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By W. N. Miner, R. O. Elliott

Electrical-resistivity )measurments were made be-trueetz room temperatrive and 1.5 oK on five different stocks of cerium metal, and the results were correlated with the types, amounts, and distribution of the impurities present. Magnesium, which appeared to be distributed as a solute throughout the cerium matrix, was found to have a large effect on the residual resistivity, 1 at. pct Mg being sufficient to increase the residual resistivity by about 10 microhm-cm. The formation of ß by repeated thermal cycling between room temperature and liquid-helium temperature is attributed to the deformation and faulting that occurs during the ? D a transformation. In preparation for starting a proposed study of cerium-rich alloys, we examined samples from severa1 stocks of cerium metal in order to choose the purest stock for future use in making the alloys. Low-temperature electrical-resistivity data were used to gain initial information about the purities of the stocks. Additional information was subsequently obtained from chemical analyses, density measurements, optical metallography, and electron-micro-probe analyses. Cerium that has been annealed at high temperature and cooled to room temperature has the fee crystal structure (? phase) with a = 5.16Å. When cooled further, in the region between about 250" and 150°K, some of the fee phase transforms to the double hcp form (ß phase) with a = 3.68 and c = 11.92Å. The remainder of the room-temperature fee form (and perhaps some of the hexagonal phase) transforms electronically in the vicinity of 100° K to the more dense or "collapsed" fee form (a phase), a - 4.85A, by transferring about 0.5 electron per atom from the 4f level to the valence band. Very little work related specifically to the effects of impurities on the physical properties of cerium has been reported in the literature. Gaume-Mahn1, 2 has studied the effects of calcium, magnesium. iron, silicon, and tantalum on the electrical resistivity and magnetic susceptibility of cerium between 60o and 300°K. Gschneidner, Elliott, and McDonald3 have discussed the effects of total impurity content on the hysteresis of the a —? (reversible) transformation and on the formation of the 4 and "a-? intermediate" phases. Smith and Morrice* have reported the effect of total impurity content on the resistivity of cerium at 4 and 293°K. In none of these reports, however, is it apparent that the distributions of the impurities were determined, L.r., whether the impurities were present in inclusions or in solid solution in the matrix is not mentioned; nor does it appear that the phase purity of the cerium was always considered. In the present study, five different stocks of cerium were involved. One was represented by a single sample of electrowon cerium, which was all that had remained from a stock of high-purity material obtained from the U.S. Bureau of Mines, Reno, Nev., in 1959. The other four stocks were recently purchased from commercial sources and were specified to be 99.9 wt pct pure. EXPERIMENTAL Cerium stocks designated as #1, #2, #4, and #5 were obtained from commercial suppliers for the specific purpose of finding a reliable source of high-purity cerium. Although the purity level of the cerium was specified to be 99.9 pet, the specifications did not include limits as to the amounts of various impurities that would be acceptable. Consequently the chemical analyses of the different stocks varied widely. Stock #3, which had been obtained from the U.S. Bureau of Mines and which was the purest on the basis of chemical analyses, consisted of a single specimen of electrowon cerium. It was included in the examination for purposes of comparison. Table I contains the chemical and spectrographic-

Jan 1, 1968

By Mehmet Guney

During the last decade various modifications of room and pillar and sub-level methods have been tried in an effort to eliminate gob-fires, dangers from roof falls, surface subsidence and to increase efficiency of extraction in the Armutcuk Mine, Turkey. It was eventually decided that the most likely system to give maximum benefits in view of existing geological conditions and coal seam characteristics was a system of cut-and-fill stoping employing hydraulic stowing. This paper has attempted to examine the trends of working techniques of hydraulic stowing. In addition, the results achieved and technical problems involved are discussed.

Jan 1, 1968

By E. Alan Haley

Accurate and economic control of line and grade on long tunnels, large structures, excavations and waterways, has been a problem to surveyors and engineers for decades. The conventional method of surveying, incorporating a level, transit, and a number of surveying technicians, has proven, in the past, to be a very expensive and time-consuming operation. Alignment with a laser has solved most of the problem. Figure 1. With the advent of the Perkin-Elmer Model 5620 Construction Laser, use of laser light is now both dependable and economically feasible for unlimited applications in modern construction and surveying. The laser projects a continuous, narrow red beam of brilliant light, providing a constant alignment reference, and will not interfere with operations.

