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By A. R. Taylor Jr.

The heat capacities of a-quartz form beryllium fluoride were measured at approximately 3° intervals from 8° to 300° K., using an adiabatic calorimeter. At 298.15° K the heat capacity and entropy were 12.39 cal/deg mole and 12.75 ±0.04 eu respectively. Enthalpy measurements were made with an ice calorimeter at approximately 30° intervals on the quartz and glassy forms of beryllium fluoride between 300° and 1,200° K. A melting point of 825° K and an 0,-8 type transition at 500° K with a heat effect of 75 ca1/mole were deter-mined from the enthalpy data for the quartz-type sample. Beryllium fluoride glass crystallized spontaneously into the quartz modification at 500° K. The heat of the reaction BeF2 (a-quartz) .... BeF2 (glass) was found to be 1,125 ±16 cal/mole at 298° K by solution calorimetry. This value, when corrected to 273° K, was used to correct for the heat absorbed by the formation of glassy BeF2 when the sample was dropped into the ice calorimeter from temperatures above the melting point. Using corrected enthalpy measurements, the heat of fusion was determined to be 1.13 kcal/mole at 825° K.

Jan 1, 1965

By J. P. Hirth, C. S. Hartley

A simple graphical technique is presented for rapidly determining the ratio of resolved shear stress on slip systems in single crystals to the applied stress (Schmid factor) for various simple states of stress. Master plots are presented which, when used in conjunction with an appropriate stereo-graphic projection, allow one to determine the Schmid factor for all slip systems in a crystal of given orientation. It is shown that one such plot suffices for simple tension or compression, flex-ural bending, and biaxial compression, while a combination of two different plots must be used for torsion and simple shear. STUDIES of the deformation behavior of single crystals are most valuable when the applied stresses are resolved onto the various slip systems of the crystal. A careful study of the available slip systems and proper selection of the state of stress used and the specimen orientation can then yield quantitative information about the probability of specific dislocation reactions, the strength of barriers to plastic flow, and the mechanisms of yielding and flow in general. It is the purpose of this work to analyze some common states of stress used in deformation studies and to present a simplified way of determining for these cases the ratio of the resolved shear stress on the slip systems to the applied stress (Schmid factor). I) CALCULATIONS We first define two orthogonal coordinate systems: one based on the specimen geometry (a right circular cylinder of radius, R, is considered here) and one based on the particular slip system of interest. The unit vectors and angles specifying the two coordinate systems and the relationship between them are listed in Table I. The relationships among the various angles and unit vectors are shown on a stereographic projection in Fig. 1. The transformation matrix between the (XI X2 X3) and (x'1 x'2 x'3) system is x1 x2 x3 X'1 a11 al2 a13 x'2 a21 a22 a23 x'9 a31 a32 a33 where in this case the direction cosines aij are given by a11 a12 a13 aij = a21 a22 a23 a31 a32 a33 sin 0 cos F cos 0 sin F cos 9 = -cos 0 cos F sin 0 sin F sin 6 [1] 0 -sin F cos (p In terms of Eq. [I.], the stresses sij, referred to the slip system, are determined from oij, referred to the specimen axes, by1,2

Jan 1, 1965

By A. Hellawell

Binary alloys of compositions intermediate between solid-solubility limits and eutectic compositions have been completely separated into primary phases and eutectic by freezing unidirec-tionally at very slow rates (10-6 to 10-5 cm per sec). The alloys examined were Pb-1 wt pct Ag, Al-20 wt pct Cu, and Al-42 wt pct Cu. The compositions and proportions were close to those expected from the phase diagrams and provided information about the solid/liquid interface at certain free zing rates. DURING the directional freezing of an alloy the solute distribution is controlled by the efficiency of mixing in the liquid,'" whereas diffusion in the solid state is of negligible importance. It is known3 that mixing by convection is very efficient, but complete segregation is only achieved at very slow freezing rates4-6 or with forced stirring in the liquid. ' Yue9 and Yue and clark10 have previously illus- trated partial separation of primary phases in alloys close to eutectic compositions. In the present work, taking binary alloys of compositions intermediate between the limits of solid solubility and eutectic compositions, it has been possible to achieve complete separation of the primary phases by directional freezing at very slow rates. METHODS AND RESULTS The alloys concerned were Pb-1 wt pct Ag, A1-20 wt pct Cu, and A1-42 wt pct Cu. As may be seen from the relevant diagrams,11 these alloys should segregate into approximately equal proportions of primary solid solutions and alloy of eutectic compositions. Specimens, -12 cm long and 1 cm wide, were frozen in horizontal tubes by withdrawal from a furnace. The lead alloy, prepared from materials of 99.999 pct purity, was sealed into evacuated Pyrex tubes and the aluminum alloy of similar purity contained in graphite boats under vacuum. The molten alloys were seeded with some 3 cm of solid to prevent irregular initial freezing rates and the last portions to freeze were ignored. At the slow freezing

