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By C. W. Eggert

"The idea for this talk came to me last year when I was attending the Canadian Gold Metallurgists Meeting. I talked about it to a friend of mine who is an authority on mineral dressing, particularly the theoretical end of the business. He remarked that this was an excellent technical note, why don't you write it up. This is what I have for presentation this morning. I hope in presenting this type of idea in this way it is in keeping with the tradition of the Canadian Gold Metallurgists which was to function on a not too sophisticated level and where operators could get together and trade ideas in an informal way.My basic thesis is that it should be possible to evaluate screen analyses by the application of the standard statistical probability theory. In any statistical analysis the sample is the first consideration. If we look at existing methods of size evaluation we find it is usually based on the fact that a given particle will pass one square aperature and not another. One system of standardizing how these aperatures will be set up is based on Rittenger' s work with the ratio of hole sizes proportional to the square root of 2. Keeping in mind the limitation we have accepted this as our method of 11 sizing"" in attempting to apply standard statistical methods to screen analysis."

Jan 1, 1968

By P. H. Wendland

Calculations are presented for the design of a silicon photodiode in which the incident light beam makes multiple passes between the detector surfaces. Total internal reflection is used for this "light-trapping" effect. By this means, the optical path length can be extended to several millimeters, while the electrode separation remains less than 102 cm, as required for nanosecond response time. Data are presented for a Schottky barrier photodiode constructed on a multiply reflecting silicon base wafer. It is shown that the long-wavelength response is considerably extended in such structures without a corresponding sacrifice in high-speed response. The development of efficient and powerful lasers at 1.06 p has stimulated interest in detectors which operate at this wavelength. In typical silicon photodiodes, for detecting 1.06 p radiation, the requirements for high speed and high sensitivity are mutually exclusive. Since the absorption coefficient is only 25 cm-', a lo-'-cm path length is required to absorb 92 pct of the incident 1.06 p radiation. If the electrode separation is greater than 10 cm, however, the carrier transit time will be greater than 1 nsec. This problem can be solved by allowing the incident light beam to make multiple passes between the electrodes. The optical path length can then be extended to several millimeters, as required for complete absorption, while the electrode separation remains less than 10' cm, as required for nanosecond response time. In a typical photodiode geometry, one ohmic contact and one rectifying contact are formed on the two opposite surfaces of a base wafer, and the wafer thickness determines the electrode separation. The objective of the multiple reflection design is to allow all 1.06 p radiation to enter the detector front surface and to form the back detector surface so that no 1.06 radiation can exit. Total internal reflection at the back detector surface is well-suited for light trapping of 1.06 p radiation because the relatively large dielectric constant of silicon leads to a critical angle of 16.5 deg for total internal reflection. LIGHT TRAPPING It is well-known that, as light passes from one medium such as air into another medium such as glass or silicon, the angle of refraction is always less than the angle of incidence. In the limiting case, where the incident rays approach an angle of 90 deg with the normal, the refracted rays approach a fixed angle +, beyond which no refraction is possible: this is called the critical angle. It follows from Snell's law that where = critical angle, n - index of refraction of air, n' - index of refraction of the medium. Applying the principle of reversibility of light rays, all internal angles of incidence greater than +, will produce total internal reflection and "light trapping". The index of refraction of silicon at 1.06 p is 3.5,' and the critical angle is thus 16.5 deg. Fig. 1 shows these relationships for silicon. This very small critical angle in silicon is significant because all incident angles between 16.5 and 90 deg will produce total internal reflection and "light trapping". This effect can be implemented with a "prismlike" geometry, so that incident light can be introduced into the sample without loss and "trapped". PHOTOSIGNALS A precise knowledge of the absorption coefficient at 1.06 in silicon is of critical importance to the design of fast and efficient silicon photodiodes for 1.06 radiation. Dash and newman2 show a value of 25 cm-l, and our measurements have corroborated this value. Assuming that the collection of photoinduced minority carriers is perfect, the quantum efficiency of a photodiode is dependent only on the absorption coefficient. It then follows from Lambert's law that where QE is the quantum efficiency in pct, a is the absorption coefficient, d is the optical path length, and the reflectivity at the surface is assumed to be completely suppressed by an optical interference layer. Fig. 2 gives the maximum quantum efficiency for 1.06p radiation of a silicon photodiode with optical path length d, using Eq. [2]. The ultimate response time of a fully depleted photodiode to an incident light pulse can be considered to be the arrival times of all photoinduced carriers at the contacts, i.e., the minority carriers at the junction interface and the majority carriers at the oppo-

Jan 1, 1968

By F. G. Miller

To improve coal flotation Bethlehem Steel Corporation's Research Department has been working on a number of related problems based on both physical and chemical factors. The ideal is of course full understanding of the interrelated effects of both sets of factors. However, detailed studies5 of each physical factor have produced immediately usable results in commercial coal flotation and are providing the bas is for our current work on the effect of chemical factors. Since these detailed studies provided the basis for the present investigation of froth sprinkling, their key results are highlighted here. For example, for a highly floatable bituminous coal, particle floatability was shown to be directly related to the percentage of coal surface available for bubble attachment and inversely related to particle mass. The data also underscored that in a given size range the addition of mineral matter to a particle makes flotation more difficult both by adding to the mass of the particle and by decreasing the amount of coal surface available for bubble attachment. Size also affects particle floatability in that as the size of particles of a given specific gravity increases, mass increases and the ratio between coal surface area and mass of the particle decreases. Flotation tests showed that any recovery of the coarsest particles in a coal feed is accompanied by progressively higher recovery of finer and finer particles. Consequently, fine high-specific-gravity particles are recovered with the coarse good coal. As a result, when the entire 14M x 0 size range is processed by froth flotation, the good coarse coal is contaminated with high-specific-gravity fines. It is the small quantities of these fines that must be rejected from the froth product if flotation efficiency is to be increased above its present level.