Jan 1, 1968

By D. C. Reynolds

Recent experiments with II-VI compounds have shown that they hazle considerable potential for laser applications over a broad region of the optical spectrum. It may be possible to cover the spectrum continuously from 3200A (ZnS) to the far infrared (CdHg:Te) since HgTe is a semimetal. At this writing laser action has been observed in ZnS, Zn0, CdS, CdSe, CdS:Se, CdTe, and some of the CdHg:Te alloys. Of particular interest are those lasers operating in the zlisible and near ultraciolet regzons of the spectrum where detectors of high sensitivity are available. The lasing transitions in II-VI compounds are bound exciton transitions some of which have been identified in auxiliary experiments. High efficiencies and low thresholds for lasing hare been achieved almost exc1usively in plutelet-type crystals. The greater crystalline quality exhibited by the phtelet-type material is shown to result from the crystal growth habit. Phonon scattering- of conduction electrons to the ground-state exciton is discussed ill relution to Lou thresholds and high efficiencies for lasing- observed in the CdS:Se solid solutions. The first successful semiconductor laser operation was achieved in the III-V compounds. It is possible to choose a material in this group that will operate between approximately 0.65 and 8.5 . There are at least two reasons why one would like to have a laser operating at shorter wavelengths. First, it would be easier to experiment with a laser operating in the visible region of the spectrum, and also more desirable to have high-in tensity visible light sources. Second, the most sensitive photomul-tiplier detectors are available in the visible and near ultraviolet regions of the spectrum. It is known that II-VI compounds are direct-band-gap semiconductors and as such offer the potential of operating at any specified wavelength between 3200 (ZnS) and 7772A (CdTe). Light emission from II-VI compounds has been the subject of numerous investigations for many years. These investigations were all primarily concerned with noncoherent emission. It has been only recently that coherent emission from these compounds has been observed. To date, laser operation has been demonstrated in CdS, CdSe, and the solid solutions of CdS:Se, ZnS, ZnO, and CdTe. These compounds cover an appreciable portion of the optical spectrum from the ultraviolet to the near infrared. In considering laser applications, the use of lasers in communication's systems offers many desirable features. In any operation of this type one must consider the losses in transmitting the radiation from the source to the detector. Atmospheric absorption in the visible and near ultraviolet is variable and greater than in certain regions of the infrared. It might be concluded that for long-range communication systems an infrared laser operating in a spectral region that is coincident with a transmission window in the atmosphere would be preferable. However, one cannot overlook the possibility of operating a system in the sensitive region of a highly sensitive photomultiplier detector or other light-amplifying system. LASER CONSIDERATIONS To produce a source of coherent radiation it is necessary to achieve a population inversion. In the case of semiconducting materials it is necessary to raise the electrons from one energy state to a higher-energy state relative to it. In semiconductors, this population inversion can be achieved by three different techniques: 1) Current Injection. This technique uses a p-n junction biased in the forward direction. Large numbers of electrons are injected from the n region into the p region, and recombination occurs close to the junction. An inverted population is obtained in this region and the recombination radiation propagates parallel to the junction. This type of pumping has been used in the GaAs junction-type lasers but has not been successfully employed in the II-VI compounds. 2) Optical Pumping. In this case, one uses photons to obtain a population inversion by exciting electrons to higher-energy states. The pump sources are flash lamps or arc lamps and, occasionally, other laser sources when such sources have the appropriate energy for exciting the electrons. The disadvantage of this type of pumping is that flash lamps put out a rather broad spectrum of radiation, whereas the laser material has a rather narrow region of absorption. This results in an inefficient process. Laser sources provide efficient pump sources but the number of usable wavelengths is limited. 3) Electron Beam Pumping. In this technique, the laser sample cavity is bombarded with electrons having energies in the range from approximately 10 to a few hundred kv. The bombarding radiation excites electrons from valence to conduction band states in the semiconductor, giving rise to an inverted population. This type of pumping has been used successfully in several 11-VI compounds.

