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By W. S. Cavender

The Round Mountain mining district, Nye County, Ne- vada, was discovered in 1906 on claims owned by Lewis D. Gordon. Initial mining operations uncovered gold veins of spectacular richness, and within a few days of discovery, Gordon sold his controlling interest for some $87,000. From this sale emerged the Round Mountain Mining Co., predecessor of Nevada Porphyry Gold Mines, Inc., the latter destined to become the major property owner in the area. Vein mining in the district continued sporadically into the early 1930s, yielding 9.3 Mg (330,000 oz) of gold plus substantial silver credits from approximately 626 kt (690,000 st) of ore. In addition to the lode deposits, the early miners recognized the placer potential in the alluvial fan material accumulated around the west and north sides of Round Mountain itself. Intermittent placer operations were carried out for a number of years, and in the 1940s and 1950s, Round Mountain Gold Dredging Co. worked the placers under a lease from Nevada Porphyry Gold Mines. The last placer operation terminated in 1959 when it, like some of its predecessors, proved uneconomic. Total placer production for the district is estimated at 3657 km (4 million yd) of gravel containing 59 Mg (210,000 oz) of gold and possibly 2.0 to 2.3 Mg (70,000 to 80,000 oz) of silver. Round Mountain is a small hill situated on the east flank of the Toquima Range in central Nevada. The hill is com- posed of relatively flat-lying Tertiary rhyolitic ash flow tuffs, which overlie Paleozoic metasediments and Cretaceous granites. Throughout the surrounding Round Mountain mining district, most of the known gold ores occur in the tuffs, although the metasediments and granites are also mineralized. Mineralization is structurally controlled, principally by a series of northwest-trending shears and shattered zones. Vein, stockwork, and disseminated ores occur, usually containing simple quartz-pyrite-gold mineral assemblages. The gold itself is electrum, having a silver content of 30% to 40%. In September, 1967, Elwood Dietrich, a prospector and mine promoter, obtained a purchase option on the 4452 ha (1 1,000 acres) of mineral rights held at Round Mountain by Nevada Porphyry Gold Mines. The original option had a buy-out price of $1 million and was established through Dietrich's friendship with officers of Nevada Porphyry. In April, 1968, Dietrich conveyed his option to Ordrich Gold Reserves Co., a partnership created by a group of west coast investors, mostly employees of the airline industry. There- after, Ordrich invested considerable funds in trying to test and develop the property, but soon recognized the need to seek financial and technical support from the mining industry. In December, 1968, Dietrich contacted Wayne Cavender, then Regional Geologist, Southwest, for Copper Range Exploration Company (CRX) in Tucson, Arizona, and made a data presentation. Shortly thereafter, Cavender was appointed Manager of Exploration and Chief Geologist for Copper Range Co. (parent company of CRX), New York City, and he asked C. Phillips Purdy, CRX Regional Geologist, Northwest, to make an initial property examination. Purdy's one-week field study took place in March, 1969, and resulted in a recommendation that CRX pursue its investigation of the property. The presence of low-grade gold mineralization in both the alluvial gravels and in the bedrock was verifiable, but the placer was deemed to have the greater immediate economic mining potential. At that time, gold was in the $1.41/g ($40 per oz) price range. Working from Purdy's information, Cavender decided to attempt acquisition of the property, and the first in a long series of negotiations was initiated with Ordrich. Basically, CRX felt that the placer had a promising potential for several reasons, including (I) past operators had recovered free gold but not the gold contained in the pebble fraction of the gravels; (2) past operations appeared to have been ineffectively designed or managed and not costefficient; and (3) the price of gold appeared to be poised for an upward move. Negotiations with Ordrich were prolonged and difficult, with CRX competing against several ma* mining companies, but finally an agreement was reached, effective June I, 1970. Gold was then back to $35. It is believed that, in

Jan 1, 1985

By Hsun Hu, R. S. Cline

The effect of rate of deformation on texture formatiotz has been studied with cube-oriented single crystals of 3 pct Si-Fe, compressed 80 pct at two widely different rates. Compression at a low rate (crosshead speed, 0.1 ipm) produces large orienta-tional changes and coarse deformation bands, whereas little change in orientation is observed, particularly at the surface of the crystal, when compressed at a high rate (impact velocity, -500 ips). Thin plates of mechanical twins are produced at the high rate, but their contribution to the deformation texture is practically negligible. The crystal deformed at a high rate has a lower hardness and a more uniform dislocation structure and is morc resistant to recrystallization. There is also a dilference in the recrystallization texture between the slowly and rapidly compressed crystals. These results indicate that plastic flow is less "turbulent" at high strain rates than at low strain ratcs. THE behavior of metals under high-speed deformation has been the subject of wide study in the past decade. Most of these works were concerned with mechanical properties during testing at high rates of loading, the resulting structures, and the theoretical aspects of the observed phenomena. The present status of knowledge and research activities in this field has been documented in recent publications.17' There is, however, very little information available in the literature concerning the effect of high-speed deformation on the texture formation in metals. The possibility of an effect of rate of deformation on texture is suggested by the microstructural differences observed between normally and very rapidly deformed samples. Aside from the strong tendency for twinning (and phase transformation in certain metals) in high-speed deformation, the slip-line patterns and the dislocation configurations show marked differences as a result of large differences in the strain rates. For instance, in mild steel in static and dynamic compression, Campbell and co-worker3,4 observed that coarse slip occurred on several systems in specimens deformed at normal strain rates, whereas specimens deformed rapidly showed only fine slip on fewer systems, the slip-line pattern being very similar to that in specimens deformed at low temperatures and at normal strain rates. The absence of multiple slip was also noticed by Dieter5 in shock-loaded nickel. The dislocation configuration in an iron shock loaded at 70 kbar pressure was shown by Leslie et al.6 to be similar to that produced by light rolling at low temperature—the dislocation lines were mostly straight and uniformly distributed. These observations suggest that the mode of deformation at high strain rates is notably different from that at low strain rates. Consequently, the nature and the extent of lattice reori-entation during deformation should also be different. This investigation was undertaken to test this idea. MATERIAL AND METHOD The remaining part of a single-crystal ingot of a 3 pct Si-Fe alloy,* prepared for an earlier investi- gation,1 was used in the present studies. Specimens 9/16 in. square and 0.365 in. thick were cut from this ingot with (001) planes parallel to the square surfaces, and the [loo] and 1010] directions parallel to the edges of the specimen, within ±1 deg. These machined crystals were etched to remove distorted metal, and annealed at 1300°C for 24 hr in a purified helium atmosphere. The annealed crystals had a hardness of 161 Dph. The crystal orientation was rechecked with X-ray back-reflection techniques. In high-strain rate experiments the crystal was compressed in a Dynapak machine to approximately 80 pct reduction in thickness (from 0.360 to 0.070 in. with an impact velocity of -500 ips). Thus, the duration of loading was approximately 6x 10-4 sec, and the average strain rate was about 103 sec-1. As a result of this rapid, severe deformation, the specimen became a roughly circular thin disc. The original shape of the crystal, however, could still be recognized by a diffusely outlined square area in the center of the disc. For compression at a low speed, the crystal was deformed in a universal testing machine at a rate of crosshead movement of 0.1 ipm. Compared with

