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By B. D. Lichter

In a previous paper, Oelsen, Schuermann, and Hey-nertl pointed out the possibility of obtaining complete thermodynamic functions for alloy systems from calorimetric measurements alone. Specifically, if the heat content of a heterogeneous, multicomponent system is known as a function of temperature and composition, then it is possible to derive the heats, entropies, and free energies of formation of liquid phases and of solid intermediate phases of fixed composition. The authors present equations and graphical techniques applicable to eutectic systems and systems with intermediate phases without solid solubility at lower temperatures. eijering has considered possible extension of the treatment to systems with complete solid-state miscibility at lower temperatures; however, experimental difficulties practically restrict the method to systems with very limited miscibility in the solid state. The purpose of this note is to present an alternative derivation of the heats and entropies of formation of liquid phases and of solid intermediate phases from heat-content measurements alone. Fig. 1 shows three types of phase diagram to which the analysis may be applied. If the heat content is determined as a function of composition x, at temperature T, we have quite generally and the heat of mixing of the liquid is obtained directly from heat-content measurements. If the temperature T lies in a two-phase region (solid-liquid) then

Jan 1, 1967

By F. V. Shallcross

Physical properties of thin films of CdS and CdSe formed by vacuum deposition onto glass sibstrates have been studied as a function of deposition and processing conditions. The crystallinity and surface features of CdS films were examined using electron microscopy and electron and X-ray diffraction techniques. The films were poly crystalline; the preferred orientation and crystallite size increased with film thickness, substrate temperature, and deposition time. The CdS films consisted primarily of hexagonal-phase material, in contrast to similarly prepared CdSe films which have previously been observed to contain mixtures of cubic and hexagonal phases. As-deposited CdS films showed no major dependence of Hall mobility on crystallite size or degree of preferred orientation. Hall mobility and carrier concentration in CdS and CdSe .films were measured at various temperatures; both parameters increased with temperature and yielded activation energies which depended on fabrication conditions. Surface-desorption phenomena and overcoating of the semiconductor with SiO affected the observed electrical properties significantly. THIN films of cadmium sulfide1,2 and cadmium sele-nide3,4 have been employed by various workers as semiconductors in the insulated-gate thin-film field-effect transistor, known as the TFT. These devices are most commonly made by vacuum deposition of all materials onto an amorphous substrate such as glass. A knowledge of the microstructure and electrical properties of semiconductor layers used in the thin-film transistor is essential in order to form a realistic model for the device and to improve its performance, reproducibility, and reliability. This paper will describe studies of the physical properties of vacuum-deposited CdS and CdSe films prepared under various conditions. Structural characteristics examined in- cluded phases present, crystallite size, nature of preferred orientation of crystallites, surface roughness, and structural homogeneity throughout the film thickness. Electrical properties measured were Hall mobility and conductivity and their dependence on temperature and ambient. Thin-film properties are affected by many fabrication parameters including purity and physical form of evaporant, deposition rate, film thickness, design and temperature of the evaporation crucible, geometry of the deposition chamber, nature of the residual atmosphere, composition and temperature of the substrate, and details of postdeposition processing. PREPARATION OF FILMS In this work the semiconductor films were deposited in a conventional oil-diffusion-pumped system with pressures in the 10-8 torr range. The CdS evaporant was obtained from the Eagle-Picher Co. as a high-purity coarse-grained crystalline powder; the CdSe was a high-purity sintered powder supplied by the Harshaw Chemical Co. The evaporation crucible was a resistance-heated molybdenum-wire basket coated with aluminum oxide and filled with a quartz wool plug at the top. The source to substrate distance was usually 10 cm. This region was enclosed by a Pyrex inner cylinder. The substrate was heated with an overlying Pyrex plate coated with tin oxide. The substrate temperature was controlled using a thermocouple attached to the lower side of the heater. This thermocouple was calibrated against another thermocouple attached to a dummy substrate and by observation of melting points of various metal films deposited in the system. The substrates were polished borosilicate glass plates and conventional glass microscope slides. Substrate preparation included cleaning with an ultrasonically agitated detergent bath followed by isopropanol-vapor de-greasing. Film thickness was measured interferomet-rically during and after deposition. STRUCTURE OF CdS FILMS Structural studies were performed on CdS films using electron diffraction, electron microscopy, and

Jan 1, 1967

By A. M. Starfield

The study of strain waves in rock over the past decade has, for the most part, been an investigation related, but not applied, to rock blasting; the design of rock blasts has proceeded on a basis that is independent of strain wave research. This duality is reflected in the paper by Dr. Clark.1 While the greater part of the paper is devoted to a discussion of spherical waves in elastic and visco-elastic media, it is in an entirely unrelated section, the section on scaling and cratering, that the practical approach to rock blasting is found. Work done by the U. S. Bureau of Mines, as described in the paper by Duvall, Atchison, and Fogelson,2 has established a correlation between crater dimensions and the peak compressive strain in the rock. Strain wave measurements have thus been used to compare explosives but have not, as yet, been applied to the planning of a production round once an explosive has been selected. The optimum burden, for instance, is still determined either by experience, empirical formulae (e.g. that of Langefors 3), or a cratering experiment and the theory that has been developed around that proposed by Livingston.4 Even then there is some ambiguity in applying deductions from short, concentrated explosive charges to the long charges often used in practice (although Bauer 5 reports doing this with considerable success) and wave theory has until recently thrown no light on this problem, being confined, with only a few exceptions, to spherical charges. The hesitation in applying strain wave theory has probably been due to two questions that have not been answered satisfactorily: just how important is the strain wave in rock breakage, and if it is important, under what conditions will the wave break rock? This paper is an attempt to answer the first question, to avoid the second question by an admittedly oversimplified assumption, and then to investigate the implications of this assumption for blasting with long cylindrical charges.

