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By T. A. Sullivan

Refining in a molten salt electrolyte was investigated as a means of recovering nickel containing less than 1 percent and preferably less than 0.2 percent cobalt from nickel products containing up to 5 percent cobalt. Electrolytic separation of nick and cobalt was accomplished in a molten KCl-LiCl-NiCl2 electrolyte. Nickel containing less than 0.10 percent cobalt was routinely prepared. Factors that influenced the transfer of cobalt to the refined product were the nickel concentration of the electrolyte, the cobalt concentration of the electrolyte, the ratio of nickel to cobalt in the electrolyte, and cathode current densities. A method of recovering the cobalt from the electrolyte was developed. The possibility of preparing high-purity nickel by this process was shown, as well as the preparation of various cobalt-nickel-tungsten alloys.

Jan 1, 1968

By C. Gary Reiness

A safety glass eyepiece which had been repeatedly exposed to mine environment over a number of years was studied to determine some of its optical properties. In the regions from 385 to 400 mµ and from 625 to 760 mµ, the transmittance was less than the 89 percent required by the American Standard Safety Code for Head, Eye, and Respiratory Protection. From 200 to 320 mµ the relative transmittance of two parts of the eyepiece was found to vary widely, having a maximum of 38 percent difference at 315 mµ. Irradiation of the glass by ultraviolet light caused enhanced absorption in the range from 200 to 1,200 mµ. There was a time-dependent increase of 1016 color centers per cubic centimeter throughout this range after 36.5 hours of irradiation. The rate-of-growth curve for the optical density, at 243.5 mµ and 23° C, was resolved into linear and saturable components, indicating zero order and first order

Jan 1, 1968

By D. S. Cahn, D. W. Fuerstenau

Specimens of glass, plexiglass, and naturally occurring minerals were irradiated by a 15-joule ruby laser pulse to determine criteria for the fracture of nonmetallic solids by internal thermal stresses. Fracture did not occur in those specimens with either a very high or very low internal absorptance or with a high spectral reflectance. If significant amounts of melting and vaporization do not occur at the surface of irradiation, the specimen will fracture if a derived 11fracture stress" exceeds the ultimate tensile strength of the specimen. The purpose of this investigation was to determine criteria for the fracture of nonmetallic solids by internal thermal stresses which are caused by absorption of laser irradiation. A laser produces a very short pulse of light which has a high energy density distributed over a very narrow part of the visible spectrum. The laser system used in this investigation had an energy output of 15 0 joules at a wavelength of 6940 A. Fracture in a non-metallic solid, then, would be caused by the absorption of light energy by that solid, and subsequent conversion of this energy to heat or mechanical energy. Fracture is caused by internal stresses that result from rapidly imposed nonequilibrium thermal gradients. ANALYSIS OF CONDITIONS FOR FRACTURE BY LASER IRRADIATION For this analysis, the laser beam is assumed to be circular and centered on the junction of the major and minor axes of a rectangular specimen. The laser beam forms a cylinder of radius rb extending through the specimen width. The beam cylinder may be then thought of as a heated mass constrained by a surrounding unheated mass. The instantaneously heated cylinder will at-

Jan 1, 1968

By George M. Meisel

This paper is devoted to a discussion of the factors governing design of concentrators for large grinding circuits. Emphasis is placed on the manner in which use of ever larger grinding mills has affected the size of grinding bays, service cranes, gear reducers and electric motors, and the selection of ancillary equipment for cushioning of the starting load of large mills. Information is presented on the effect of using large grinding mills on the capital and operating costs of concentrators, e. g. : (Fig. 1) ? Benefits in lower cost of mills, drives and materials handling equipment, plant space, power, grinding media, operating labor and maintenance, and in ease of instrumentation and automation. ? Penalties in distribution of materials from the grinding mills to multiple lines of equipment which have not been developed to commensurately large sizes, and higher cost of ancillary equipment.