Jan 1, 1965

By D. M. Schuster, E. Scala

The elastic effects occurring in the matrix of a composite reinforced by discontinuous fibers were studied by means of photoelastic techniques. A hirefringent plastic was employed as the matrix material with high-strength a Al2O3 whiskers as the reinforcing fibers. It was found that for whiskers aligned parallel to the tensile load direction: (I) Matrix reinforcement occurred along the length of the whisker to within about 5 diameters of the whisker tip for a length to diameter ratio, L/D, of 40. (2) Significant stress concentrations were created in regions immediately surrounding the tips; the fine as-formed tapered ends exhibited the minimum stress concentration whereas the square-ended whisker produced relatively high values, K r 2.5 for L/D = 40. (3) The axial and radial stress distributions could he determined quantitatively; the stress distribution at the whisker-matrix interface was in general agreement with theoretical calculations. (4) The highest source of stress concentration occurred at points of fracture in whiskers which had ruptured after incorporation into the composite. Whiskers aligned perpendicular to the load direction neither reinforced nor caused appreciahle stress concentrations in the matrix. ThE properties of composites have generally been formulated empirically on the basis of macroscopic tests. There are still many questions concerning the mechanical and chemical interactions occurring at the interface between the reinforcing fiber and its matrix. Continuously reinforced plastics and dispersion-hardened metals represent the two extremes of composite reinforcement. Whether artificially produced or formed in situ, the whisker composite falls between these two extremes and is an example of discontinuous fiber reinforcement. The effect of fiber shape, size, surface condition, and end configuration on the stress distribution in the matrix is important since the presence of stress concentrations, especially in any high-strength, thin-wall structure, could become the cause of catastrophic failure. DOW,' in his theoretical discussion of discontinuous fiber reinforcement, has pointed out that appreciable stress concentrations occur at the tips or ends of the reinforcing fibers. It is the purpose of this study to examine directly, by means of the photoelastic technique, the stresses which occur in the vicinity of a discontinuity or whisker tip and to measure qualitatively and quantitatively the effects of whisker geometry when embedded in a birefringent matrix material. The use of sapphire (a A1,O3) whiskers was decided upon as the reinforcing agent because of their high elastic modulus (E- 60 X 106 psi) and in some cases strengths in excess of one and a half million psi. Sapphire whiskers are of further practical interest since they retain large fractions of their strength up to temperatures approaching the melting point (3720oF).2 The whiskers were grown, by the vapor-phase reaction commonly employed,3 as part of this study to insure a physically uniform supply. Tensile and bend tests were performed to verify that the whiskers were of the expected ultra-high strength. The high-strength whiskers can be identified and selected from the combustion boats by surface perfection, shape, and size; otherwise, strength values can vary by a factor of ten or more. Macroscopic defects are quite common on the surface of large bladed whiskers and the principal experiments were conducted with hexagonal whiskers of about 0.002 in. diameter and lengths ranging from 0.1 to 0.4 in. Upon completion of these two phases of the experiment, several birefringent resins were evaluated. A plastic, developed by Zandman,4 which is supplied by the Budd Co., was found most suitable and was used as the matrix material for the whisker composite throughout the study. It has a sensitivity of 60.5 lb per in. order, calibrated in tension and cures without introducing residual stresses. Young's modulus for this matrix material is 430,000 psi in the fully cured condition. Since good wetting and bonding between the sapphire and the matrix material is essential to the interpretation of the results, a wettability test was performed. The contact angle was measured to be 168 deg where perfect wetting is defined as 180 deg; therefore, the Budd Plastic wets the sapphire

Jan 1, 1964

By R. R. French

Investigations were conducted by the lndiana Geological Survey for some dry methods of bene-ficiating low-grade gypsum ore. Seventy-two batch and continuous flow tests were performed with a roller mill, rod mill, pebble mill, electronic color sorter, electrostatic separator, and an air separator. Approximately 650 size analyses and 550 chemical analyses were performed during the investigation. Batch samples were tested by the Survey, and most of the continuous flow tests were handled by com-mercial laboratories. INTRODUCTION Although many companies producing gypsum have been interested in dry beneficiation, very little information has been published in the past. One of the most comprehensive investigations was reported by the Canadian Department of Mines.5 Other reports of interest have been published by the Canadian Department of Mines,' the South Australian Department of Mines,2 and the U.S. Bureau of Mines.3 Some beneficiating practices, such as hand picking, selective mining, crushing and screening, milling, and air classifying, were already in use in the Canadian industry prior to MacPherson's investigations.5 MacPherson examined the effect of tabling, air separation, screening, flotation, electrostatic separation, calcining, washing, and various types of milling, in his efforts to eliminate dolomite, limestone, and small amounts of silica and clay from the gypsum ore. RAW MATERIAL Gypsum and anhydrite occur within the lower part of the St. Louis Limestone (Mississippian) in southwestern Indiana. Gypsum in single beds 10 or more ft thick occur at Shoals, Martin County; near Freedom, Owen County; near Bloomfield, Greene County; and in the Devonian strata of LaPorte County. Only the Shoals deposit has been exploited commercially. The western edge of the Shoals deposit is contaminated by a continuous bed of shale, about 1 1/2 to 2 ft thick, near the top of the evaporite and by thin continuous strata or irregular masses of carbonate rock. The low-grade material used in these investigations was obtained from the waste pile of the National Gypsum Co.'s plant at Shoals. The waste ore averaged about 67.4% gypsum and was contaminated by various amounts of shale, dolomite, and limestone. All the material had been previously crushed and screened to minus 1 1/4 to plus 3/8 in. X-ray analyses of powdered, sedimentated, gly-colated, and heat-treated samples of the shale showed that it was composed of slightly structurally disordered illite, Fe-rich chlorite, and very finegrained disseminated silt. The clays and silt were partly cemented with carbonate material. Light-gray argillaceous limestone and gray or brown porous dolomite made up most of the carbonate rock contamination. Crushing Characteristics: The rate unweathered gypsum, carbonate rock, and shale reduce in size was determined by crushing handpicked samples in a rod mill and screening at minus 100 mesh (.0059 in.). Fig. 1 graphically represents the data. These data indicate that carbonate rock should be relatively easy to separate from gypsum, but that shale should be difficult to separate from gypsum by differential crushing. Controlled Samples: Eight rod mill tests of hand-picked samples of mixed gypsum and shale and mixed gypsum and carbonate rock were made. Sample weight and crushing weight were standardized, but the scalping screen size was varied from 3 to 10 mesh (.265 to .0787 in.) in order to obtain the optimum purity and recovery. The data obtained from the tests (see Table I) illustrate that the relatively hard carbonate rock allows appreciable beneficiation (13.6 to 18%), but the low strength gypsum and shale allows only minimal separation (3.1 to 7.5%).* Semi control led Samples: During the investigation considerable slaking of the shale was noted when the ore was subjected to alternate wetting and drying. As demonstrated in laboratory tests, as much as 76% shale can be removed by two cycles of wetting and drying in a 48-hour period with subsequent screening at .265 in. Five ore samples, stockpiled and weathered, were screened, rod-mill crushed and rescreened at .157 or .187 in. with excellent results (Table 11).

Jan 1, 1967

By P. S. Kotva

Dislocation substructures in superalloy matrices of varyzng co)npositions have been studied. In general, it has been found that the alloys can be classified into ''high", ''medium", and "low" stacking fault energy classes based on the type of dislocation substructure observed in the matrix and that the substructure can be correlated to the stacking fault energy. The effect of different types of dislocation substructure and dislocation reactions on the intragranulur precipitation of carbide phases has been studied. In a Ni-Cv-Mo-Fe matrix, precipitation of MC carbides in association with stacking faults has been observed. In most superalloys, solid-solution strengthening and precipitation hardening are the chief mechanisms employed to achieve strength. The latter contribution to strength is usually achieved by the precipitation of / in certain wrought alloys. Insufficient attention has been given to the problem of obtaining strength in su-peralloys by controlling precipitation of carbides on imperfections within the matrix. The present work was undertaken to investigate the dislocation substructure in various superalloy matrices, to study the effect of such substructure on subsequent precipitation of carbides in the matrix, and to investigate whether certain modes of precipitation of carbide phases found in austenitic stainless steels2"4'6 would occur in nickel-base alloy matrices with dislocation substructures of the same type as those found in austenitic steels. 1) EXPERIMENTAL TECHNIQUES Five-pound heats of the various alloy compositions reported here were vacuum-cast. The ingots were given light deformation by rolling to break up the as-cast structure and then homogenized for 24 hr. HASTELLOY alloy X (nominal composition: Ni-2OCr-17Fe-8Mo-0.05C) was homogenized at 2150°F and In-cone1 625 (nominal composition: Ni-20Cr-5Fe-8Mo-3.5Cb-0.05C) was homogenized at 2280°F. Fabrication of 0.004-in. sheet was achieved by cold rolling with intermediate annealing treatments being carried out at the same temperature as those used for homogeniza-tion. Each solution anneal was followed by quenching. The aim of this procedure was to redissolve as much of the primary carbide phase as possible. Samples of the 0.004-in. sheet were cut and encapsulated in quartz capsules and then heat-treated in the tube furnaces. Thin foils were prepared using an ethanol-10 pct perchloric acid bath at 32°F and at a voltage of 22 v. A "window" technique was employed. Observations were made on a JEM-7 electron microscope operating at 100 kv. 2) EXPERIMENTAL RESULTS a) Types of Dislocation Substructure. Fig. 1 shows a schematic correlation between stacking fault energy, SFE, and the type of dislocation substructure observed in various matrices of nickel- and cobalt-base alloys. A precise quantitative determination of stacking fault energy is not implied in the figure but the correlation between stacking fault energy and the type of dislocation substructure obtained allows alloys to be divided into three classes in analogy with the classification employed by Swann and ~uttin~' for binary alloys of copper. Class I alloys are associated with a "high" SFE and show a cellular substructure of dislocations as typified by the micrograph of a thin foil of pure nickel deformed 4 pct at room temperature in Fig. 2. With decreasing SFE the tendency toward cell formation is lessened and dislocations tend to be arranged in coplanar groupings. Examples of this class of alloys with "medium" SFE are provided by the mi-crostructure of solution-heat-treated, quenched, and deformed thin foils of HASTELLOY alloy X, "Waspaloy" (prior to any aging), and Inconel 625. Fig. 3 shows a thin-foil micrograph of an alloy of Inconel 625 composition, solution-heat-treated, quenched, and deformed 5 pct at room temperatures. No evidence of any cell structure can be obtained in materials of "medium" stacking fault energy, Fig. 3, even after severe deformation. The stacking fault energy of the alloy shown in Fig. 3 is, however, not low enough to make the dissociation of dislocations visually obvious. As stacking fault energy decreases further, with successive addition of solute in the matrix, there is an increased tendency toward dissociation of dislocations and cross slip becomes progressively more difficult. Eventually, when the stacking fault energy is "low" enough, complete dissociation of dislocations is seen to occur as shown in Figs.