Jan 1, 1968

By I. M. Bernstein

The steady-state creep behaviov of zirconium and zivcaloy-2 was examined in the temperature vatlge 520° to 620°C A1 low stresses the creep rates were cimracterized by a linear stress dependence; at highev stresses the stress dependence was much more pronounced. Temnperature-cycling tests yielded values for the aclivation enevgy for creep. Various tlzeories were examined in the ligltt of- the experimental re-sults and it mas concluded that the low-stress creep behavior is the result of the stress-direcled diffusion of vacancies along gain boundaries. It has been observed,"&apos; usually under conditions of high temperature and low stress, that creep deformation can occur for which the steady-state creep rate is linearly dependent on the applied stress. For magnesium and certain magnesium alloys, Harris and ones&apos; and ones&apos; have argued that this type of creep occurs by mass transfer as a result of the stress-induced generation and migration of vacancies, along a gradient defined by the stress direction. Jones&apos; demonstrated that the rate-controlling diffusion path is sensitive to grain size and temperature, and that by suitable control of these variables creep could occur by vacancy diffusion either predominately along grain boundaries or through the lattice. Recently, Jones3 suggested from an examination of limited high-stress data for zircaloy-2, composition in Table I, that significant diffusion creep could occur at low stresses, at least between 375" and 500°C, controlled by grain boundary vacancy diffusion. This process could have an important implication in assessing the role of zirconium alloys as a structural or cladding material in certain classes of nuclear reactors, since it predicts creep deformation far in excess of any estimates based on extrapolating slip creep data from higher stress levels. If the diffusion creep process occurs it should be possible to describe the total steady-state creep rate of zirconium and its alloys as the sum of two terms, Eq. [I]; the first term relates to a slip creep process important at high stresses and which is manifested by a much more pronounced dependence of creep rate on stress4 than diffusion creep and the second to a process controlled by mass transfer,5&apos;6 dominant at low stresses: where A and BI are parameters which can depend on structure, Ql and Q2 are the activation energies for the particular creep process occurring, and n describes the sensitivity of the creep rate on stress. It is the purpose of this paper to present some direct experimental evidence in support of this view. It is recognized that other analytical approaches have been proposed to explain data of this kind and these will also be discussed. 1) EXPERIMENTAL PROCEDURE Flat creep specimens (gage length 1 by 0.25 by 0.02 in. approx) were prepared from cold-rolled, argon-remelted, crystal bar zirconium and cold-rolled commercial-grade zircaloy-2, the analyses of which are given in Table I. The specimens were annealed at a pressure of < 10-5 Torr at temperatures from 625" to 675°C for 2 hr and slow-cooled. This treatment produced stable grains of average size (defined here by the average linear intercept) of for zirconium and -4xin. (-10 p) for zircaloy-2. The specimens were tested in a dead load tensile creep rig. The stress was maintained constant by adjusting the applied load after approximately each 1 pct of strain. The specimen temperature was controlled to better than +1°C. This system had a small thermal lag, so that rapid temperature changes were possible. To minimize corrosion, the specimens were tested in high-purity (99.95 pct) argon, further dried,

Jan 1, 1968

By H. I. Kaplan, C. Laird

Pulsating contpresslon experiments have been carried out on coppev single crystals in order to test the adequacy of mechanisms which have been suggested for stage I cvack grouth when tension-compression loading is the mode of- applying stress. Although dejorrrzation continues slowly for many millions 01 cycles under Pulsating compression stresses both within slip bands formed in the first cycle and by the creation of new bands, the morphology of these bands is not typical of fatigue slip bands in general and neither initiation of cracks nor propagation of artificially induced cracks was observed. It is therefore concluded that 1) initiation and growth of cvacks in fatigue is a consequence of repeatedly reviersed, microplastic deformation rather than intermittent, unidirectional deforma-tion, 2) gvowth of- cracks in polycrystalline specimens FAILURE of a plain specimen subjected to cyclic tension-compression stresses is known to take place by two stages of cracking.1,2 The first stage is characterized by propagation along slip planes roughly at 45 deg to the stress axis, in the outermost layers of the specimen, and at a rate of the order of angstroms per cycle. The average macro orientation of a stage I crack is normally at right angles to the stress axis,3 however, except in a few cases, e.g., single crystals in suitable orientation, when both the micro and macro directions of propagation are at 45 deg to the axis. After a stage I crack has penetrated to such a depth that the stress on the remaining section of metal is significantly increased, stage II crack propagation succeeds stage I, at right angles to the stress axis both micro and macroscopically. Direct evidence of the processes occurring during a subjected to pulsating compression stresses is caused by the setting-up of local tensile stresses due to interactions between grains, and 3) both unslipping mechanisms and operation of the "plastic blunting process " within a single slip band are adequate descriptions 01- stage I growth, being fundamentally similar. The slip mode of a material, however, is considered to control whether unslipping or the plastic blunting process takes place. Thus materials of planar slip mode fauor unslipping while those hacing a wavy mode, and capable of cross slip, can fail in stage I by the plastic blunting process. Similarly, and perhaps more importantly, reversed torsion and tension-compression modes of applying stress may be expected to cause the unslipping mechanism and the plastic blunting process, respectively. single stress cycle4,5 shows that stage II crack propagation takes place by a repetitive plastic rounding and closing of the crack tip. This mechanism has come to be called the "plastic blunting process".6 On the other hand, the extreme smallness of the phenomena occurring in stage I growth prevents elucidation of its mechanism by direct observation. Many suggestions have been proposed for this mechanism,&apos;"-" most of them involving some kind of random or systematic unslipping process. It is possible, however, that the mechanism of stage I growth is essentially the same as that of stage 11, but occurring on a much smaller scale.6 In this situation, it has been observed that cracks propagate along slip bands comprising dislocation cell structures and bounded on either side by regions of different dislocation density and distribution." Since there is evidence that such bands are softer than their matrix, * it may be expected that the plastic blunting process occurs within a single slip band during stage I growth, rather than on two gross bands as in stage 11, when the acting stress is greater.= The blunting of the crack tip allowed by coordinated