Jan 1, 1965

By Herbert A. Wendel

Reaching the miner with safety education" is R the ultimate goal, the main objective, of every safety program in the mining industry. If we can get safety education to every worker, and it is properly learned, enforced and obeyed, we should eliminate at least 85% of all potential accidents. We should then have very few accidents as a result of unsafe behavior, which, in turn, would allow us to concentrate most of our future efforts on preventing the types of accidents which are caused by faulty or defective machinery, equipment, tools and materials. An uninformed or uninitiated person would think that it should be a rather simple process to reach the miner with a safety education. Theoretically he would be right because here we get involved in a matter of semantics. When we say "reaching the miner with safety education" we actually mean that this education must also be accepted and learned by the miner; we intend to mean that safety must be observed and followed at all times. But in order to realize our complete meaning of the phrase, we must find the solution for a number of problems and obstacles which are well known to management and safety personnel.

Jan 1, 1965

By L. Ekstrom, J. P. Dismukes

The homogeneity and microstrcture of zone-leveled Ge-Si alloys haw been investigated by sellera1 physical techniques and by metallography as a function of growth rate in the range 3 x 10 1x10 cm-sec', and as a system of alloy composition throughout the system. The temperature gradient at the solid-liquid interface was about 50 deg-cm-' Cellular or dendritic structures char-acteristic of constitutional supercooling were ob-served except at very slow growth rates, which ranged from about 2 x 10 cm -sec for Ge 1 sio alloy to about 2 X 10'5 cm-sec'1 for Ge .sSio.s alloy. Using a simple model similiar to that employed for dilute solid the dependence upon compo-sition over the entire system of the critical growth rate for the onset of constiutional supercooling was calculated, and was .found to he in good agreement with the experimental results. THE recent discovery of the low thermal conductivity of Ge-Si alloys' at high temperatures has revealed that these alloys have high efficiencies for thermoelectric-power generation.', Therefore, a reliable method was needed for the preparation of homogeneous samples required for definitive measurements throughout this alloy system. Due to the low diffusion rates in the solid alloys, the segregated samples obtained by quenching a melt are not readily homogenized by annealing.475 However. isothermal solidification from a melt of constant composition can produce uniform material. Of the available semiconductor crystal-growth procedures, the zone-leveling technique6 applied to a complete solid-solution alloy system by Wang and Alexander' and by others provides a simple method of doing this. In the present work, the homogeneity and microstructure of zone-leveled alloys have been correlated with growth conditions, and the conditions for preparing homogeneous Ge-Si alloys have been established. This has provided insight into the solidification process of alloy semiconductors. EXPERIMENTAL PROCEDURE Sample Preparation. The Ge-Si alloy phase diagram4 shown in Fig. l(a) consists of a complete series of solid solutions. The zone-leveling technique used to prepare most of the samples consists of moving a zone of liquidus composition (C1) through charge material of the corresponding solidus composition (C,), as is illustrated in Figs. l(b) and l(c). To prepare the charge materials, high-purity germanium and silicon were pulverized in a steel hammer mill, cleaned magnetically, and melted together to make uniform chill castings. The zone leveling was carried out in a resistance-heated furnace similar to that of Mitrenin et al.' shown in Fig. 2. However, a few specimens of high silicon content were prepared by the Czochralski technique. The growth rate ranged from 3.5 x X6 to 1.2 X 10~3 cm-sec-'. Temperature gradients in the solid and in the melt were determined by recording the temperature as the molten zone passed over a Pt-Pt 13 pct Rh thermocouple contained in a small

Jan 1, 1965

By R. Barany

The heats of formation of anhydrous ferric sulfate and anhydrous indium sulfate were determined by solution calorimetry. At 298.15° K the heats of formation from the metal, rhombic sulfur, and oxygen were -615.6 ±O.7 kcal/mole for ferric sulfate and -649.6 ±O.6 kcal/mole for indium sulfate. Heats of decomposition at 298.15° K are given for the reaction that forms metal oxide, sulfur dioxide, and oxygen) and for the reaction that forms the metal oxide and sulfur trioxide.