Jan 1, 1968

By D. G. Westlake

THE structure observed in thin foils by transmission electron microscopy is not necessarily representative of the initial bulk material. We have shown that hydrogen, originally present in a specimen of vanadium, niobium, or tantalum, can be concentrated by the thinning operation used to prepare foils from the bulk materials.' These foils exhibited domain walls indicative of a tetragonal distortion of the bcc unit cells, probably caused by ordering of the hydrogen in preferred interstitial sites. We believe this ordering does not occur at room temperature in the bulk material which contains less than 1 at. pct H. In a continued effort to prepare metal foils whose hydrogen concentrations remain constant during preparation, we have developed some new chemical and electrothinning techniques for vanadium. Each of the procedures presented in Table I produced foils that were thin enough for transmission electron microscopy. The experiments described below were performed to test the effect of each thinning procedure on hydro-

Jan 1, 1968

By Frank G. Horino

The Bureau of Mines studied the uniaxial compressive strength of model rock pillars as a function of the angle and spacing of noncohesive planes of weakness. The model pillars were prepared from NX 2-l/8-inch diameter drill core of limestone, sandstone, and granite, and the planes of weakness were diamond saw cuts ground flat and smooth. The angle of the planes of weakness, measured from the horizontal, varied from zero to 57° in approximately 15° increments. When two planes of weakness were used, the thickness-to-diameter ratio of the wafer was 1/4, 1/2, and 1, Approximately 400 model pillars were tested in uniaxial compression. The results indicate that the uniaxial compressive strength of model pillars decreases rapidly as the angle of the plane of weakness increases from 30° to 57°, and that the spacing of these planes of weakness has only a minor effect on the strength. The effect of the number of horizontal planes of weakness, with a spacing of 1/4 and 1/2 of the diameter, upon the compressive strength of model pillars was also investigated. These results indicate that as the number of planes of weakness increases the compressive strength of the pillar decreases. Normalizing the data provides useful estimates of model pillar strengths for any rock type.

Jan 1, 1968

By Robert A. Laurence

Ore deposits in the Southern Appalachians are ( 1) sedimentary or syngenetic, ( 2) epigenetic, and ( 3) residual. In general, deposits characteristic of high temperature and pressure are found in the Blue Ridge and Piedmont provinces and those of low and intermediate temperature and pressure, including the sedimentary ores, are found in the Valley and Ridge and Appalachian Plateaus provinces. Residual deposits are present throughout the area. Recognition of several periods of intrusion and metamorphism in the Appalachians has changed former concepts which held that most mineralization was of late Paleozoic age in a zonal pattern including all four provinces. Many deposits probably are of early or midPaleozoic age. Similarly, recent studies in geomorphology indicate that the formation of residual deposits is a continuous process and not related to specific cycles of peneplanation.

Jan 1, 1968

By R. E. Reed, C. J. McHargue

Single crystals of aluminurn were reduced 90 pct in diameter by extrusion at 296" and 77°K. The resultant double fiber texture had a strong (111) component with a weak (001) component. The relative anzounts of these components varied with starting orientation. Decreasing the Lemperatuve of defovtnation increased the amount of (001) texture component in crystals with inilia1 orientations near (111). The starting orientation and temperature of deformation strongly affected the morphology of the (001) component. The effects of orientation and Lemperatuve upon the distribution of the (001 ) texture component in extruded aluminum single crystals were rationalized on the basis of deformation band formation and interaction. MANY papers since the early 1920s have discussed the occurrence of the double fiber texture (111) + (001) in wires and rods of deformed fcc metals. Aside from the reporting of experimental results for the various metals under a variety of fabrication conditions, emphasis has been placed on two related problems. One problem deals with the prediction of ideal end orientations based on the glide systems and flow directions. The other problem seeks the reason why different amounts of each component may be produced by the same fabrication schedule for metals apparently having the same deformation systems. Some of the difficulties in developing a satisfactory explanation have their origin in the experiments themselves. One mistake has often been the assumption of an initially randomly oriented specimen or complete ignorance of effects of starting orientation. Recent studies by Grewen and Wassermann,1 Cullity and co-workers,2' and McHargue4 have shown that the initial orientation may be the most important factor in determining the final orientation. Hence only limited comparisons of data from different studies can be made unless all conditions of the initial material are specified. Another question has been the nature of the (001) component. Hibbards suggested that any (001) present was the result of re crystallization during fabrication. Although Fleischer6 found no (001) texture in aluminum swaged at room temperature, and Dayal 7 found that component to disappear at very high reductions, a double fiber texture has usually been reported for aluminum. Vandermeer and McHargue showed that, while some (001) in aluminum may be the result of recrystallization, much of this component has its origin in the deformation process. Ahlborn and Wassermanng found the (001) component in silver deformed at low temperature not to be the product of recrystallization.