Jan 1, 1967

By G. Krauss, J. M. Thompson, H. Y. Kumagai

Boron-doped p-type and arsenic-doped n-type source materials were used to deposit thin silicon films on amorphous fused quartz substrates by cathodic sputtering in argon atmospheres. All as-sputtered films were found to have high electrical resistivities of about 104 ohm-cm, despite controlled variation of the substrate temperature from 50O to 400°C. The high resistivity of the n-type films persisted even after postdeposition heat treatments as high as 1000°C, while p-type films showed a sharp decrease in re-sistivity to values on the order of 1 ohm-cm or lower after heat treatments above 650°C. X-ray and electron diffraction, together with transmission electron microscopy of the p-type films, revealed that the improved electrical properties resulted from two distinct processes. A primary crystallization or recovery within the pains, which were approximately 200Å diam in the as-sputtered films, accompanied the initial sharp drop in resistivity at 650°C. Following this process, a secondary recrystallization or discontinuous grain growth was nucleated in films heated at 1000°C. The resulting significantly increased size of certain grains and the corresponding decrease in grain boundary area accompanied an additional decrease in resistivity after heat treatment at 1000°C. The properties of thin silicon films are of interest because of their possible application in device technology. Although evaporated silicon films on amorphous substrates1-3 and both sputtered and evaporated germanium films4-' have been studied in some detail, sputtered silicon films have not been widely investigated. It has been observed that evaporated silicon films deposited at substrate temperatures below approximately 600°C are amorphous.1,3,9,10 At substrate temperatures higher than this, the films are polycrys-talline, sometimes exhibiting a fiber texture with the fiber axis normal to the substrate surface.' Similar results have been obtained with germanium films, although in this case the substrate temperature for the amorphous to crystalline transformation is reported to be as low as 150OC.5 The mechanism of film deposition by cathodic sputtering differs markedly from that of thermal evaporation. It might be expected, therefore, that the properties of sputtered and evaporated silicon films would also differ. The purpose of our study was to determine the effects of deposition conditions and heat treatments on the electrical resistivity, structure, and composition of thin silicon films sputtered on fused quartz substrates. EXPERIMENTAL DETAILS Apparatus. A schematic diagram of the sputtering apparatus is shown in Fig. 1. The vacuum chamber was enclosed by an 18-in.-diam by 12-in.-high Pyrex bell jar mounted on a stainless-steel base plate. Access holes in the base plate were used to supply argon gas to the chamber, to allow for various electrical feedthroughs, and to provide mechanical motion to the shutter between the source material and substrate. The chamber was evacuated by a pumping system consisting of a 720 liter per sec oil diffusion pump backed by a 13 cu ft per min mechanical pump. Ultimate pressures of less than 1 x 10-6 torr could be achieved. The substrates were securely mounted on the stainless-steel substrate holder by quartz tabs held in place by stainless-steel screws. Temperatures of the substrate holder were measured by a thermocouple inserted within the holder. A quartz lamp was used to heat the holder and temperatures as high as 420°C could be maintained. Deposition Conditions and Procedure. The substrates used were polished fused quartz slides 116 by 1-12 by 3 in. and were outgassed at 200°C for 1 hr at a pressure less than 1 x 10-5 torr before film deposition. This was followed by a presputtering period of 2 hr during which the movable stainless-steel shutter was so positioned that deposition on the substrate was prevented. At a sputtering voltage of 5000 v dc and an argon pressure of 0.03 torr, the cathode cur-

