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By W. E. Howlett, R. L. Slobod

Jan 1, 1965

By Arne Landsberg

A study of the chlorination kinetics of germanium, silicon, iron, tungsten, molybdenum, columbium, and tantalum has been made to determine the effects of temperature, chlorine concentration, geometric surface area and gamma radiation. The reaction products were volatile at the temperatures used this making it possible to follow the reaction rates by weight loss of the solid. Chlorination rates of germanium, silicon, and iron were found to be directly proportional to chlorine concentration while the rates for tungsten, molybdenum, columbium, and tantalum were proportional to the 0.5 to 0.6 power of chlorine concentration. A good correlation of reaction rate and geometric surface areas was not obtained because the true surface area of the samples could not be measured. Intense gamma radiation had no effect on reaction rates. The Arrhenius activation energies determined over the temperatures used are as follows: Germanium, 27 kcal/mole (233°-241° C); silicon 33 kcaL/mole (375°-517° C); iron, cold rolled, 20 kcal/mGle (259°-325° C) annealed, 21 kcal/mole (293°-337° C); tungsten, 43 kcal/mole (617-776° C); molybdenum, 37 kcal/mole (445°-4910 C); columbium) 34 kcal/mole (229°?255° C); and tantalum, 29 kcal/mole (370°-449° C).

Jan 1, 1965

By H. G. Sell, G. W. King

An investigation was made of the lensile proper-ties of recrystallized high-purity tungsten and a W-1 pel ThO2 dispersed-phase alloy over the temperature region of 800° to 2400°C. The thoria addition resulted in a modest strengthening effect over the entire temperature region. A decrease in ductility of both materials occurred above 0.5 Tm which was caused by void formation. Current theories of IT has long been recognized that a second phase of hard particles has a strengthening effect on a pure metal. At low or intermediate temperatures (<0.5 Tm), the strengthening effect is thought to arise mainly from the interaction of dislocations with dispersed particles. Above 0.5 Tm, dynamic recovery processes greatly alter the deformation mechanisms from those simply involving glide, and grain bound- strengthening by a dispersed second phase do not adequately explain the tensile results. Melallographic examination suggests that the improved strength of tire alloy results from the effect of thoria on the mierostructure. Stress-dependent thermally activated processes were found to occur high temperatures. aries may act as sources of weakness rather than strength because of grain boundary sliding. Grain boundary sliding at high temperatures has been postulated to be the primary factor giving rise to the formation of voids or cavities at grain boundaries1-3 which in turn cause premature failure and poor ductility.4 Voids, once formed, can grow by the condensation of vacancies from the equilibrium concentration&apos; or from the excess vacancies produced by the deformation.4,5 The high-temperature tensile properties of unalloyed tungsten have previously been investigated by Sikora and Ha116 and also by Taylor and Boone.7 The purpose of the present work was to investigate

