the necked section. Since then, other studies have disclosed that such cracks may form by the coalescence of voids nucleated in this region where hydrostatic tension is highest.2-4 Rogers and Crussard et al.' have emphasized void formation and reori-entation along localized shear bands as a mode of crack propagation. pines6 has considered the tensile rod as a bundle of fibers joined by weak interfaces, which subsequently separate to allow individual fiber contraction. The notion of cavity growth and coalescence by purely plastic processes was discussed by Cottrell: who added that the tensile reduction-of-area ought not to be sensitive to temperature. On the other hand, it has been observed that the reduction-of-area is greatly increased if tests are carried out at high temperaturesa or under high hydrostatic pressure.' Fracturing anisotropy in wrought products lends support to the idea of void formation from preexisting flaws strongly aligned by earlier processing.''-l2 There is evidence that many voids result from the fracturing of inclusions or separation at the inclusion-matrix interface Another possibility is that voids grow out of pore volume produced in the initial solidification and never fully removed in later working. In general, a structure 3f particles, pores, and weak interfaces can be expected, at least in materials of engineering interest. Vacancy condensation has been suggested as an alternative mechanism of void formation for materials considered to be inclusion-free.13 Yet experience has shown that tensile reduction-of-area increases with purity, to the extreme of rupture as so often observed in single crystals. Adiabatic shear has an important bearing on ductile fracture. It occurs when the decrease of flow stress, as a result of local temperature rise from heat generated during straining, becomes larger than the increase due to strain and strain-rate hardening. As demonstrated by experiments on punching of plates,14 a large temperature rise may be brought about by rapid straining. Adiabatic flow as a result of the high strain rate reached in an ordinary tensile specimen just prior to separation may account for the cone formation in cup-and-cone fracture;14 evidence of such local heating has been presented.15 For geometrical reasons, however, pure sliding along the conical surfaces is unlikely, and separation under tensile forces is probably an important accompanying feature of the shear.7 In deformation processing operations, a high shear-strain rate may exist at boundaries between plas-