Jan 1, 1969

By Paul G. Shewmon

The migration of slightly solzrhle spherical particles through a solid under the infllrence of a temperature gradient is analylzed for the cases of various transport mechanisms. It is shown that the variation of the velocity of the particles with radius, r, depends on the dominant mechanism of matter transport around or through the inclusion. Thus the velocity varies as r-1 jor surface-dijf1~sion controlled migratzon. is independent of r for volume diffusion in either phase, and varies as if the rate is determined by an interfacial reaction (n is the order of the interfacia1 reaction). These same results hold tor the migration of a cvlinder of length much greater than its radius. and .for other types of potential gradients, e.g., an electrical field. These equations are combined with recent electron-microscopic ohservations to show that the rate of migratzolz of small helium-silled bubbles through copper is determined by surface diffusion of the metal atoms. With these equations and the temperature gradients attainahle in an electron-microscope joil, the dominant transpar/ mechanism (or any migrating pnrtzclos can he determined. AS a result of fission, rare-gas atoms are created in the hot fuel element of a nuclear reactor. These insoluble atoms precipitate to form bubbles of the gas in the fuel. The subsequent migration and coalescence of these bubbles is thought to play a dominant role in the swelling of fuel elements which in turn can limit the fuel-element life. As a result of this practical problem and because of the relative simplicity of the system, workers in several laboratories have imbedded rare-gas atoms in metals with the aid of an accelerator and studied the formation and behavior of the bubbles that form on annealing. Recently Barnes and Mazey have studied the migration of such helium-filled bubbles in copper foils using the electron microscope and the temperature gradient that can be induced in the foil by the electron beam. They found that the smaller bubbles moved faster than the larger ones. It is shown below that, if this is true, the rate-controlling step in their migration is surface diffusion of metal atoms instead of volume diffusion, vapor transport, or an interfacial reaction. The analysis given is in no way limited to gaseous inclusions so the variation of velocity with particle size for any relatively insoluble precipitate particles could be used to obtain information about the relative importance of surface diffusion, volume diffusion, and interfacial reaction in such two-phase systems. VOID MIGRATION IN A TEMPERATURE-GRADIENT ANALYSIS Barnes' studies indicate that helium does not dissolve or diffuse in metals to a measurable extent, so that when the voids move they must do so through the movement of metal atoms from the leading to the trailing sides of the void.' Thus voids might move by surface diffusion, diffusion of vacancies in the surrounding lattice, or vapor transport. We consider first the case of flow by surface diffusion alone. We assume that there is a force, in the sense of irreversible thermodynamics, tending to move the atoms around the bubble in a given direction. We designate this direction as the x axis and the force per atom as Fa. The net rate of flow of atoms from one side of the bubble to the other, under the influence of this force, is the surface flux, Js, times the cross-sectional area available for flow, A,. A, is taken as the circumference times the thickness of the high-diffusivity surface layer 6. Thus where 51 is the atomic volume. For bubbles to advance a distance dx, a volume equal to nr : dx must flow around the void so that The minus sign enters because the bubble moves in the direction opposite to that of the force on the atoms. Equations for volume diffusion and diffusion through the vapor can be obtained in the same manner. For vapor transport we have Ag = and the ratio of the densities of metal atoms in the gas and the solid (pg/pl) enters so that

Jan 1, 1964

By Klaus Detert

Fifteen and 18 pct Ni maraging steel and several binavy and ternary alloys of the iron-rich corner of the Fe-Co-Ni system have been studied. After annealing in the austenite range, these alloys were deformed slightly by cold rolling and subsequently aged. Compavison of experimental measurements at various processing stages indicates that small degrees of deforn~ation (5 to 10 pct reduction in thickness) do not influence hardness and strength or the aging kinetics. Electrical resistivity and ductility are somewhat redu]ced and the coercive force is substantially lower when compared to identical samples which were not deformed. The results are explained in terms of retained austenite which transforms into martensite with the small amount of deformation. RECENTLY there has been increasing interest in maraging steel for applications in electric power generators requiring a high ratio of power to weight.' Fifteen pct Ni maraging steel has been investigated to evaluate its properties and performance for application as high-strength magnetic rotor steel,' and a thorough investigation of the precipitation and transformation processes in this alloy has been conducted in this laboratory.3 The influence of deformation, which preceded the aging treatment, was also studied. It was found that a small deformation in the order of 5 pct has a rather striking effect in reducing the coercive force. Other interesting effects on the properties caused by such deformation have led to the more detailed studies reported herein. EXPERIMENTAL METHOD The methods used to produce the samples from 15 pct Ni maraging steel have been described elsewhere.3 The general procedure of hot forging and cold rolling to sheet has been followed. The composition is included in Table I which also contains the composition of the 18 pct Ni maraging steel grade 250 studied. More data about the material and the processing of the 18 pct Ni maraging steel have been recently reported.4 The experimental alloys of binary and ternary Fe-Ni-Co alloys were made by levitation melting in an argon atmosphere and casting into rod-shaped ingots 7 mm thick weighing 20 g. From these ingots 25-mm-long rods were machined to study the phase transformation by a dilatometer. These rods were then cold-rolled to strips, 2.4 mm thick. Annealing for austenitizing was done in tube furnaces in an argon or helium atmosphere followed by cooling in the water-cooled portion of the tube. Aging was done in a salt bath containing a neutral blend of Alkali nitrates and nitrites. Vickers hardness was measured using a load of 50 kg for 15 sec. Tensile tests were carried out on a hard beam tensile tester at a strain rate of 5 X lo-' per sec using flat samples with a gage length of 37.5 mm and a cross section of 1.25 by 6.25 mm. Estimated sensitivity was 5 K x strain and 0.35 kg per sq mm stress. Magnetic saturation was determined on small cylindrical samples, 2.5 mm in length and diameter, by measuring the force exerted by the gradient of a magnetic field of 1000 oe per cm in a mean field of 11,500 oe. The measured values could be reproduced within *1 pct. Coercive force was measured by a precision-type magnetic field probe in a magnetic coil as described by Foerster.5 The magnetizing field was 1300 oe. The samples were 5 cm long, 1 cm wide, and 2.4 mm thick. he coercive force was measured to within +0.1 oe. Electrical resistivity was measured by using a potentiometer on flat strips with a gage length of 100 mm and a cross section of 2.5 by 0.5 mm. The accuracy of the measurement was 0.1 pct but the reproducibility of the measured specific resistivity among different samples was in the order of 1 pct. The method used to prepare the samples for electron transmission has been reported elsewhere.3 RESULTS Fig. 1 shows the influence of deformation after annealing on the resistivity, hardness, and coercivity. The samples were annealed for 30 min at 1000"C,