Jan 1, 1968

By D. W. McGlashan

[Comideha;tion o 4 chyakd- chem and aLtuctund phopetttiu o auRdide nm&, The in~o/uncction gained h ;to be uned ;to iM;tmph& ( I! dnukey bho hen mind-aundacu , ( 2 ) modidicakio~n 06 ;the minmd n~tdacu, and (3) eac;tiom at ;the mind adac fnom ;thu e baic din oipfina, concep;tc, wLth hegattd ;to .the changen kha;t awtgacu undehgu, heac;tiom kha;t might take place, ,the geom&y 04 ;the inkmduce, ;the nkde 04 diddmenk &om and iom in ;the intmdace, and okhm phyaicd and chemicd pttopemXu od an intmdace mun;t be developed, weighed and appfied. The au/tho~ ded wah thue concep;tud connidmatiom @om which hypokhuu me n& ko denchibe khe envhomenkd-ivttadaciae hela;tiomhipa doh nevmd nddide minettah, The ch&enge and moltivation in khe hu eattch h in a henhe a deattch doh baic dad and helcctiomkipa needed doh accompfi he&.] INTRODUCTION Qualitative and quantitative explanation of particulate solid separations are unknown entities because of the lack of adequate models and mathematical relationships to explain the activity occur- ring between the solid and liquid phases. It is a transitional region in which it is difficult to ascertain the mechanisms of adsorption of ions, molecules, etc. on mineral surfaces, as well as other secondary reactions which occur in interfacial regions. Thus, in this paper the authors deal with conceptual considerations from which hypotheses are set forth to describe the environmental- interfacial relationships for sulfide minerals.

Jan 1, 1968

By Charles C. Fatino, Joel S. Hirschhorn

Loose compacts of strained and annealed stainless-steel powders were sintered at various temperatures and times to determine the effect of residual strains on the sintering behavior. The atomized powders were prepared by annealing, ball milling, and rean-nealing. The residual strains and domain size were determined by a Fourier analysis of X-ray diffvaction dala. The specimens were prepared by siwzultaneously sintering cylinders of both strained and unstrained powder. The evaluation of the sintered compacts included density measurements, metallographic examinations, and analyses of X- ray diffraction data. The results of these studies reveal a definite increase in sintered density and sintering rate for the strained powders. THE pressure compacting of metal powders causes deformation of the particles, mechanical interlocking, and increased contact area. After the deformation, severe residual strains remain in these particles. The subsequent contributions of these strains to the sintering process have been considered to be negligible, since the recovery and recrystallization temperatures usually occur prior to the temperature required for the sintering process. Sintering is con-sidered to be the process by which the powders are transformed into solid compacts at temperatures below their melting points. The sintering operation for stainless steel usually takes place in the range of 2050" to 2400°F (0.84 to 0.95 T,, where T, is the absolute melting point or liquidus temperature) while the temperature required for recovery is approximately 1800°F (0.75 T,). However, it has been shown for several metal powders that densification becomes significant in the range of 0.35 to 0.45 T,.' It is the purpose of this study to determine what effect residual strains have upon the sintering behavior of stainless-steel compacts. Loose compacts were selected for study in order to isolate the strain contributions and eliminate the variables inherent in sintering of pressure-formed compacts. Additional variables were minimized by using only one mesh size, one composition, one particle shape, and also by simultaneously sintering both types of powder. Very little work has been carried out previous to the present study to delineate the effect of strains on sintering behavior. Lenel et 01.2 observed that residual stresses in copper compacts caused shrinkage at comparatively low temperatures. Delisle3 loose-sintered ball-milled electrolytic iron and observed that bonding among particles began at a lower temperature as compared to the behavior of annealed powder. Increased densification of ball-milled oxide powders has also been noted.4'5 EXPERIMENTAL PROCEDURES Powder Preparation. The powder used for this study was a commercial-type 316L stainless steel made by the atomization process. A typical chemical analysis is: C- 0.025 pct Mo- 2.2 pct Cr-18.6 pct Ni-12.5 pct Fe—Balance The atomizing process is essentially the rapid freezing of liquid droplets. This nonequilibrium cooling causes coring to occur and two distinct phases are present within the solid particle, the austenitic phase and the ferritic phase. Due to the presence of this ferritic phase, the particles tended to fracture as well as become cold-worked during the subsequent ball-milling operation. (It was also found that this type of cooling produced a broadened and shifted

Jan 1, 1968

By David C. Jonson, W. Bruce MacKenzie, Arthur A. Bookstrom, Vaughn E. Surface, Neil K. Muncaster, Stewart R. Wallace