Jan 1, 1967

By W. C. Winegard, J. R. Carruthers, A. Plumtree, L. R. Morris

The unidirectional solidification of dendrites containing central twin planes was studied in A1-Ti alloys. Once nucleated, the twinned dendrites are a Twore ejficient form for solute redistribution and therefore grow in preference to the normal columnar dendvites. Comparison of these twinned dendrites to adjacent colunmar dendrites by means of decanting experinzents and electron-probe rnicvoarmlysis indicates that these special dendrites grow with less undercooling than normal dendrites. These findings are further supported by the effect of forced convection on the dendrite morphologies. COMMERCIAL semicontinuous cast ingots of most aluminum alloys frequently exhibit large grains which appear to be composed of hundreds of parallel, continuous, thin lamellae. This structure has been termed "basaltic",' "fiederkristall", or, commonly, "feathery grain". The lamellae are 'about 100 p thick, several inches long, and each lamella contains a central (111) coherent twin boundary. The feathery grain has been reported to have a (112) direction2 and a (110) direction4 in the twin plane parallel to the casting direction, in contrast with the usual columnar structure where a (100) direction predominates. Aust et uZ.~ proposed that the twin boundaries were growth twins nucleated by stacking faults on the octahedral planes. chalmers6 has suggested that feathery grain may grow by a re-entrant edge mechanism, as proposed by wagner7 for twinned dendritic growth in germanium. Cahn et ~1.~ have concluded that the occurrence of feathery grain is evidence of some form of lateral layer growth rather than the atomically continuous growth normally observed in metals. The postulates by Chalmers and Cahn would seem to be contradicted by the work of Nakao~"' who showed that feathery grain only occurs when growth rates are high and the aluminum contains some solute. Specifically, Nakao found that in order to obtain feathery grain, in small castings solidified unidirec-tionally upward, the rate of growth must be above 2.4 cm per min and a critical solute concentration must be present. Below this solute concentration the grain structure was totally columnar. The critical solute concentration was found to be approximately: 0.04 wt pct Ti, 2 wt pct Cu or Mg, and 8 wt pct Zn. As pointed out by Chalmers it is not obvious why a twin-plane re-entrant edge mechanism would occur in aluminum which is thought to have a diffuse solid-liquid interface. The present experiments were undertaken to determine the growth mechanisms in- volved and to study the solute segregation in more detail. EXPERIMENTAL PROCEDURES Alloys ranging in composition from 0.05 to 0.23 wt pct Ti* were prepared from 99.9 pct pure Ti and 99.993 pct pure Al. Two-hundred-gram samples of A1-Ti binary alloys were solidified unidirectionally and vertically upward from a water-cooled copper base, in a heated insulated mold. The 1-in.-diam, 6-in.-length mold was made of Marinite (manufactured by Johns-Manville Co.). The mold was attached to a 24-in. pivoted arm such that by dropping a weight the mold was rotated 180 deg, throwing the liquid metal from the solid. In this way, the solid-liquid interface was revealed by decanting. A sketch of the decanting mold is shown in Fig. 1. The alloy was poured into the mold at temperatures ranging from 680" to 750°C, partially solidified by water cooling from the base, and decanted after a measured time interval. Growth rates for each metal-pouring temperature were calculated from solidification-time vs length solidified curves. Temperature gradients in the melt were measured using four No. 34 gage thermocouples which protruded into the mold cavity. Grain orientations were determined by X-ray diffraction using Laue back-reflection techniques. Grain substructures were examined metallographically, using polarized light, by applying a thin epitaxial anodic film to polished sections after the method of Hone and pearson." Titanium micro segregation was measured by electron-probe microanalysis using a NORELCO AMR/~ with a mica crystal and proportional-flow counter. Several of the cast samples exhibited feathery and columnar dendrites growing in the same direction and

Jan 1, 1967

By P. G. Shewman, T. L. Wilson

Using published surface-diffusion (D,) data and published sintering equations, it is shouln that surface difusion should dominate the neck-growth stage of intering for all materials in which D, has been measured (six metals and A1as). Also, grain boundary diffusion can be expected to contribute appreciably to shrinkage and possibly to neck growth below some critical temperature of the order of 70 pct 01- the absolute melting temperatuve. In view of the widespread conclusion in previous sintering work that volume diffusion dowzinates neck gvowth, experiments were conducted using spherical copper powders to test this conclusion. Scaling studies on neck growth at 950°and 1020°C clearly demonstrated that suyface diffusion dorninates. Kinetic studies on shrinkage gave more equivocal results that indicated an increasing role of' grain boundary transport at lower temperatures. Five diarszeters from 100 to 300 u were used in the scaling sludy and a temperature range of -650' 10 950 C was covered in the shrinkage studies. All experiments were conducted in dvy hydrogen. In 1949, Kuczynski published his now classic paper on the determination of the transport mechanism in sintering from the time laws of neck growth. In the interim, these laws have been applied to many systems and slightly modified by several authors. Essentially all these authors concluded that, for crystal- line materials, the dominant transport mechanism in neck growth is volume diffusion. This stems from the observation that the neck radius increases about as t"5 and that the activation energy approximates that for lattice diffusion. A related but independent series of studies stems from Mullins' rigorous analysis of the growth of the groove formed where a grain boundary meets a free surface." xperimental work stemming from this analysis has shown that for each crystalline material studied (Au, Ag, Cu, Ni, Fe, Pt, Al2O3) surface diffusion was clearly the dominant transport mechanism for groove widths up to the order 10 to 20 p. The ratio of the quantity of material being carried by lattice diffusion to that carried by surface diffusion increases linearly with the groove width, so surface diffusion is dominant for all widths under 10 to 20 u. The analysis of the relative contributions of surface and volume diffusion to grain boundary grooving, and to neck growth in sintering, shows that they are quite similar. Thus, using the available surface-diffusion data and the approximate equations of Kuczynski, or the more rigorous recent equations of Nichols and Mullins, 3 it can be shown that the small necks between particles must grow almost entirely by surface diffusion. The purpose of this study was to re-examine the basis for the conclusion that the neck-growth stage of sintering proceeds by volume diffusion. Using spherical copper powders, of several different diameters, precise experimental measurements were made of both neck growth and shrinkage. Application of Herring's scaling laws to the neck-growth data clearly indicated that neck growth occurred by surface transport, even though the neck radius increased as or Using the recent analysis of Mullins and Nichols as well as published data on surface diffusion, it is shown that the observed time law, as well as actual rate of neck growth, can be satisfactorily explained by a surface-diffusion mechanism.