Jan 1, 1964

By Thomas R. Mager

An in.t!estigation has been made of the equilibrium conditions at 1200°C in the reaction between hydrogen sulfide gas and sulfur dissolved in Fe-Si alloys From this the equilibrium constant, activity coefficient, and activity of sulfur in solution were calculated. A number of studies of the equilibrium of sulfur with iron and iron alloys have given closely agreeing results from which the activity and free energy of the dissolved sulfur may be found. Sherman, El-vander, and chipman1 discussed the significant researches of dilute solutions of sulfur in liquid iron prior to 1950, and the results of this study indicated that the relationship between the ratio of PH2S/PH2 in the environment and the percentage of sulfur in solution is not a linear one. Morris and williams2 studied the equilibrium conditions in the reaction between hydrogen sulfide gas and sulfur dissolved in liquid iron and Fe-Si alloys, and reported that silicon dissolved in iron has a pronounced effect on the equilibrium conditions. They found that the activity of sulfur in iron is increased by the addition of silicon. At a silicon content of 4 pet the activity coefficient of sulfur was about twice that for sulfur dissolved in pure iron. Sherman and chipman3 investigated the chemical behavior of sulfur in liquid iron at 1600°C through the study of the equilibrium: H2 + S = H2S; K = PH2S/PH2 . 1/as [1] From the known equilibrium constant of the reaction between H2, H2S, and S and the experimental data, the activity of sulfur in the melt was determined. They found that the activity coefficient of sulfur defined as fs = as/%s is increased by silicon and decreased by manganese. Morris4 and Turkdogan5 also reported that manganese decreases the activity coefficient of sulfur in liquid iron and iron-base alloys. A recent technique of sulfur analysis developed by Kriege and wolfe6 of the Westinghouse Research Laboratories permits an accurate sulfur analysis of 0.5 * 0.2 ppm in the range of 0.1 to 3 ppm, whereas in the range of 3 to 50 ppm the accuracy is ±1 ppm. This technique of sulfur analysis was utilized in this experiment. Previous unpublished data reported that sulfur analysis by the combustion technique was not accurate below 20 ppm. EXPERIMENTAL PROCEDURE Five 5-lb ingots of high-purity Fe-Si were prepared. Three of these ingots were prepared without the addition of manganese but with a variation of silicon contents from 2 to 4 pet. The remaining two ingots contained 3 pet Si with the addition of manganese. Ingots were made at each of three silicon levels: 2, 3, and 4 pet. No alloys were made with less than 2 pet Si since below approximately 1.8 pet Si the binary alloy exhibits a to ? transformation. The two additional ingots of 3 pet Si-Fe were made at each of two manganese levels: 0.20 and 0.50 pet. To minimize the effects, if any, of impurities on the activity of sulfur on Si-Fe, the best metals available were used for melting. All ingots were vacuum-melted in magnesium oxide crucibles. After obtaining samples for chemical analyses, the ingots were processed. This consisted of hot rolling and subsequently cold rolling the alloys. Each ingot was hot-rolled at 1000°C, reheating between every pass to minimize grain growth. All heating was done in a protective argon atmosphere. The slabs were hot-rolled to strips 50 mils thick. After hot rolling, all the material was pickled to remove the scale formed on the surface of the strip during hot rolling. The material was then cold-rolled to 12-mil strips. Single strips of the material used in this experiment were hydrogen-annealed at 1200°C for 16 hr in an alumina tube. Chemical analyses of strips M-1, M-3, M-4, M-7, and M-8 are given in Table I. Sulfur, silicon, and manganese analyses were made from the millings from the cold-rolled 12-mil strips. The oxygen analyses were made from slugs of the as-cast material. The hydrogen sulfide used in these experiments was supplied from cylinders containing a mixture of argon and 1 pet hydrogen sulfide. The parts per million of hydrogen sulfide were determined from the analysis of the exit gas of the annealing furnace during each anneal. The flow rate of hydrogen was approximately 1 liter per min in all anneals. The

Jan 1, 1964

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 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 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 A. Lawley S. Schuster

The tensile behavior of copper foils prepared from rolled bulk material has been studied over the thickness range 2 to 53 , and for a range of pain sizes. For foils of comparable grain size, having the cube texture and tested along (100), yield strength increases with decreasing foil thickness t below -26p, with a corresponding decrease in ductility. Deformation occurs in the form of localized slip clusters distributed throughout the gage section. To the extent that the tensile strength (10 to 18 kg mm-) is unaffected by foil thickness, and that the foils possess fair ductility, the stress-strain behavior resembles that of bulk material rather than that of whiskers or evaporated films of comparable dimensions. The dependence of yield strength o on foil thickness t below -26p is of the form: oy = oo + kt-1/2. Possible explanations for the stress increase are considered based on 1) the dependence of active dislocation source length on foil dimensions, 2) the locking of surface sources, or the blocking of mobile sources at the surface due to surface film. It is now well-established that filamentary whiskers of many materials show exceptionally high strength compared with bulk crystals.'-11 As the diameter of the whiskers decreases to -1, the observed fracture strength approaches, and in certain cases exceeds, the calculated shear stress for the nucleation of slip in a perfect crystal.' In general, the stress-strain curve is entirely elastic, with strains at fracture approaching 1 pct. Similarly, thin films12-24 of evaporated or electrodeposi-ted material have been shown to possess tensile strengths three to seven times that of bulk material, with total strains at fracture -1 to 2 pct. In the present study, attention has been directed to the room-temperature tensile behavior of thin foils of copper over the thickness range 2 to 53, prepared from rolled bulk material. Yield stress, ultimate tensile strength, elongation to fracture, and work-hardening behavior are measured as a function of grain size and foil thickness. Structurally such foils are superior to either evaporated or electrodeposited films, and in the recrystallized condition exhibit considerable ductility. Apart from preliminary work by Sumino and Yamamoto25 on the work-hardening behavior of rolled and recrystallized copper foils, no systematic tensile studies have been carried out on material of this form. EXPERIMENTAL PROCEDURE Tensile specimens were prepared from 99.995 pct purity rolled copper foils of thickness 2, 6, 12, 26, and 53, obtained from the Hamilton Watch Co., Lancaster, Pa. Irrespective of specimen shape, it is necessary to use tensile foils with edges free from notches or tears. To this end, any form of cutting operation was excluded, and the tensile foils prepared using a photoengraving process, the details of which are described elsewhere.26 Since tensile data are required under conditions of uni-axial stress, the specimen shape is extremely important. Ideally, the foil should be infinitely long, allowing a gradual taper from the grip area to the gage section; however, from a practical standpoint, long foils are easily damaged during testing. A modified tensile specimen was therefore selected having a parallel gage section 1.25 by 0.20 in. with a tapered shoulder section increasing to 0.5 in. at the grips, and an over-all length between grips of 4 in., Fig. 1. In practically all tests, these foils fractured within the parallel gage section. By approximating the foil contour (Fig. 1) to a hyperbola it is possible to analyze the stress distribution in the tensile foil using two-dimensional elasticity

