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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 John C. Draper

Little precise information is available on the effect of mining on the surface topography. It is often assumed that after mining the surface will simply sink. This is not an infallible conclusion as is well illustrated in two of the three examples herein. This paper describes the results of an attempt to precisely measure the surface movement in the area around coal pillars left in place for three oil wells in a completely mined and caved area at the Harwick Mine of the Duquesne Light Company. The dates when the various measurements were made are shown on the data sheets and indicate the rate of surface movement. These oil wells are identified as wells Nos. 2, 3, and 6. This mine property is located on the north side of the Allegheny River at Cheswick, Pennsylvania, and extends in a northerly and westerly direction about five miles. The three well pillars are situated on the westerly side of the Bessemer and Lake Erie Railroad some 2,000 feet from Rural Ridge, Pennsylvania (Fig, 1).

Jan 1, 1964

By R. M. Hudson

The removal of nitrogen from a nitrogenized low-carbon sheet steel that contained 0.011 wt pct N was determined during heat treatment in Hz-N, mixtures. TIze process followed a first-order rate law; that is, plots of the logarithm of nitrogen content in steel were linear with the time of treatment at a given temperature. The rate of removal increased with an increase in temperature from 900" to 1300°F. By 1400°F the rate in dry hydrogen had decreased to a value intermediate between the rates at 1200" and at 1300°F; in wet (2.47 vol pct water vapor) hydrogen the rate at 1400°F was less than the rate at 1300°F and nearly the same as the rate at 1200OF. The rate at a given temperature increased as the 3/2 power of hydrogen concentration in the atmosphere. While wet atmosplzeres were generally more effective than the corresponding dry atmosplzeres, the effect of water vapor was much less pronounced than the influence of hydrogen content. NITROGEN is the principal agent in the strain aging of ferrite, the effect of carbon being secondary.' To eliminate the return of the yield point after straining and aging, it is claimed2 that the amount of nitrogen in solution in steel must be reduced to 0.0002 wt pct. Strong nitride-forming elements (titanium, vanadium, zirconium, and aluminum) can act to eliminate strain aging by combining with nitrogen. It is extremely difficult to decrease the nitrogen content in commercial steels to the low level required by conventional coil annealing because of the poor contact between the strip surface and the reactive atmosphere. However, a variety of gas-metal reactions can be effected by use of the open-coil annealing method,3 in which the metal surface is fully exposed to the atmosphere. With this possibility in mind, the Applied Research Laboratory has studied the influence of time, temperature, and atmosphere composition on the removal of nitrogen from low-carbon sheet steel. MATERIALS AND EXPERIMENTAL WORK Samples from a commercial nitrogenized low-carbon steel (0.010 in. thick) in the cold-reduced condition were used. The chemical composition of this steel is given in Table I. The gas mixtures used are listed in Table 11. The moisture content in the "wet" annealing atmospheres was controlled at a +70°F dew point (2.47 vol pct water vapor) by passing the gas mixture through a glass tube packed with a solid mixture of 10 pct anhydrous oxalic acid and 90 pct oxalic acid dihydrate held at 127°F; this technique has been described previously.4 For "dry" atmospheres, the gas mixtures were passed through a cold trap immersed in liquid nitrogen. A hinged-top Hevi-Duty electric furnace was used with a Vycor-glass furnace tube. When the furnace was at the desired temperature, the gas mixture was passed through the furnace at a flow rate between 1.1 and 1.2 cfh; coupons (size 3 by 3/4 in.) of the steel were pulled into the center of the Vycor-glass

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 H. R. Ogden, E. S. Bartlett, A. G. Imgram