In mid-Tertiary time a wet silici-alkalic magma penetrated the Precambrian rocks of what is now the Tenmile Range of Central Colorado and formed the Climax Stock. The stock is a composite one and was intruded in four separate irruptions, each giving rise to a major hydrothermal event. The first three of these produced large stockwork ore bodies that cap and flank the tops of their respective source intrusives; the fourth, and last, yielded almost no commercial mineralization. The ore bodies and their related zones of alteration are circular to ring-shaped in plan and arcuate in section. The different phases of the stock are so positioned with respect to each other that many of the circular and arcuate zones of mineralization and alteration overlap or are juxtaposed. Evidence of a time separation between the different ore bodies is found in certain dikes that were intruded between periods of mineralization and are well mineralized in one ore body but are barren in another. If it is assumed that the parent magma at Climax contained 10 per cent "water," that the "water" contained 0.1 grams per liter of molybdenum, and that the processes of extraction were 100 per cent efficient, then approximately 10 cubic miles of magma would be required for the formation of each ore body. The volume requirements, taken in conjunction with the cross-sectional areas of the different phases of the stock to explored depths, suggest to the authors that each magma chamber was columnar, extended to a depth of thousands of feet, and was connected with a much larger master reservoir. The repetition of similar intrusive, structural, and hydrothermal events, indicates periodic tapping of this reservoir. A regular chemical evolution of the parent magma is suggested by the systematic change in metal ratios and differences in the sites of deposition, relative to the source intrusive, in each of the four separate igneous hydrothermal stages. The preparation of ground was due to changes in magmatic and/ or hydrothermal pressures within the igneous-hydrothermal columns; small, repeated, up and down movements of the rock enclosing the tops of the columns formed the stockwork fractures into which the mineralizers penetrated. The forceful emplacement of each successive phase of the Climax Stock resulted in a slight doming and rotation to the westward of the earlier-formed geologic features. Postore normal displacement along the Mosquito fault is estimated at about 9000 feet. Part of one ore body was cut by the fault and lies at depth below the Paleozoic sedimentary strata on the hanging wall. On the footwall side of the fault, subaerial erosion and glaciation removed a large part of one ore body and uncovered the top of a second.

Jan 1, 1968

By C. M. Mason

A method for evaluating the relative incendivity of detonating cord in natural gas-air mixtures was developed. The method consisted of firing short lengths of cord in bundles to determine the number of strands per bundle which would ignite natural gas-air mixtures 50 percent of the time in the 45-cubic-foot gallery of the Bureau of Mines. The relative efficiency of a flame quenching agent, potassium acid tartrate (KHT), when incorporated in both the pentaerythritol tetranitrate (PETN) core and the polyethylene sheath, was explored. The effects of sheath thickness, sheath composition, core weight, and core composition were evaluated. The bundle method established a quantitative scale for evaluating the relative incendivity of cords. The relative incendivity determined by the bundle method was then compared with the incendivity of 100-foot lengths of detonating cord when initiated in 8 percent natural gas in the 640-cubic-foot gallery of the Bureau of Mines.

Jan 1, 1968

By E. N. Harshman

The Wind River Formation of Eocene age is the host rock for large high-grade uranium deposits in the Shirley Basin. The major deposits are in a northwest-trending belt of sandstones that were deposited in stream channels and that were lithologically favorable for uranium accumulation. Paleotopography influenced the character and position of the belt. The major deposits within the belt are at, or near, the margins of large tongues of altered sandstone formed in the most transmissive parts of thick sandstone beds. At least two tongues of altered sandstone are present in the belt, one of which is 5 miles long, 3 miles wide, and 70 feet thick; the other tongue is somewhat smaller. Ore bodies consist of a few hundred tons to several hundred thousand tons of material containing from 0.10 to about 2.00 per cent U3O8. The ore mineral is uraninite associated with pyrite, marcasite, hematite, and calcite. Deposition is believed to have taken place when neutral to slightly alkaline, oxidizing, uranium-bearing ground water, on entering the basin, encountered a reducing environment. The reductant may have been H2S of biogenic origin. Geology played an important role in discovery, exploration, and development of ore in the Shirley Basin.

Jan 1, 1968

By Ralph B. Adair

The Bureau of Mines conducted laboratory and small-scale, continuous tests of weathered mica-pegmatite ores from Randolph County, Ala., to determine the feasibility of recovering commercial-grade mica concentrates by flotation. Two flotation methods were used in continuous tests for recovery of mica. One method utilized acid-cationic flotation for the recovery of coarse mica and alkaline-anionic-cationic flotation for recovering fine mica. This method yielded mica concentrates containing 98.6 percent mica with a recovery of 85.9 percent. The other method was based on the Bureau-developed alkaline-anionic-cationic method, and yielded concentrates containing 97.5 percent mica with a recovery of over 90 percent. In both methods, preconcentration of the ground ore on a Humphreys spiral was employed to reject over half of the feed in a product virtually free of mica.