Jan 1, 1968

By P. R. Sahm, T. V. Pruss

Mixtures of fine GaSb and Gds as well as preal-loyed GaSbl,As, powders were hot-pressed at 690°C and 25,000 psi. Dense alloys with compositional gradients of less than 5 pct were obtained from mixtures containing about 20 mol pct GaAs. For x < 0.2, there were increasing compositional gradients, and for x > 0.2 a GaAs-rich second phase appeared in the microstructure. Densification as well as alloying wlechanisms were enhanced by dissociation and, possibly, oxidation reactions of the powders. Densification of coarse prealloyed material, however, primarily depended on plastic flow phenomena and required temperatures just below solidus and pressures of 50,000 psi Thermal and electrical properties were measured. Although in no case was the figure of merit of melt growth materials approached closer than to within 25 pct, the better overall thermoelectric properties were found in coarse-grained, prealloyed materzals which had been compacted to near theoretical density and where grain regrowth had been induced. Similar results are believed to hold in other binary 111-V compound systems if processed under similar conditions. The densification of unalloyed GaSb powders during pressure sintering (= hot pressing) was shown to depend strongly on powder particle size.&apos; Fine powders displayed a "liquid skin effect" that enhanced compaction through the presence of liquid gallium, whereas coarse powders compacted predominantly by plastic flow. The liquid skin effect, in particular, appeared attractive for alloying GaSb with other, higher-melting, III-V compounds, and to densify these in a one-step operation. This is of special interest in the case of III-V compound alloys as the conventional techniques of melt growth or long-time annealing of powders2 is very time-consuming, especially in cases where a large separation of liquidus and solidus can be expected, such as in GaSbl alloys.2 It was felt that experimentation with this system, a particularly unfavorable example, would allow us to extrapolate to several other, more favorable, cases. Uses of Ill-V alloys are most evident in thermoelectric energy conversion devices.&apos; For this reason certain thermal and electrical properties were measured and compared to those of melt-grown material and to hot-pressed prealloyed powders. EXPERIMENTAL PROCEDURE The pressure-sintering apparatus has been previously described.&apos; Using this equipment, both powder mixtures of GaSb with GaAs and prealloyed GaSbl-,As, powders were hot-pressed. The mixtures were pre- pared from cast GaSb and melt-grown GaAs. The prealloyed material was obtained from stoichiometric melts, initially heated to 1200°C in an evacuated quartz ampoule, and then annealed in the solidus-liquidus interval. A typical annealing cycle consisted of a heating to 850°C (1 hr), extended successive annealing at 750°C (65 hr), and slow stepwise cooling (25 hr) to below solidus. The GaSb, GaAs, and GaSbl-,As, materials were ground in a vibrational mill to particle sizes below 500 . A jet mill reduced these further where necessary. Fine powders were analyzed by Coulter counting for their size distribution. Average sizes by volume were calculated from the data. Mixing of the powders, where necessary, was carried out through rapid vibrational motion. The hot-pressing operation consisted of a degassing period of 15 hr, in most cases at 690°C, followed by several hours of compression, normally 25,000 psi at 690°C for powder mixtures and 50,000 psi at 710°C for prealloyed powders. The chemical compositions were confirmed by X-ray fluorescence analysis. To estimate the degree of solid solution achieved, lattice parameters were determined and interpreted according to Vegard&apos;s rule. In addition, optical microscopy helped to correlate the relative amounts of the phases present as well as the degree of porosity to the measured density. To reveal grain boundaries, polished surfaces were etched4 with H 2 O:H 2 O:HCl = 2:l:l. In several cases microscopic concentration gradients were monitored by electron-probe analysis-. RESULTS AND DISCUSSION Alloying and Densification of GaSn-GaAs Powder Mixtures. After preliminary experiments showed that no appreciable alloying took place in mixtures of coarse GaSb (22.5 p) and fine GaAs (2.5 p) powders, hot pressing of mixtures was confined to fine powders only (3.1 and 2.4 p, respectively). Alloying and densification apparently occurred simultaneously with a grain regrowth mechanism which depended on the presence of a liquid phase.&apos; The liquid phase was provided by the dissociation of GasbS particles into liquid gallium and antimony above 555°C. This not only enhanced grain regrowth and densification, as in unalloyed GaSb,&apos; but took on additional importance here for the alloying process. Alloying was speeded up by the resulting liquid-solid interaction as compared to the very slow solid-state diffusion process normally expected at these temperatures.&apos; The results obtained with a series of powder mixtures have been compiled in Table I. It is seen that for mixtures with less than 20 mol pct GaAs, x < 0.2, the compositional ranges increased and for x > 0.2 a GaAs-rich phase and free antimony appeared in the microstructure in sizable amounts.