Jan 1, 1968

By G. G. Hancock, H. H. Johnson

Hydrogen gas at atmospheric pressure is shown to cause substantial embrittlement in a martettsitic high-stretzgth steel. Subcritical crack growth is observed at very lom stresses and with high growth rates. It is suggested that an adsorbed layer of hydrogen atoms at the crack-tip surface provides the damaging hydrogen. Oxygen in small quantity, as little as O.7 pct by volume, is shown to eliminate subcritical crack growth in gas environments caused by hydrogen or water vapor. However, dissolved oxygen in water has little or no influence upon crack-growth rates. Oxygen-stopped cracks may be restarted by water, or by hydvogen or water vapor if oxygen is removed from the environment. These observations are interpreted in terms of preferential adsorption of oxygen at the crack tip and the formation of an oxide barrier. RECENT investigations1-3 have demonstrated that environmental factors are frequently responsible for delayed failure in martensitic high-strength steels. The environment causes crack initiation from preexisting cracklike flaws at unexpectedly low stresses, often far below the uniaxial yield strength. The crack then propagates at a rate controlled by the environment and the crack-tip stress-field intensity; during this period crack propagation will cease if either the stress or the aggressive environment is removed, and this may be considered a definition of subcritical crack growth. Fracture occurs when the crack has grown to a critical length, such that the fracture toughness of the steel is exceeded. Several liquids are known to cause delayed failure, but water and water vapor are the most severely damaging of the environments investigated to date.'-3 It has been suggested that hydrogen produced during corrosion reactions may be the actual embrittling agent2 The severe embrittlement caused by water vapor inevitably raises the question as to whether other gas environments are damaging. Previous work4'5 has demonstrated that high-pressure hydrogen (2250 psi or greater) is an effective embrittling medium, as measured by such criteria as reduction in area, notch tensile strength, and time to failure. Moreover, the embrittlement was eliminated by the addition of small quantities of air or oxygen to the high-pressure hydrogen, but it was not influenced by additions of nitrogen or argon.4 In the present study attention is focused upon gas environments at atmospheric pressure, in particular hydrogen and oxygen. The influence of these constituents upon the initiation and growth of a crack from a pre-existing cracklike flaw in a high-strength steel was determined directly by the electric-potential method of monitoring crack growth. MATERIALS AND PROCEDURE The H-11 steel was supplied by the U.S. Naval Research Laboratory as 3 by 12 by 0.065 in. sheet specimens with 1-in. transverse center slots. The slot tips were finished by Elox machining to a radius of 0.001 in. or less. The yield strength was 230,000 psi; chemical composition and heat-treatment schedule are given in Table I. The experimental apparatus, precracking procedure, and incremental loading sequence have been described previously.3 In the only significant change, precracking was sometimes carried out by a hydrogen embrittlement and baking technique. All experiments were conducted at room temperature; the hydrogen gas environment was purified by a commercial palladium purifier. Crack initiation and propagation were followed by the electric-potential method,'-3 using a calibration that has been recently dicussed. Stress-field intensities at the crack tip were computed by the conventional Irwin frmula; the plasticity correction was negligible and therefore not included. EXPERIMENTAL RESULTS A striking brittleness associated with molecular hydrogen at atmospheric pressure is demonstrated by the data in Table I1 and Fig. 1, which indicate that subcritical cracks in hydrogen initiate at lower stress-field intensities and propagate more rapidly than in fully humid argon. Ki and Kf are the crack-tip stress-field intensities at initiation and termination of subcritical crack growth, respectively. Termination, of course, corresponds to fracture. In both hydrogen and humid argon Ki is less than Kf

Jan 1, 1967

By Brahm Prakash, R. Schuhmann

Chemical conditions for flotation and nonflotation of quartz with oleic acid as collector and barium, calcium, aluminum, iron, and tin as activators were studied using a simple vacuum-flotation technique in glass-stoppered graduates. The detailed study of barium activation led to an interpretation based on ideal Langmuirian chemi-sorption. FLOTATION of quartz is of practical importance as something to be avoided in soap-floating many types of ores. Clean, unactivated quartz is not floated with fatty acids and soaps, such as oleic acid and sodium oleate, in the quantities normally used for flotation. However, data in the literature indicate that almost any multivalent cation will activate quartz if given an opportunity. Thus, a common problem is to prevent activation of quartz by the various inorganic cations inevitably present in flotation pulps. Wark and his coworkers1 have demonstrated the reversibility of the chemical reactions and adsorptions involved in the activation, depression, and collection of the common sulphide minerals. The procedure in much of their work was to bring a mineral surface to equilibrium with solutions of known pH, collector concentration, and activator concentration, and then to test the floatability of the mineral by contact-angle measurement. From the data, graphs were constructed with pH and reagent concentrations as coordinates. These graphs show fields of flotation and fields of nonflotation, separated by narrow transition regions whose locations are shown by so-called contact curves. From the shapes and locations of the contact curves, which roughly separate fields of flotation from fields of nonflotation, a quantitative understanding of the interaction of the reagents with each other and with the minerals often can be deduced. The study of quartz flotation to be described in this paper follows in broad lines the approach of Wark and coworkers. That is, pH, activator concentration, and collector concentration were varied to find equilibrium conditions of flotation and non- flotation, and the results are presented graphically by means of contact curves. However, instead of testing for floatability by measuring the contact angle on a polished surface, a simple vacuum flotation technique was developed and used. Purified oleic acid was the collector and terpineol the frother. Barium activation was studied in some detail, and exploratory studies were made of activation with calcium, aluminum, ferric iron, and stannic tin. Preparation of Materials Quartz: Large lumps of high-grade vein quartz were crushed dry in a cone crusher and rolls. The —20, +28-mesh portion was screened out and used in the subsequent steps. This material was passed through a high-intensity magnetic separator to discard iron, then leached twice with hot concentrated HCl and washed repeatedly with distilled water. The cleaned sand was then wet ground with porcelain balls in a porcelain pebble mill, deslimed repeatedly by settling and decantation to discard —800-mesh material, and again washed with hot HCl followed by distilled water. The resulting stock of quartz was stored under water. Chemical analysis gave 99.8 pct SiO2. Table I gives the size analysis of the quartz used for flotation tests. Calculations from these data, using shape factors given by Gaudin and Hukki9 indicate a specific surface of about 500 cm2 per g. Blank flotation tests in distilled water, and in water with added frother, showed the prepared quartz to be completely nonfloatable and thus indicated the absence of organic contamination. Oleic Acid: The preparation of oleic acid was based on fractional vacuum distillation of methyl oleate2,3 followed by regeneration of oleic acid, and finally fractional crystallization of oleic acid from acetone solutions at low temperatures." The pure oleic acid was stored in a refrigerator. The iodine number of the oleic acid was found to be 90.0 (theoretical 89.93). Oleic acid was used in the form of a dilute water solution of sodium oleate, after preliminary flotation tests showed no effects of form of addition and order of addition of reagents when an adequate conditioning time (that is, 30 min) was provided. Other Reagents: Sodium hydroxide solutions low in carbonate were prepared by first making 1:1

Jan 1, 1951

By J. S. Aronofsky

The first step in a quantitative analysis ot the mechanism of oil displacement by water in a fractured reservoir is usually conceded to be the solution of the differential equation describing the saturation distribution of two immiscible fluids flowing in a porous medium, where the capillary pressure is taken into account. In such a system the production mechanism may consist of displacement of oil both by the flow of water due to natural or artificially imposed pressure gradients and by imbibition, which implies a flow of water not due to external pressure gradients. Owing to the presence of the two oil displacement mechanisms, the mathematical model given by the differential equation intended to describe the system may not properly represent the behavior of the physical system. In fact, in the reservoir the rate of water advance may be very slow, and in the case of a fractured reservoir with a great number of large fractures, the pressure difference determining the flow of water through the matrix may be much less than 1 lb/'psi over lengths of a few feet. In such a case, imbi-bition (the exchange between oil in the matrix and water in the fractures resulting from capillary forces) may become, with time. a significant element of the production mechanism. It occurred Lo the authors, however, that without going into a physical analysis of the process of production, it might be possible by means of simple abstract reasoning to throw some light on the variation of recovery with time under conditions occurring in a highly fractured oil reservoir with rising water table. The object of this paper is to present both the reasoning and its application to a reservoir of the highly fractured type. Specifically, the analysis given here was undertaken to try to explain the increase of recovery (as defined later) with time as observed in this reservoir, without having to assume unlikely variations in the reservoir parameters with depth. This attempt has been successful as will become clear upon comparison of the computed recoveries with the actual field data. ABSTRACT MODEL Let us consider a small volume. of porous matrix saturated with oil at time, t = 0. Let the process of oil displacement by water start at time, t = t,,. At some time, t, the process will have terminated. Then a volume of oil equal to or smaller than the original oil contained in the matrix will have been produced. The first basic assumption that describes the model and guides the forthcoming reasoning is that the oil production from the small volume. dv, is a continuous monotonic function of time and that it converges to a finite limit. Such an assumption is not inconsistent with the results of laboratory waterflood tests as well as with results of imbibition tests where this is, in fact, observed. The second basic assumption is that none of the properties which determine the rate of convergence change sufficiently during the process to affect this rate or the limit. Let it be assumed that the form of the function of time relative to production from the matrix volume. dv, is given by where V,(t) is the volume of oil produced up to that time t. R is the limit toward which the recovery converges, A is a constant giving the rate of convergence, and V,(t) is the volume of oil originally in place in the volume, dv. It should be noted that recovery at time I will be understood here to he It follows that r. tends to R as t tends to infinity. CONSTRUCTION OF RESERVOIR FROM ABSTRACT MODEL Let the reservoir consist of a series of identical blocks of porous matrix stacked vertically and separated by fractures. Let each of these blocks satisfy the conditions of our abstract model. These conditions are: (1) that recovery is a continuous mono-tonic function of time converging to finite limit, and (2) none of the properties that determine the rate of convergence change sufficiently to affect the rate or the limit. Let water be rising in fractures so that oil production from any part of the block starts when the water comes in conLact with it. TOTAL RECOVERY FROM THE RESERVOIR COMPARED TO RECOVERY FROM A SINGLE MODEL ELEMENT As stipulated in Eq. 1, in the case of the abstract model,