Jan 1, 1965

By G. R. Kotler, W. A. Tiller, H. V. Ashcom, S. O&apos, Hara, W. C. Johnston

The grain-refinement effect of electromagnetic stirring of Sn-Pb alloys during solidification is investigated at higher field strength and in larger-sized samples. It is found that the grain-refining effect is due to a crystal multiplication phenomenon rather than a nucleation phenomenon. The effect increases with sample size for a fixed field strength and a fixed supercooling bath temperatures. The effect in other alloys was investigated. IN a recent publication1 it was reported that significant grain refinement could be produced during the solidification of a supercooled melt of Sn-Pb alloy when a critical degree of electromagnetic stirring was present in the melt. Thus, for a particular supercooling, AT, a critical magnetic field, Hc, existed at which the number of grains per unit volume, n, increased rather abruptly by a factor of 103 to 104 as the field, H, was increased by a small amount. It was further found that the undercooling at which the melt spontaneously nucleated, ?Tn, was independent of the magnetic field. These authors matched their experimental results against the qualitative expectations of existing theories and found each theory somewhat unsatisfactory. One important question that was not answered in this previous work was "should the effect be classed as a nucleation phenomenon or as a crystal-multiplication phenomenon?" Other valid questions that need answering are: i) do higher magnetic field strengths alter the nature of the results?; ii) what is the effect of higher lead content in the alloy?; iii) what changes occur when one extends the experiments to larger-diameter samples?; and iv) is this a universal effect applicable to the grain refinement of all materials? The present work directs its attention to answering these five questions. The

Jan 1, 1965

By H. L. B. Gould, Jr. Wenny D. H.

TO date there has been but limited interest in alloys of 80 to 95 pct Co and Fe with or without other additions. In 1932, S. R. Williams' reported practically zero magnetostriction for the 90 pct Co-10 pct Fe alloy. This same composition was used for pole pieces to control the magnetic field in magnetrons operating at high temperatures.' In 1947, a 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn composition was investigated3 for use in ballast lamps because of its high temperature coefficient of resistance. Recently, as part of a survey of ductile and malleable magnetic alloys capable of being processed to thin gages for possible applications in memory devices, the high Co-Fe alloys have been re-examined to determine their fabricating and magnetic characteristics. Alloys from 80 up to 95 pct Co and Fe with and without additions such as vanadium were prepared. In general these all had excellent ductility and malleability. Wire was drawn to thin gages without difficulty and fine hard-drawn wires flattened to 2) The phenomenon may have potential in estimating the carbon content of molybdenum. A given solution-treating temperature and cooling rate could perhaps be calibrated so that the area fraction of surface covered by carbide could be interpreted in terms of carbon concentration. By segregating to the surface, a big "magnification" of the carbon content is obtained, which should make the method cheap, direct, and sensitive and, therefore, perhaps of interest to the molybdenum industry. This work was conducted at Battelle Memorial Institute. Financial support by the Aeronautical Systems Division, United States Air Force, under Contract No. AF 33(657)-7376, is gratefully acknowledged, and the writer is thankful for the experimental assistance of Miss Marjorie Cantin. ribbon without splitting. Similarly, strip was cold-rolled as much as 99.75 pct reduction to a 0.25 mil thickness without intermediate anneals. Samples of round and flat wire and foil, in the severely cold-worked and annealed states, were checked for magnetic characteristics. The alloys exhibited widely divergent magnetic characteristics depending on the processing and heat-treating procedures used in preparing the samples. Direct-current hysteresis loops showing the different magnetic characteristics of 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn alloys are shown in Figs. 1 to 8 inclusive, while Figs. 9 and 10 show the loops for an alloy of 82 pct Co, 11.75 pct Fe, 5.6 pct V, and 0.65 pct Mn. Figs. 1 and 2 show the high remanence and exceedingly square-loop characteristics of the hard-drawn wire and ribbon roll flattened therefrom. With the change in processing from roll flattening to flattening by drawing through flat diamond dies the resultant change in texture is accompanied by the drastic change in the shape of the loop as shown in Fig. 3. This skewed loop on annealing reverts to a more normal loop as shown in Fig. 8. The most unique loops are obtained with flat rolled strip. These are shown in Figs. 4 and 5. In the case of the hard-rolled material, Fig. 4, there is little change in induction until the magnetizing force reaches 50 oe. From 50 to 60 oe there is a sharp increase in induction to over 15,000 gauss, which for all practical purposes is saturation. The induction remains at a constant value while the magnetizing force decreases to 40 oe. At this point the