THE tensile and notch tensile ductile-to-brittle transition characteristics of several refractory metals and alloys have been well documented.1-3 Electron-beam melted tantalum and columbium have been shown to retain excellent ductility at very low temperatures. Some indications of brittle behavior (low ductility and cleavage fracture) were observed with columbium tested at -253oC, but no similar effects were noticed with tantalum. Increasing the interstitial oxygen content in these two materials resulted in the detection of indications of brittle behavior at higher temperatures, although good ductility was retained in both bases at -196°C when they contained about 1 at. pet 0. Detailed descriptions of the impact transition behavior of these two materials at various purity levels have not been available. This technical note describes the effect of interstitial oxygen on the impact properties of wrought, fibered tantalum and columbium and compares the transition behavior to the previously determined tensile transition characteristics. Tantalum and columbium impact specimens with three different interstitial oxygen levels indicated in Table I were tested at temperatures ranging from -196o to 300°C. Oxygen additions were made to 1/2-in.-diam bars of electron-beam melted material in a Seiverts Apparatus. The oxygenated bars were then homogenization-annealed to obtain uniform cross-section hardnesses and swaged to

Jan 1, 1964

This paper generalizes open stopes into elliptical cross sections and applies the results of calculations based on the mathematical theory of elasticity to indicate stress distribution on the boundaries of such stopes. These show both compressive and tensile stresses and provide an ex-planation for the development of excessive dilution in shrinkage toping. Introduction T HE stress pattern around shrinkage stopes is identical with that around other stopes under the same physical conditions. However, a shrinkage stope ends as an unsupported open stope, and the method i limited to the stress range within which the rock is generally self-supporting. If it is acceptable to generalize the outline of a shrinkage stope into an elliptical cross section, then the graphs of Geldart & Udd (1) (see also Panek (2) and Denkhaus (3)) provide a good base for approximating the stress distribution as mining progresses. However, with failure conditions in the walls, the axis ratio, as cut

Jan 1, 1964

By E. Buehler, H. J. Levinstein

The temperature ranges in which the three inter-metallic phases in the Nb-Sn system form have been determined and the composition and structure of two of the three phases has been established. The kinetics of the formation of Nb3Sn in cored wire samples has been studied in the temperature range of 800° to 1050°C. From 800°to 950°C the rate of formation increases by four orders of magnitude. The rate-controlling step for the formation process in this temperature range appears to be the diffilsion of tin through NbSn. At higher temperatu~es a change occurs in the mechanism of the formation process such that up to a temperature of 1050°C the rate of formation of Nb3Sn does not increase above the rate observed at 950°C. For temperatures helow 950°C the current-carrying capacity of the wire increases with increased percent reaction reaching a maximum value when the formation process is 90 to 95 pct complete. The maximum current-carrying capacity obtainable in this temperature range is independent of the temperature. Above 950°C tlze current-carrying capacity obtainable in the wire decreases with increasing temperature of formation. A model is proposed which accounts for the ohserved behavior. RECENTLY, Buehler et a1.l reported the results of an investigation of the process variables which influence the superconducting properties of Nb3Sn-cored wire. These results indicated that at least four variables affect the properties of the manufactured wire. These include composition, particle size of the starting powder mix, temperature of heat treatment, and time of heat treatment. In order to understand completely the role of these variables, it is necessary to have an accurate knowledge of the phase equilibria in the Nb-Sn system. At the present time, phase-equilibrium diagrams for the Nb-Sn system have been published by a number of investigators.2-5 The diagrams differ as to the number of phases present, the composition of the phases, and the temperature range of stability of the phases. The present investigation was undertaken in order to resolve these differences. Since the investigation of Buehler et al. demon- strated that the length of time at the temperature of heat treatment affected the superconducting properties of Nb3Sn, it is apparent that it is necessary to understand the kinetics of the formation process as well as the equilibrium conditions before a complete understanding of the system is possible. As a result, the kinetics of formation of the various phases in the system were also studied in this investigation. EXPEFUMENTAL PROCEDURE Diffusion couples and sintered powdered compacts were employed in the phase-diagram investigation. The diffusion couples were made by filling 1/8-in.-ID monel-sheathed niobium tubes with tin. The monel sheath was employed to facilitate drawing.' The tubes were then drawn to a tin-core diameter of 32 mils. Samples approximately 3 in. long were then cut from the drawn composite. The tin was drilled out of the ends to a depth of 1/4 in. and niobium-wire plugs were inserted into the ends and peened over. The monel was removed by etching in concentrated nitric acid, after which the samples were sealed in evacuated quartz bulbs and heat-treated in a resistance-wound tube furnace. The samples were quenched into ice water upon removal from the furnace. The diffusion couple samples were examined metallographically employing a chemical etching solution consisting of 10 ml of saturated chromic acid per g of NaF. In addition, two anodizing solutions were used for phase-identification purposes. The first was the picklesimer7 solution; the second consisted of equal parts by volume of 30 pct H2O2 and concentrated NH4OH to which 1 g of NaF was added per 25 ml of solution. The anodizing conditions for the second solution were 2 v and 100 ma with a tin cathode. The powdered compacts were made by pressing previously mixed powders of 99.9 pct pure Sn and 99.6 pct pure Nb supplied by the United Mineral Co. into cylinders 3/8 in. in diameter by 1/2 in. long. The cylinders were then sealed in quartz tubes and heat-treated in the same manner as the diffusion couples. The samples were examined metallographically and by X-ray diffraction techniques. Since it was desirable to be able to correlate the kinetic data with current-carrying capacity, the type of specimen chosen for this part of the investigation had to be a compromise between the optimum system for studying kinetics and one which was suitable for making current-carrying capacity