Jan 1, 1964

By P. Hadzeriga

Ion exchange techniques have been growing fast and spectacularly in all phases of Science for the last two decades, but still its acceptance as a unit operation in Metallurgy is resisted. Mainly this is because ion exchange procedures are thought of as glamorous techniques by which only relatively expensive metals are to be recovered. Perhaps this concept comes from the early and basic marriage of uranium and other high price metals and ion exchange procedures. The general trend is that ion exchange technique requires equipment and materials which are too expensive to economically perform a chemical step whenever "cheap" commodities are produced. However, we are here presenting a means of utilization of waste hydrochloric acid by an ion exchange technique. We have studied this from the engineering and economic standpoint in a number of variations of the main procedure discussed here and we-conclude that under proper economic circumstances, the cost of the ion exchange material as well as the equipment and labor involved in the ion exchange section, is by no means unreasonable.

Jan 1, 1964

By Melvin P. Silverman

The literature on methane-oxidizing bacteria is reviewed in regard to (1) the growth and isolation of cultures by special techniques; (2) the distribution of these organisms in nature and descriptions of individual species; (3) the physiology of methane-oxidizing bacteria as influenced by temperature, light, pH, aerobiosis versus anaerobiosis, and carbon and nitrogen sources; and (4) the biochemistry of methane oxidation revealed by studies with intact cells and subcellular systems. Present practical applications of methane-oxidizing bacteria are limited to prospecting for natural gas and petroleum deposits. Desirable areas for future research are discussed as well as some possible applications such as (1) the removal and/or early detection of methane gas in coal mines by intact cells or enzyme preparations; (2) the generation of electrical energy by microbial fuel cells using methane as fuel; (3) the growth of methane-oxidizing bacteria on methane for their food value; (4) the purification of hydrocarbon gas mixtures using methane-oxidizing or other alkane-oxidizing bacteria; and (5) the synthesis of methane from mixtures of H2 and CO or H2 and CO2 by me thane-forming bacteria.