Jan 1, 1965

By A. J. Kauffman

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

Jan 1, 1965

By B. E. Warren

Jan 1, 1965

By B. A. Kulp, R. R. Reeber

Lattice parameters for the wurtzite form of' CdS mere measured by powder X-ray diffraction techniques over the temperature range 26° to 1000 K'. A negative thermal -expansion coefficient was determined parallel and perpendicular to the c axis below 13.5°K. Near 808°K, the curves of the a, parameter, the differential thermal expansion, and the resistivitv vs absolute temperature exhibited a reversible discontinuity. j\. direct determination of the lattice parameters of CdS over an extended temperature range is of particular use in interpretation of the effects of high pressure on the band structure of semiconductor materials. For example, Langer' has studied the effects of pressure on the absorption edge of CdS from 77°K to room temperature. In order to properly interpret his results it is necessary to know the change in lattice constants as a function of temperature for the wurtzite, zincblende, and rocksalt2 modifications of this material. Thermal-expansion measurements for CdS, wurtzite phase, have previously been determined over a limited temperature range.s74'5 The zincblende phases, of other compounds with similar bonding, have been investigated by Novikova et a! .'' Previous thermal-expansion measurements for metals with hexagonal symmetry have for the most part used bulk sample techniques for low-temperature result. Most X-ray measurements at low temperature have been on materials with cubic symmetry.'jQ The use of X-ray powder-diffraction techniques offers a convenient and accurate method of measurement over a wide temperature range. The X-ray method, besides measuring unit cell size, also provides information about change in structure type and the nature of some of the stacking defects present. I) EXPERIMENTAL PROCEDURE The thermal expansion was measured by X-ray powder-diffraction techniques. Lattice parameters for the range 300" to 1000°K were determined in a 19-cm Unicam camera. From 26" to 300°K a 34-cm back-reflection camera with the Van Arkel" film arrangement was used. The sample was bonded to a copper cold finger below a helium, hydrogen, nitrogen, oxygen, dry ice, or ice brine bath in a metal cryistat. che inner bath was surrounded by another one for radiation shielding. Nitrogen was used in this outer bath for the very low-temperature runs while dry ice and acetone was used for the 195°K point. CuKa X-rays, filtered with a nickel foil, entered the cryostat through a 0.001-in.-thick aluminum window. During a typical 9-hr exposure the sample was continuously rotated through a 30-deg arc. Heat losses from the sample holder limited the minimum temperature attained to 26°K with helium in the inner dewar. Temperature calibration between 25" and 125°K was determined with an Allen Bradley 300-ohm carbon resistor. The resistor was attached to the back of the copper finger with a thin layer of silicone grease. Liquid He, HZ, N2, and O2 baths were used to calibrate the resistor. Temperature variation is estimated to be *2"K with a slightly higher uncertainty at room temperature and 264°K. The thermal expansion of high-purity germanium from 373" to 900°K was measured as a calibration for the Unicam camera. This value was compared with the known value1' for the thermal expansion. A discontinuity in the thermal-expansion coefficient of the CdS a, parameter was observed. Similar discontinuities in the resistivity and differential thermal analysis at the same absolute temperature indicate that the temperature error is *5°K in the temperature range above 500°K. Temperature errors in the Unicam camera below 500°K are appreciably higher due to large gradients in the resistance furnace. II) SAMPLE PREPARATION The CdS was Eagle Picher ultrapure grade. The crystallite size range of the as-received powder