Jan 1, 1968

An oxide ore heap (80,000 ton assaying 2 per cent copper) and a sulphide ore heap (300,000 ton assaying 1&#183;7 per cent copper) are being leached in series in a closed circuit system. The ore is friable and weatherseasily giving severe percolation problems. These were eased by applying liquors at 235 gal/min to trenches 2 ft wide and 6 ft deep along the full length of the heaps.Cementation recovery was improved from 20 per cent to over 80 per cent by regular intermittent agitation of the iron using a back hoe unit.Liquor pH is controlled by acid addition, and iron content is controlled by a bleed-off set according to predictions made from a pH-Eh diagram drawn for the liquor components. These controls, together with acyclic wetting and draining procedure, have raised production from 6 ton/week to 10 tdn/week of 80 per cent copper.

Jan 1, 1968

By E. A. Mihok

A pilot plant for treating mine drainage by neutralization with limestone was designed, fabricated, and operated by the Bureau of Mines. The process consists of (1) producing a very fine (minus 400-mesh) limestone slurry, (2) mixing the slurry with the mine water, (3) aerating the resulting mixture to remove carbon dioxide and precipitate iron, and (4) separating the solids from the liquid by sedimentation. A mine discharge of pH 2.8, containing 1,700 ppm total acidity, 36 ppm ferrous iron, and 360 ppm total iron, was treated at rates from 300 to 400 gpm. The treated water ultimately reached a pH of 7.4 and contained no detectable iron. The resulting sludge compacted to approximately one-third the volume of sludge from mine water neutralized with lime. The advantages of the limestone process, compared with the conventional lime process are as follows: Widespread distribution and lower cost of run-of-mine, indigenous limestone; simplicity of plant design; reduced hazards and plant operating and maintenance costs accruing from the use of a less reactive chemical agent; higher solids concentration of the precipitated sludge; and no deleterious effect caused by accidental overtreatment. While total process costs could not be determined, it is conservatively estimated that the cost of treating mine water by the limestone process is one-third to one-half the cost of the lime process, depending on the characteristics of the water to be treated and the availability and quality of limestone used.

Jan 1, 1968

By J. E. Dodge

Tasu, currently an open-pit operation, services the primary crusher from two areas by ore-pass raises. The problems encountered and advantages gained are discussed. Mine equipment and operating practices are covered, together with blasting practices, line drilling and the pre-shearing necessary to stahilize the pit walls.

Jan 1, 1968

By Stanley W. Sundeen

2.3-1. Introduction. The subject-"Preliminary Evaluation of Coal, Metallic and Industrial Mineral Deposits for Surface Mining&apos;-seems at first glance to be definitive and not likely to be misinterpreted. Nevertheless, there are widely divergent opinions as to what is meant by "preliminary" and even as to what is meant by "evaluation." Some definition and qualification is necessary in order to provide a readily recognized basis for discussion. Evaluation evokes the idea of organizing extant data and judging its significance especially in the economic sense. It also may evoke the concept of the physical processes of acquiring the data that will characterize the deposit such as the geologic mapping, drilling, etc. Castle (5) considers that evaluation may embrace psychological aspects wherein human traits as, for example, over optimism might cause the evaluator to overlook obvious project weaknesses. In this chapter, evaluation is discussed primarily from the viewpoint of economically appraising a project from data available at a given point in time. The qualifying adjective "preliminary" is not easily defineable. In fact, some kind of evaluation proceeds, if not continuously, intermittently over the full span of exploration and early stages of development of a deposit. Bailly (1) comments: "Sometimes, before starting exploration in new areas or countries for a given commodity, we establish models to define what minimum combinations of re- coverable grade and tonnage are needed to give the minimum acceptable rate of return established by corporate policy. Then, before starting physical exploration in any target area we try and guesstimate optimistically what best &apos;geometry-grade-tonnage&apos; can be expected. If these are acceptable in light of above minimum combinations, exploration is started as soon as funds are appropriated for the target area.&apos;&apos;