Jan 1, 1968

By Arthur W. Ruff

The iron-ore beneficiation and shiploading facilities of the Marcona Mining Company are at San Nicolas Bay which is on the Peruvian coastal desert about two hundred and seventy miles south of Lima. The mines are at elevation of 2,500 ft. Crude ore is transported from the Mine primary crushers to the beneficiation plants by ten miles of overland belt conveyors. After the predominantly magnetic ore is reduced to minus 3/4 in. in the secondary crushing plant, the ore is ground by rod and ball mills and concentrated with magnetic separators. The concentrate slurry is pumped to a thickening and filtering installation for desliming and dewatering. Pelletizing is accomplished with a Lurgi and also a Dravo-Lurgi machine. Deep-water shiploading facilities are available close to the beneficiation plants. Figure 1 shows a flowsheet of the general operation. Pelletizing operations are scheduled 24 hours a day and 365 days per year. A maximum tonnage rate with a high percentage of operating time is necessary to produce the three and one half million tons per year required from the two pellet lines. Process control is a major responsibility and of primary concern to all Operating personnel. The particle size, moisture, and chemical composition of the filter cake must be closely controlled to get uniform high-grade pellets. Key points are sampled routinely and analyzed on a two-hour basis to provide the necessary structure and chemical data to maintain a superior final product. The iron content of the pellets is held between 65.3 and 65.8 percent with 4.0 percent Si02. Sulfur is below 0.04 percent and copper is below 0.02 percent in the finished pellet.

Jan 1, 1968

By D. E. Wolfson

The Bureau of Mines carbonized 21 coal samples from Fayette, Greene, and Washington Counties, Pa., at 900° C, using the Bureau of Mines-American Gas Association (BM-AGA) method, and determined yields of products and physical properties of the coke. These samples represented high-volatile A Pittsburgh, Sewickley, Waynesburg, and Upper Freeport and medium-volatile Upper Freeport and Lower Kittanning coals. About 20 percent of all coals presently carbonized in commercial coke ovens in the United States are mined in Greene and Washington Counties, principally from the Pittsburgh seam. Sulfur content of the Pittsburgh coals in these counties is moderately high (1.0 to 3.2 percent) but, because of extremely large reserves, accessibility to eastern United States markets and excellent blending characteristics to yield strong coke, these counties will continue to be an important source of metallurgical coals in the future. Most coals from the other seams contained more than 2 percent sulfur, which would limit their use as metallurgical coals.

Jan 1, 1968

By R. S. Shoemaker

Expanded markets for copper in the past few years and a consequent search for new ore bodies have revitalized the widely known but seldom applied method of producing copper called heap leaching. This term should be differentiated from dump leaching in that the latter is applied to dumps of mixed oxide and sulfide ores (although either may predominate) that have been too low grade to beneficiate and have, therefore, been stripped off the higher grade underlying sulfide ores. Heap leaching is defined here as the process applied to oxide ores which have been mined solely for the purpose of leaching. In this case, all costs of mining the ore become a part (and a substantial one, as will be shown) of the cost of the copper produced, whereas in dump leaching the mining cost has already been accounted for as a stripping cost for the sulfide ore. Of course, with newly opened ore bodies, stripping costs may be divided through accounting procedures, between the copper produced by the mill and that obtained by leaching, but in general this type of operation must be economic on the basis of the sulfide ore alone. Heap leaching, as a beneficiation method, is unique in that it is the only process used for the recovery of a metal in which the time involved from mining the ore to metal production is measured in months instead of hours or at the most, days, Then too, after the ore body has been depleted and mining has ceased, metal production will continue for some substantial period of time. Heap leaching is also unique because unlike any other method of beneficiation, metal recovery cannot be accurately forecast ahead of time and recovery will never approach that of a conventionally milled sulfide ore or even that of a vat leached oxide ore. Counter-balancing this drawback, however, is the relatively low capital expenditure necessary to put a heap leaching operation into production and the consequence that smaller ore bodies which would not support the higher capital cost involved in a vat leaching plant can be made into producers. Stated more simply, in heap leaching the operator accepts low recovery in exchange for low capital costs and the break even point, that is, where the operator should go to vat leaching with its higher recovery and higher capital costs, is a matter of economics and also, to a great extent, a matter for the nature of the ore to decide. For instance, an ore that will vat leach in 7 to 10 days using 7 pounds of sulfuric acid per pound of copper produced might use double or triple that amount of acid during the months that are required for heap leaching.