Jan 1, 1965

By C. J. Beevers

Tlze influence of zirconium hydride precipitate mprphology on the fructure of Zr-H alloys tested at strain rates of 10- sec at 20° and - 196°C and at strain rates of -500 sec.-1 at 20°C has been inves-tigated. The critical stage in the embrittlement of these alloys was the fracture of the zirconium hyhide precipitates to form large interval cracks at a stress of 25,000 10 137,000 psi. In specimens con-temping up to 100 ppm H the preciptates existed as isolafed platelets in the zirconium matrix and their fracture as enhanced by low temperature (—196°C) and high strain rate (-500 set-f) loading. These resl~lts lead to the conclusion that the rate of strain hardening of the zirconium metal controls the frac-tzrm of the hydride platelets. Increased hydrogen contents of 500 to 2000 ppm resulted in an increase in the 1)volume fraction and size of precipitates and crlso led to crack propogation in the hydride at both 20 and —196C at the low strain rates (10&apos;* sec-&apos;). Quenching led to refinerment of hydride precipitate size and reduced the degree of embrittlement at — 196°C; this effect is attributed to the absence of fracture of the fine precipitates. The formation of zirconium hydride precipitates has been shown to be the cause of hydrogen embrittlement of zirconium.&apos; Several investigators&apos;-" have studied the problem in broad outline, demonstrating that impact-loading conditions, testing temperatures below room temperature, and increasing hydrogen content produce increased brittleness. For example, Muehlenkamp and schwope2 showed that the transition temperature for notched impact tests was raised from 150" to 350°C on increasing the hydrogen content from 45 to 490 ppm. The degree of embrittlement is also controlled by the morphology of the zirconium hydride precipitates. The solubility of hydrogen in zirconium decreases from 600 ppm at 550°C to 10 ppm at 20"C,~ so that the form of the zirconium hydride precipitates (ZrH2) can be modified by varying the cooling rate through the Zr-aZr + ZrH2 phase boundary.= Forscher showed that quenching a specimen containing 35 ppm H from above 315°C resulted in a reduction in area of 70 pct at -196"C, whereas slowly cooling from above 315°C resulted in a ductility of half this value. The role of the hydride precipitate in the fracture process has been examined by Young and schwartz6 and more recently by westlake.&apos; From metallo-graphic observations on slowly cooled Zr-H alloys they have suggested that cracks are nucleated in the hydride precipitates by the interactions of twins in the zirconium metal with the hydride. The experiments reported in this paper show that crack propagation in the zirconium hydride precipitates is the critical stage in the embrittlement of Zr-H alloys. The factors influencing fracture of the hydride precipitates and crack propagation in the zirconium metal will be related to the problem of embrittlement. EXPERIMENTAL TECHNIQUES The zirconium used in these experiments was produced from an ingot of vacuum arc-melted iodide zirconium forged down to 1 in. diameter at 800&apos; to 850°C. The 1-in.-diameter bar was surface-machined and cold-swaged to 0.375 in. diameter. After a vacuum anneal at 800°C for 1 hr the hardness was 60 to 70 Vdh. The total impurity content was approxi-

Jan 1, 1965

By Jerry W. Ramsey

The Bureau of Mines examined a low-, a medium-, and a high-volatile Pennsylvania anthracite by densimetric methods using four mesh si.s of each anthracite. Using high-pressure mercury the macropore volumes and distributions of these pore volumes determined, densities in mercury were calculated, and specific pore vo1.r. ware obtained from these mercury densities in conjunction with helium densities. The helium densities were also used with the ultimate analyses of these anthracites in calculating structural parameters by statistical densimetric methods. The effect of 106 or 108 rads of gamma irradiation in the presence of air and in vacuum upon the properties studied with two mesh sizes of each anthracite. Results of the statistical densimetric method seem to show some breakdown of condensed ring structural units at the lower irradiation level, with subsequent polymerization at the longer period of gamma irradiation. The structural parameters obtained also indicated that in going from high- to low-volatile anthracite, either the number of condensed rings per structural unit increased, or the degree of polymerization increased.

Jan 1, 1965

By Robert E. Barieau

In the design of plants to separate helium from natural gas, it is necessary to estimate the enthalpies of the various streams at various positions in the process. This Bureau of Mines report surveys the various methods that have been used to determine enthalpies and gives information on the organizations with such capabilities. The minimum information required for developing an enthalpy diagram is presented, and the relative merits of the various methods are discussed. It is concluded that methods that require no mass flow rate or energy measurements are to be preferred.