Jan 1, 1968

By W. A. Backofen, B. C. Wonsiewicz

The Plasticity transition in magnesium was studied by plane-strain compression of single crystals and polycrystalline material at temperatures from about 20" to 307°C. Reduction of single crystals along the c axis was accommodated by twinning on {1011) and retwinning on (10 12}, followed by basal shear in the doubly twinned volume. Deformation in that mode can result in sufficient independent shears for arbitrary shape change. Fracture in c axis compression, below about 100°C, has been related to excessive shear caused by unloading from the stress for {1011} twinning (-50 ksi at 20°C) to that for slip within the twin (-3 ksi); ductility follows from heating because the stress difference is lowered and the twin volume, in which elastic strain energy is dissipated on unloading, is increased. The stress for (1011) twinning is strongly temperature-dependent but not given by a critical resolved shear stress law. The latter is attributed to the influence of stress concentration from prior intersecting shear on nonbasal planes, the former to the temperature dependence of the preliminary slip. THE basic symmetry of hcp crystals has the effect of limiting the number of independent slip systems and making twinning an important deformation mechanism. The general result in wrought polycrystalline aggregates is a more or less sharply developed texture (or preferred orientation) which underlies a strong anisotropy in mechanical behavior. Knowing how the one influences the other is essential background for the use of such materials. Magnesium was of interest in this work because of the unexplained plasticity transition that it undergoes somewhere in the neighborhood of 200°c.''~ At lower temperatures plastic deformation before fracture in polycrystalline material is limited, while at higher temperatures extensive deformation is possible. The transition temperature commonly determines the lower limit of the range in which magnesium is worked. The limited ductility can be traced to a lack of independent crystallographic shears. A minimum of five are required for arbitrary shape change.' Around room temperature, however, slip on all known systems provides only four.' In each case, the slip direction is in the (0001) basal plane so that slip does not allow strain along the c axis. With increasing temperature, more slip occurs on the ( 1011) pyramidal plane and the ( 1010) prism plane but without change in direction.'?' Thus, that development alone cannot explain the transition temperature.

Jan 1, 1968

Jan 1, 1968

By J. G. Patterson

"The depressive action of sodium cyanide on chalcocite has been investigated and found to be unstable. Flotation results show that with the addition of sodium cyanide to the system chalcocite is initially depressed but rapidly recovers with time, provided there is sufficient oxygen present.lt is proposed that the unstable depression is due to the reaction of cyanide with adsorbed xanthate and copper ions at the chalcocite surface to form soluble copper complexes. When all the free cyanide has so reacted, xanthate anions can then re-adsorb on the chalcocite surface and the flotation will recover. Results are presented to verify the the above mechanism."