Jan 1, 1967

By S. A. LoPilato, J. T. Smith

SEVERAL techniques have been evaluated for cooling the throat area of rocket-nozzle inserts to prevent erosion or fracture of the inserts during exposure to high operating temperatures and pressures. Self-cooled composites, such as infiltrated tungsten, have shown considerable promise for these applications. These composites can be fabricated by infiltrating the refractory matrix with a lower-melting metal or non-metal which is insoluable in tungsten. During firing, the lower-melting substance undergoes a series of continuous endothermic phase changes which absorb sufficient heat to maintain the nozzle matrix material at or below a safe operating temperature. At present, the state-of-the-art has reached a point where the refractory matrix density and microstruc-ture have been established as the critical parameters to be controlled for optimum self-cooled performance.'" Nondestructive testing has been utilized to ensure that porous tungsten billets were of uniform density and free from cracks or other defects prior to fabrication into rocket nozzle inserts. Ultrasonic-velocity techniques have been employed because of their reliability and reproducibility. The purpose of this note is to present and interpret the test data developed for porous tungsten matrices. For evaluation purposes, tungsten powders with Fisher subsieve sizes of approximately 4 and 18 p have been obtained for study from four commercial sources: the General Electric Co., Wah Chang Corp., Fansteel Metallurgical Corp., and Kennametal, Inc. Porous tungsten matrices were fabricated from the powders by hot pressing in induction-heated graphite die assemblies. Typical billets ranged from 3 in. diam, 2 in, high to 5 in. diam, 5 in. high. The ultrasonic-velocity measurement technique employed was through transmission, pulse echo at a frequency of 1.0 mc using matched barium titanate crystal transducers. The testing equipment included a pulsed ultrasonic generator, an amplifier, a specimen holder, and an oscilloscope, as shown in Fig. 1. The porous tungsten thickness was measured to i 0.0005 in, with precision micrometers while the oscilloscope achieved 0.02 psec time measurement accuracy. The time for a sound wave to pass through the billet, the bulk wave velocity, was calculated to 0.5 pct using Eq. [l]: V-} where V = bulk wave velocity, in. per psec, T = specimen thickness, in., and / = time, psec. To develop inspection standards, the bulk density of a porous tungsten billet was determined by the ASTM water-immersion technique.3 The ultrasonic-velocity measurements were completed at seventeen positions for each billet and averaged to develop a characteristic standard velocity for a particular tungsten powder at several density levels. A plot of ultrasonic velocity vs density is presented in Fig. 2 for six different tungsten powders. This graph has been established as

Jan 1, 1967

By E. Hoek

The stability of a rock structure depends primarily upon the extent to which fracture develops within the structure, The prediction of the extent of potential fracture, the first step in the study of fracture development, involves a knowledge of both the stress distribution in the structure and the criterion which governs rock fracture under various stress conditions. While a great deal of research effort has been devoted to the development of techniques for analyzing the stresses in mining and civil engineering structures1-3 and to the investigation of the fracture mechanism of rock 4-6 relatively little attention has been paid to the application of available knowledge to the solution of practical engineering problems. This paper describes a photoelastic technique for the determination of potential fracture zones in certain types of rock structures. A practical example, based upon a problem which might be encountered in designing the layout of deep-level mine excavations, is given as an illustration of the application of this technique. STRESS ANALYSIS AND ROCK FRACTURE In deciding upon the technique to be used for the solution of a problem involving the prediction of rock fracture it is necessary to consider: 1) What type of stress information is required to satisfy the fracture criterion for rock; anti 2) How this information can most conveniently be obtained. It has been established, both theoretically 4,7 and experimentally 5,6,8that the fracture of hard rock depends primarily upon the relationship between the algebraically greatest and the algebraically smallest of the

Jan 1, 1967

By N. Mungan, F. W. Smith, J. L. Thompson

Adsorption of polymers and transport, rheology and oil recovery efficiency of their solutions were studied in the laboratory to evaluate the use of polymers in waterflood-ing. While a tenfold mobility reduction was obtained with polymer concentrations as low as 0.05 per cent by weight, the mobility reduction depended on the type of polymer, molecular weight, salinity and pH of water, crude oil and capillary properties of the porous media. Choice of a suitable polymer and a workable concentration will have to be tailored for each application. Little reduction in the residual oil saturation can be expected from polymer flooding. Improvement in the volumetric sweep efficiency is possible hut the extent of the improvement can best be evaluated by properly designed field testing. Some aspects of the field use of polymer floods are discussed. INTRODUCTION Waterflooding is a simple, inexpensive secondary recovery method and is being used widely. Innumerable laboratory studies have been made to unravel the fundamentals of the displacement of oil by water and to find the ways of most efficient oil recovery. These studies and a great many field case histories have revealed that the prime cause of poor oil recovery is the inefficient and incomplete sweep of reservoir volume by the injected water. Sweep efficiency is affected by many factors of which the mobility ratio is an important one. Mobility ratio M is defined here as the ratio of water to oil mobilities: M = (k»/y,r)/(k,JJJJ........(1) In Eq. I, the permeabilities are the effective permeabilities and depend on fluid saturations and, hence, change during the different depletion stages in a flood. A wide practice is to use the effective water permeability at residual oil saturation and the effective oil permeability at interstitial water saturation in Eq. 1. If the mobility ratio is greater than one, the mobility ratio is unfavorable and water, being more mobile than oil, would finger through the oil zone resulting in poor oil recovery efficiency. If the mobility ratio is favorable (one or less) the displacement of oil by water occurs more or less in a pistonlike fashion. In some waterfloods. the mobility ratio is unfavorable and any additives by which the mobility of water can be decreased would favor more efficient oil recovery. The thing to bear in mind, however, is whether or not the improvement in oil recovery is sufficient to more than pay out the cost of the additives needed. For example, materials like sugars, alcohols and glycerine reduce water mobility by thickening the water, but the cost of material requirement precludes any field application. For an additive to be useful in water-flooding, it must bring about a large reduction in water mobility at low concentrations; it must be adsorbed only negligibly; and it must not completely plug up the formation. Some synthetic organic polymers have shown promise of meeting these requirements and have been used in the field.'-W owever, no in-depth studies of the rheological, adsorption and oil displacement characteristics of polymer solutions have been reported. The present work is a study of these properties. EXPERIMENTAL In this work, concentrations are given on a weight per volume basis; 0.5 per cent concentration means 0.5 gm of polymer is dissolved in enough water (or NaCl solution) to make 100 ml. A bactericide, usually 0.1 to 0.2 per cent by volume of 38 per cent formaldehyde solution, was used in the polymer solutions. The NaCl solution was 30,000 ppm. Some properties of the polymers studied are given in Table I. Physical properties of all cores used are in Table 2. Flow behavior of polymer solutions was studied by three consecutive flow tests in cores. First, water (or brine) was injected at constant rate of about 1 ft/D to obtain the water mobility. Then, filtered polymer solution (prepared in water or brine) was flowed through the core. Since the rate was constant, increase in the pressure drop across the core reflects decrease in the mobility. Finally, the core was flooded with water (or brine) to study recovery of mobility. The Alundum cores which were used in