Jan 1, 1965

By R. B. Anderson

SULFUR poisoning of iron catalysts in the Fischer-Tropsch synthesis was investigated at the Bureau of Mines, because synthesis gas produced from coal contains sulfur compounds. Tests of two typical iron catalysts with synthesis gas containing known concentrations of H2S were made to determine catalyst life as a function of sulfur concentration to ascertain the type of gas purification required. Fixed beds of activated steel turnings and a fused iron oxide catalyst were investigated in sulfur poisoning tests at 21.4 atmospheres with IH2+100 gas containing 6.9, 23, or 69 mg S as H2S per cubic meter (0.3, 1.0, and 3.0 gr per 100 cu. ft.). In tests of reduced catalysts at constant temperatures, more than 80 percent of the activity was lost when 0.5 mg S/g Fe was introduced. Poisoning of nitrided or carbided fused iron oxide catalysts to a given extent required more than twice as much sulfur than for the corresponding reduced catalyst. When the synthesis temperature was increased to compensate for loss in activity, tests of the fused iron oxide catalysts at constant productivity could be continued for 19 to 98 days. The tests were terminated by clogging of the reactor, presumably caused by carbon deposition. One objective of the present work was to determine if synthesis gas, purified by the Bureau of Mines&apos; hot-potassium carbonate process for removing H2S, OOS, and CO2, is suitable for synthesis on iron catalysts. The sulfur content of the gas purified by tills process is in the range of concentrations used in the present work. In constant-productivity tests of nitrided fused iron oxide catalysts with synthesis gas containing 6.9 mg S/m3, catalyst lives are nearly long enough for serious consideration of tills mode of operation. However, factors relating to selectivity and stability of the catalyst indicate that this type of operation is impractical for a commercial process. On this basis additional gas purification, such as iron oxide boxes following a hot potassium carbonate scrubber, is desirable.

Jan 1, 1965

By A. J. Kauffman

This study compiles data on the zircon resources of the Pacific Northwest States, Alaska, and California, to determine the productive capability of industrial concerns to make ductile zirconium and hafnium, and to investigate markets for the nonmetallic products of zircon. West coast zircon resources are large but mostly marginal to submarginal. Development of a stable and profitable zircon mining industry on the west coast will depend upon recovery and utilization of the other associated heavy minerals needed by regional and national markets. The west coast has the only completely integrated facility for processing zircon sand to reactor-grade zirconium and hafnium and for making fabricated products from these metals. The future of the zirconium metal industry appears to be good because of increased use of the metal for nuclear propulsion and power-generating plants.

Jan 1, 1965

To enable ammonium nitrate-fuel oil (AN-FO) to be used on an equal weight basis with nitroglycerine explosives, smaller diameter bore holes became necessary with consequent modifications to drill steel and burden on holes. Detonation of AN-FO in small diameter holes proved successful both with and without primer charges but some alterations were required to adapt anoloders to the smaller holes.Important factors in training all operators in the new charging method were the retention of improved fragmentation, avoidance of excessive overbreak and keeping wall rock dilution to an absolute minimum. The successful storage of ammonium nitrate in climatic conditions with daily temperature fluctuations above and below the critical 90&#176;F has been achieved.INTRODUCTIONTechnical aspects of ammonium nitrate-fuel oil (AN-Fa) blasting agent are well covered in recent literature. This paper deals primarily with the manner of its introduction as the principal explosive underground at Great Boulder Gold Mines Ltd. and with the many problems encountered in the process. Following reasonably successful experimental firings in June 1962&apos;, using granular ammonium nitrate and an anoloder, permission was granted by theWestern Australian Mines Department to carry out test work in selected areas of the mine. The permit allowed for fuse firing only, and for a mixture of AN-Fa containing between 5t and 6 per cent fuel oil, with an adequate primer.The use of AN-Fa on an equal weight basis with nitroglycerine explosives, involved smaller diameter holes with alteration to ground burden and modification to drill steel.Initial tests indicated that it was apparent that AN-Fa could not replace gelignite on an equal weight basis if the...