Jan 1, 1968

By E. T. Turkdogan, Klaus Schwerdtfeger

OelSEN and Maetz1 detected some 20 years ago the existence of a miscibility gap in iron oxide-CaO-P2O5 slags melted in iron crucibles at about 1400°C. Because of the importance of this system for the dephos-phorization of steel in the basic Bessemer process, equilibria between liquid iron and selected iron oxide-CaO-P2Q slags have been measured since by numerous investigators.2-5 When in equilibrium with metallic iron, the iron oxide of the slag is present mainly as FeO. In connection with oxygen-blowing steelmaking processes, it is useful to know the phase relations in the slag system at higher oxygen pressure, when major parts of the iron oxide are present as Fe2O3. This problem was investigated by Turkdogan and Bills7 by equilibrating the oxide mixtures contained in platinum crucibles with CO2-CO mixtures at 1550°C. It was found that increasing the Fe2O3 content decreases the composition range of the miscibility gap strongly so that the miscibility gap has almost disappeared at pco2/pco = 75. This result was refuted by the careful work of Olette et a1.,&apos;&apos;&apos; who equilibrated their slags with controlled Ha-H2-Ar gas mixtures. Their equilibrium measurements, at 1600°C and at oxygen pressures of 5 x 10"* and 10"5 atm, showed that the oxidation state of the iron has almost no influence on the formation of the miscibility gap. The present experiments were undertaken to check the previous results of Turkdogan and Bills. The experiments were performed at 1625°C in the strongly oxidizing atmosphere of air (PO2 = 0.20 atm) for which no experimental data are available. About 10 g of slag were melted in platinum crucibles and held at constant temperature for 1 hr. After equilibration, the crucible was rapidly pulled out of the furnace and cooled in air. The platinum crucible was removed from the sample. The two slag layers were carefully separated with a small diamond disc, and the surface of the top layer, which may have changed its oxidation state during cooling, was removed. The slags were crushed and analyzed chemically for CaO, P2O5, Fe2+, and Fetotal. The starting mixtures were prepared by sintering the desired amounts of reagent-grade 2CaO . P2O5 - H2O, CaCO3, and Fe2O3. Sintering and subsequent crushing were done three times to ensure homogenization. Molybdenum wire resistance heating was used. The furnace was provided with a recrystallized alumina reaction tube which was left open to air at the top. The temperature was controlled electronically. The reported temperature was measured with a Pt/Pt-10 pct Rh thermocouple and is estimated to be accurate within +5°C. The composition of the equilibrated melts is given in Table I. For the graphical illustration of these quaternary slags the type of projection suggested by Trömel and Fritze10 was used. In this representation, Fig. 1, the composition point of a mixture within the tetrahedron Fe2O3-CaO-P2O5-FeO is projected into the Fe2O3-CaO-P2O5, triangle (triangle I) so that the direction of projection is parallel to the side FeO-Fe2O3, and into the triangle Fe2O3-P2O,-Fe0 (triangle 11) so that the direction of projection is parallel to the side CaO-P2O5, of the tetrahedron. The projected point has the coordinates wt pct CaO, wt pct P205, and wt pct (FeO + Fe2O3) in triangle I and wt pct FeO, wt pct Fe2O3, and wt pct (CaO + PzO5) in triangle 11. Both triangles are turned into the same plane around the Fe203-P20, side of the tetrahedron. An illustration of the projection of a quaternary point in the present system is shown in Fig. 1. The advantage of this type of projection is that all four components for an equilibrium curve can be read directly from the diagram. The present results are shown graphically in Fig. 2. The curves depicting the miscibility gap are dashed in parts where no experimental points were obtained. The composition range covered by the miscibility gap

Jan 1, 1968

By Paul W. Johnson

An evaluation is made of a lime-soda sinter process for extracting alumina from anorthosite. In this process, alumina is extracted by sintering anorthosite with soda ash and limestone, and then leaching the sinter with a dilute sodium carbonate solution. The sodium aluminate solution formed during leaching is separated from the residue and treated with lime in autoclaves to remove dissolved silica before alumina trihydrate is precipitated with carbon dioxide. The trihydrate is then calcined to a-alumina. Two options, dry grinding and wet grinding, are used in the sintering step. For plants producing 1,000 tons of alumina per day for the dry grinding and wet grinding options respectively, the estimated operating costs are $75.40 and $74.36 per ton of alumina when charging $2.50 per ton for anorthosite and $1.00 per ton for limestone. The fixed capital costs based on a Marshall and Stevens chemical equipment index of 240.0 are $76 million and $70 million respectively. This process, when treating anorthosite, using either option, is not competitive under current economic conditions with the Bayer process treating bauxite to produce alumina.