By P. W. Bennett, E. M. Elkin

A new technique for the recovery of palladium and platinum and sludge from go12 electrolyte eliminates many of the drawbacks of the zinc-dust cementation process. In the electrolytic refining of gold by the Wohwill method, the electrolyte contains about 100 gpl gold as AuCl, and 100 gpl free hydrochloric acid. Any palladium and platinum contained in impure gold dissolve and accumulate in the electrolyte. When their concentration approaches that of gold, it becomes desirable to discard the electrolyte and to recover the gold and the palladium and platinum. As practiced at Canadian Copper Refiners until recently, discarded electrolyte was treated with sulfur dioxide to precipitate the gold. 2AuCl3 + 6H2O + 3SO2 —2Au + 6HC1 + 3H2SO4 The gold precipitate was filtered off, washed with water, and melted with scrap anodes. The wash water was added to the gold-free filtrate and treated with zinc dust to cement the palladium and platinum. PdCl2 + Zn — Pd + ZnCl2 PtCl4 + 2Zn—Pt + 2ZnCl2 The precipitate was separated and sold as Pd-Pt concentrate, and the barren filtrate and wash water were discarded. The receipts of palladium and platinum at this company were too small to warrant their refining. The process suffered from a number of disadvantages. Handling the gold-free solution was disagreeable, as it was laden with sulfur dioxide even after blowing with air overnight. Subsequent treatment with zinc dust was also troublesome. A large excess of zinc dust was required. Spray, acid mist, and vigorous evolution of hydrogen accompanied the reaction. The Pd-Pt precipitate was grossly contaminated with occluded unreacted zinc and with yellow granules of sulfur, thought to be formed by the reduction of sulfur dioxide and its derivatives. Repeated boiling of the precipitate with hydrochloric acid and washing with water decreased somewhat, but did not eliminate, the zinc. After drying overnight, the precipitate hardened to a clinkerlike mass that was difficult to grind. Grinding, handling, and packing created heavy dusting. Even weighing in an analytical balance generated dust, indicating that the powder was easily charged with static electricity. The total palladium and platinum content of the powder varied from 56 to 72 pct, with an average of 65 pct. The powder dissolved in aqua regia with difficulty, leaving a small amount of insoluble residue. However, the main drawback of the process was the strongly hygroscopic Pd-Pt product. The powder showed a marked though erratic increase in weight and a corresponding decrease in assay on exposure to air, even during the course of laboratory analysis. Such changes were the source of disagreement between Canadian Copper Refiners and the buyers of concentrate. The cause of the change in weight is believed to be hydrogen, liberated by the action of zinc dust on hydrochloric acid. Some of this hydrogen was adsorbed so strongly by the precipitate that it could not be driven off during the drying. On exposure to air it oxidized catalytically, forming water. Experiments soon showed that the entire process of treatment of discarded electrolyte then in use would have to be changed. A small quantity of apparatus was moved into the gold room, and experimentation was held to a minimum compatible with the development of a new process. PALLADIUM AND PLATINUM PRECIPITATION It was thought that zinc could be replaced with a reagent other than a hydrogen-evolving metal. Semiquantitative experiments showed that platinum and palladium could be precipitated completely from the gold-free solutions with such well-known reagents as sodium formate, formic acid, formaldehyde, and paraformaldehyde. Sodium formate was the preferred reagent, since the other three are volatile and somewhat toxic. The gold-free solutions used were those saturated with sulfur dioxide, partly freed of sulfur dioxide by aerating overnight, completely freed by boiling, as well as strongly and weakly acidic, neutral, and alkaline solutions. The reactions are complex and can be represented by these over-all equations: PdC1, + HCOONa — Pd + NaCl + HC1 + Co2 PtCl4 + 2HCOONa — Pt + 2NaCl + 2HC1 + 2CCX, Strongly acidic solutions required as much as five times the theoretical amount of sodium formate as did solutions neutralized to pH 4.5. Increasing the pH decreased the consumption of

Jan 1, 1965

By D. H. Carlson, J. H. Johnson, C. F. Renders

Introduction Diesel-powered vehicles are used extensively in underground mines throughout North America. The bulk of the diesel vehicles found in underground mining operations are used for loading and ore haulage, as well as for transportation of personnel and supplies. Along with the advantages of using diesels underground is the disadvantage associated with diesel-tailpipe particulate-matter emissions (DPM). The concentration of DPM in the ambient air of US underground metal mines is not now regulated by the Federal Mine Safety and Health Administration (MSHA). However, recent studies have shown DPM to be mutagenic (National Institute of Occupational Safety and Health, 1988), and the American Conference of Governmental Industrial Hygienists (ACGIH) has recommended that the exposures of per¬sonnel to DPM be limited to an 8-hr time-weighted average concentration (threshold limit value or TLV) of 0.15 mg/m3 (Anon., 1995). The authors, while making measurements in a number of US underground mines that use diesel haulage equipment, found mine air DPM concentrations ranging from 0.2 to 2.36 Mg/M3 (McCawley and Cocalis, 1986; Watts et al., 1989; Cantrell et al., 1991; Haney, 1992; US Bureau of Mines, 1992; Watts, 1992; Watts et al., 1995). If the proposed DPM TLV were to be adopted as a permissible exposure limit (PEL) for US underground mines, the proposed limit of 0.15 mg/m3 PEL would be lower than any of the concentrations measured in the earlier studies and would represent more than a 15-fold reduction from the maximum 2.36 mg/m3 concentration. A 0.15 mg/m3 PEL would also represent a 4.5-fold reduction from the average 0.68 mg/m3 measured mine ambient air DPM concentration reported in this paper. Other diesel tailpipe emissions that are now regulated underground include carbon monoxide (CO), with a PEL of 50 ppm; nitrogen dioxide (NO,), with a PEL of 5 ppm; nitric oxide (NO), with a PEL of 25 ppm; and sulfur dioxide (SO,) with a PEL of 5 ppm. Because the concentrations of these gaseous pollutants and DPM are affected by the state-of-maintenance (Waytulonis,1992), it is important that a means be developed to measure emissions from engines that are now in service to determine when maintenance is needed. The current study was the result of an inquiry by mine¬maintenance personnel who had been receiving complaints about high concentrations of diesel soot (DPM) in mine headings from load-haul-dump (LHD) vehicle operators. Mine-maintenance personnel were searching for an objective test to determine if the diesel tailpipe particulate emitted was excessive. The mine was also evaluating electronically controlled, two-cycle, naturally aspirated, direct-injection diesel engines on some of their JCI (John-Clark Inc.) load-haul-dump (LHD) vehicles. These LHD vehicles were used to haul freshly blasted ore from mine headings to a feeder breaker. The feeder breaker breaks down the larger chunks and feeds the broken ore onto a conveyor. Michigan Technological University, in past studies, developed an emissions-measurement apparatus (EMA) ca¬pable of measuring diesel vehicle tailpipe pollutant concentrations (Chan et al., 1992; Chan et al., 1993; Carlson et al., 1994). At the time of the study reported here, most of the mine's LHD vehicles used a 12-cylinder, four-cycle, naturally aspirated prechamber diesel engine. The study was undertaken in cooperation with mine maintenance supervisors from late 1992 through July 1993. The objectives were to compare diesel exhaust emissions between the 6-cylinder, two-cycle, electronically controlled, direct-injected diesel engine and the 12-cylinder, four-cycle, prechamber diesel engine and to, then, use the data collected, in conjunction with mine ambient air measurements, to demonstrate the application of the "deterioration factor" (Chan et al., 1992), which is a measure of the state-of-maintenance of mine-vehicle engines that are now in service. The information would be used to identify vehicles that need maintenance to reduce emissions. The data reported here are unique in the sense that they combine underground diesel vehicle ambient and tailpipe