Jan 1, 1965

By James A. Roberson

THE mechanical behavior of molybdenum has become a matter of considerable interest in recent years because it has a reasonably high strength at high temperatures. Various aspects of its fatigue behavior have been investigated previously,1-3 and the results can be summarized as follows. Recrys-tallized molybdenum exhibits a fatigue limit which decreases continuously with increasing temperature. The ratio of fatigue-limit stress to ultimate tensile stress is high (0.6 to 0.8) and reasonably constant. The present work was undertaken to determine the effect of variations in environment on the fatigue of molybdenum stressed in fully reversed axial tension compression. In order to provide a basis to which these data could be compared, a complementary series of fatigue tests were made in vacuum. All of the specimens used were made from one mill lot of unalloyed molybdenum which had been vacuum-arc melted, worked down to 1-in.-diam bar, re-crystallized, then warm-worked to 5/8 in. diam. The interstitial content by weight was as follows: C—0.022 pet, 02-0.0026 pet, Hz-0.0001 pet, and N20.0002 pct. The average grain diameter in the transverse direction was about 0.035 mm, and the average grain length was about 0.15 mm. Typical tensile-test data are shown in Table I. None of the specimens tested exhibited an upper yield point.

Jan 1, 1965

By C S. Walker

This paper analyzes the physical, operational and economic site conditions which were conducive to the design of a diesel-electric power plant wherein the over-all use of the thermal energy of the fuel exceeds 80 per cent. The heat energy supplied to the diesel engines is recovered in power generation, vapour phase cooling, waste heat boilers, air to exhaust gas heat exchangers and lubricating oil coolers. Electric boilers are also integrated into the plant design to enable the ratio of electric power output to heat recovery to be varied to suit the seasonal and daily variations. The criteria relative to thermal and electric power design requirements are discussed, and the design details of some parts of the plant which conform to these criteria are illustrated. Some data in regard to the actual operation of the plant over a short period are also included. Introduction THE Cantung mine (Canada Tungsten Mining Corporation) is located some 180 miles north-east of Watson Lake, Yukon Territory. It is situated on the upper reaches of the Flat river at an elevation of about 3,700 feet.

Jan 1, 1965

By R. E. Caffrey, S. K. Tung

This paper reports some of tile results obtained from the vapor-phase reaction of a volatile metal halide with a hydrogen and carbon dioxide mixture in an epitaxial-deposition chamber. Tile oxides deposited were silicon di oxide, aluminum oxide, mix-12tves of silicon di oxide and aluminum oxide, and titanium oxide. Tile deposited silicon di oxide was transparent and amorphous and had a density and index of refraction similar to that of thermally grown silica. The vote of etching was determined. The thickness uniformily of the oxide was found to he related to the aerodynamics of the system employed for deposition. A clear silicon di oxide layer was found to be dependent upon the quality of the surface prior- to aside deposition. The process parameters affecting the vale 0f deposition were studied. The deposited aluminum oxide was transparent, holy-cl-ysttrlliile, and possessed remarkable resistance to hydrofluoric acids. By measurements it has been shown that the deposited aluminum oxide is both insulating and continuous. ThE cleanness of an epitaxial silicon surface both immediately after growth and during device processing is thought to be one of the major factors contributing to the electrical properties of a final device. The advantage of protecting an epitaxial silicon wafer surface with an oxide grown immediately following epitaxial deposition is obvious. The successive growth of silicon and silicon diox- ide in epitaxial apparatus was studied by Steinmaier and loem.' They formed silicon dioxide films on a silicon substrate by adding water vapor to the silicon tetrachloride-hydrogen mixture in an epitaxial system. They also showed that, when a gaseous mixture of carbon dioxide and hydrogen is injected, water is formed only at elevated temperatures. Thus the reaction of water vapor and silicon tetra-: chloride will be limited to a relatively small reaction zone near the substrate. This paper reports some results of oxide films obtained from a vapor-phase reaction of a volatile metal halide with a hydrogen and carbon dioxide mixture in an epitaxial-deposition chamber. EXPERIMENTAL APPARATUS The system employed for the oxide deposition is a modification of a vertical system used to produce high-resistivity silicon layers by the hydrogen reduction of silicon tetrachloride.' The modification shown schematically in Fig. 1 consisted of an additional carbon dioxide gas stream which entered the reaction chamber with a hydrogen stream saturated with metal halide vapor and a diluting hydrogen stream. Silicon dioxide layers made from a mixture of silicon tetrachloride, hydrogen, and carbon dioxide gases will be discussed first. EXPERIMENTAL RESULTS 1) Factors Affecting the Rate of Oxidation. An epitaxial silicon layer was deposited by the hydrogen reduction of silicon tetrachloride on an n-type,

Jan 1, 1965

By Kenneth N. Weaver

Portland cement can be made from relatively abundant industrial minerals and rocks, and this may explain why cement producers placed little emphasis on geology during the early days of the industry. After World War II, however, the industry began to recognize the need for geological exploration, and some of the larger companies began to build a permanent geological staff. This development had its roots in the following factors: Rapid expansion of the industry; closing of many cement plants due to inadequate raw materials; necessity for upgrading the quality of portland cement; and the increasingly large capital investment required to build new cement plants, which in turn, required a higher degree of accuracy in reserve calculations. Whereas the geologist's function during the active expansion of capacity was primarily in exploration, one of his major functions today is the development of existing reserves.