Jan 1, 1964

The iron ore deposits of the Port Hedland district of North Western Australia are associated with band'ed sedimentary iron formations that form part of the local succession of folded and faulted Archaean volcanic and sedimentary rocks. The iron formations are regarded as the protore beds or sources of the iron which became concentrated by supergene processes to form commercial grade iron ore deposits.Iron oxide deposits occurring in situ within the protore beds are considered to be of residual-replacement origin, due to supergene leaching of gangue minerals and' deposition of secondary iron oxides in their place, Two types of deposit have been recognized. Lode deposits are deep lenses of massive hematite located adjacent to major faults. These deposits are thought to be very old and to have originated by supergene processes during the long period of erosion represented by the major unconformity between the Archaean rocks and the overlying Proterozoic beds. The other type, known as crust ore deposits, are shallow cappings of hematite and goethite on hills formed by the outcrops of steeply dipping protore beds. These deposits could have originated as far back as the early Mesozoic and it is possible that the ore-forming process is continuing at a slow rate at the present day.Deposits formed by erosion and re-deposition of material derived from pre-existing residual-type deposits are known as derived deposits. These include conglomerates and scree accumulations of various types and ages and pisolitic deposits formed by supergene leaching of transported detritus. Derived deposits range in age from early Proterozoic to Recent. The presence of pebble accumulatio,ns of lode-type hematite in the Proterozoic basal conglomerate provides good evidence that lode hematite deposits existed in pre-Proterozoic times.INTRODUCTIONThe existence of iron ore deposits in the Port Hedland district of Western Australia has been known since the beginning of the century, but little attention was paid to them untIl the 1930's, when the Commonwealth Aerial, Geological and Geophysical Survey of Northern Australia carried out investigations of most of the then known mining fields of the Northwest Division. The only iron...