Jan 1, 1968

By R. T. Southin

Cast ingots of 99.99 pct purity A1 and aluminum/copper alloys containing up to 2 pct Cu have been found to contain four zones rather than the three previously accepted, i.e., chill, colummar, and equiaxed zones. The fourth zone consists of a coarse dendritic layer across the top surface of the ingot which is open to the atmosphere. It is also found that the grains in the equiaxed region have a "cornet" shape, with a head which is coarsely dendritic and a tail which grew with the same structure as the columnar grains. Experiments using mechanical barriers, and others involving the elimination of the surface dendrile layer, have indicated that nucleation of the equiaxed zone is caused by the showering of dendritic particles from this surface dendrite layer. These particles are the dendritic heads found in the comet grains. A mechanism of nucleation and growth of these comet grains is put forward. Experiments with a number of other metals and alloys suggests that these conclusions may apply generally to ingots cast without the addition of nucleating agents, and solidified under normal conditions. THE macrostructure of cast ingots may contain the following three zones: i) a peripheral zone of fine equiaxed grains, commonly called the chill zone; ii) a zone of columnar grains extending inwards from the chill zone; iii) a central zone of equiaxed grains; these are normally larger than the chill grains. All three zones are not necessarily present in any particular ingot since their existence and magnitude depend upon the casting conditions and composition of the cast material. The mode of formation of zones i and ii is fairly well understood. However, the cause of the central equiaxed zone remains a matter of conjecture. Previous theories put forward to explain the mechanism of nucleation in the equiaxed zone have been examined by Chalmers1 and Winegard.2 At the time when the present work was carried out the most re -cent hypothesis was that due to Chalmers,1 who recognized more fully than previous workers that conditions in this zone during solidification were not conducive to nucleation. In his hypothesis, he suggested that nuclei were formed near the mould wall during the very early stages of solidification, and that they can drift into the central zone by convective motion. This was supported by evidence from experiments using mechanical barriers to stop the drift of nuclei. A similar hypothesis had previously been put forward by Genders.3 More recently, Jackson et al. 4 have observed that dendrite arms in organic compounds can melt off during solidification. They have postulated that this occurs in metals and alloys, and that the dendrite arms which have been freed from the main dendrite act as nuclei for the equiaxed zone. In the present work, critical metallographic examination has shown that there is a fourth zone in the macrostructure of cast ingots which is a dendritic layer over the top surface of the ingot. It is also shown that there is a relationship between this zone and nucleation of the equiaxed zone. EXPERIMENTAL DETAILS The alloys examined were prepared from super -purity aluminum of 99.99 pct min purity (spectro-graphically detected impurities of Cu, Fe, Si, and Mg) and copper of 99.98 pct min purity (spectrographically detected impurities of Si, Zn, As, Fe, Pb, Bi, Ni, Sn, Mn, Ag, Cr, and Al). Three compositions of ingots were examined, containing 0.0, 0.1, and 2 pct Cu, respectively. The alloys were melted in an alumina-lined salamander crucible using a medium-frequency electric induction furnace; when the appropriate casting temperature was reached, the alloys were cast without degassing or fluxing treatment. The mould used was made of electrode graphite and had the following dimensions: external diameter 6 in., height 9 in., with a mould cavity 8 in. deep and a diameter tapering from 5 in. at the top to 4 in. at the bottom. Casting temperatures used were generally in the order of 70" to 90°C above the liquidus and the mould was at room temperature before casting. Inserts kere placed in the mould cavity in some experiments. These consisted of either an 18-g stainless-steel tube of 2 in. diam held axially in the mould i in. off the bottom and extending 1 in. out of the top of the mould or a "trap-door" barrier of stainless-steel gauze of 24-mesh held horizontally in the mould 31/2 in. down from the top. The construction of this insert is shown in Fig. 1. All inserts were preheated prior to casting to prevent chilling. RESULTS The macrostructures of ingots of the three compositions are described, in terms of the three generally recognized zones, in Table I, and illustrated in Figs. 2(a) to (c). The most interesting observation in this table is that relating to the shape of the equiaxed grains, which were not in fact equiaxed but of almost tear-drop shape. Closer examination of these grains showed that each consisted of a head which had a coarse dendritic structure and a tail which always grew in the opposite direction to heat flow, and which had the same structure as that of the columnar material of the ingot concerned; i.e., in the pure aluminum and 0.1 pct Cu alloy it was cellular and in the 2 pct Cu alloy it was cellular-dendritic. Identification of original cast grains was greatly hampered in the super-purity aluminum ingots, and to a lesser degree in the 0.1 pct Cu alloy,

Jan 1, 1968

By U. Storck

"Shaft sinking for exploitation of the deep potash beds in Saskatchewan involved great difficulties from the very first because of the need to exclude from the shaft the high-pressure water encountered in the overburden. Control of the troublesome Blairmore quicksands was achieved relatively quickly by use of the freezing method and by lining with cast iron tubbing. The unsolved problem remained, however, of sealing the water-bearing Devonian where the formations had extremely low permeability and were thus hard to grout. Long experience in German potash mines had shown that the permanency of the whole mine would be seriously endangered if large amounts of unsaturated salt water were allowed to flow in from the shaft wall and merely removed by pumping. The prevention of water movement and the resulting dissolution of salt in the overburden were known to be most important. In the Alwinsal shaft, water flow from the Devonian has been prevented by the use of a steel and concrete sandwich lining similar in principle to a kind of lining introduced a few years earlier, and for another reason, in German coal shafts. As its installation is neither more expensive nor more time consuming than that of cast iron tubbing lining, this same lining was also chosen as protection against the Blairmore quicksands. The great advantage of the steel lining, in addition to its relatively high strength, is the fact that it is possible to make the joints of the individual segments absolutely and permanently water-tight by means of tested welds. The virtual dryness of the Alwinsal shaft will also result in lower costs because significant corrosion of all its steel installations, including skips, cage and ropes, will be prevented."