Jan 1, 1965

By Larry A. Haas

The Bureau of Mines constructed a torsion effusion apparatus to measure the equilibrium vapor pressure of pure metals, alloys, and compounds at temperatures up to 1,500° K. The reliability of the apparatus was established by determining the vapor pressure of silver. The data obtained on solid and liquid silver in the temperature range 1,200° to 1,500° K can be expressed by the following equations:

Jan 1, 1965

By C. H. Schack

Extractive metallurgy techniques currently employed to recover silver from primary ores and secondary scrap were reviewed and evaluated to identify and delineate metallurgical problems whose resolution would increase the supply of silver from domestic materials. The survey revealed that practically all primary silver is recovered by froth flotation concentration of various types of ores, followed by smelting and refining of the separate lead, copper, and zinc concentrates. Silver losses during the complex processing are, with rare exception, inconsequential. Furthermore, any silver production gain from base metal ores, which contribute about two-thirds of the total primary silver, is directly dependent in improvement in the market for the base metals. Statistical data on new and old silver scrap are wholly inadequate to make reliable conclusions about scrap processing problems and the possibility of increasing the recovery of silver from the many forms of secondary silver- bearing materials. The available information indicates (1) that efficient silver reclamation practices are employed by the larger users of silver, and (2) that recovery of additional secondary silver involves solution of problems of collection rather than of processing. Several possibilities exist for limited increases in silver production from primary ores by improvement in metallurgical practices. Specifically, research is needed to (1) solve the problem of recovering silver from the copper ores of the Copper Range district, Michigan; and (2) devise economically feasible methods for recovery of silver from presently marginal or submarginal ores that because of grade, location, and frequently complex nature cannot presently be exploited by conventional techniques.

Jan 1, 1965

By L H. Warren

The types of equipment available for generating a plasma have been reviewed. The efficiency and potential of the plasma generating equipment used in performing extractive metallurgical reactions have been determined. A general classification of the reactions that might be per-formed in a plasma has been proposed. Experimental work done on extractive metallurgical plasma reactions, heat transfer between the plasma and solids, and the quench of the products of plasma reaction has been summarized. From the preliminary results it appears that the high-intensity are or the transpiration-cooled anode plasma torch offer the most promising areas for further research. C ONSIDERABLE world-wide research effort is currently being devoted to the development of processing technologies which employ the new high-temperature generating devices that have appeared over the past few years. The plasma flames produced by these devices offer the potential for subjecting materials to any single gas or mixture of gases at temperatures up to 20,000°K. With these conditions available, many reactions in extractive metallurgy,

Jan 1, 1965

By T. C. Davis

Nine organic derivatives of fluorine, silicon, boron, and aluminum were purified for thermodynamic studies using distillation, zone melting, and gas liquid chromatography, The unusual properties of these compounds required the development of special techniques for handling and purification. To determine purities of purified samples, new techniques for analyzing spectral data were developed.

Jan 1, 1965

By H. A. Schrecengost

Information presented herein was gathered by examination of 29 fluidized-bed thermal coal dryers and by conferences with manufacturers and users of such equipment to determine what safety features could b incorporated in design, installation, and op ration to minimize fire and explosion hazards. Fire and explosion hazards are inherent in certain types of coal dryers in that high temperatures are employed; the sizes and volatility of material handled are capable of propagating explosions; and drying gases are seldom, if ever, low enough in oxygen content to prevent ignitions of dust clouds, distilled gases, or their combinations. This is especially true for fluidized-bed dryers in which the coal is dried in air suspension and in which atmospheric air is constantly introduced to temper the heated furnace gases. Occurrence of fires on hated bedplates, in dust collectors, and in hot gas inlets was common in nearly all the dryers examined. Forceful explosions which produced external effects had occurred in 11 (39 percent), and internal "puffs" or ?bumps? had occurred in at least 24 (79 percent) of the plants examined in the study.