Jan 1, 1967

By Robert E. Ogilvie, Zvonimir Ban

Oxidation experiments were conducted above 600°C to investigate the oxidation products formed on the surface of MoSi2. Results are presented which indicate that minor iron impurities play a key role in the oxidation behavior of MoSi2 above 600 °C. Based on considerations of the crystal chemistry of the oxidation products, MoSi2 with rhenium and iron additions was found to be resistant to oxidation in the pesting temperature range. AS early as 1914, Honigschmidtl observed that some silicides of molybdenum exhibited high resistance to oxidation at elevated temperatures. This fact did not arouse much interest until 1950, when Kieffer and cerwenka2 examined this property in more detail. They found that Mo-Si alloys with approximately 70 pct Mo (by weight) could be heated to 1600°C in an oxidizing atmosphere without any significant damage. The surface was found to be protected by the formation of an extremely thin silica glass layer which had no tendency to spa11 during subsequent thermal cycling. In 1955, Fitzer3 discovered that even solid bodies made of MoSi2 completely oxidized within a relatively short time when exposed to the air in the temperature range from 300° to 600°C. To describe this phenomenon he proposed the name "molybdenum disilicide 'pest' ", clearly analogous to the previously observed "tin plague" ("tin pest") which, however, arises as the result of a phase transformation. Studies performed by Fitzer and, in particular, one published recently by Berkowitz, Blackburn, and Fel-ten,' comprise the most extensive research to date on the pest phenomenon in MoSi2, as far as the fundamen- tal mechanism of the process is concerned. The first of these studies revealed the existence of a crystalline phase which appeared at the surface at 750°C and dissolved in the glassy silica layer at 1150°C. The logical assumption was that this phase was some reaction product of MOO3 and SiO2. The formation of a reaction product of this type seemed probable since it had been mentioned by Glemser and Lutz6 in a paper describing their studies of molybdenum oxides; however, this assumption was later disproved.8 It is our belief that information concerning the exact nature of this crystalline phase may be important for a better understanding of both pesting and the protection mechanism. Therefore, since the only available general description of the pest phenomenon was that of Fitzer, it was decided to reproduce his experiments. These experiments established that, in addition to the "pest" and "nonpest" temperature range, an intermediate region exists between 600" and approximately 650°C. This region is characterized by the appearance of a variable amount of yellow to orange colored crystals. The electron-beam microanalyzer was used to qualitatively determine their composition. Iron and molybdenum were found to be major constituents. This result can be explained based on the following facts: 1) iron, according to literature data,* is the most common impurity in molybdenum powder, and its content can be as high as 0.25 pct; 2) technical silicon powder usually contains iron; 3) steel ball mills are often used for the crushing and grinding of MoSi2. In order to clarify the exact role of iron, it was deliberately added to a stoichiometric mixture of molybdenum and silicon. The observed results corroborated the previous experiment, proving that iron (probably as some silicide phase) concentrates along the grain boundaries. I) EXPERIMENTAL PROCEDURE A) Oxidation of MoSi2 with Iron Additions. 1) Specimen Preparation. Specimens were prepared by both

Jan 1, 1967

By H. M. Strong, R. A. Oriani

THE technological interest attaching to light, age-hardening alloys for structural uses has been pointed out to one of us.1 A potentially interesting alloy would be titanium-rich Ti-Mg alloy, provided that sufficient solid solubility exists. or could be induced at high pressure. and provided also that age hardening can be induced by proper temperature and/or pressure annealing. It was decided therefore to explore the feasibility of producing a Ti-Mg alloy in the high-pressure apparatus. Experimental. Three high-pressure runs have been carried out. In each case the geometry of the sample was that of a cylinder of titanium of commercial purity, into which a narrow hole had been drilled along the axis; this hole was filled with magnesium wire,