Jan 1, 1964

By M. Shelef, A. W. Fletcher

The effect of alkali sulfates in promoting the sul-fation of nickel and copper in a bulk sulfide flota -tion concentrate by fluidized bed roasting has been studied in the laboratory, and it was shown that the various alkali sulfates promote sulfation to approximately the same extent. The sulfation of a mixture of synthetically prepared iron and nickel oxide and of nickel ferrite has also been studied. Nickel sulfation was promoted by high ratios of Fe:Ni and by the presence of sodium sulfate. THE work described in this paper was a continuation of earlier studies into the role of alkali sulfates in promoting the sulfation roasting of nickel sulfides1,2 in an endeavor to determine how the system was affected by the presence of compounds of iron and copper. The earlier work1 showed that, in the sulfation of NiO at 680°C, the reaction was limited by the formation of an impermeable film of nickel sulfate on the oxide surface. The relative effect of the various alkali sulfates in promoting nickel sulfation varied in the order: Li > Na >Cs > Rb > K A study of alkali sulfate/ nickel sulfate interactions at high temperatures showed that the promoting action was due to the fact that the nickel sulfate product layer sintered and agglomerated only when the more active additives were present. This resulted in the formation of discontinuities in the nickel sulfate layer so that diffusion of the sulfating gases to the NiO surface was no longer impeded and the reaction could proceed to completion. A similar explanation was used for the observation that sodium and lithium sulfates promote the oxidation of NiS to NiO at temperatures below 750°C since small amounts of nickel sulfate were formed during oxidation.2 It was of interest to study the effect of alkali sulfates on the sulfate roasting of a sulfide flotation concentrate which is typical of material treated commercially. In order to control temperature it is essential to roast sulfides in a fluidized bed and this technique was therefore used, although the batchwise operation of a small-scale laboratory reactor does not reproduce all conditions which prevail in full-scale continuous plant. The results obtained are therefore only comparative, and cannot be used for predicting the optimum conditions for metal extraction. The sulfation of synthetically prepared mixed oxides of nickel + copper and nickel + iron and of nickel ferrite was also studied to evaluate the relative effects of alkali sulfates with more complex systems. SULFATION ROASTING OF A SULFIDE FLOTATION CONCENTRATE The bulk sulfide flotation concentrate used in this work contained 7.92 pct Ni, 1.74 pct Cu, 35.66 pct Fe, and 31.28 pct S. The sulfide minerals present in order of abundance were pyrrhotite FeS, pyrite FeS2, pentlandite (FeNi)S, and chalcopyrite CuFeS2. Two samples described as coarse and fine were used. The coarse sample, which was a flotation concentrate (58 pct plus 300 mesh), was ground to 100 pct minus 350 mesh to produce the fine sample. Before roasting, the sample of sulfide concentrate was agglomerated by wetting witli a solution of the alkali sulfate (or water), thoroughly mixing, and drying at 110°C. This gave a cake which was gently crushed and screened, the -18 +100 mesh fraction being used for fluidized bed roasting. A similar-size fraction had been used by the authors in pilot plant work with a 4-in.-diam fluidized bed reactor.' In this work it was found that the molar ratio of additive to the total iron + nickel + copper content of the sulfide sample should be adjusted to a value of approximately 0.06, as this was the optimum amount necessary for nickel sulfation. Experimental. The fluidized bed reactor consisted of a quartz tube approximately 60 cm long and 30 mm in diameter resting in a vertical tube furnace. The sulfide bed (30 g) was supported on a bed of -4 +12 mesh quartz particles 3 cm high, which rested on a sintered quartz disc welded to the tube. The temperature of the furnace was controlled with a variable transformer to give a final bed temperature of 680°C. The bed was fluidized with air or mixtures of air + 10 pct v/v SO2, at a total apparent gas velocity of 60 to 65 cm per sec at 680°C. The SO2 was introduced into the fluidizing air stream only when the oxidation of the sulfides was completed. At the end of the roasting period the calcine was leached with boiling water and the

Jan 1, 1964

By R. Maurice King

In the operation of today's large scale ore-processing mills, it is extremely important to have some way of making an objective evalu¬ation of the performance of the available flotation reagents. Attempts to do this may often result in inconclusive findings since the magnitude of the difference in the mill results for any two reagents is apt to be quite small compared to the variability introduced by the process and 'the analytical procedures used to measure them. In cases where two reagents give vastly; different mill results, evaluation becomes a simple matter and as such deserves no further attention here. A question of primary concern, however, is how a mill can go about evaluating the performance of two reagents which may, for example, give a difference of only 0.001% copper in the-tailings or of 0.2% in copper recovery. The casual observer may feel that such small differences may be of little importance, but in a mill-whose daily tonnage is between 30 and 40 thousand, these differences could mean a substantial savings. Before the presentation of an actual example of a reagent testing scheme designed for just this-purpose, perhaps a few minutes should be devoted to a review of some statistical methodology to be used later in the discussion.