Jan 1, 1968

Gas well tests were performed on 17 wells in the Roma area. The procedure used in the test programme incorporates an initial isochronal test followed by what is described as the "two flow drawdown" technique. The second flow of the two flow drawdown test was conducted for sufficient time to allow transient investigation of the surrounding reservoir. This combination of tests allows the evaluation of stabilized production capacity in addition to the determination ,of several important reservoir characteristics.It also provides a qualitative indication of reserves, by reflecting the presence or absence of reservoir boundaries within the drainage area affected during the test.

Jan 1, 1968

By Richard A. Dick

In this report commercial blasting compounds are classified according to their nitroglycerin (or equivalent explosive oil) and ammonium nitrate content as dynamites, gelatins, blasting agents, military explosives, and blasting , accessories. The ingredients and more significant properties of each explosive are tabulated and briefly discussed. Data are summarized from various handbooks, textbooks, and manufacturers' technical data sheets, together with the author's personal experience; however, this report is not intended to be a technical handbook, since it does not deal with blasting techniques. Instead, it seeks to acquaint the reader with the great variety of explosives, available, their advantages and disadvantages, and their general areas of application. Properties discussed are weight strength, cartridge strength, detonation velocity, density, detonation pressure, water resistance, and fume class. The weakness of the strength rating system and the importance of detonation pres- , sure, density, and detonation velocity in rating explosives are discussed. The terms "blasting agent" and "slurry," which are often misused, are defined. Trends indicate that blasting agents (that is, blasting mixtures with none of of the ingredients singly classified as an explosive), particularly high-density slurry blasting agents, will dominate the explosives field in the future.

Jan 1, 1968

Using a cylindrical hydrocyclone with a long vortex finder as the separator, a batch sizer was developed for the fast comparative sizing of the coarse solids normally encountered in mineral pulps.Operating times as short as 2 or 3 min gave separations ranging from 16 mesh down to the subsieve sizes.Reproducibility was good and sensitivity was adequate for most applications.