Jan 1, 1965

By James S. Browning

The Bureau of Mines conducted laboratory batch and pilot plant flotation tests to determine the technical feasibility of recovering commercial-grade mica from a California micaceous schist. Best results in the laboratory batch tests were obtained using sodium carbonate and sodium silicate for pH control and quartz depression, and a combination of fatty acid and cationic reagents as the mica collector. In continuous pilot plant flotation tests, an alkaline fatty acid-cationic method recovered about 70 percent of the mica in a concentrate analyzing 95.6 percent mica.

Jan 1, 1965

By F J. Kelly

A chemical process, based on laboratory investigations, is proposed for the production of high-purity niobium oxide from a pyrochlore-perovsk1te flotation concentrate produced from ore obtained at the Oka, Quebec property of Columbium Mining Products Limited. The method developed included the decomposition and dissolution of the flotation concentrate with hot, concentrated sulphuric acid. The dissolved niobium was purified and concentrated by a solvent extraction step, using methyl isobutyl ketone as the extractant. The niobium was recovered from the extractant with ammonium fluoride solution from which niobium oxide was precipitated with ammonia. Finally, the filtered and washed precipitate was calcined. Ninety-six per cent of the niobium was recovered in a product analysing 99.9 per cent Nzo.. The reagent cost was in the range of $1.00 to $1.25 per pound of niobium recovered. Introduction OVER the past few years, Columbium Mining Products Limited has been engaged in the development of a niobium-bearing mineral deposit in the vicinity of Oka, Quebec. One phase of this program resulted in a flotation process capable of producing concentrates containing up to 50 per cent Nb205? Flotation pilot-plant

Jan 1, 1965

By John Nagy

Results of initial research by the Bureau of Mines are given on the dust explosion hazard of float coal and on the related factors of occurrence, rate of production, sampling techniques, transport, and deposition of float coal. Tentatively, it is suggested that where float coal deposits prevail, a mini-mum of 80 percent incombustible be maintained in the top 1/8-inch layer to neutralize the explosion hazard of the surficial coal deposit.

Jan 1, 1965

By Wilbur I. Duvall

A linear array of shot and gage holes 30 feet deep in a granite outcrop was used to compare the size and shape of radial strain pulses produced in the rock when short cylindrical charges of cast composition B were detonated axially or at one end. The axially detonated charges produced radial strain pulses that had shorter rise times and larger peak strain than the strain pulses produced by end detonated charges.