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 I. B. Cadoff, J. C. Bilello, R. Rosenberg

Diffiusion of magnesium into the surface of LiF crystals to controlled depths and subsequent heat treatments provided a wide range of surface zone harahesses and structure, The bend strength of the LiF crystals was increased by as much as an or-dev of magnitude. Ductility was achieved when dislocation generation occurred in the diffusion zone or when dislocations penetrated to the surface from the intevior. A critical surface hardness of 130 to 140 kg per sq mm was found helozu which generation could take place in the diffusion zone and ahoue which the zone was impenetrable, This hardness was obtainable by several methods, among them the aging of quenched MgF2 -LiF solutions to produce MgF, precipitation. Maximum hardness was ohtained in quenched specimens with no visihle evidence of MgF,. Diffusion-zone formation followed a parabolic rate law and an activation energy of 20.9 kcal per mole was obtained for the process. RECENTLY, the properties of ionic crystals as related to surface condition have been receiving much attention, specifically the transitions between ductile and brittle behavior. Originally Joffe 1 showed that NaCl crystals could be made ductile by immersion in water and related this to the elimination of surface microcracks. Aerts and DeKeyser 2 and Gorur 3' have subsequently shown that ionic crystals are inherently ductile and are embrittled through contact with air. Machlin and Murray4 hypothesized that a layer of NaCIO3 produced by contact of ozone with NaCl induced embrittlement by acting as a barrier to outward dislocation flow. westwood,' Rosenberg and Cadoff,9 and Bilello and cadoff' have reported surface strengthening of LiF crystals by coating with a magnesium compound and then heat treating for adherence. The major effect of the coat was to inhibit dislocation-slip lines from reaching the specimen surface. westwoods showed microcrack formation and fracture to be caused by slip-band interactions at the surface. The material presented in this paper is an extension of the work reported earlier by Bilello, Rosenberg, and cadoff'6,7 and illustrates the wide range of surface properties and bulk behavior obtainable by use of heat-treated magnesium-diffused surface regions in LiF crystals. EXPERIMENTAL PROCEDURE The LiF single crystals were obtained from the Harshaw Chemical Co. Some batch to batch variation was observed; therefore all specimens for a given test series were cleaved from the same crystal. The typical dimension used was 1 by 0.1 by 0.40 in. Surface damage resulting from cleavage was removed by chemically polishing in a 2 pct NH4OH solution. Each group of specimens was given a vacuum anneal at 700°C for 4 hr to provide a base standard for measuring comparative effects of various surface treatments. To produce the reacted surface zone, the annealed specimens were immersed in a boiling suspension of MgF, in doubly distilled HzO, agitated slbwly for 30 sec, removed, and dried at room temperature. Uniform coatings of MgF, were deposited with a thickness of approximately 5 mils. It should be noted that this technique can be modified for use with crystals which are soluble in water by using boiling absolute alcohol as the dissolving medium. This was found effective for the coating of NaCl with MgF2. The diffused surface zone was obtained by annealing the coated samples at elevated temperatures in a vacuum of lob4 mm Hg. Penetration depth was controlled by varying the annealing time from 1/2 to 28 hr. After heat treatment, the samples were tested for bend strength and hardness. Load was applied by four-point bending in a hard-beam testing jig. Four-point rather than three-point bending was used to provide a wide area of constant stress and to minimize the effect of localized inhomogenities in the specimen. The deflection rate was 8 x min-' and the distance between knife edges was 1/4 in. Load-time curves were obtained from a chart recorder coupled to the machine and converted to resolved shear stress on the shear plane vs deflection, as plotted in the figures. The unstressed portions of the sample outside of the two outer knife edges were used for the microhardness studies. Microhardness measurements were made with a Bergsman tester attached to a Reichert metallograph. All hardness impres-

