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By A. G. Starliper

The Bureau of Mines made laboratory investigations to determine the feasibility of utilizing fine tungsten wires to reinforce a number of nonferrous metals and alloys and a superalloy, S-8l6. The composites of tungsten filament and metals were chosen to attain elevated temperature strength and corrosion resistance. Oriented clean or precoated tungsten wires were incorporated with the other metals by extrusion, swaging, and infiltration casting. Although widely varying characteristics were found in the composites, none were considered satisfactory for high-temperature use, chiefly because of reactions between the matrix metal-tungsten surface. Diffusion, solution, and chemical reactions between matrix and tungsten wires were sufficiently slow for some combinations, such as 15 v/o 8-816, to exhibit increased high-temperature strength for a limited time. A few metals failed to wet or bond to the tungsten surfaces, while a few responded after precoating with a third metal.

Jan 1, 1968

By C. Altstetter, Y. Huang, E. de Lamotte

Nitrogen was introduced into pure niobium (colutn-bium) and dilute Nb- Zr alloy wires by equilibration with pure nitrogen gas at high temperatures. Room-temperature hardness was correlated with the alloy composition, heat treatment, and microstructure. Hardness was found to be most sensitive to the amount of nitrogen in solution; however, a significant hardening up to 500 Dph look place upon aging of quenched alloys. A coarse dispersion of nitride did not significantly increase the hardness of the material though the nitride was found to have a hardness of 1400 Khn. BY now the marked effect of nitrogen on the properties of bcc refractorv metals is we ll-documented. There are few studies, however, in which the state of the solute has been carefully controlled. Indeed, the composition-temperature-pressure relationships in nitrogen-refractory metal systems have been determined precisely for only niobium and tantalum.'-4 Most investigations on niobium have dealt with alloys High-nitrogen alloys cleaved on (100) planes and had negligible ductility. Precipitation was found to occur in either a discontinuous or a continuous fashion, depending on the composition and cooling rates. Upon cooling, the precipitation first proceeded discontinu-ously by the nucleation of nilride needles at subbound-aries and subsequent growth of a two-phase microcon-stituent. At lower temperatures continuous precipitation occurred in the subgrain interior ahead of the discontinuous precipitation interface. containing nitrogen, carbon, and oxygen in significant but uncontrolled and, in several instances, undetermined amounts. Thus, there has been some uncertainty regarding the presence and the distribution of precipitates. This paper presents results which relate the hardness and microstructure to the heat treatment and nitrogen content of niobium and Nb-Zr alloys. Niobium rod* produced by the Wah Chang Corp.