Jan 1, 1968

By F. R. Lee

This publication lists permissible equipment approved by the Bureau of Mines during 1965 and 1966 (calendar years), except for breathing apparatus and explosives. The purpose of this publication is to inform the public about approved equipment for safe use in underground mines.

Jan 1, 1968

By B. D. Nash

The object of this research was to investigate the technical feasibility of preparing chromium metal by the thermal decomposition of bisbenzene chromium. Bisbenzene chromium, a pi-bonded sandwich type organometallic compound, was thermally decomposed under reduced pressure to form a metal plate on a heated substrate. Metal recovery was close to 100 percent of theoretical, with deposition rates up to 20.8 mg/hr/cm2. Metal purity was dependent not only upon the purity of the starting material, but also upon the sublimation rate of bisbenzene chromium. Total detectable metallic impurities ranged from a low of 18 ppm to several hundred ppm. In general, metallic impurities were less than 100 ppm. Carbon, the major nonmetallic impurity, ranged from less than 0.3 percent to more than 10 percent. The carbon contamination is most likely a result of the decomposition of the organic portion of bisbenzene chromium. An unusual property of some of the deposits was their outstanding corrosion resistance. Unlike pure electrolytic chromium, which dissolves readily, these deposits were insoluble in hot mineral acids.

Jan 1, 1968

By C. J. Frosch, J. A. May, H. G. White, C. D. Thurmond

Gallium phosphide epitaxial layers were grown from the vapor phase on undoped single-crystal galliurn arsenide substrates in silica tubes by an open-tube wet-hydrogen process. The epitaxial layers were grown over a range of water pressures at three substrate temperatures. Excess donor concentrations were determined by surface barvier capacitance measurelrzents without removing the layers from the substrates. The excess dmlor concentration, ND-NA, is fo~ind to vary approxilnately inversely with the pressure of water added to the hydrogen carrier gas. This is the relationship that would be expected for singly ionized silicon donors on gallium sites in extrinsic galliunz phosphide, with the silicon coming from the SiO generated by the reaction of hydrogen with the silica tube. An increase in the partial pressure of water in the hydrogen stream decreases the SiO pressure. The results indicate that ni, the intrinsic hole and electrmt concentration for gallium phosphide at the three substrate temperatures, is smaller than the concentration estimated from available data for the density of states effective masses and the energy gap. Mass-spectrographic measurements confirm that the dono?, introduced into gallium phosphide is silicon. The equilibrium concentrations of silicon in vapor-flown gallium Phosphide have been estimated from available thernzodynamic information that includes the solubility measurements of silicon in gallium phosphide in equilibrium with a gallium-rich liquid phase. Satisfactory agreement with the measured silicon concentrations is obtained. FROSCH1 has described an open-tube process for growing single-crystal Gap from the vapor phase by a GazO transport mechanism. The method depends upon the reaction of H20 in an H2 carrier gas with a heated source of polycrystalline Gap which provides the necessary vapor species. When the temperature of these vapor species is lowered, super saturation occurs and single-crystal Gap will deposit on a suitable substrate. Unintentionally doped single crystals of Gap grown by the wet H2 process in silica tubes are n type. Evidence is presented to show that the donor introduced is silicon, and that a qua si-equilibrium model accounts for the inverse dependence of the donor concentration on the water partial pressure and predicts the magnitude of the donor concentrations. Ainslie et al. experimentally showed a similar inverse relationship between the carrier density and oxygen pressure for GaAs. Emission-spectrographic analyses showed a decrease in the silicon concentration with increasing oxygen overpressure for GaAs. Cochran and Foster suggested the theoretical possibility of suppressing silicon contamination by using Ga20 generated by the reaction of gallium with water vapor. 1) EXPERIMENTAL The apparatus and procedures are essentially the same as those described by Frosch.' The apparatus consists of a 25-mm-ID SiO2 tube extending through a controlled high-temperature flat zone for the location of the polycrystalline Gap source and a downstream temperature gradient falling at a rate of about 14°C per cm. The latter provides the region of super saturation for the location of the single-crystal substrate. The partial pressure of water in the inflowing hydrogen stream, pA2, O was controlled by mixing me-tered proportions of dry H2 with H2 saturated with H2O vapor at 0°C. The total gas flows were about 200 cu cm per min in all experiments. The Gap sources were prepared by pulverizing boat-grown polycrystalline ingots to pass a 20-mesh sieve. The substrates were cut from an undoped single-crystal boat-grown GaAs ingot purchased from Monsanto. This ingot had a carrier concentration of about 1015 atoms per cu cm, a resistivity of about 5 ohm-cm, and a mobility of about 5000 sq cm per v sec at 25°C. Substrates with dimensions of 1 by 1 by 5 x lo-' cm were employed. The growth faces were chemically polished (111) arsenic faces. Epitaxial layers, at least 7.5 x 10-3 cm thick, were grown,. This required from 1 to 24 hr depending upon the Pii2Q values and the temperatures. In all of the runs, the source temperatures were 50°C higher than the substrate temperatures. Samples were prepared