Jan 1, 1965

By G. W. White

Over the past several years, the steady progress of gas lift from a mysterious art into a developing science has been traceable through the many fine papers that have appeared in Journal of Petroleum Technology. Consequently, this magazine has rightly become a standard for the serious students of gas lift all over the world. The following discussion is offered in a sincere attempt to accurately present certain topics covered in the subject paper in the light of acknowledged state of the art procedures. INSTALLATION DESIGN The first point to be questioned is the author's installation design, beginning with Eq. 6. The use of 1,200 psi in the spacing equation instead of the 1,275 psi noted as available seems, at first glance, to be a simple arithmetic error. Upon further examination, it appears evident that both this 75 psi plus the 100-psi safety factor must be subtracted from available kickoff pressure because of conditions imposed by the characteristics of the ASC valve (see Fig. B-1). Pressure-charged valve design is incorrectly penalized by spacing the first valve using only 1,100 psi. The use of such a high back-pressure makes it appear that a typical ASC installation would require no more valves than a comparable conventional valve installation. Using a value of 100-psi tree pressure, the well could be valved to 11,000 ft very conservatively with seven pressure-operated valves, but would still require 11 ASC valves. The use of 400-B/D spacing gradient for a 140-B/D rate is not an accepted practice using precharged valves. The author would have done well to note the advantages to be gained by reducing the 500-psi tree pressure, which is clearly explained by Beadle, Harlan and Brown.' In Step 1 of Part III of the continuous flow discussion, the author incorrectly applies the Poettmann and Carpenter curves.2 Item 2 is an incorrect statement. An excellent reference on this point is the paper by Baxen-dell and Thomas.' VALVE MECHANICS The next topic relates to the mechanics of precharged valves. Eq. 2 for the ASC valve can be used to describe the condition of equilibrium, wherein the valve is closed with opening pending. When this equation is used to determine relative values of casing, dome and tubing pressure with conditions approaching the transition value, some strange results are obtained. The following uses the author's symbols and values given on page 689. Fig. B-1 shows the condition that exists at the moment an ASC valve has been uncovered during the unloading process (Condition I). The obvious result is a locked condition. The basis for the curve is shown on the figure which includes 1,000 psig casing pressure to uncover the valve. If injection gas is not bled off the casing until the pressure is decreased by an amount exceeding the stabilizer discharging valve pressure, upward adjustment of the casing pressure is mandatory for the valve to open and unloading operations to continue. In Condition I the dome pressure exceeds the casing pressure by 20 psi, and the tubing pressure required to open the valve is 1,212 psig. This tubing pressure would not exist under the assumed conditions. In Condition I1 the casing pressure is increased to the dome pressure, and the tubing pressure required to open the valve is 1,102 psig. It is apparent that the casing pressure must be increased to a value exceeding the dome pressure before unloading operations could continue. In Condition I11 a maximum casing pressure of 100 psi (stabilizer charging valve set pressure) above the dome pressure is reached, and the tubing pressure required to open the valve is 549 psig. The author's statement after Eq. 5 that "the minimum tubing pressure required to open an ASC valve is equal to the casing pressure at depth less the transition pressure of the valve" is incorrect except for Condition I11 only. Otherwise, the equation is invalid.