Jan 1, 1967

By G. N. Goldberg, Robert A. Rapp

The steady-state kinetics and microstructures of simultaneous internal oxidation and external scale formation were investigated for the oxidation of Cb-Zr and Ch-Zr-Re alloys in pure oxygen at 1000°C. For each binary alloy, a constant rate of scale formation was observed at steady state; the internal oxidatton zone reached a steady-state, time-independent thickness. The dependence of the scaling rate on zirconium content exhibited a maximum at a low zirconium colttent; more concentrated alloys oxidized at a slower rate than pure columbium. This composition dependence of the scaling rate may be partially attributed to the effect of the internal oxidation process as an intenla1 sink for oxygen, with the formation of voluminous, and relatively impermeable ZrO2 precipitates. However, the morphologies of the ZrO2 internal oxide precipitates also affected the scaling rate. The internal oxide precipitates were distributed uniformly in the external scale. The steady-state thicknesses of the internal oxidation zones were not in agreement with those predicted theoretically from an idealized simple model. However, in this particular alloy systen1 the ideal model is not satisfied experitmentally. For ternary Cb- Zr - Re alloys with Nr10e = 0.02 or 0.05, the steady-state thicknesses of the internal oxidation zones were less than those for the corresponding binary Cb-Zr alloys. For ternary alloys with NRe(0) - 0.05, a more adherent and much less porous external scale was formed, and a reduction in the kinetics of scale formation was observed. A number of authors'-7 have reported linear oxidation kinetics for the reaction of pure columbium at 1000°C in air or in oxygen of about 1 atm pressure. A thin and tightly adherent oxide layer is found at the metal/oxide interface beneath a porous external layer of scale. Although the suboxides CbO and CbO2 represent thermodynamically stable phases at 100O°C, generally only Cb2O5* is identified as a reaction product in quenched specimens. Studies at 1000°C at lower oxygen pressures8,10 (Po2 - 10-4 Torr) show that both CbO and CbO2 do form and that CbO2 is a protective oxide. The growth of CbO2 results in parabolic kinetics until Cb2O5 is nucleated and grows. Apparently because of the large volume change associated with its formation, Cb2O5 is porous and does not serve as a diffusion barrier; linear kinetics prevail after the surface is covered with Cb2o5. On the basis of these observations, several authors5,9,10 have suggested that the linear oxidation of pure columbium at 1000°C in air or oxygen of 1 atm is limited by a Loriers-type mechanism,11 whereby the total rate or reaction is controlled by ionic diffusion through a thin layer of CbO2 which is maintained at a constant thickness throughout the linear oxidation. However, the concept of a Loriers model for a three-phase CbOlCbO2 Cb2O5 scale, with the only oxygen activity gradient across the NbO2 phase, is not self-consistent. Further, the suboxides CbO and CbO2 were not observed in the high-temperature X-ray diffraction study of columbium oxidation by Goldschmidt.8 From investigations in which the large PO2, dependence of the linear scaling rate was demonstrated, the importance of an oxygen adsorption or dissolution step has been suggested.4,5,7,10,12 Thus the mechanism for the linear oxidation of pure columbium remains quite controversial. Since further insight into the oxidation mechanism of pure columbium is not provided by this investigation, the authors wish to emphasize at the outset that their experimental results are not interpreted in terms of a particular rate controlling step for the oxidation of pure columbium. Previous investigations13-18 of the oxidation of Cb-Zr solid-solution alloys in air or oxygen at 1000°C suggest a remarkable dependence upon zirconium content. For an alloy of bulk zirconium mole fraction, N2r(0) equal to 0.05 or 0.10, the oxygen uptake is reported to be as high as four times greater than that for pure columbium;13,14 for alloys with NZr(0) 0.05 or 0.10 the oxygen uptake is reported to decrease with increasing NZr(0); to a minimum uptake of about one quarter that for pure columbium at NZr(0): = 0.50.13-15Since zirconium forms a more stable oxide (ZrO2) than the lowest columbium oxide (CbO), and since columbium exhibits a high solubility19,20 and diffusivity21,23 for oxygen, the internal oxidation of the zirconium component to ZrO2 is expected at a reaction front ahead of the advancing metal/scale interface. The external scale is then formed at the metal/scale interface by the inward migration of oxygen through the scale, probably through a series combination of molecular and ionic diffusion. Internal oxidation in conjunction with external scale formation has been investigated by Maak24 for the oxidation of dilute Cu-Be alloys in pure oxygen at 850°C. For cu-Be and many other binary alloys,24-27 very small, essentially uniaxial internal oxide particles are formed in the most dilute compositions; for somewhat more concentrated alloys. the internal oxide particles precipitate as platelets or needles. From pertinent solutions to the diffusion equation, Maak28

Jan 1, 1967

By J. B. Cheatham, C. E. Murphey

Presently, computer control of Borobolic direction cannot be obtained during drilling, and most straight-holc drilling methods attempt to resist hole deviation rather than control direction. Many of the theories advanced as possible explanations of the cause of hole deviation are Summarized berein. A new correlation of physical partables is introduced to indicate bow factors such iis drill collar stiffness clearance and hit weight influence borehole deviation, .A methord is proposed for predicting the rate of change of hole angle when drilling conditions are changed. INTRODUCTION Control of borehole direction during drilling can be difficult and costly. Unintentional crooked holes are often lrilleti in dipping formations and many times directional drilling is required when the surface location is not directly above the target area —- for example, at offshore and mountainous locations. Prilllng progress can be greatly hindered in either air or liquid drilling when it be comes necessary to use low bit weight to prevent excessive hole angle build-up. If hole inclination becomes too great, drill pipe drag becomes excessive and fishing risks are increased, logging is more difficult and problems of differential sticking, key seating and fatigue failures may be encountered. Dog-legs and key seats are more serious problems than steep inclination angles: therefore, reducing rate of direction change is preferred to attempting to maintain absolutely vertical holes. Consequently, a straight inclineti hole is preferable to a nearly vertical crooked hole containing numerous dog-legs. In this paper, theories of the cause of hole deviation and analyses of drill string behavior under down-hole conclitions are summarized. Methods for computing hole deviation are presented und systems for resisting deviation as well as neans for provic!ing control of holt- direction are iliscusseI. A new correlation of physical variables is introduced tu indicate how factors such as drill collar stiffness, clearance and bit weight influence borehole deviation. A method is oroposeti for predicting the rate of change of hole anFrle when drilling conditions are clianged. IIEVIEU' OF PREVIOUS WORK ON HOIaE DEVIATION Significant progress in the theoretical analysis of hole deviation problems has been made in the past 1 5 years. The pioneering work has been primarily a result of the efforts of Lubinski and Woods.l-5 In 1950, Lubinski 1 considered the buckling of a drill string in a straig:rt vertical hole, a problem also considered by Willers6 in 1941. It wns concluded that very low bit weights must be used to prevent hole deviation resulting from drill collar buckling. The use of conventional stabilizers was proposed2 in 1951 by Mac Donald and Lubinski as a method for permitting greater Sit weights to he carried without drill collar buckling. These authors pointed out that a 2° nearly vertical spiral hole can cause severe key seatinp, and drill pine near, wilereas n 3 straight inclined hole with deviation all in one direction, while not vertical, will not result in serious drillirig or producing problems. Studies were continued with an investigation of straight inclined holes by Lubinski and Woods3 in 1953. In this paper they concluded that perfectlv vertical holes cannot be drilled even in isotropic forriations unless extremely low bit P-eights are used. .l'l~ey postulated that constant drilling conditions produce holes of constant inclination angle and varying conditions cause the hole to drill at a neiv equilibrium angle. This analysis was not concerned with drill string buckling since it was based on an equilibrium solution in which the ~irill string Was presumed to lie along the lower side of the hole abcrve the point of tangency. Weight of the drill collars below the point of tangency tends to force the hole toyard the vertical, whereas the weight on hit tends to force the hole aurav from the vertica l. The concept of an anisotropic formation Lvas introduced as an empirical method for explaining actual drilling data and as a means for extrapolating known deviation data to otiier conditions of hit