Jan 1, 1968

By Forrest V. Williams

The dislocatiorl and stacking-fault structuve of epitaxial GaAs1-,PX lms been examined by chemical etching. The layers were groun in the (100) direction and etch Pils were developed on (111} planes which nad been lapped and polished on the epiLaxia1 layevs. Tile effecL of the jollolcing cariables on the quality of the epilaxial layers has been examined: doping leuel, grouth rate, and composition. High stacking-faullL densilies weve found in the GuAsi_xpx layers. These are not observed in heavily dolled epitaxial layers tzar in layers with low phosphorus compositions. The dislocatiorz density in GuAsi-x px was highest at the sub-stvate- epilaxia1 layer interface. Composilion changes introduced dislocations in the epitaxial layers. ManY semiconductor p-n junction lasers of Group TIT-Group V compounds and their alloys have been reported in the past several years. Laser action at visible wavelengths in GaAsl-x,Px was first reported by Holonyak and Bevacqua. GaAs, a direct transition semiconductor which lases, and Gap, an indirect transition semiconductor which does not lase, form a continuous series of solid solutions.2 Laser junctions can be fabricated in GaAsl-xPx crystals with phosphorus compositions up to about 40 mol pct. In addition to the production of coherent radiation in these crystals, the efficient recombination radiation of p-n junctions in this material has equally important potential in the development of low-power semiconductor lamps. To achieve a high conversion efficiency of electrical to optical energy in p-n junctions in this material, the relation of physical properties of the crystal to luminescence efficiency must be better understood. Although the electrical, optical, and device properties of GaAsl -xPx junction lasers are understandably of considerable interest, the work to date indicates that the more serious problems are the chemical and metallurgical difficulties encountered in the growth of this material.3 In addition to the problems of chemical purity, crystal imperfections, such as dislocations and stacking faults, can be expected to affect both the efficiency of the radiative recombination process and the perfection of the p-n junction.3 The last requirement, i.c., that of the perfection of the p-n junction, is a particularly troublesome one in the fabrication of laser diodes. To obtain good laser diodes, the p-n junction must be flat, which permits the radiation to be reflected from the resonant cavity boundaries. Junction planarity is extremely sensitive to the crystal perfection of the semiconductor material. Also, it is known that at high dislocation densities (-105 per sq cm) it has not been possible to build laser junctions in GaAsl-xPx . Few studies have been reported on the crystal defect structure of GaAsl-,P,. The first serious study seems to be that of Wolfe, Nuese, and Holonyak,3 who examined the dislocation structure of monocrystalline bulk (nonepitaxial) material grown by halogen vapor transport. In this paper are reported some observations on the dislocation and stacking-fault structure of GaAsl_,P, crystals grown by a vapor transport process on substrates of GaAs. EXPERIMENTAL Crystal Growth. The GaAsl-xPx crystals were grown in an open-tube flow system, using two sets of reagents. GaAs, Pr(red), and HC1 were employed in one method. The transport reaction is =950JC GaAs+HC1 = GaCl +1/4As4 +1/2H2 and the deposition reaction is 2GaAs1-xPx +GaCl3 Composition control is obtained by the flow rate of the HC1 and the vapor pressure of the P4, which is maintained in a separately controlled furnace. The second method has been described by Ruehr-wein4 and utilizes gallium, AsH3, PH3, and HC1. The same transport and deposition reactions as above are involved. Composition control is obtained solely by the flow rates of the three gases involved. All of the crystals were grown on chemically polished GaAs substrates oriented on the (100) plane. The thicknesses of the epitaxial layers were typically 100 to 300p. Revealing of Dislocations. Dislocations were re-vealed on both the( 111 ) and { l l l }b faces by chemical etching. The specimen to be examined was mounted at 54.7 deg, lapped on glass with 3-p alumina, polished on cloth with 3-p diamond paste, and, to remove work damage, chemically polished at room temperature for

Jan 1, 1968

By Charles L. Thomas

A novel, highly sensitive, and reproducible nzetlzod for the determination of hydrogen in solid materials is presented. The procedure requires equilibration of the specimen with hydrogen gas, rapid quenching, and hot vacuum extraction of the dissolved gas with subse-quent quantitative analysis by mass spectroscopy. Good linearity is obtained for the Arrl~enius plots of the investigated metals. The advantages in the use of this method over that of Sieverts aye discussed. The solubility data for copper are in reasonable agveewzent with a considerable number of other inuestigations, wllile those fov silver are considerably lower than previously reported. The first known solubility data for gold are presented. Solubility equations and heats of MUCH of the data which are available on the solubility of hydrogen in various metals and alloys have been obtained by the classical Sieverts method.&apos; The method involves the measurement of a decrease in pressure of a gas in a calibrated system, and the calculated contraction in volume is attributed to the solubility of the gas in the metal sample. The procedure requires several corrections, such as the solubility of the gas in the container walls and the diffusion of the gas through these walls, as noted by Steacie and .Johnson2 and others. In addition, errors may be incurred due to reactions between metal surface impurities, such as oxides, and the saturating gas. The precise calibration of the measuring system where large thermal gradients exist can present additional difficulties. Also, accurate volumetric measurements of small quantities of gas are difficult. Many of the objections to the Sieverts method were overcome on solid materials by Ransley and ~eufeld,~ who first saturated the metal with hydrogen and performed a subsequent extraction and measurement of the gas by chemical means. Eichenauer and pebler4 and Eichenauer, Kiinzig, and pebler5 measured the diffusion coefficient and solubility by following the degasification of a sample as a function of a rate of increase in pressure in a previously evacuated system. Here again, however, the procedure involves many of the corrections of the Sie-verts method. The present investigation deals with the solubility of hydrogen in solid copper, silver, and gold by a technique which eliminates many of the aforementioned corrections and possible errors. This procedure requires equilibration of the specimen with gas, rapid quenching, and hot vacuum extraction of the dissolved gas with subsequent quantitative analysis by mass spectroscopy. EXPERIMENTAL Two completely separate systems were employed to accomplish first, the equilibrium saturation of the sample and second, the extraction of the dissolved gas. Saturation Apparatus. The saturation apparatus, illustrated in Fig. l, consisted of a vertically mounted quartz tube with a three-way valve for vacuum or hydrogen near the top and an outlet near the bottom leading to a butyl phthalate seal. The bottom end of the tube was terminated with a joint accommodating an O-ring sealed "Asco Stirring Gland" (The Emil Greiner Co.). This gland facilitated movement of the thermocouple without introduction of air into the system. The upper portion of the tube (above the furnace) was water-jacketed. A Welsh 1405-B mechanical pump provided the necessary system evacu-

Jan 1, 1968

By John D. Smith

This paper describes how a knowledge of inherent rock characteristics can aid the mining engineer in his design of a mining method for a massive domelike structure. The paper shows how the pertinent rock characteristics were measured and analyzed and how the data obtained was used for design purposes. This analysis was conducted in 1964 in a producing salt dome, since that time, mine management has tried certain of the recommendations for mine design changes. The results of such changes are presented.