Jan 1, 1968

By Klaus Schwerdtfeger

The equilibria in the Cr-N system have been investigated in the temperature range 1100° to 1310°C by reacting chromium powder with Nz-Hz gas mixtures. The solubility of nitrogen in chromium in equilibrium with chromium subsitvide ("Cr,N") is given by Chromium subnitride is nonstoichiotnetric; its nitrogen content is always less than that corresponding to the formula CrzN. The lattice paranzeters of quenched samples have been measured; c, and a. parameters are found to increase with increasing nitrogen content. The growth rate of the subnitride layer on chromium plates was measured by a thermogravimetric technique, using a silica spring balance. The self-diffu-sivity obtained from the theoretical analysis of the parabolic rate constant is found to decrease with increasing nitrogen content, i.e., with decreasing vacancy concentration in the nitrogen sublattice. The intrinsic nitrogen diffuivity is derived from another series of rate measurements using "CrzN" plates; the intrinsic diffusivity, DN = 3.2 X 10-a cmZ sec-' at 1200 C, is found to be essentially independent of- the subnitride composition. The concentration gradient was measured in a chromium subnitride layer by the X-ray method and found to be consistent with the derived diffusivity value. TWO chromium nitrides are known to exist:' the nonstoichiometric subnitride "CrzN" and the nitride CrN. In the present work the kinetics of the formation of chromium subnitride from chromium and nitrogen have been investigated at 1100" and 1200°C. In additional experiments the relevant equilibria have been measured. The data are used to evaluate the diffusivity of nitrogen in chromium subnitride. Since chromium nitrides are often found in chromium-containing steels, the results are expected to be helpful in the interpretation of the chemical reactions between chromium steels and nitrogen. Equilibria in the Cr-N system have been determined by several investigators.2"3 The rate of nitriding of chromium was measured by Arkharov et a1 .' in ammonia in the temperature range 800" to 1200°C. The parabolic rate law was observed. Due to the undefined nitrogen activity of the ammonia atmosphere, it is dif- ficult to interpret these rate data theoretically. An additional difficulty arises from the fact that the two-layer scale consisting of CrN and "Cr2N" was formed at the temperatures below 1030°C. The rate of nitriding of technical chromium (95 pct) was measured by Zaks in nitrogen at -1 atm in the temperature range 800" to 1300°C. EXPERIMENTAL METHODS The chromium samples were reacted with Nz-HZ gas mixtures in a vertical tube furnace, wound with Pt-10 pct Rh resistance wire. The gas-tight reaction tube was of high-purity recrystallized alumina. In nitrogen solubility measurements the nitrogen content of chromium was determined by the Kjeldahl method, on samples quenched in the cold part of the furnace. The nonstoichiometry of the subnitride and the nitriding rates were measured thermogravimetrically using a sensitive (+0.1 mg) silica spring balance. For the equilibrium measurements samples of 1 g of chromium powder contained in high-purity alumina crucibles were used. In order to remove most of the oxygen and nitrogen impurities from the chromium, the samples were initially annealed in purified hydrogen until a constant weight was obtained. The chromium plates (approximate dimensions 2 by 1 by 0.08 cm) used for the rate measurements were machined from ingots obtained by arc-melting of iodine-processed chromium. According to manufacturers' specifications the purity of the chromium powder was 99.9 pct Cr and that of the iodine-processed chromium 99.99 pct Cr. Our own spectroscopic analysis of the chromium powder yielded 0.02 pct Fe, 0.05 pct Mn, 0.05 pct Si, and 0.02 pct Ti as major impurities with all the other detectable elements below 0.005 pct. The nitrogen partial pressure of the gas phase was controlled by mixing prepurified hydrogen and nitrogen with constant pressure head capillary flowmeters. Oxygen and water vapor were removed from the mixed gas by passing it through columns of platinized asbestos (450°C) and anhydrone. The gas flowed upward in the furnace with flow rates of 300 to 500 cu cm per min (25"~). Gas tightness of the furnace system was ensured by pressure checks at regular intervals. The furnace temperature was controlled electronically in the usual manner. The reported temperatures were measured with a Pt/Pt-10 pct Rh thermocouple and are estimated to be accurate within ±$C The X-ray measurements were made with a Debye-Scherrer camera and a diffractometer using chromium radiation {\Ka = 2.29092A). EQUILIBRIUM MEASUREMENTS The experimental results of the equilibrium measurements are contained in Tables I to In. Fig. 1 shows the solubility of nitrogen in solid chromium in the temperature range 1100" to 1310°C. In Figs.

Jan 1, 1968

By Alten F. Grandt

Surface mining consists of the removal of the geologic strata overlying the coal seam usually with large electric shovels, draglines or bucket wheels. The method produces more or less parallel ridges or peaks of cast overburden, usually called "spoil banks". The mined lands vary widely in their inherent characteristics to produce a vegetative cover and thus can be put to a wide variety of uses. Use is the key to economic and social benefits. Physical and Chemical Characteristics of Soil Material of Surface Mined Lands after surface mining operations, the soil material is a heterogeneous mass whose physical and chemical properties are dominated by the character of the geologic strata overlying the coal. These strata are highly variable in thickness and character. They may include the surface soil, loess, glacial till, sands, shales, slates, limestone and sandstone rock. The method of mining with the several types of mining equipment will also affect the resultant mined area.