Jan 1, 1964

By R. I. Garrod, R. A. Coyle

The shapes and positions of X-ray reflections from specimens of copper, steel, and aluminum alloy haue been examined in the elastic and plastic ranges both while the specimen was under stress and in the unloaded condition. For the aluminum alloy the shape was unaltered by the application of stress either within the elastic limit or in the plastic range provided that no additional plastic strain was induced. In copper the broadening accompanying plastic deformation was very slightly reduced when the specimen was unloaded. A similay but more marked elastic component of broadening was also found for steel, but in this case below the yield stress. Line profiles corrected for instrumental and particle-size broadening indicate very large internal stresses in local regions of the plastically deformed metals. The results are discussed in terms of a recent suggestion that the heterogeneous dislocation distribution between the cells and their boundary walls plays a major role in the peak shifts and broadening of the X-ray reflections. STUDIES of the X-ray line profiles from strained polycrystalline aggregates concentrate usually on one or the other of two main parameters: a) the displacement of the peak of the intensity contour from its position for a strain-free aggregate, or b) the shape of the profile. From peak shifts data can be obtained either on the relation in both the elastic and plastic ranges between applied external stress and average lattice strains in a given (hkl) direction, or, alternatively, on the residual lattice strains which are present after a plastically deformed specimen is unloaded.' On the other hand, the shapes of the broadened profiles from cold-worked metals can be analyzed to separate the broadening produced by small particle size and by heterogeneous lattice strains.' In this paper the terms "size broadening" and "strain broadening'' are used in the general sense adopted by warren.' In the past, apart from two early qualitative observation, it has been customary to examine only the movements of the peaks of the profiles while the specimen is actually under load, since the line broadening induced by plastic strain remains after removal of the external stress. Consideration of the implications of existing data of this type suggests, however, that fruitful additional information on a number of fundamental aspects might be gained by careful examination of whether the X-ray line profile is in fact different in the loaded and unloaded states of the specimen. By taking advantage of the sensitivity and convenience of modern diffractometer techniques it is possible to explore with relative ease the magnitude and importance of any elastic effects which may be superimposed upon the well-known permanent changes in profile. The main aim of the work to be described was thus to investigate this point for typical metals and alloys. For this purpose annealed specimens were extended first elastically and then plastically and the positions and shapes of X-ray reflections were recorded. Initially it was anticipated that prime interest would center on observations within the plastic range; it has been found, however, that small changes in profile sometimes occur both before and after the nominal elastic limit of the material is reached. It is shown that the results obtained have important implications in relation to the structural changes and processes associated with deformation. I) EXPERIMENTAL To enable the diffraction lines to be recorded while the specimen was under uniaxial-tensile stress, a small hydraulic testing machine was designed and constructed for direct attachment to the goniometer of a Philips diffractometer. The specimens, which were machined from 1/2-in.-diam rod and had a central rectangular section 3/8 by 1/16 in. over a gage length of 1 in., were held in the machine by split collets mounted in grooves in the cylindrical ends of each specimen. No special precautions were taken to ensure precise axiality of loading. Constant oil pressure was maintained by a lever and weights system and transmitted to the loading rig by flexible pipe. The actual load on the specimen was measured by a load cell in the machine to an accuracy of * 1 pct. To enable smooth X-ray profiles to be obtained the specimen and machine were oscillated continuously during recording through *7-1/2 deg about the normal half-angle position of the goniometer. The three materials chosen for the investigations were high-purity copper as representative of a ductile fcc metal, a low-carbon steel for a bcc metal, and an aluminum alloy as a material in which the proof stress/ultimate strength ratio is high. Details are as follows. a) Copper. 99.999 pct purity. After machining the specimen surface was polished mechanically and

Jan 1, 1964

By A. W. Fletcher

A nickel-copper sulphide concentrate was treated in a pilot plant at Warren Spring Laboratory during 1961, by a hydrometallurgical roast-leach- solvent extraction process devised to cleanly separate the metal values, and produce acid sulphate liquors containing the metals. It is shown that 86 percent of the nickel and 95 percent of the copper could be leached from the calcine, after a sulphatizing roast on finely ground flotation concentrate. Iron was removed from the leach liquor by limestone neutralization with a small loss of values. Copper and nickel were separated by solvent extraction with naphthenic acid in kerosene after partial neutralization of the iron-free liquors with ammonium hydroxide. Hydrogen sulphide and chlorine were used to remove zinc (and residual copper) and cobalt impurities respectively. The recovery of pure copper and pure nickel, by electrowinning, from the acidic solvent extract strip liquors finally produced, appears technically feasible.