Jan 1, 1968

By J. C. Scully, G. Sanderson

The electrolytic formation of y hydride in thin foils of Ti-5Al-Z.5Sn alloy and four Ti-A1 binary alloys has been studied by electron microscopy and electron diffraction. Two orientation relationships have been found: THE adsorption of hydrogen by titanium alloys from aqueous solutions has been widely reported. This can occur, for example, in both alkaline&apos; and acidic2 pickling baths, in chemical polishing374 and electro-polishing Solutions,3,4 during cathodic polarization5" and under certain corrosion conditions,7,8 Etching reagents may also produce visible precipitates, sometimes after an aging period.9 During an investigation into the stress corrosion susceptibility of a titanium alloys by thin foil electron microscopy many observations have been made of hydride precipitation which has been deliberately promoted by techniques that are described below. The characteristics of hydride precipitation are reported and the observed crystallographic orientation relationships are discussed with reference to distortion in the titanium lattice created by the presence of the hydride. EXPERIMENTAL TECHNIQUE One grade of commercial titanium and five alloys were examined. Their composition and hardness values are shown in Table I. All the materials were in the form of thin sheet, 0.05 to 0.065 cm thick, which had been annealed after cold rolling. Foils suitable for transmission electron microscopy were made in two ways: a) by chemical polishing; and b) by elec-tropolishing. The solution used for chemical polishing was a mixture of 44 pct HF and 73 pct HNO3 in the volumetric ratio 2:3. During this polishing specimens were manually moved up and down in the solution. The reaction was veFy rapid, specimens thinning to foil thickness (2000A) in 5 min. Since chemical polishing solutions tend not to cause hydride contamination if they are kept cool3 no attempt was made to prevent the solution from becoming hot during the thinning operation. Electropolishing was performed at -30° C with a mixture3 composed of 295 cu cm methyl alcohol, 175 cu cm n-butyl alcohol, and 30 cu cm perchloric acid with an applied voltage of 40 v after chemically thinning specimens to approximately 0.017 cm thickness in a cool solution of 44 pct HF, 40 vol H2O2, and water in the volumetric ratio 1:6:3. EXPERIMENTAL RESULTS 1) Ti-5A1-2.5Sn Alloy. The Ti-5A1-2.5Sn alloy was severely contaminated by hydrogen during the chemical polishing. Foils obtained in this way contained large amounts of the y hydride phase. A typical micrograph is shown in Fig. l. The laths were identified as the hydride phase by selected-area diffraction of a large number of foils examined in a tilting stage that could be turned through 40 deg. Using the lattice spac-ings of the alloy obtained by X-ray diffraction as a standard the a value of the hydride was determined fromo the electron diffraction patterns to be 4.38 to 4.40A. The accuracy of this figure is only about ±2 pct. Further evidence of the identification was obtained by vacuum annealing chemically polished foils of the alloy at 500°C. This resulted in the dissociation of the hydride with the production of dislocations and possibly vacancy loops as shown in Fig. 2. The hydride