Jan 1, 1968

By Ray W. Carpenter, Ralph Hultgren, Raymond L. Orr

Heats of formation of Au-Zn alloys of compositions Au3Zn and AuZn were rneasured at several temperatures by liquid tin solution calorimetry. The data for Au3Zn show that much smaller heat and entropy effects are associated with the a2- a1 transformation than for the a1 - a transformation. This result is consistent with reported X-ray diffraction studies which indicate that the a1 and (a2 phases have ordered structures which only slightly differ, whereas the a phase is disordered. The heat of formation of AuZn(ß') does not change significantly between 322o and 8000 K, confirming that the ß' alloy remains highly ordered to high temperatures. Not many measurements have been made of the energies of order-disorder transformations in alloy phases. In many cases these energies may be conveniently determined by measuring heats of formation as a function of temperature. Many alloy phases approximately obey Kopp's law of additivity of heat capacities; as a consequence their heats of formation do not change with temperature. In ordered alloys, however, a decrease in degree of order with increasing temperature will contribute an endothermic component to the heat of formation. Thus, for ordered phases where other anomalous contributions to heat capacity in the alloy or its pure components are absent, a measured change in the heat of formation may be attributed to the energy of disordering. A portion of the Au-Zn phase diagram1" is shown in Fig. 1. The composition AuZn(ß') has a well-ordered superlattice structure of the CsCl type at room temperature. The alloy is considered to remain ordered to its melting point,1 although, from X-ray diffraction data and electromotive force measurements of zinc activities, Terpilowski3 concluded that considerable disordering began at -673°K. The Au3Zn composition is a disordered fee solid solution (a) at high temperatures. Between 693o and 543oK, the ailoy orders to form the a1 phase, having a structure based on the L12(AuCu3) type, but with a regular distribution of ordering faults in the c direction, making it tetragonal. Below 543oK, the alloy orders further by means of slight atomic shifts, without diffusion, yielding a complex long-period orthorhom-bic superlattice structure, a2.4-7 Heats of formation of Au3Zn(a2) and AuZn(ß') were measured at 363°K by Biltz et al.8 by aqueous solution calorimetry. Heat capacities of several alloys between 14.9 and 38.4 at. pet Zn in the range from 373" to 723°K were measured by Iwasaki ef al.6 Stoichiometric Au3Zn, however, was not included in the alloys measured, the nearest composition being 26.1 at, pet Zn. Also, the heating rate used for the measurements, 2 deg per min, may not have permitted equilibrium to be reached in the neighborhood of the transformations. Heat contents of solid and liquid AuZn were measured between 488o and 1138°K by Kubaschewski.9 It was decided to determine the ordering energies of Au3Zn and to check on the possible disordering of AuZn by measuring the heats of formation of these alloys at several temperatures. The present paper reports measurements by liquid tin solution calorimetry of the heats of formation of the three phases of Au3Zn at temperatures within their regions of stability, and of AuZn at a low (322°K) and a high (800°K) temperature. EXPERIMENTAL Alloy Preparation and X-Ray Examination. Ten-gram ingots of Au3Zn and AuZn were prepared by melting weighed amounts of gold (99.95 pct Au) and zinc (99.99 pet Zn) together in sealed evacuated Vycor tubes at 1060°K, followed by rapid quenching. The resulting ingots were homogenized at 900°K for 10 days. The Au3Zn alloy lost no weight in preparation, the loss from the AuZn alloy was enough to introduce an uncertainty of only 0.1 at. pet in its composition. Filings for X-ray examination were taken from various parts of each ingot and strain-annealed at 723°K for 20 min in vacuo. The Au3Zn filings were quenched rapidly to retain the disordered phase. Diffraction patterns were determined with an X-ray dif-fractometer using copper Ka radiation.

Jan 1, 1968

By H. V. Makar

Laboratory tests were performed to obtain a quantitative description of the effectiveness of sodium sulfate (Na2SO4) for removing copper from molten iron and to determine the effectiveness of Na2SO4 on actual auto scrap. The tests were conducted on induction melted heats of iron averaging 0.58 and 1.50 percent initial copper and on cupola-melted auto scrap containing 0.45 percent initial copper. The Na2SO4 was added in powder form in amounts ranging from 2.9 to 43.8 percent of the weight of iron being treated. The data showed that copper removal for the various Na2SO4 treatments followed a similar trend, regardless of the iron composition that was tested. The equation Y = 1 - e-3.23x approximately reflects the relationship between copper removal and amount of Na2SO4 added, where Y is the fraction of copper removed and x is the ratio of the weight of Na2SO4 added to the weight of metal treated. Copper removals ranged from 3.3 to 74.5 percent and reductions down to less than 0.10 percent final copper were achieved in the auto scrap. Copper removals were generally accompanied by sulfur removal, and initial sulfur contents ranging from 0.10 to 0.20 percent were reduced to as low as 0.02 percent. High temperatures and long slag reaction times tended to induce copper and sulfur reversion from the slag, but, generally, the Na2SO4 treat¬ments were effective up to approximately 2,820° F with reaction times not exceeding 7 minutes.

Jan 1, 1968

Open cut mining of the Black Rock chalcocite ore started in 1963. A ground movement monitoring programme was commencing in the early stages of mining when signs of instabilityof the western wall became apparent. Eventually 100.000 cu vd, of overburden Were removed beyond the rim of the western wall in an attempt to stabilize the slope. Subsequent decpenlug and mining till the final batter angle of 45 resulted in deterioration and mining was stopped 38 ft short in the ulltimte design deplh of 520 ft.Investigations showed that the geology of the western wall , was a major factor in the instability of this wall. A block jointed model was made 10 illustrate some of the pehomena observed. Quallatative agreement was found between the model deformation and the field measurements obtained.The results of the monitoring programme clearly show the value of this work In respect to the conlrol of the mining operatIon...