Jan 1, 1965

By L. W. Holm, G. G. Bernard

Laboratory experiments were conducted to determine the effect of foam on gas flow in porous media. Previous studies have indicated that foam may be applicable as a restrictive agent in influencing underground gas flow. Foam was found to be exceedingly effective in reducing the permeability of porous media to gas. Consolidated and unconsolidated sands with specific permeabilities of 100 to 146,000 md had, in the presence of foam, gas permeabilities that were less than 1 per cent of the specific permeability; in many cases the gas permeability was practically zero. Foam reduced the gas permeability of loose sand to a much greater degree than that of a tight sand. For example, the permeability of a 125,000-md sand was reduced to 3 md while the permeability of a 4,000-md sand was reduced to 7 md. This effect should cause, to some degree, selective plugging of high permeability channels in various oil displacement processes. The presence of oil in a porous medium decreased the effectiveness of foam in reducing gas permeability; apparently oil acts as a foam depressant. However, it was found that certain foaming agents were very effective in reducing permeability even. in the presence of oil. Also, continuous injection of other foaming agents increased their effectiveness, when oil was present. The effect of foam on permeability of porous media to gas was studied as a function of foaming agent concentration and injection rate, absolute permeability, total pressure, pressure gadient, length of porous system, brine concentration and time. INTRODUCTION The use of surface active agents in flood water to increase the recovery of oil has been studied in the laboratory and in the field for decades, with rather limited success. In recent years a new approach to the problem was proposed. Instead of using an aqueous solution of surfactant as an oil recovery agent, Bond and Holbrook2 proposed that the oil recovery agent be a mixture of surfactant solution and gas. In their method, a water-soluble surface active agent with foam-producing characteristics is injected into an underground formation as an aqueous slug. This slug is followed by gas to produce a foam within the rock. Foams are defined as "agglomerations of gas bubbles separated from each other by thin liquid films'! A foam is fundamentally an unstable system. The foam process for oil recovery has since been studied by other investigators. Fried 1 has shown that foam can displace from porous structures oil that normally is unrecoverable by conventional water or gas drives. This superior oil displacing action is believed to be the result of several factors: (1) foam introduces into the reservoir many resilient interfaces of various sizes and curvatures, which increase the probability that a proper combination of forces for oil displacement will be created; (2) foam has appreciable viscosity which improves mobility ratio and contact efficiency; (3) foam accentuates the trapped gas effect because high gas saturations are possible without producing high gas/oil ratios. Deming4 studied the effect of various foam properties on the displacement of liquid. He found that (1) high foaming ability favors high displacement efficiency; (2) high foam stability is not necessary for high displacement efficiency; (3) displacement efficiency decreases with increase in plasticity of foam and (4) displacement efficiency is unaffected by surface tension of foaming agent solution. One of the important aspects of this oil recovery process is the effect of foam on gas permeability. The simultaneous flow of gas and liquid in porous media has been studied by numerous investigators and a large amount of literature exists on the subject. In this previous work, gas and liquid have generally been considered as essentially independent phases, whose flow characteristics are related through the saturation parameter. Foam, however, is a material with properties that are considerably different from those of its components; for example, the viscosity of a foam is greater than either of its components. Gas flow in a porous medium in the presence of foam should be considerably different