Jan 1, 1968

By A. Grant Elliot, H. W. Lavendel

qualitative picture has been developed to describe the oxidation behavior of TaSi2-coated tantalum and CbSi2-coated columbium. These systems have a significantly lower inherent oxidation resistance than MoSi2-coated molybdenum does. This stems primarily from the fact that Ta2O5 and Cb2O5 are nearly as stable thermodynamically as SiO2, whereas MoO2 or Moos are not. Further, diffusion of silicon in the Ta- and Cb-Si system is considerably slower than in the Mo-Si system. These ,factors prohibit the mechanism of selective oxidation of- silicon which accounts for the oxidation resistance 01- MoSi2-coated molybdenum. The silicide can be stabilized by adding suitable Modifiers which increase the thermodynamic stability of the silicate formed during oxidation. Modifiers, such as aluminum, can be inroduced into solid solution in the coating. in controlled amounts through proper selection of the source in the pack cementation process of coating fov~rzatiorz. Addition of aluminum to TaSi2, coatings on tantalum was effective in moderately increasing the oxidation resistance. EXTENSIVE experimental work and analysis have established the nature of the oxidation behavior exhibited by MoSi2- and MoSi2 -coated molybdenum-base alloys, and defined the conditions for maximum protection against oxidation of the substrate.&apos;-* The oxidation resistance of MoSi2 in the temperature-pressure range of 1100°C-PO2 > 10-5 atm to 1900°C— PO2 > 10-1 atm is due to the formation at the surface of a continuous film of SiO2 which results from selective oxidation of silicon. Under the prevailing kinetic conditions, this film is stable toward the molybdenum silicide with which it comes in contact. Initially molybdenum oxidizes also, but it forms volatile species. SiO2, however, nucleates and grows as a condensed phase. Once a continuous film of SiO2 has formed, the oxidation rate falls to that observed for the oxidation of pure silicon indicative of diffusion through the oxide film as the rate-controlling mechanism. This oxidation behavior is of course highly dependent upon temperature and oxygen pressure. Bartlett and Gage13 and Bartlett, McCamont, and Gagelb define precisely this dependence in terms of the oxygen partial pressures and silicon diffusivities required to support a stable SiO2 film. At low temperatures (near 500°C—the "pest" region) silicon diffuses too slowly to be selectively oxidized. Hence, molybdenum and silicon oxidize readily in proportion to their stoi- chiometry. At high temperatures and low pressure, SiOz dissociates to form volatile SiO(g), and a protective film cannot be maintained. Application of the MoSiz/Mo system is limited to temperatures below 1900oC, the eutectic between MoSi, and MO5Si3.5 The oxidation behavior of MoSi2-coated molybdenum is essentially the same as that outlined above with the exception that the MoSi2 is not in equilibrium with the molybdenum substrate. At the temperatures under consideration silicon will diffuse rapidly into the molybdenum eventually converting the coating to MosSi3.4 The rate constant for subsequent decomposition of Mo5Si3 into Mo3Si plus silicon, and/or the diffusivity of silicon through Mo3Si then becomes low enough to allow active oxidation of both molybdenum and silicon with subsequent degradation of the specimen. A stable silica film can be formed but at temperatures and/or oxygen partial pressures higher than those required with MoSi2 present as a source of si1icon.l, 4 Because of the similarity between the silicides of molybdenum and those of columbium and tantalum one would expect similar oxidation behavior for coatings in the respective systems. This is not entirely the case, however, as shown by the experimental results reported herein. Regarding tantalum and columbium disilicide coatings on tantalum and columbium substrates, respectively, the oxygen arriving at the surface of the coating partitions itself nearly equally between the metal and the silicon, and a two-phase oxide layer (Me2O5 plus SiO2) is always formed. The diffusion of silicon in the tantalum and columbium silicides is relatively slow, compared to that in the molybdenum silicides, which further enhances this equipartitioning of oxygen. Thickening of the coating during service by inward diffusion of silicon into the substrate is correspondingly slow, and the effective thickness of the coating at the roots of cracks and defects is only slightly changed providing high probability for premature coating failure. Furthermore, the SiO2 glass that is generated is not thermodynamically stable with respect to the coating. The metal silicide tends to reduce the SiO2 liberating either free silicon or SiO. The situation can be improved by suitably modifying the coating such that the stability of the protective glass which is generated during service is increased. Thus, selective oxidation of silicon and the modifying agent will occur, and the silicide coating will not tend to reduce the oxide layer. Modifying agents can be introduced into the coating by the pack cementation process. Using sources containing the modifier at controlled chemical potentials allows control of the coating composition. Partially substituting aluminum for silicon in TaSi2 coatings by forming a Ta(Si,Al)2 solid solution was effective in moderately increasing the oxidation protection.

Jan 1, 1968

By Reinhard H. Wöhlbier, George E. Aiken

8.4-1. Introduction. Surface excavating is done on a continuous basis with a variety of machines: 1) trenchers and ditchers, 2) conveyor loaders, and 3) bucket-chain and bucket-wheel excavators (BWE). Surface mining is largely concerned with only the last two machines, although some of the conveyor-loader types are often used by contractors for large-scale earth moving, and the engineer should be aware of these applications. This chapter is restricted to discussing only the bucket-chain and bucket-wheel excavators, with special emphasis on the latter. Continuous digging with these machines is done with evenly spaced buckets on either an endless chain or on the periphery of a rotating wheel. The bucket-chain digger excavates and takes the material away from the face with the same machinery. In the case of the bucket-wheel machine, these two functions are separate. Material is excavated by the buckets and then flows in a continuous stream via a transfer to the conveyor system, which in turn transports it to the discharge point. The wheels are adjustable in rpm and mount 6 to 12 buckets of equal size. These are classed as celled, cell-less or semicelled. The digging ladders for both types can move simultaneously in the horizontal and vertical planes. Ladder control is similar to the operation of a bucket-line dredge. Some ladder-chain and all wheel excavators have the machinery deck and superstructure mounted on a 360° swing circle. Other chain diggers have a fixed machinery deck. Deep and/or high cutting models are available in either the chain or wheel excavator. Machines can be either rail or crawler mounted, but the trend is to crawlers. Many of the early ladder-chain, rail-mounted excavators have been converted to crawlers. These may be either of the single or bogie type, depending on the conditions. Large machines usually use the superior three-point crawler suspension.

Jan 1, 1968

By A. T. Yu

A recent analysis completed by the United States Department of Commerce predicts that the 1968 Gross National Product will reach a record high of 864 billion dollars. As our nation annually increases its total output of goods and services, as has been the trend, the consumption of steel and its most basic raw material - iron ore - also must increase, To deliver the most economical unit of iron ore to the blast furnace, each segment of the transportation system must be co-ordinated and utilized to its highest degree of efficiency. In some cases, such as with the water segment of the system, a new investment in capacity will be required.

Jan 1, 1968

By H. Colijn

Feeders are used to provide a means of control for the withdrawal of bulk materials from storage units, such as bins, bunkers, silos and hoppers. This control function can only be performed properly as long as the bulk materials flow by gravity to the feeder in a uniform and uninterrupted fashion. A feeder can do many things, but it should never be considered a suction pump: During the past few years various papers have been written and presented on feeders and their application. 1,2,3,4,5,6,7,8,9)* It is not the intent of this paper to cover the same ground, and the readers are therefore ad¬vised to consult the referenced publications for supplementary information. This paper will be confined to some specific design criteria of bin feeders, such as feeder load and power requirements. Special attention is given to the basic design criteria of vibratory feeders.

Jan 1, 1968