Jan 1, 1968

By A. Hellawell

Specitlrens of the Al-Ge eutectic alloy have been frozen unidivectionally at rates between 2.5 x 10-6 and 2.5 x 10-4 cm per sec and the structure examined by optical and X-ray methods. There is no epitaxial relationship between phases, the aluminum having random orientation and the germanium a preferred (011) fiber textuve. Lamellar colonies which are BINARY eutectic alloys occur between either silicon or germanium with the metals aluminum or silver. common in this alloy are constructed from axial and nonaxial (111) plates of germanium which are related by a variety of twin configurations. Irregular or globular regions of the microstructure are composed of continuous single crystals of each phase, the germanium being heavily twinned. There is limited solid solubility in these systems, and the eutectic phases all involve diamond cubic with fcc crystal structures. In the microstructures of these eutectic mixtures the silicon and germanium crystals exhibit an almost infinite variety of shapes which are notably sensitive to

Jan 1, 1968

By D. S. Burgess

The characteristics of gas-phase detonations were observed in 20 instrumented firings within earthen tunnels, in 100 such detonations in a 24-in-diam by l63-ft-long steel pipe, and in about 200 smaller scale firings. Most of the fuels studied were representative hydrocarbons--acetylene, propane, gasoline, and a roughly equimolar mixture of methylacetylene, propadiene, and propane. In a pipe with two closed ends, the detonable limits were demonstrated to be very nearly the same as reported limits of flammability. The side-on impulses (pressures integrated over 200-msec intervals) were shown to be the same function of concentration regardless of whether deflagration or detonation had occurred. In a pipe with only the initiation end closed, the impulses of all fuel-air systems tended toward the same level when averaged over comparable ranges of fuel concentration; the lower pressures with saturated hydrocarbons were nearly compensated by longer durations of pressure transient. In all fuel-air systems, unexpectedly high impulses were obtained with slightly lean mixtures. In earthen confining structures, the impulse, of the explosion was efficiently converted into momentum of the failing wall. In the configurations studied, an earth velocity of about 20 fps was critical to overcome the soil's resistance to shear. The destructive effect was determined by gas pressure rather than by total energy release. The assignment of a "TNT equivalent" to an explosive gas mixture is discussed in terms of the confinement of the mixture.

Jan 1, 1968

Jan 1, 1968

By J. E. Zeilinger

This Bureau of Mines report describes the preparation characteristics of the significant coalbeds of Clarion County, Pa. Of the 15 samples collected, 1 was of metallurgical quality as received, 4 could be sufficiently upgraded to provide acceptable products, and the remaining 10 samples could not be upgraded to metallurgical quality because their sulfur contents could not be lowered to meet the standard. For steam or power generation, 1 sample was of low sulfur content as received, 1 sample could be upgraded to low sulfur content, and 10 samples could be upgraded to medium sulfur content. The original sulfur content of the remaining three samples can be appreciably reduced by removal of the sink 1.58 specific gravity material; however, these coals would be classified as medium sulfur coals both before and after removal of the sink material.