Jan 1, 1999

By R. V. Hughes, J. N. Breston

Conclusions drawn by previous research workers with reSPect to the relation between Pressure gradients and/or velocity and oil recovery obtained by laboratory water flood tests have been in disagreement probably due to variable procedures and unnatural conditions and materials. The Bradford Laboratory of the Pennsylvania Grade Crude Oil Association as part of its secondary recovery research program has conducted nineteen water floods on two long cores of widely differing characteristics in an attempt to clarify this relationship and make it an aid in predicting flooding pressures in the field. Unlike previous research procedures the present experiments were conducted with the aim of duplicating field conditions as closely as possible by using long unextracted consolidated cores, a live crude, and natural brines for both flooding and, connate water content. Also, the pressure gradients and flooding velocities were representative of field conditions where similar sands were being flooded. Eleven floods on one core and eight floods on the other core showed increased recoveries and lower residual oil saturation with increased flood pressure gradients and flood velocities. A marked decrease in recovery was obtained from both cores at very low flood velocities. This pressure versus recovery relationship is shown to hold up to the point of water breakthrough and also up to the 100 and 1 produced water to oil ratio point. INTRODUCTION The possibility of water flooding oil sands was suggested by Carl1 of the Pennsylvania Geological Survey in 1880. It is not known when the practice was tried intentionally for the first time, but its beneficial effects were noted in the annual production rate of the Bradford field as early as 1907. The practice was illegal in Pennsylvania until 1921. Early water floods in the Bradford field usually consisted of shooting or splitting the casing secretly to permit subsurface waters to enter the producing sands under hydrostatic head. As it was noted that the benefits of water flooding seemed to be proportional to the quantity of water dumped into the well many also began to utilize surface sources after the practice became legal. It was probably during the middle 20's before many producers realized that the pressurehead of the water upon the producing sand determined the rate and quantity of water that would enter the sand. Hence, rate and quantity of production appeared to be a direct function of input pressures. By 1927 a few producers had ventured the installation of pressure pumps in order to increase water-input rates and production through the combination of hydrostatic and hydraulic pressures. The adoption of pressure flooding and the "five-spot" drilling pattern in the Bradford field were essentially simultaneous. Water-input pressures in 1930 seldom exceeded 300 p.s.i. at the well head or 1100 p.s.i. at the sand face. Since that time, water-flood producers in the Bradford-Allegany fields have gone to higher and higher pressure until today 600 p.s.i. at the well heads is called a low pressure flood. Many high pressure floods now operate at 1300-1400 p.s.i. at the well head. The limiting and advisable pressure at the sand face has been pronounced as that pressure just under what is required to lift the overburden or to cause formation parting: According to this rule any water flood operation utilizing well-head pressures nearly equal in pounds per sq. in. to 1.1 times the average depth in feet to the top of the producing sand would be considered as a high-pressure flood. Despite the higher pressure trends in the Bradford-Allegany field operations and the results of early laboratory water flooding research, the desirability and benefits of high input pressures are still questioned by many operators, particularly in midwestern water flood operations. The present paper recounts a series of 19 laboratory water floods using two long, consolidated cores of widely differing characteristics saturated with live crude and flooded with oil field brines in an effort to simulate field conditions under • various pressure gradients and flooding velocities. For both cores, higher recoveries and lower residual oil saturations were obtained at higher pressure gradients and flood velocities. This relationship is shown to hold up to the water breakthrough point and also up to the 100 to 1 produced water to oil ratio point.

Jan 1, 1949

By Joseph L. Gillson

IT is a somewhat curious circumstance that the newest of the Institute's several awards should be conferred in the oldest of our several professional fields—for there is little question that geology and mining have antedated metallurgy and petroleum. Perhaps so did geophysics. After all, one geophysical instrument, the magnetic compass, has been successfully employed for many centuries. Young in years the Jackling Award may be, but in distinction—whether in terms of the title it bears or in terms of the first three medalists (Reno Sales, E. D. Gardner, and the late Father MaceIwane)—the Jackling Award is already one of the ranking awards of the Institute. The name of the 1957 medalist will bring added luster to an already illustrious roll. J. L. Gillson was born and brought up in Evan-ston, Ill., in an area characterized by singularly flat and uninspiring topography, and devoid of ore deposits and even of bedrock—a most unlikely environment from which to expect a future Jackling medalist to emerge! On graduating from high school he enrolled as a chemistry major at Northwestern University. At the end of his frkshman year his scholastic prowess had won him a prize of two chemistry books. But these went unread, for about this time he came under the spell of U. S. Grant, that distinguished and enthusiastic geologist who for many years was head of Northwestern's geology department. From thence forward Joe was a dedicated geologist. After a Navy interlude in World War I, he went to MIT for graduate work, substituted for the late Professor Palache for one year at Harvard in mineralogy, received his doctorate at MIT and stayed on as a meniber of the MIT faculty, where the geology department was headed by that great dean of all economic geologists, Waldemar Lindgren. In 1926 Joe spent a summer looking into barite deposits for the du Pont Co., and since 1928 he has been du Pont's chief geologist. Do men who lead such active lives in our exploration organizations generally have permission to publish their observations? Do they generally find time to publish, even if they have permission? Alas, no. But in Joe Gillson's case, yes. His bibliography runs to well over two score papers, including one of the very first papers in this country on the applications of petrography to problems of Portland cement. He has written on such topics as the origin of talc and the genesis of ilmenite, fluorspar, and alkaline rocks. Each year for a number of years his annual reviews of industrial minerals in the Mining Congress Journal have been eagerly awaited. - Do men who do so much to advance their science have anything left to give to the advancement of their profession? In Joe Gillson's case, yes. He has been a vice president of the Mineralogical Society of America and has been active in the councils of the Society of Economic Geology, particularly in their research programs. This year he is president of the American Geological Institute, currently perhaps the most challenging post to which a geologist may be elected. His contributions to AIME scarcely need documentation, so I shall mention only three—his chairmanship of the Committee on Democratization of the Institute, a committee whose work and recommendations brought a new and hopeful leaven to AIME at a time when this was sorely needed; his chairmanship, a few years ago, of the Industrial Minerals Division; and his current place on the Board of Directors as Vice President of the Institute. Such' a catalogue of contributions and achievement, even as condensed as I have had to make it, certainly merits the Jackling Award. Yet, implicit although not often expressed in the conferring of most awards is the hope that besides recognizing a distinguished career, it will provide stimulus for further effort. In the present instance, such an expectation is already well on the way to fulfillment. Only recently Joe Gillson has undertaken the editorship of a new and greatly revised edition of the Institute's Seeley Mudd volume, Industrial Minerals and Rocks. And so, Mr. Chairman, it is with pleasure and enthusiasm that I present Dr. J. L. Gillson for the 1957 Jackling Award.

Jan 1, 1958

By W. W. Stephens, W. J. Kroll, H. P. Holmes

THE only two methods for producing commercial quantities of malleable zirconium, up to now, have been using magnesium reduction of the anhydrous chloride under a neutral gas, and using purification of raw zirconium by the iodide dissociation method on a hot filament. The purity of the metal obtained by the latter process is about the same as that resulting from the chloride reduction, with the exception of the oxygen content, which may be about 0.05 pct lower in the iodide metal. Even traces of oxygen have a strong hardening effect on zirconium. Since, in the iodide process, the impurities, Si, Al, Fe, Ni, and Mg in the raw zirconium used, are carried over, it would appear uneconomical to use this method of refining solely to eliminate the traces of oxygen, unless very soft metal is desired. One important step to improve the iodide method, namely, dissociating pure iodide made from carbide and recycling the iodine, which would change this refining process into a method for extracting zirconium from the ore, has not yet been made. The Bureau of Mines, by using the chloride reduction, wanted to produce quantities of a reasonably pure and malleable metal at low cost for large-scale industrial use. This aim has been achieved, and a pilot plant permitting production of 600 lb of malleable zirconium per week will be described (fig. 1). Briefly, the Bureau of Mines process consists of reducing purified gaseous anhydrous zirconium chloride with fused magnesium under a noble-gas atmosphere. The reaction product, magnesium chloride, and any excess magnesium metal present are removed from the sponge zirconium in the next step by fusion and evaporation in a good vacuum at about 925°C. In this process, care is taken to keep air out of contact with the hot metal, which otherwise would contaminate the product with oxygen and nitrogen. Both these impurities embrittle zirconium even when present in an amount as low as 0.1 pct. A number of previous reports1-3 describe the method and the various improvements that finally led to a workable process. The major steps made were the production of large quantities of carbide, which is the raw material for producing the chloride, its chlorination with reasonable efficiencies, and the elimination of iron trichloride contained in the raw chloride, as well as that of the zirconium oxide which is always present in this product. The physical nature of the anhydrous chloride, which sublimes at 331°C at atmospheric pressure and melts at 420°C under a pressure of 25 atm, made it necessary to provide a special safety device on the purification and reduction vessels in the form of a lead-alloy seal, permitting escape of excess gases if pressure tended to build up. The main difficulties encountered in the reduction and in the following step, salt separation in a vacuum at elevated temperature, were caused by the material from which the reaction pot was constructed—iron. This metal reacts with zirconium at about 940°C with formation of a eutectic. The last step, salt separation by evaporation of the magnesium and magnesium chloride in a vacuum, is quite unconventional and has not been used before on such a scale. It is only due to the improved construction of high-vacuum pumps, especially oil-diffusion pumps, that such a method could be used. The various steps of the Bureau of Mines process, as described in the general outline above, may be summarized as follows: (1) production of the carbide, (2) chlorination of the carbide, (3) purification of the raw chloride, (4) reduction of the pure chloride with fused magnesium, (5) separation of excess magnesium and magnesium chloride in vacuum at elevated temperature, and (6) melting of the sponge obtained. Production of Carbide The arc furnace, described in a previous report,' was improved both to reduce the graphite consumption caused by the burning of the bottom plates and to concentrate the heat in order to obtain better power efficiency. This was achieved by providing the bottom with graphite plates entirely embedded in refractory bricks, the contact with the current being made with three water-cooled copper plugs. Figs. 2 and 3 show the arrangement. The crucible, made