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

By W. G. Kegel

Coal mining today is confronted with numerous problems, all of which affect in some way the ability of the operator to produce profitably. The major endeavor, therefore, is a quest for cost lowering techniques. Complete belt haulage from shuttle car to river barge appeared to be a step in such a direction. A deep look into all aspects proved this to be more involved than just the installation of such a belt line. With this paper, we will attempt to present to you the problems and requirements of design and installation of an all-belt haulage system, believed to be the longest underground belt installation in the world at this time. The first and most important item is the justification of an all-belt haulage system. The following is a brief history of the coal property and the facts affecting our decision.

Jan 1, 1964

By H. B. Weaver

The development of a method to manufacture diamonds has been rated as one of the out- standing scientific achievements of our time. The story is both interesting and significant. This paper will quickly review history of diamond and manufactured diamond. Next, it will discuss manufactured diamond as a product -- how good is it -- and what is the significance of this scientific achievement. And finally, present a few thoughts about the future of this technology and this product. For centuries, diamond was found only in alluvial deposits, primarily in the Golconda fields of India. As a result, man knew nothing of the process by which the stones were formed. In 1860, diamonds were found in South Africa under completely different conditions. Here, for the first time, they were found in volcanic pipe -- their mother ground. These volcanic pipes are roughly cylindrical columns of rock which go deep within the earth. The theory as to the formation of diamond was presented by the geologists in that era. The theory states that molten rock was thrust up through a layer of carbonaceous shale where it picked up the carbon necessary for diamond formation. It was generally agreed that diamond was formed approximately 240 miles below the surface of the earth, thus indicating that extremely high temperatures and pressures were involved.

Jan 1, 1964

By F. V. Lenel, J. A. Dromsky

The influence of thermal and mechanical treatments upon the elevated-temperature stability, the microstructure, and the mechanical properties of aluminumaluminum oxide alloys is investigated. Compacts from atomized and flake aluminum powders were sintered at temperatures just below the melting point of aluminum in a vacuum of 10-4 Torr for several hours and were then hot-extruded. During this treatment the hydrated oxide present on the surface of the powder particles decomposes, the water vapor produced reacts with the aluminum forming additional oxide, and the hydrogen developed is removed by diffusion to the surface. Extrusions of compacts so treated are stable at temperatures up to the melting point of aluminum and do not form blisters and internal defects typical of extrusions from untreated powder. Electron micrographs of extrusions from unsintered compacts show long parallel oriented platelets typical of the IN previous investigations1,2 the properties and structure of aluminum alloys were described which had been produced by cold compacting aluminum powder and then hot pressing and extruding the compacts. Both the structure and the properties of these alloys differ significantly from those of commercially produced aluminum-aluminum oxide alloys. When commercial alloys are produced, they are given a sintering treatment in air at about 600°C between cold compacting and hot pressing.3 During this treatment the hydrated oxide, which forms the coating on the aluminum-powder particles from which the alloys are prepared, is decomposed.4 The chemically bound water which is released reacts with the aluminum and forms aluminum oxide and hydrogen. Most of the hydrogen is eliminated by hydrated oxide skins on the original powder particles, while the oxide particles in extrusions from sintered compacts are broken up. The strength of extrusions from treated powder is somewhat lower, but their ductility is considerably improved over that of extrusions from untreated powder. The slip-trace patterns on electron microgvaphs of extrusions which had been strained in tension before replication indicated that the grain size of the extruded alloys was approximately the same as that of the original powder particles. Coarse-grained alloys were produced by severe cold work and annealing of the extrusions. They have significantly lower room-temperature strength, but about the same ductility as the vacuum-sintered fine-grained alloys. The size and shape of oxides in the coarsegrained alloys is similar to those of the fine-grained alloys, but the particles are somewhat more uniformly distributed. diffusing to the interior or exterior surfaces of the compact, but it is difficult to eliminate all of it because the solubility of hydrogen in solid aluminum is very low even near its melting point. Extruded alloys which are not sintered before hot pressing and extrusion appear quite sound upon metallo-graphic examination, but develop severe surface blistering and internal fissuring when they are heated to elevated temperatures after extrusion. Fissures and blisters have been observed even in commercial alloys which had been sintered in air, although they are much less severe.' Because of the importance of this sintering treatment it was studied in this investigation in a modified form, using vacuum sintering rather than sintering in air, to insure more complete elimination of occluded hydrogen. The technique is described and the effect of the treatment upon the structure of the alloys is documented. It has been known for some time that extruded aluminum-aluminum oxide alloys are very finegrained, but an exact delineation of grains in electron micrographs has not been possible. In the conventional metallographic-etching techniques etchants attack the interface between the second-phase particles and the matrix in the alloys much