Jan 1, 1968

By Y. H. Liu, G. W. Powell

Thin foils made from the gold-rich region of- short (0.15 mm)Au-Ag diffusion couples annealed at 880°C for 1 hr were examined in ax electron microscope and the structures were compared with that of pure gold subjected to identical heat treatments. The couples underwent Plastic deformation (bending) during the diffusional anneal. The foils prepared from the diffusion zone have a higher dislocation density and incidence of subboundaries than pure gold. The plastic bending of the couple can be interpreted in terms of the climb of edge dislocations, which are pavallel to the bend axis, along the direction of diffusion. THE interaction of lattice defects during interdiffu-sion between two metals has been considered by several investigators. In particular, da Silva and Mehl,1 Barnes,' and Bardeen and Herring3 have proposed models based on interactions between point and line defects to account for the Kirkendall effect (marker movement). Each of these models is based on dislocation climb, which can either add or remove lattice planes, induced by an under- or supersaturation of vacancies. A theoretical treatment of the nucleation and growth of voids by the condensation of vacancies has been presented by Seitz.4 Stresses can arise in a binary diffusion couple as a result of the vacancy flux and the gradient in the lattice parameter. rinkmman' has investigated the effects of diffusion-induced stresses on void formation; the results of his analysis suggest that voids can form and grow under the influence of these stresses in the absence of an excess vacancy concentration. The relationships between vacancy supersaturation and diffusion-induced stresses and void formation have been elucidated also by Balluffi and seigle6 who concluded that the stress generated by a vacancy supersaturation aids the growth of voids. Experimental evidence which indirectly shows that stresses are produced by chemical diffusion has been obtained by several researchers.2,7-9 This evidence consists in part of the observation by light microscopy of the formation of subgrains, a process characteristic of the high-temperature deformation of some metals during creep.'0 More striking, however, is the plastic bending of short (0.2 mm) Cu-Ni couples observed by Barnes2 and of boron-doped silicon crystals reported by Queisser.9 Diffusion-induced dislocations in iron and silicon have been investigated by Ainslie et a1.11and Schwutte and Queisser,12 respectively, the former using transmission electron microscopy and the latter an X-ray transmission technique. Matthews and Crawford13 observed the formation of boundaries by the climb of interfacial misfit dislocations in thin, vapor-deposited Au-Pd couples diffused in situ in an electron microscope. In order to obtain additional information on the phenomena associated with defect interaction and diffusion-induced stresses in binary couples, an electron transmission study of foils prepared from the diffusion zone of short Au-Ag couples was undertaken. The initial objective was to investigate the processes occurring at various points of the diffusion zone. Subsequent research demonstrated that foils could be prepared only from the gold-rich region of the diffusion zone using the technique described herein. EXPERIMENTAL PROCEDURE Preparation and Annealing of the Diffusion Couples. The couples were made from annealed, high-purity (99.999 pct). polycrvstalline gold and silver sheets (0.075 mm thick). Shall (0.075 by 5 by 17 mm) elec-tropolished coupons of gold and silver were pressure-bonded by heating the two metals in a graphite device to 770°C and holding at this temperature for approximately 30 min. The quality of the bond was ascertained by metallographic examination at 150 times. Each couple subsequently was annealed at 880°C for 1hr; under these conditions, the extreme portions of the

Jan 1, 1968

By John D. Ridge

Here are summarized 162 papers, published between 1933 and 1967, that deal with various aspects of ore genesis. Emphasis is placed on additions to, or modifications of, ore-formation theory, no matter what type of deposit is discussed. More space is given to papers on the formation of base-metal sulfides solely because more papers are written on this subject. The final conclusion is reached that a chemically and geologically sound theory for the genesis of ore deposits can be built around the concept of concentration of ore e’ements in a magmatically produced ore fluid and around such surface processes as may act to concentrate economically valuable materials from rocks of any origin exposed at the surface.

Jan 1, 1968

By Ronald P. Hollenbeck

Shales in the Appalachian Region of Kentucky and Tennessee were sampled and tested to determine their use as raw materials for the manufacture of lightweight aggregate by the rotary-kiln method. Nine samples were obtained from eastern Kentucky and 143 samples were obtained from eastern Tennessee. As a result of preliminary testing of these samples, two sources in eastern Kentucky and 11 sources in eastern Tennessee were resampled for rotary-kiln tests. The rotary-kiln tests showed the two sources in Kentucky and seven sources in Tennessee contained shale that would produce satisfactory aggregate. Lightweight aggregate processed from these nine sources was tested in concrete shapes and was found to be suitable for use in structural concrete.

Jan 1, 1968

By N. E. Hanna

An investigation was made of pressure pulses produced by unconfined explosive blasts in underground openings. Four tests were made with TNT or modified amatol charges ranging in weight from 60 to 2,000 pounds; each test involved either single or multiple charges. Pressure-time profiles were obtained using mechanical self-recording pressure gages. The cube-root scaling law for peak pressure was found to be valid within about 1 tunnel diameter; at greater distances, the pressures obtained along direct paths were generally higher than this scaling law would indicate.

Jan 1, 1968

By J. G. Donaldson

The Bureau of Mines investigated the formation of boron and boron-carbide coatings by vapor-phase reactions. Optimum parameters were determined for hydrogen reduction of boron trichloride and for the fonnation of boron-carbide coatings on graphite by reaction with the depositing boron. At 1,300° C, about 85 percent of the boron was deposited. Tungsten substrates did not react with the boron deposit; other substrates reacted to various extents. The hydrogen reduction of boron tribromide was briefly investigated. Boron carbide was deposited at 1,300° C by adding methane to the boron trichloride-hydrogen feed gas. The chemical composition of the vapor-deposited boron carbide approximated B4C. A method of etching B4C was developed to study its microstructure. When boron was deposited on graphite at 1,500° C, very hard, uniform, strongly adherent coatings of B4C were formed that might be useful in rocket nozzle applications.