Jan 1, 1968

By Edward W. Parsons

The transverse force developed by expansion-shell rock-bolt anchors on the wall of a drill hole as the bolt is tensioned was measured by the Bureau of Mines using a device specially designed and fabricated for attachment to a universal testing machine. Load cells equipped with electrical-resistance strain gages provided the data from which the transverse force, in pounds, was calculated. Seven different expansion-shell anchors were tested, and the ratio of transverse force to bolt-tension load was found to range between 0.98 and 1.94 to 1.0. The drag load appeared to be the major cause of the transverse-force variation, but the relative effects of individual factors that affected the ratio between the transverse force and the bolt tension were not determined.

Jan 1, 1968

By W. C. Winegard, C. J. Simpson, C. J. Beingessner

VARIOUS organic compounds, such as borneol, carbon tetr a bromide, and hexachloroethane, solidify as transparent plastics with a fcc structure. Each of these substances undergoes a solid-state transformation from the plastic phase to a brittle phase at temperatures slightly above 20°C. Since it was known that these plastic crystals solidified like metals,1 it was decided to investigate the possibility that solid-state grain growth would occur in the same way as it does in metals. Two-dimensional grain growth in thin films of plastic organic compounds has been studied with the aid of cinemicrophotography. Samples varying in thickness between 250 and 1000 @ were prepared by subliming a thin layer of the compound onto a microscope slide plate which was then covered with a second slide plate.

Jan 1, 1968

By R. P. Agarwala, M. S. Anand

Using residual activity technique, the diffusion of palladium, silver, cadmium, indium, and tin in alunzinum has been studied in the temperature range of 400" to 630°C. The diffusivities (in units of square centimeters per second) have been expressed as: IMPURITY diffusion in aluminum,1-9 silverand lead5 for cases of low solid solubility of the impurity in the host metal has yielded frequency factors in the range of l0-6 to l0-9 sq cm per sec whereas the activation energy is practically half the self-diffusion activation energy value. From the observed values of frequency factor, activation energy, and entropy of activation, it has been suggested' that these solutes are not diffusing by vacancy or interstitial mechanisms but by a mechanism which should be consistent with such low values of the diffusion parameters (Do and Q). However in spite of extensive work on these types of systems, the mechanism of diffusion is still not well understood. The present investigation on the diffusion of palladium, silver, cadmium, indium, and tin in aluminum has been carried out to throw further light on the diffusion mechanism in systems, where the solid solubility is very low (except for the case of silver). The results are discussed on the basis of solid solubility and the structural changes involved owing to the presence of the solutes in aluminum solid solution. An attempt has also been made to apply the existing theories of charge5-8 and size8 difference between the solute and the solvent. EXPERIMENTAL PROCEDURE Specimens (1/2 in. diam by 3/8 in. high) were machined out of pure aluminum (99.995 wt pct) rod obtained from Johnson Mattheys. They were sealed under vacuum in quartz tubes and annealed at 620° C for several hours; the grains thus developed were sufficiently large to eliminate the possibility of diffusion along the grain boundaries. The flat ends were prepared carefully after polishing as described previously,10 Radioactive nitrates of cadmium, indium, and tin and chloride of palladium containing, respectively, cd115, 1n114, sn113, and pd103 were dissolved in distilled water and mixed with 30 pct acetone. By means of a micropipet a drop of this solution was placed on a smoothly polished and lightly etched surface of the specimen. Due care was taken to see that the solution spread uniformly on the surface of specimen without trickling down its sides. Radioactive silver was elec-trodeposited using a AgCN-KCN bath. The amount of sample deposited in all the cases was not more than 0.1 µ thick. The samples were then sealed in quartz tubes in vacuum. The cadmium samples were sealed in a purified argon atmosphere to avoid evaporation. The samples were then diffusion-annealed. The temperature of annealing varied between 400° and 630°C and was controlled to ±5°C. On heating to -400°C,the deposits of cadmium, indium, and tin, which were of the order of 0.1 p in thickness, were converted to their respective oxides. The contribution of oxygen present in the lattice of aluminum due to these oxides has been calculated and found to be less than 10 ppm in all cases. Oxide method has already been used by other workers11'12 in diffusion studies without any controversy on the issue. However, in some of these investigations, metallic deposition was also tried. The diffusivities calculated from these measurements were found to agree very well with the diffusivities obtained by using the oxide method. Thus it is assumed that the measured diffusivities represent true diffusion coefficients. Since palladous chloride decomposes at about 500°C, the deposited samples which were to be diffusion-annealed below 500°C were heated in vacuum for a very short time at 500°C to allow the decomposition of palladous chloride to palladium metal. Time taken in decomposition of nitrates to oxides and chloride to metal was negligibly small as compared to the period of the diffusion anneals. The residual activity technique13 was used to study the diffusion profiles where thin layers from the specimen surface were removed by grinding it parallel to a flat surface on a 600-grade carborundum paper. The specimen was washed, dried, and weighed, the differ -ence of the weight being the measure of the thickness of the layer removed. After each such abrasion and weighing, the total residual activity on the surface of the specimens was measured by counting 0.656, 0.94,