Jan 1, 1967

By K. S. Lane

The problem of stability of slopes in reservoirs is one of real interest in civil engineering. The problem is whether the valley walls will remain stable or whether they are likely to slide as conditions are changed by storage of water in the reservoir. If major slides are indicated, as on the walls of relatively steep canyons, one must estimate whether they will be so located and of sufficient size as to interfere with operation of the reservoir-as by blocking the outlets, or by displacing sufficient water to over-top the dam in a huge wave. Some cases involve problems in soil mechanics for slides in earth or weaker rock; other locations need the assistance of rock mechanics for slides in harder rock. While this is not a new problem, attention has recently been focused on its importance by the hugh landslide into the Vaiont reservoir in 1963, which claimed the lives of over 2000 people and forced abandonment of the dam and powerhouse. VAIONT RESERVOIR SLIDE Fig. 1 shows Vaiont Dam in Italy which is a double curvature arch, 875 ft high, located on a tributary of the Piave River, north and west of Venice. When completed in 1960 it was the highest arch dam in the world. In 1960 a sizable landslide (some 700,000 cu yd) occurred on the left abutment a short distance above the dam. Following this, the reservoir was held down for construction of a by-pass tunnel through the right valley wall to insure connection with the upper end of the reservoir in event of further slides. In October 1963 a giant landslide occurred on the left valley wall, over a width of some 14 miles (see Fig. 2). Over 300 million cu yd slid into the reservoir, displacing the water and forming a hige wave 700 ft above the top of the dam as it hit the opposite, or right, wall of the valley. The wave then passed some 500 ft over top of the dam, followed down the tortuous winding canyon and debouched into the

Jan 1, 1967

By J. D. Prater, H. R. Spedden, E. E. Malouf

With the expansion of copper leaching of the various mine wastes at the Kennecott properties, additional copper recovery facilities have been required. A research and development program has been pursued to determine a suitable economic approach to the processing of the additional leach solutions contemplated. lnvestigations on laboratory and pilot plant scales covered electrowinning, solvent extraction, launder and vat type cells, activated launders, precipitation drums, and precipitation cones. This paper contains information on the development and use of a new precipitation-cone-type copper recovery plant, which provides many advantages over older systems. The application of research findings to the old art of leaching copper from copper-bearing mine waste has resulted in a significant contribution of copper to over-all copper production. For example, at the completion of the current expansion program at the Kennecott properties in the United States, copper produced from waste dump leaching will amount to about 25% of the total production. Formerly only 2% was derived from this source. This planned expansion of copper leaching focused attention on the problem of developing more efficient methods for the recovery of copper from greatly increased volumes of copper-bearing solutions.1 The detailed investigations which have been made in laboratory pilot plant and plant tests for the recovery of copper from copper-bearing solutions have included electrowinning, solvent extraction, ion exchange and cementation with iron in launders, precipitation drums, activated launders, and precipitation cones. The results of these investigations have led to the development of a new precipitation cone-type copper recovery system providing many advantages over older methods. ELECTROWINNING OF COPPER FROM COPPER-BEARING SOLUTIONS The direct electrowinning of copper from relatively dilute solutions of copper-bearing mine water, namely solutions containing 10 to 20 lbs of copper per 1000 gal, has always been an attractive possibility.2,3 By this method, high-purity copper powder can be recovered with a power consumption of 3.5 kwh per Ib of copper. However, once the solution strength de-

Jan 1, 1967

By R. A. Deju, R. B. Bhappu

The theory of electrophoresis is briefly outlined and an apparatus which may be used for electrophoretic studies is explained. The results obtained using this apparatus are in agreement with those obtained by other investigators. How to solve some of the complications which occur in the measurement of zero charge and zeta potential is explained. It is believed that the apparatus described in this paper will allow rapid measurements of zeta potential, zero point of charge, electrophoretic mobility and zeta coefficient. For many years the phenomenon of electrophoresis has been studied, and much work has been done in designing an apparatus for better measurements of mobility, zeta potential and zero charge of minerals. Up to the present, most electrophoresis experiments have involved cumbersome equipment and tedious microscopic observation. The modified cell proposed in this paper obviates these drawbacks by using a Rayoscope together with a special system of lenses and filters. It therefore allows a faster and more accurate measurement of zero charge and particle velocity. THEORY Most authors currently regard zeta potential as the potential difference in an otherwise uniform medium between a point some large distance from the surface of the mineral and a point on the plane of shear. Fuerstenau,1 Miaw,2 and Gaudin and sun3 have performed some calculations of zeta potential using Henry's equation.4 Their results show wide discrepancies, probably due to differences in the past histories of the minerals used. The authors have also noticed this difference on determining the zero point of charge of quartz as shown on Table I.