Jan 1, 1968

By Larry Kaufman, Joan B. Berkowitz-Mattuck, Edward V. Claugherty

The oxidation characteristics of hafnium and zirconiunr diboride were measured between 1200 and 2200'K by a thermal- conductivity method which continuously ttzeasures the rate of reaction of oxygen with the diboride and by a metallographic air oridation method zuhich provides a measure of the total arr7ount of bovide conuerted to oxide for a given time interval. The oxidized specimens obtained from the tl~eritaal-coi~ductitrity method were also examined by quantitatire metal-lographic procedares. The significant results obtained in this investigation reveal that metal-rich compositions of lzafi~iutil diboride proride the most oxidation-resistatzt material up to 2000°K; hafnium diboride is tmre oxidation- resistant titan zirconium diboride at all tempevatures examined; the morphology of the oxide formed on H/B2 and Llie temperature coefficient qi. the oxidation rate constants change at the temperature of ttze monoclinic to tetragonal phase transition] in HfO2; the oxidation of neither HfB2 nor ZrB2, results iN catastrophic Jazlure at lorc. oxygen pressures; and pvefevetztial gvaLti boundary oxidation was not obsevued for either HfBi or ZYB, A comprehensive study of the high-temperature characteristics of refractory transition-metal di-borides is currently in progress. This program has included investigation of the physical, thermal, and thermodynamic properties of TiB2, ZrB2, HfB2, NbB2, and TaB2. In addition, aspects of the synthesis and fabrication of such materials have been studied. In view of the diverse nature of this research, a number of other laboratories have actively participated and contributed specific capabilities for analysis and characterization of these materials. As a consequence, an extensive description of the relevant properties of these compounds has emerged which is central in evaluating their high-temperature (1200" to 2500°K) performance. To date, information on thermodynamic stability, specific heat, and vaporization characteristics,1 hot hardness and electrical resistivity,1, 3 therma1 expansion:'4 and thermal conductivity 1, 5 has been presented. This information has been generated on materials of the highest purity (98.5 to 99.9 wt pct Me + B) and density currently available. Samples fabricated by zone melting6 and high-pressure hot pressing"3'7 techniques have been used to generate suitable specimens for all of the aforementioned studies. dation characteristics of the most oxidation-resistant of these materials, hafnium and zirconium diboride, is presented and a description of the synthesis and the experimental procedures used to prepare and characterize specimens is given. The high-temperature range under consideration (1200" to 2200°K) and the known dependence of oxidation characteristics on sample chemistry, density, and oxidation conditions required a close coupling of the synthesis, fabrication, and evaluation procedures.8 This was accomplished by continual surveillance of chemical composition of starting materials before and after specimen fabrication and by evaluation of density, phase constitution, and microstructural features prior to and after oxidation exposure. I) PROCUREMENT AND CHARACTERIZATION OF STARTING MATERIALS In view of the current state of the art in fabricating refractory boride materials, the methods used in preparing samples for the present study are given in detail as follows: starting materials were purchased in high-purity powder form and fabricated by high-pressure hot pressing into 0.40 by 1.00 in. bars from which oxidation specimens were obtained. The hafnium diboride used in this study was purchased from Wah Chang Corp.; the zirconium diboride from U.S. Borax and Chemical Co. These powders were routinely characterized by quantitative chemical analyses for metal, boron, carbon, oxygen, nitrogen, and iron, by qualitative emission-spectrographic analysis for trace impurities, by X-ray procedures for extraneous phase identification, and by powder densitometry for comparison with X-ray (theoretical) density. Hafnium and zirconium metal and elemental boron were also purchased as high-purity powders and characterized for impurities by emission-spectrographic analyses. The hafnium diboride was procured in three shipments which were designated as HfBl.g7(1), HfB1.88(2A), and HfB2.12(2). The indicated stoichiometry is based on the atomic ratio of total boron to total hafnium; the number in parentheses identifies the shipment number. Shipment 1 was 5 1b, shipment 2A, 1 1b, and shipment 2, 8 1b. The zirconium diboride was procured as a 20-1b shipment and designated as ZrB1.89(1). A small quantity of purified zirconium diboride was also supplied and designated ZrB1, 9(P). The averaged results for chemical analyses which were generally performed according to the procedures set forth in the compilation by KrieGe9 are presented in Table I. Qualitative spectrographic analyses indicated that Ca, Cr, Ti, Si, Zr (in H~B~), and A1 were present at levels between 0.01 and 0.10 wt pct. Other metallic elements were found to be less than 0.01 wt pct. Since it is virtually impossible to purchase these materials in the desired quantities (5 to 20 lb) as single-phase compounds it is necessary to obtain

Jan 1, 1968

By J. L. Reuss

The Bureau of Mines investigated the technical feasibility of smelting copper concentrates containing chalcocite (Cu2S) and native copper using nonpyritic sulfur-bearing materials to aid matte formation. The procedure consisted of combining various proportions of commercial chalcocite concentrate, smelter slag, fluxes, and matte-forming constituents to produce charges of comparable compositions. The mixtures were charged in fire-clay crucibles and smelted in an induction furnace at 1,300° C. The research proved that either sulfur or gypsum can replace pyrite as a matte-forming material, and that gypsum produces an exceptionally high-grade copper matte. The addition of small quantities of metallic iron to the nonpyritic smelting charge furthers the removal of sulfur, improves the recovery of copper, and makes it possible to utilize gypsum as the exclusive flux and matte-forming ingredient, thereby eliminating the necessity of adding limestone.

Jan 1, 1968