Jan 1, 1968

By W. W. Gerberich

SINCE the original formulation of fracture mechanics concepts,&apos;y2 relatively little work has related the fracture mechanics description of metal behavior on a gross, structural component scale to the behavior of its microstructural constituents. The purpose of this note is to suggest the utilization of fracture mechanics to describe material behavior on a microscopic scale. A Fracture Concept for Two-Phase Structures. A critical displacement concept considering the tough unidirectional phase in a relatively brittle matrix is first examined. It is assumed that a flaw exists at position 1 as depicted in Fig. 1. As the crack moves from position 1 to 2 the plastic zone could be of the shape described with the size approximated by the Dugdale3 model: where c is the half-crack length, OO is the applied stress, and oyS is the yield strength. Hahn and Rosen-field4 have presented a simple fracture criterion for homogeneous materials based upon the displacement at the crack tip. They also have shown the equivalence of the critical displacement, v*, to fracture toughness by Kc = (2v*oysE)1/2 [2] The displacement at the crack tip is given by and the displacement at any distance in front of the crack tip may be determined knowing the plastic zone size and utilizing the development of Goodier and Field.5 Recalling Fig. 1, the value of v* for fracture in material M1 may be calculated from Eq. [2] providing the critical stress intensity factor is known. As the material is loaded, when vc > vM1 the crack moves from position 1 to position 2 where it encounters the tough second phase. If vc2 < vm2, then the crack will be arrested providing the width of the M2 phase is sufficiently large. This condition is necessary since the displacement at position 2 has increased due to the longer crack length. Thus, the displacement at the distance X (representing the dimension of the second phase) in front of the crack may be larger than the critical displacement for failure in the brittle material. If v, > vm, then failure will proceed in the brittle material. The value of v, may be calculated as indicated above. This latter consideration is the same as predicting fracture of a brittle second phase at some distance in front of a crack located in a ductile matrix. Experimental Evidence. On a macrostructural scale, tungsten wires in a ductile Be-Cu matrix are seen to fracture well ahead of the main crack front in Fig. 2. Utilizing a Kc value of 14.2 ksi-in.1/2 obtained by Schroder et al.6 for as-received tungsten, the critical displacement 2v*, for fracture is calculated from Eq. [2] to be about 6.5 X 10-5 in. The crack tip displacement, 2vc, is calculated from Eq. [3] to be 0.0028 in. indicating that fracture would occur at a considerable distance in front of the crack tip. From the ratio of v*/vc and the plastic zone estimate of Eq. [I], the distance in front of the crack tip at which a tungsten wire should fracture is calculated to be about 0.195 in. As shown in Fig. 2, a fractured wire occurs at a distance of 0.140 in. (fractured in three places), not at 0.250

Jan 1, 1968