Jan 1, 1951

By C. H. Li, R. D. Carnahan, R. J. Stokes, T. L. Johnston

When silver chloride deforms by pencil glide at temperatures of 26ºand 72°C, grain size has no effect upon the proportional limit and the material necks down to a knife edge under tension. At -196ºC, deformation takes place on fewer slip systems to produce straight slip traces, the flow stress becomes sensitive to grain size and fracture occurs by cleavage from an intergranular source without any reduction in area. THERE are significant differences between the appearance of the slip bands formed in silver chloride and in the alkali halides at room temperature. The bands in sodium chloride, e.g., are fine and geometrically straight, whereas in silver chloride they are coarse and wavy.' Such differences in the slip behavior prompted us to inquire what the effects of grain boundaries might be on the mechanical properties of these solids. As an introduction to a general study of ionic poly-crystal behavior, we have investigated the effect of grain size on the stress-strain relationships in silver chloride at different temperatures. We have chosen silver chloride chiefly because polycrystals can be easily prepared free from cracks and macroscopic voids by conventional techniques. Moreover, as we shall see, the slip behavior can be readily modified by changing the temperature. It will be shown that the effect of grain size on the yield stress of silver chloride is strikingly dependent upon the temperature of deformation and that this temperature effect comes about through a change in the number of slip systems which operate at the onset of plastic flow. EXPERIMENTAL PROCEDURES Polycrystalline tensile specimens were made by recrystallizing cold-rolled AgCl sheet. Thirty-gram quantities of AR grade silver chloride powder were melted in a low heat capacity furnace, cast into cylindrical forms 3/4 in. in dim and approximately 1 in. in length and then extruded with a 16:l reduction ratio into rods 3/16 in. in dim. Extrusion temperatures were varied from room temperature to 350°C. In order to impart various degrees of cold'work to the extruded rod. All extrusions were then cross rolled to sheet 0.040 in. in thickness at room temperature and machined to form tensile specimens having a gage length of 0.750 in. with a width of either 0.250 or 0.145 in.* Annealing was carried out in an air oven at 200°C for periods up to 20 hr. specimens having average grain diameters ranging from 0.024 to 0.40 mm were prepared by varying the extrusion temperature and annealing time in the conventional manner. To obtain specimens with grain sizes larger than 0.40mm, lightly deformed thin prisims of silver chloride single crystals (supplied by Harshaw Chemical Co.) were recrystallized. Grain size determinations were made by an intercept method and revealed that the grains were equi-axed. Laue back-reflection X-ray patterns showed little tendency to form a preferred orientation texture. Specimens which were to be used for the slip band studies were polished by immersion in fresh boiling concentrated NH,OH for 60 sec. They were then etch polished for 10 sec on each side by hand lapping on a stationary velveteen lap wetted with a dilute Hypo solution (5 g of Kodak Acid Fixer in 100 cc H20). Finally the specimens were rinsed in warm water and alcohol, blown dry and carefully mounted in the tensile machine for testing. Tensile tests were performed at three temperatures, namely, 26º, -72º, and -196°C. A screw-driven hard tensile machine was used at a constant strain rate of 0.006 in. per in. per min. Loads were determined with a light- proof ring fitted with A-18 strain gages and extensions were measured with a 0.0001 in. dial gage. Constant level baths of alcohol with dry ice and liquid nitrogen were used to maintain the two lower test temperatures. EXPERIMENTAL RESULTS Reproducibility—In view of the light sensitivity and reactive nature of silver chloride, it was necessary to determine whether reproducibility depended upon either exposure to light or to the condition of the surface. However, during the course of the work it became clear that variation of laboratory lighting

Jan 1, 1962

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The effects of grain size and shape on alloys of titanium with nitrogen and aluminum have been determined. Increasing a grain size decreases strength and hardness and increases impact resistance. Quenching from the ß field produces subgrain markings delineating a plates in Ti-N alloys but not in Ti-AI alloys. This suggests a precipitation from the high nitrogen alloys. ALPHA titanium alloys are single-phase alloys with the hexagonal-close-packed structure of a titanium. If these alloys are worked and annealed within the a field, equiaxed structures result in which strength is derived from the solid solution of the alloying elements present. Strain hardening can be used to increase further the strength of a titanium alloys. This is the only other mode of strengthening the a type of alloy. Quenching from the ß field has been noted by many investigators to have little effect on the strength of iodide titanium and on commercial titanium. Ti-A1 alloys were found to be little different in hardness, whether annealed in the a field or quenched from the ß field.' These facts illustrate a characteristic of a titanium alloys: they are insensitive to heat treatments from the ß field. Underlying this heat-treatment insensitivity are the facts that the a-ß field is generally narrow in a titanium alloys, the transformation-temperature range increases with a-stabilizing content, and the a solubilities of the alloying elements are greater than the ß solubilities. When quenching is done from the ß field, there is no supersaturation of the alloying elements in the acicular transformation structure produced. Welds in a titanium alloys generally are ductile, because no transformation hardening occurs during cooling.1,2 Other desirable features of a alloys are: no thermal-stability problem, excellent toughness, and retention of strength at elevated temperatures better than a-ß or ß alloys of comparable room-temperature strength. The prime factors governing the properties of a titanium alloys are the amount and kind of solute present. This can change the a phase from a soft, tough material into a hard, brittle material with no apparent change in microstructure. Moreover, brit-tleness can exist over a wider alloy-content range, without change of phase, than in most other metals. The solutes for a titanium may be divided into interstitial and substitutional types. Oxygen and nitrogen dissolve interstitially in rather large amounts, extending well through the brittle range, and the transformation-temverature ranges are raised in the process.:' , carbon has a maximum interstitial solubility of about 0.5 pct at the peritectoid temperature, while at lower temperatures the solubility decreases to about 0.2 pct.3,5 Substitutional a solutes include aluminum and tin. Aluminum has a high a solubility of 25 pct Al, and increases the transformation-temperature range markedly.6,7 Tin has a high a solubility of about 20 pct, but has a relatively innocuous effect on the transformation-temperature range.' The choice between interstitial and substitutional solutes generally has been conceded to the substitutional solutes because of a belief that they do not have as adverse an effect on ductility and notch toughness. However, a recent investigation8 on the effect of hydrogen on titanium has shown that this element, which is not under compositional control, has a powerful detrimental effect on notch toughness. Hydrogen was shown to form a hydride which is practically insoluble (about 0.002 pct) in a titanium at room temperature, although the solubility at the eutectoid temperature of about 300°C is relatively high, about 0.16 pct. Limited data were presented on the effect of hydrogen on a alloys, where the same impairment of toughness as in unalloyed titanium is found. The work reported here describes the effects of interstitial and substitutional solutes on 1—the mechanical properties of high purity titanium free of titanium hydride and 2—the influence of structural variables on these properties. Nitrogen was selected as an example of an interstitial solute with high solubility and aluminum as a substitutional solute with high solubility. All compositions were well within the ductile range, since it was not intended to study the brittleness problem here, but to study only the factors influencing optimum mechanical properties. Procedures The alloys were prepared from iodide titanium as 1/2 Ib ingots double melted to insure homogeneity.