Jan 1, 1967

By J. W. Downey, A. E. Dwight, R. A. Conner

In a previous paper' we have reported the existence of a number of AB2 Laves phases in which A is a member of the scandium group (including the 1an-

Jan 1, 1967

By N. G. W. Cook

When an excavation is made underground the original rock stresses are removed from the surfaces of the excavation. These surfaces converge to partially close the excavation and the superincumbent rock mass moves down towards the excavation. If the convergence of the surfaces of the excavation were controlled, energy generated by their motion against the controlling forces could be extracted. Since the total forces in the rock mass are not significantly affected by the excavation, stress concentrations arise around the excavation, which compensate exactly for those stresses no longer transmitted through the excavation. These phenomena give rise to two general principles which provide the basis for analyzing the effects of making any underground excavation. The first of these is that the total force resulting from the stresses across any plane in the rock, including any plane through the excavation, must be the same before and after the excavation is made. The second of these is that energy must necessarily be released as a result of making an underground excavation. It is instructive to consider the implications of these two principles for two extreme cases of material behavior between which the actual behavior of rock must lie, namely, the behavior of a fluid and the behavior of an elastic solid. For the purpose of analysis in this paper, an underground excavation is defined as an excavation in which the smaller horizontal dimension of any open void at a particular horizon is less than the depth of that horizon below surface. In the case of a fluid, any unsupported excavation would fill immediately, as a fluid cannot sustain shear stresses. For the same reason, stress concentrations could not arise and the forces across any plane would necessarily be the same before and after excavation. If the filling of the excavation were controlled by forces applied to the surfaces of the excavation, an amount of energy equal to the product of the fluid pressure

Jan 1, 1967

By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-'. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.' and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner's3 data for cation self-diffusion, D:, using Wagner's theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner's data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-' at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967

By C. G. Dunn

This note describes a method for revealing micro-structures in tantalum through an {hkl} effect which was found during a study involving amorphous and crystalline tantalum oxides. Three steps are involved. First, an amorphous film of Ta2O5 is formed anodically1 on the surfaces of the tantalum. The amount needed depents on the thickness of the substrate tantalum; 1600Å of oxide, however, is generally satisfactory in the 1/2 -mil (12 µ) to 3-mil thickness range. The film at this point is uniform in color. Second, the anodized specimen is heated to 800°C in. vacuo during a period of a few minutes and held at temperature for 5 min. During such a treatment some oxygen leaves the oxide through dissolution into the substrate tantalum (e.g., at 10-8 Torr oxide films thinner than about 800 completely disappear on 5-mil strip). Considerable crystallization of the amorphous oxide also occurs adjacent to the metal/oxide interface but not throughout the oxide thickness. The thickness of oxide needed as a residue is not too critical; values between 500 and 1000Å (optical estimate') may be most useful. (The presence of a residual oxide layer after the heat treatment usually is not apparent; in fact, in most instances the surfaces have a metallic appearance. This can be the case also for thicker residual films needed in the detection of a crystalline oxide phase by surface X-ray diffraction—e.g., if the initial oxide film is 3000Å thick, enough crystalline oxide is formed for X-ray detection.) The third step eliminates the metallic appearance at the surface and reveals (or produces) a varied colored film of tantalum oxide. Two methods can be used and both will be illustrated. If the specimen is dipped in 48 pct HF for a few seconds, the tantalum is found to be covered with a multicolored oxide. Moreover the colors correlate with the grain structure of the substrate tantalum through an orientation dependence of the type illustrated in Fig. 1, where results of an orientation analysis by the Laue X-ray method have been plotted. Other film conditions would have provided a different set of colors for the same orientations. Any such correlation, however, provides a basis for a qualitative assessment of the distribution of orientations in a large sample. The cold-rolled structure of tantalum foil produced by a recrystallization anneal and a cold-rolling reduction of 95 pct is not easily obtained by usual metal-lographic methods.' The structure, however, is easily revealed by the present technique, Fig. 2. The alternative third step is to reanodize the specimen. The optical nature of the final anodic film depends on the presence of the crystalline oxide phase; color variations indicate optical thickness variations in the film. As the reanodization voltage is increased from zero, straw and light brown colors appear (as usual), followed now by variations in color from grain to grain depending on {hkl} orientation. Suitable end points, which are determined by voltage and time, are easily established. Fig. 3, for example, shows the grain structure developed in 5-mil tantalum strip during a 30-min re-crystallization and grap-growth anneal at 1800°C. An anodic film of 1600Å thickness was added prior to the special 800°C anneal. Reanodization was done at constant current density (near 0.2 ma per sq cm) in an aqueous solution of H3PO4 (0.01 pct) and was terminated after the initial brown colors were replaced by a deep blue at approximately 30 v. Although good grain contrast can be obtained with bright field illumination, even greater contrast for black and white micrographs may be obtained with polarized light, as in Fig. 3.

Jan 1, 1967