Jan 1, 1968

By Sabri Ergun

Previous studies of magnetic separation of pyrite from coals have been reviewed critically. Magnetic susceptibilities of United States coals of differing rank have been measured. The effects of crushing, magnetic mixing, drying, weathering, and heat treatment on the enhancement of the magnetism of pyrite have been analyzed. The importance of size distribution of pyrite in the coal and the necessity of crushing to liberate the pyrite has been discussed. It has been found that the inherent susceptibilities of the carbonaceous, mineral-free portions of coals (? -0.5 X 10-6 in cgs units) and of relatively pure pyrite isolated from coals (? -0.3 X 10-6) do not permit efficient separation of pyrite from coal; the average susceptibility of the magnetic fraction of coal must be raised to 3 X 10-6. Friction forces encountered in crushing sedimentary pyrite embedded in coal do not increase its susceptibility. Subsequent weathering or heat treatment below 400° C leads to the formation of iron sulfate and hence increases the effective paramagnetism of pyrite. Ferromagnetic compounds of iron are not formed in significant quantities at temperatures below 400° C. The degree of liberation and apparent susceptibility of pyrite are the most important parameters in its separation. It is concluded that effective beneficiation of coals can be achieved by magnetic separation. A sufficient increase in the susceptibility can be achieved by converting less than 0.1 percent of pyrite into ferromagnetic compounds of iron. Such conversions occur only at temperatures >500° C. An investigation of the dielectric properties of coals and pyrite in the frequency range 0.1 to 60 Mhz indicates that the imaginary dielectric constant of the pyrite is about 100 times larger than that of coal. Exploratory experiments indicate that pyrite can be selectively heated to temperatures above 500° C without appreciable rise in the temperature of coal. It appears that dielectric heating of coals in the Ghz frequency range is the most feasible method of enhancing the paramagnetism of pyrite.

Jan 1, 1968

Sphalerites from Devonian cassiterite-sulphide deposits and Pb-Zn-Ag fissure veins have similar ranges of Cd contents, but the average Cd and Fe contents could indicate a small initial difference in availability of Cd between the Zeehan-Renison Bell district and the Mt. Bischoff-Waratah district. Sphalerites from banded Pb-Zn deposits (Rosebery and Hercules) are characterized by low Cd content which is a world-wide feature of such deposits in exIrusive rocks, and may indicaIe a genetic relationship between ore deposition and vulcanism.

Jan 1, 1968

Jan 1, 1968

By Thomas M. Larimer

Prior to April, 1961, the coal charge to Clairtonts coke oven batteries was 3" x 0" mine waslied coal having approximately 6.0% to 7.0% moisture. Even at this size and moisture content, the arching, rat-holing and hang-up was excessive and the effective live storage of coal was only 60% to 70% of the rated capacity of the coal bunkers, depending upon the moisture of the coal. In addition, many production delays were encountered in the time and methods required to fill the larry cars. The need for an improved metallurgical coke led to the introduction of pulverized coal to a portion of the plant in 196 1. When the full potential of the pulverizing equipment was realized, we were able to serve seven batteries in our second unit of batteries with pulverized coal through two coal bunkers. The discharge hoppers of these bunkers were equipped with air vibrators to assist the flow of pulverized coal into the larry cars. The vibrators were helpful in this respect but required considerable maintenance and caused damage to the bin plates.

Jan 1, 1968

Jan 1, 1968

By Philip C. Good

Red mud residue from Bayer process treatment of Jamaican bauxite was dewatered in batch and in continuous centrifuges. Solids content of the residue was increased from its original value of 20 to 25 percent to about 40 percent by centrifuging. Clear effluent amounting to approximately 40 percent of the slurry liquid was recovered containing dissolved alumina and soda values for potential recycle to the alumina plant" Addition of a chemical flocculant to the centrifuge increased capacity by about 35 percent. Manufacturer's estimate of large-scale equipment requirements, based on data collected in this investigation, was that a proposed installation for dewatering 16,000 tons per day of Jamaican red mud would require twenty-two 24-by 60-inch solid-bowl-type centrifuges. Cost analysis of a proposed installation, based on a Jamaican red mud tonnage of 16,000 per day, is included also.

Jan 1, 1968