Jan 1, 1955

By G. A. Moore

A brief review is given of methods designed to produce metallic iron of high purity, and typical results are listed. A recent method, utilized at the National Bureau of Standards, consists of the extraction of ferric chloride by ether, reduction of this ferric chloride to ferrous chloride, further purification of this chloride, and the subsequent electrolytic deposition of metallic iron. iron produced by this procedure apparently is softer than, and otherwise different in properties from, any iron previously prepared and contains appreciably smaller amounts of impurities. THE history of attempts to produce "pure" iron reaches to antiquity and it may be presumed that each ancient armorer who succeeded in making a better steel concluded, correctly, that he had done a better job of removing the "base metals," and incorrectly, that he now at last had a "pure" metal. Early metallurgical papers mentioned use of "pure iron" in making alloys—this "pure" iron in most cases being inferior to some commercial stocks of the present time. Improvement has been continuous, and usually at a sufficient rate to convince each succeeding group of workers that they, at last, were using the really pure metal (until the analysts also improved their techniques to again discover the impurities). These adventures were reviewed in some detail by Cleaves and Thompson.' Although the ores of a metal may be abundant, difficulties in extracting it may make the pure metal very rare. When impurities are restricted to a total of a few parts per million, nearly all pure metals become rarities. Lead, copper, gold, mercury, silver, zinc, aluminum, bismuth, and the six platinum metals are claimed to be available with total impurities ranging from 2 to 50 ppm. The present small and scattered world supply of so-called "pure" iron holds an unimpressive place in another group of 16 metals having approximately 100 ppm of foreign material. Of about 20 less rare metals, only the platinum metals are more costly to prepare. While the production of such rare varieties of iron may appear insignificant in the presence of thousand-ton operations with 95 to 99 pct metal, it must be emphasized that all researches on commercially interesting irons and steels are in fact studies of the modifications of the properties of iron by additional materials. Until the properties of high purity iron are directly measured, all ferrous research must operate without known base values. Traces of impurities may affect the properties of a metal in many ways. Infinitesimal traces of solutes, by disturbing the electronic configuration, greatly change the electrical properties of transistors and semiconductors2-3 and slightly larger traces might alter these quantities in iron. Soluble impurities which disturb the perfection of lattice arrangement not only may alter the magnetic constants and electric properties, but by their close association with dislocation phenomena probably control the very existence of the "yield point"; determine the value of yield stress; and perhaps control the selection of slip and cleavage planes. It has been speculated that impurities might even cause the allotropic transformation in iron, but in any case their rearrangement must contribute to the unreliability of heat capacity and other thermodynamic measurements. Impurities which do not remain in solution may cause even greater effects on the properties. Microscopically visible amounts of phases other than ferrite can be found in all high purity irons which have come to my attention. It can be calculated that from 50 to as little as 2 ppm of an insoluble material might be sufficient to completely film all grain boundaries in irons having grain sizes from ASTM Nos. 10 to 1. Should this occur, such films, even though invisible, may be very important in fracture problems, especially at extremes of temperature:' Studies of grain growth and diffusion normally imply consideration of a single-phase system, hence, in the presence of insoluble impurities they can be expected to give ambiguous data." High purity iron is also in demand for use as chemical and spectro-chemical standards; for work in classifying the lines of the iron spectrum; for biological work in nutrition; and for work in nuclear physics. where the presence of some sensitive

Jan 1, 1954

By B. R. Hollebone

The chemical action of molten anhydrous pyridinium chloride (pyridine hydrochloride) on oxy salts and ores of some Group IV and V metals are discussed-in particular zirconium, hafnium, niobium (columbium) , and tantalum. Laboratory-scale experiments are described whose results suggest that this reaction might provide a practicable means of converting ores of these metals to the anhydrous metal chlorides. Experimental results are given which provide some insight into the nature of the reactions and some of the compounds which could be present at intermediate stages. The treatment of ores of the more refractory metals is difficult and expensive and often demands the use of gaseous chlorine, hydrogen fluoride, or other reagents which are, if nothing else, expensive and dangerous to use. This situation is, of course, due to the strong metal-oxygen affinity resulting from the high charge and the small size of the metal ion which combine to produce such high lattice energy in the metal oxide as to defeat standard reduction methods. Thus, the characteristic of these metals which leads to one of their most important properties—corrosion resistance—is the main hurdle in obtaining the metal. Many common methods' for treating ores of zirconium and niobium (columbium), for example, proceed as directly as possible to the preparation of anhydrous halides. These halides are purified by now standard processes of solvent extraction, fractional distillation, and so on. This paper reports on preliminary stages in the development of a method of treating these ores—particularly of niobium—so as to prepare the anhydrous, volatile halides by the use of chemical reagents which are much more easily handled than those used at present. CHEMICAL PRINCIPLES The solvent action of aminium halides has been referred to periodically in the literature over several decades. The chemistry of pyridinium chloride has been discussed particularly by Audreith2 and Starke.3 However, since this is not familiar chemistry in its nonaqueous setting, it is perhaps well to point out some general metallurgical principles and applications. One can use, as point of departure, the fact that HC1 dissolved in pyridine is an acid very much the same as aqueous HC1. It thus gives essentially all the reactions of the HC1 with which we are familiar. However, when the ratio of HC1:pyridine reaches 1:l (a ratio far higher than is possible with H2O) the solution becomes solid C5F5NHC1, pyridinium chloride.* Inter- estingly, the acidic properties of HC1 persist in this medium, although they are manifest only in the molten state of the compound. Some typical reactions of divalent metal compounds which we have carried out in our laboratories are the following: 2PyHCl + Zn — (ZnCl2) + H2 + 2Py 2PyHCl + MnO — (MnCl2) + H2O + 2Py 2PyHCl + CuS — (CuCl2) + H2S + 2Py 2PyHCl + CaCO3 — (CaCl2) + H2O + CO2 + 2Py In these equations, the parentheses indicate a solvated compound which in water would be predominantly a hydra ted cation but which in molten PyHCl will more likely be a complex chloro-anion of the type MC14-. Some important physical properties of pyridinium chloride (PyHCl) are given in Table I. One sees from the data in Table I that at the temperature of molten pyridinium chloride both water and pyridine will boil away. Thus the system will be kept anhydrous. For this reason the reaction 2NbCl5 + 5H2O— Nb2O5 + 10HC1 has no counterpart in molten PyHCl. Instead, the chloride is made even more stable by the formation of a hexachloro complex: Nb2O5 + 12PyHC1 — 2PyHNbC16 + 5H2O + 10Py One interesting property of these complexes is their thermal instability which for the case of niobium can be illustrated as PyHNbCl6 — PyHCl + NbCl5 With a view to possible use of this chemistry in ore treatment, we have attempted to dissolve Pyrochlore (essentially FeO - Nb2O5) and recover the NbC15 from it.

Jan 1, 1968

By J. M. Blank, V. A. Russell

When the nucleation of silicon on a sapphire substrate is accomplished by gradually decreasing the substrate temperature while subjecting it to a constant impingement rate of hydrogen and silicon tetrachloride, the resulting deposit is characterized by widely separated islands of silicon scattered over an "open sea" of sapphire. Analysis shows that nucleation takes place mainly on sites of large adsorption energy, about 85 kcal per mole, and small surface concentration, about 108 cm-2. Crystal growth proceeds rapidly on these nuclei and results in enough depletion of Sicl4 from the ambient gas to suppress further nucleation. The technological importance of single-crystal films on dielectric substrates has prompted considerable work on the deposition of silicon on sapphire. This paper is concerned with the deposition of silicon, by the reduction of silicon tetrachloride with hydrogen, onto heated sapphire substrates. The apparatus consisted of a temperature-controlled container for the silicon tetrachloride along with gas lines and flow meters necessary to convey a hydrogen-silicon tetrachloride mixture to a reaction chamber constructed of quartz tubing. Heat for the substrate was provided by means of an inductively heated graphite susceptor. The observations pertinent to the present discussion were made with an American Optical Co. high-temperature microscope which allowed us to make motion pictures of the deposition process at a magnification of approximately 50 times. Two main categories of experiments were carried out: one on determination of critical condensation temperatures and the other on the deposition of epitaxial silicon films on the sapphire substrates. Critical condensation temperatures were determined in the traditional way by raising the substrate temperature well above that at which condensation could be expected at the impingement rates being studied and then gradually lowering the temperature until the condensation of the first silicon was observed. This was done initially with ellipsometry-type detection but it was soon discovered that the deposits were occurring as widely separated islands and groups of islands scattered over an "open sea" of sapphire. We have called these archipelago formations. They were most easily detected by optical microscopy. Data gathered from experiments of this type have been collected in Table I. Motion pictures of the formation of archipelago patterns show that the nucleation period lasts about 10 sec if the substrate temperature and impingement rate are kept constant. Essentially all of the nuclei are formed in a few seconds and all subsequent silicon deposition merely adds to the size of the established nuclei. After an archipelago formation has matured at a given substrate temperature and impingement rate, it is very difficult to stimulate any further nucleation in the open space between islands. Lowering the substrate temperature will occasionally stimulate nucleation but increasing the impingement rate hardly ever produces any more new nuclei. It should also be emphasized that the nucleation rates appear to be very small, about 104 cm-2 sec-1. They will receive special attention in the analysis section. Another series of experiments was performed employing a systematic variation of substrate temperatures and impingement rates approximating those expected to produce epitaxy. Sapphire substrates with surfaces normal to the 2233 direction were used. In contrast to the procedure that produces archipelago patterns, these films were deposited by raising the substrate temperature to a desired value at which time the silicon tetrachloride and hydrogen flow was begun. Of course, these depositions produced mainly films that were continuous. After removal from the deposition chamber, the substrate and silicon film were examined microscopically to determine the nature of the deposit and by X-ray diffraction to determine the extent to which a single-crystal film had been achieved. Results of these experiments are summarized in Table 11. Of interest for the present analysis is the fact that epitaxy appears to be confined to a fairly narrow temperature range between about 1050" and 1150°C. This also will be discussed in the analysis section. ANALYSIS In this section we shall apply nucleation theory to the data presented above with the objective of testing

Jan 1, 1967