Jan 1, 1964

By R. A. Matuszak

This paper discusses the major portion of the hoist (drag or crowd) system and it shows how static control accomplishes its major aims. In 1959, the first truly static control for Ward-Leonard equipped electric excavators was designed, developed and placed in service. The control system, originally intended only as a more modern electronic type of alternate to the proven rotating amplifier control system has since proven to be much more. When they conceived the original system, the designers had much more in mind than simply replacing the rotating amplifier with one that had no moving parts. The long range plan, which started with the initial system consisting of an SCR (silicon controlled rectifier) preamplifier and magnetic amplifier power amplifier, called for eventually, a control system low in cost and maintenance, relatively simple in design and extremely reliable. The plan also included the elimination of as many of the shortcomings of the rotating system as possible. No small accomplishment, when it is considered that the rotating control system had been, with only minor modifications, the standard of the industry for 20 years. The final step in the original design plan called for the eventual development of an amplifier that could be used as one of the basic building blocks of the future. DEVELOPMENT RESULTS Since the successful unveiling of the first static control system, continuous development has resulted in a slow, but sure progression along the path described by the original plan. The first version of the new control corrected one of the shortcomings of the rotating system by removing the necessity of operator anticipation. This was accomplished by making the system faster in response so that the operator noticed virtually no delay between his movement of the master controller and that of the machine. Thus, after the operator became familiar with the operating characteristics of the machine, he was able to become more relaxed while digging. The natural result of this accomplishment was higher production. All of the subsequent versions of this new control were even faster than the initial design. Although it was not distinguishable by the operator, the further increase in response resulted in large gains in the limiting of transient torque peaks applied to the machine while digging. Also, a more effective control of the torque and power peaks was obtained when plugging the motion being controlled to a stop. (Plugging is the use of the Ward-Leonard ability to regenerate power and absorb energy from the load to

Jan 1, 1964

By Frank G. Schwartz

VARIABLES OF composition and environment affecting storage stability of gasoline-type fuels were studied, utilizing radioactive tracers and other analytical techniques. Changes in gasoline composition brought about by aging were determined and correlated with gum formation. The amounts of reaction of selected gasoline components, measured by radioactive tracers, were determined in a gasoline-type blend and in a mixture of 17 selected pure gasoline components. The data show that sulfur compounds, nitrogen compounds, polycyclics, and olefins enter into gum-forming reactions. Certain sulfur and nitrogen compounds were found to be most reactive in the gum-forming process. Results of this study indicate that the aromatic constituents of gasolines may contribute substantially and directly to gum formation. A mixture of tetralin and indan-type compounds is reactive, and this mixture appears to be the main aromatic portion entering into gum formation. A secondary but significant amount of naphthalenes also appears to have reacted in the gum-forming process. Analyses of the sulfm compounds in a fresh and an aged fuel indicated that elemental sulfur, hydrogen sulfide, thiols, sulfides, and disulfides were depleted during aging, but thiophenes and residual sulfur compounds were not depleted by fuel deterioration.