Jan 1, 1965

By J. Alfred Berger, O. M. Katz

Selected samples of hydrided Zr-Hf alloys were rapidly quenched to voom temperature and exrtrnined metallographically, by X-ray diffraction, and through micro hardness studies to confirm high-temperutuve data Confirming experiments sllowed that there were five phases in this Lernary system: 1) hextrgonal with lattice parameters similar to that of the initia1 Zr-Hf alloy but slightly enlarged due to dissolved hydrogen; 2) fee with properties of a brittle, intermediate, hydride compound; 3) fct with c/a crvoltnd 1.07 and which appeared as a neetilelike precipitale; 4) hexagonal, designated ?, with c/a ratio of 2.37; and 5) orthorhombic, designated X, with a = 4.67, b = 4.49, and c = 5.093 and whose tnicro-st?ruct~ival nppetrl-nnce depcncled o/i, heat lvecrt~r~ent. The tetragonrrl phase never crppeal-erl witkorct the cubic hydricle. Abpecrrtrnce of 0 and A also tlependet on the hafnium content of the zirconium. A previous paper' on the Zr-Hf-H system described the thermochemical data obtained with a high-vacuum, high-sensitivity mirrogravimetric apparatus. This data presented a fairly complete picture of the phase relationships at elevated temperatures. However, it could not establish the actual crystal structures, lattice parameters, or metallographic disposition of the hydride phases. The present complementary study utilizes X-ray powder patterns along with light and electron microscopy to characterize completely the five hydrided phases found in Zr-Hf-H alloys quenched to room temperature. Crystallographic features of the zr-Hf,2,4 zr-H,5-7 and Hf-H8 systems have been summarized in Table I. Designations of a, ß, and ? were retained in the Zr-Hf-H system for the phase regions through which the pressure-composition isotherms always sloped. However, it was not firmly agreed that these were single-phase regions.' In fact, the region designated y always contained a cubic as well as a tetragonal phase after quenching to -196°C. MATERIALS Preparation of the high-purity Zr-Hf alloys has been described.' The four zirconium alloys which were hydrided contained 37 wt pct Hf (23 at. pct), 51 wt pct Hf (37 at. pct), 73 wt pct Hf (58 at. pct), and 91 wt pct Hf (82 at. pct), respectively. These were designated B-2, B-4, B-6, and B-8. Photomicrographs of the initial alloys showed the material to be quite clean as would be expected from the precautions exercised in producing them. However, there were a number of annealing twins but no other subgrain structure. In addition to the four original alloys, fifteen hydrided samples were observed at room temperature. Hydrogen compositions are given at the top of Tables I1 to V. APPARATUS The phases present at elevated temperatures were studied by quenching hydrided samples to room temperature by two different methods, both under vacuum: 1) fast cooling of the sample tubes of the microgravimetric apparatus1'9 with flowing air and 2) rapid quenching into liquid nitrogen. The cooling rate for 1) was 750° to 250°C in 30 sec. Since the microbalance chamber was not designed to permit very rapid cooling of a hydride sample, all liquid-nitrogen quenching was done in an auxiliary experiment. The auxiliary quenching apparatus consisted of a small-bore, high-temperature furnace, a sealed SiO2 tube containing the sample, and a dewar quenching flask filled with liquid nitrogen. The hydrided sample, previously quenched in the microgravimetric reaction chamber, was placed in a platinum boat in a vacuum-degassed SiO2 tube. A zirconium wire getter and degassed SiO2 rod, to reduce the internal volume, were also in the tube. After sealing the tube under vacuum the zirconium getter was heated to absorb the last traces of gas. Only the sample was heated at the reaction temperature for the desired length of time, and then the tube dropped through the opposite end of the furnace into the dewar. A quenching rate of 200" to 400° C per sec was estimated. Analyses of samples after the auxiliary experiment also showed practically no increase in oxygen or nitrogen content from heating in the SiO2 tube. All of the samples were examined at room temperature by the X-ray powder method. The majority of the powder patterns were obtained with double nickel-filtered CuKa radiation after 8- and 16-hr exposures in an 11.48-cm-diam camera. Cobalt and chromium radiation were also used to spread out the high d value end of the Pattern. Such patterns readily identified the minor phases. NO oxide or nitride lines were found. Where sharp back-reflection lines existed it was possible to reduce the

Jan 1, 1965

Experimental results are presented for the anode overvoltage as a function of current density for different alumina concentrations in an alumina reduction cell. Voltage changes due to the electrolyte resistance and also the decomposition voltage, have been evaluated as a function of alumina concentration and anode current density. From these values of voltage, changes in the total cell voltage have been derived for changes in alumina concentration for different anode current densities. The results show that for each operating current density there exists a discrete alumina concentration that defines a minimum reduction cell voltage. Discussion is made about potential savings in power consumption when the alumina concentration is controlled.INTRODUCTIONThe standard procedure in the aluminium industry when analysing the cell-voltage required for the Hall-Heroult process for reduction of alumina, is to subdivide the total voltage into the following components (e.g. Pearson, 1955; Maritell, 1960).1. ohmic drop through busbars and joints2. ohmic drop through cathode lining3. ohmic drop through anode4. ohmic drop through electrolyte5. overvoltage at anode6. electrolytic decomposition voltage.(Overvoltages ,at the cathode are of negligible magnitude at all practical current densities.)It is understandable that the voltages assigned for each factor invariably differ for different workers...

Jan 1, 1965

By Robert R. French

Commercial grade gypsum beds up to 16 feet thick is present in southwestern Indiana. The major deposits are found at a depth of 350 feet to more than 500 feet below the surface. The ore body averages about 75 to 95 percent gypsum. Two companies are currently exploiting a deposit which underlies an area of several square miles near Shoals, in Martin County. Another deposit has been located in southwestern Owen County but has not been developed. The Indiana Geological Survey is currently drilling in Greene County and is considering further exploratory work in Perry end Dubois Counties.

Jan 1, 1965