Jan 1, 1965

By J. P. Neumann, L. Raymond

At temperatures near 1000°C, only the (112) (111) slip systems are operatire in tungsten. Therefore, the substructure introduced into the billet upon rleforming a single crystal by rolling at 1000 "C can be controlled by proper selection 01. processing ral&apos;iubles. Using a reduction of 10 pct pel- pass, the (001)[110] and the (110)[001] crystals will deform by duplex slip rip to a 50 pet reduction in thickuess. These rolled single-crystal sheels are characlerized by anisotropic hardening, retention of ductility with warm working, lattice bending which is related to the conlacl (angle, and macroscopic dimensional changecs in the length bid not the width of the billet. When several slip systems become operative, a greater degree of work hardening is itztvoducetl into the crystal. This rolling- condition is characlerized by isotropic hardening, loss of ductilily with warm working, complex lattice distortions, and macro-scopic dimensional changes in both the length rind Width of the billel. IN tungsten, the {1 10}(111) slip systems are operative below room temperature,&apos; while above 700°C only the {112{ (111) slip systems are observed.2,3 In the transition region, i.e., room temperature. both systems appear. It is the purpose of this investigation to show that tungsten single crystals deformed by rolling at a temperature where only one slip system is operative generate dislocation substructure which depends on the crystal orientation. For a specific crystal orientation. the resulting dislocation substructure can be further influenced by modifying the rolling procedure. Crystals oriented for multiple slip display less substructural sensi- tivity to modifications in processing techniques than do single crystals oriented for duplex slip. Under simple slip modes of deformation, very little work hardening is introduced into a rolled single-crystal sheet. Mechanical properties such as room-temperature strength. ductility, and hardness are used to confirm the existence of the different work-hardened conditions generated within the crystal by modified warm-rolling techniques. EXPERIMENTAL PROCEDURE Material. Single-crystal billets of four different crystal orientations. grown by the Arc-Verneuil technique. were ground to a size of 0.25 by 0.375 by 3 in. In terms of their rolling plane and rolling direction, the billets had the following orientations: (1101 [001 ] (110) [110] (001) [110] (001) [100] The actual orientation of all crystals was within 5 deg of the ideal orientations. The typical impurity content of the crystals is given in Table I. Polishing and Etching. Polishing was done elec-trolytically in a 20 g per liter aqueous solution of NaOH at approximately 10 v. It was established by the Laue back-reflection X-ray technique that the surface damage due to grinding and cutting operations with a diamond wheel did not exceed 0.001 in. Therefore after each cutting or grinding operation at least 0.002 in. was removed electrolytically from the surface in order to eliminate surface effects. By lowering the voltage to 3 v, subgrain boundaries and individual dislocations are identified in agreement with Berlec 4 where the etch-pit traces on a cubic plane form a square. The etching time was about 5 sec at room temperature. Rolling. Rolling was carried out on a Loma 2-high mill (Model 600). The peripheral velocity of the 6-in.-diameter rolls was 500 in. per min, with the surface temperature of the rolls about 400° to 450° C The billets were heated before each pass for 30 min in argon to 1000 C. Oxidation of the crystals during rolling in air resulted in a thin layer of greenish-yellow WO 3 This oxide was removed after each pass by immersing the crystals for a few minutes in a boiling NaOH solution. Prior to the initial rolling pass, a surface layer of 0.001 in. was removed by polishing. The crystals were then annealed in vacuum (10-4 torr) at 2400 C for 30 min. All crystals were rolled in the same direction; i.e., the same end was always introduced into the rolls. The rolling program was conducted in

Jan 1, 1965

By B. A. Wilcox, A. H. Clauer

DURING the course of an investigation on the high-temperature creep behavior of TD Nickel* (Ni + 2) vol pct ThO2), it was observed that the creep fractures were similar in appearance to low-temperature ductile fibrous fractures and creep ruptures by cavitation. Microfractographs of fibrous ruptures are typically characterized by a dimpled appearance, with second-phase particles frequently found near the bottom of the dimples.&apos;-4 These somewhat resemble creep ruptures by cavitation, in that fracture occurs by void formation, with the subsequent growth and final merging of the voids to form a complete fracture.&apos; It is the purpose of this communication to describe the creep fracture of TD nickel and suggest a mechanism for the rupturing process. The discussion is relevant to material crept to fracture in vacuo at a constant stress of 18,000 psi, over the temperature range 900" to ll00°C. The material used in this investigation was 1/2-in.-diam bar stock supplied by Du Pont, contain- ing 2.3 vol pct Tho2. The final fabrication treatment consisted of -95 pct reduction by swaging followed by a 1-hr anneal at 1000°C. Transmission and replica electron microscopy revealed that the material had a fibered structure with a transverse grain size of -1 µ and a longitudinal grain size of 10 to 15 µ. Selected-area diffraction indicated that the fiber axis was parallel to (00l), in agreement with the results of Inman et a1.6 The thoria particle size varied from 80 to 1000Å, with an average size of 400Å, and the mean particle spacing was about 1200Å. The remarkable structural stability7 was confirmed by annealing for 6 hr at 1300°C (about &apos; 0.9 the absolute melting point). Transmission electron microscopy revealed that the only structural change was a slight decrease in dislocation density. Furthermore, recrystallization or grain growth during creep has not been observed. All specimens were annealed in vacuo at 1300°C for 3 hr prior to creep testing. The following times to rupture were obtained for vacuum creep tests at a constant stress of 18,000 psi: 900°C, 854 hr; 930°C,

Jan 1, 1965