Jan 1, 1964

The principle activities of the Explosives Research Laboratory from July 1, 1961 to June 30, 1962, are described briefly in part 1. Part 2 gives short abstracts of publications that appeared during fiscal year 1962; in general, the research reported in these publications antedates the report period. Part 3 gives the results of an investigation which, although too limited to warrant separate publication, merits presentation in some detail because of current interest in ammonium nitrate-fuel oil compositions.

Jan 1, 1964

By Charles R. Cavanaugh, John F. Elliott

The activity of nickel in liquid Pb-iVi alloys which are rich in lead was measured in the temperature region of 700° to 1100°C by means of the galvanic cell: The electrolyte used was stabilized zirconia. Tlze data were correlated using the a function, and a plot of the temperature coefficient aE/aT All subsequent calculations of the thermodynamic properties are based on these two functions. The activity, activity coefficient, and molar properties of mixing of nickel are reported. Nicke1 shows extreme positive deviations frorn ideality while lead shows a very slight positive deviation in the composition range studied The study of the activity of nickel in liquid Pb-Ni alloys reported herein was undertaken to explore the use of stabilized zirconia, an oxygen-ion electrolyte, with liquid-metal electrodes, and to obtain further information on the thermodynamic properties of the liquid binary Pb-Ni system. The cell The reversible electromotive force of the cell results from the difference in the chemical potential of the oxygen at the two electrodes: po, (left) - p~ (right) = -4E5 [I] The chemical potential of oxygen on the right is fixed by the activity of nickel in the solution and pure solid nickel oxide. That on the left is set by pure solid nickel in equilibrium with pure solid NiO. By definition: Since the chemical potential of nickel is related to the chemical potential of oxygen through the equilibrium constant for the formation of NiO from nickel and oxygen gas, the electromotive force of the cell is also expressed In this case, n is 2, E is the reversible potential of the cell, and 5 is Faraday's constant. The work of Kuikkola and wagnerl and Schmalz-reid2 has shown that the stabilized zirconia electrolyte is essentially an ionic conductor at the oxygen levels encountered in the experimental arrangement of the work, i .e., PG > 10-l7 atm. THE EXPERIMENTS The advantage of this type of reversible cell over those using a liquid electrolyte is the simplicity arising because the electrolyte also functions as one of the containing crucibles. A further simplification was the choice of the Ni (sat.)-NiO electrode as the standard. This permitted a ready check on the behavior of the electrolyte, as the potential of the cell must become zero when the right electrode becomes saturated with nickel, either because of a change of temperature or because of the addition of nickel to the electrode. It also permitted the potentials being measured to lie in the most satisfactory experimental range of 0 to 100 mv. Although it was not theoretically necessary, lead was included in the standard electrode as it assured good contact between the electrode and electrolyte. Cell Design. The general arrangement of the experimental cell assembly is shown in Fig. l(a) and the details of the cell itself are contained in Fig. l(b). The anode lead wire on the interior of the cell was connected to a coil of perforated sheet nickel. Within this coil were nickel oxide pellets which were held beneath the surface of the liquid Pb-Ni alloy. A disc of nickel oxide was held at the bottom of the external crucible (alumina) by means of the thermocouple protection tube. The nickel oxide disc and pellets were compressed dry at 10,000 psi and sintered at approximately 1000°C for an hour in air. A major experimental difficulty of reversible electromotive force cells with liquid electrodes is the selection of suitable materials for connecting

Jan 1, 1964