Jan 1, 1964

By Jack A. Kanz, Samuel R. Shortes, E. C. Wurst

Zinc diffusion into GaAs from the vapor phase through reactively sputtered SiO, films Izas been inrestigated for various zinc pressures at 1000"C. Diffusions were carried out in evacuated quartz ampules with elemental zinc and with various Zn-Ga alloys. Sputtered films have proved effective in lowering surface concentrations and preventing surface deterioration during diffusion. Approxin.ate complenzentary error-function impurity distributions were found when surface concentrations were reduced to approximately 3 -—4 x 10" atoms cm'3 or less with dilute zinc sources or by diffusion through SiO, films. Zinc difhsions in GaAs tlzrough SiO, films produced more planar diffusion fronts than were observed with uncoated zuafers under identical conditions. A) Surface Deterioration During Diffusion. Device technolorn-- in compound semiconductors has been hampered by several difficult problems not normally encountered with silicon and germanium. 111-V and 11-VI compound semiconductors generally have volatile constituents at temperatures used for diffusion. To achieve specific junction depths in reasonable lengths of time, or to obtain particular impurity distributions and doping levels, it is often necessary to use temperatures which cause surface deterioration and erosion of the wafer. The resultant surfaces are generally unsuitable for devices. The type and extent of surface damage depends to varying degrees on the particular environment of diffusion and on the particular impurity in question. The most common type of deterioration results from simple dissociation of the gallium and the arsenic during diffusin.' The deterioration process is significantly enhanced by thermal gradients in the diffusion zone, usually resulting in vapor transport and condensation at the cooler portion of the system. The resulting damage sometimes appears as a general haziness over the surface or an array of pyramidal etch pits characteristic of the particular orientation. Occasionally, erosion of the surface occurs uniformly over the wafer so that surface loss is not readily apparent. Workers in GaAs usually resort to the sealed-ampule type of diffusion system3"5 rather than the more conventional open system used for silicon and germanium. Another type of deterioration results from direct interaction of the impurity with the surface. The form of deterioration may vary from surface alloying, as in the case of zinc, to direct chemical attack and vapor transport of the reaction products, as in the case of sulfur. Surface alloying with zinc occurs at higher temperatures and source vapor pressures.4 The process is largely controlled by the amount of free gallium on the surface of the wafer in equilibrium with the arsenic lost to the system. The group-VI elements, sulfur, selenium, and tellurium, are commonly used donor impurities for gallium arsenide. These elements are characterized by high vapor pressures and high chemical

Jan 1, 1964

By F. Scott Carpenter

During the past several years, more frequent reference to Wollastonite has appeared in print, both in this country and abroad. The reason for this is the apparent growing interest in this mineral as it approaches commercial maturity. Twelve years ago, wollastonite was available in only limited commercial quantity. In 1933, a deposit in California was worked for a short time to provide a calcium silicate raw .material for the manufacture of mineral wool* It was not until the spring of 1953 that Cabot Corporation put into operation a modem commercial plant to produce this material in a variety of grades. These grades covered both a range of particle size and of particle shape. At that time, applications for wollastonite were largely speculative, although a few commercial applications in glass frits and welding fluxes did exist, For all practical purposes, it was a new material for which few commercial uses had been fully proven.

Jan 1, 1964

By Robert D. Saltsman

The inadequacy of our knowledge of the coal combustion process has long been recognized. This was expressed very well by Spicer and Finney (1). "The control of combustion processes in industry and the design of the equipment necessary for efficient burning to take place have always been very much branches of an industrial art rather than of an exact science. This has been especially true of the utilization of coal, a substance so hetrogeneous and complex in character that all too little is known about its chemical and physical composition.' During the past several years one branch of coal utilization, that of high temperature carbonization; has made significant advances from being an art into being an exact science. This has been accomplished by the development of petrographic techniques for identifying, measuring, and determining the thermal properties of the organic materials which affect the carbonization of coal and the correlation of this information with a pre-existing standard of coke quality, the stability index.

Jan 1, 1964