Search Documents

By Robert M. Doerr

The purpose of the investigation was to determine the oxidation behavior of selected tungsten-cobalt alloys. Specimens of Wand W-Co containing 0.7, 1.7, 3.4, and 9.7 weight-percent Co were subjected to pure 02 at 1,000° and 1,100° K, and specimens of W-Co containing 29.8 weight-percent Co, at 1,100° K. Reaction kinetics were determined volumetrically. For specimens other than those containing 29.8 percent Co, the reactions proceeded at about a constant rate at either temperature, indicating the formation of a scale of constant protectivity; the reaction rates were essentially independent of the Co concentration. The scales on these alloy specimens consisted principally of WO3 and CoWO4. Specimens of a 29.8 weight-percent Co alloy, consisting primarily of the W6CO7 phase, oxidized with only slight deviations from the parabolic rate law at 1,100° K. The protective scale on these specimens consisted chiefly of Co3O4, CoW04, and W1 8°49; Co3O4 was outermost, and the W18O49 was adjacent to the alloy. The results suggest that the Co-rich outer scale inhibited the inward transport of 0 to an extent sufficient to greatly limit the amount of the nonprotective WO3 formed, so that protective W18O49 formed instead.

Jan 1, 1967

By S. J. Aresco

The Bureau of Mines has been active in promoting the purchase of coal for Government use under specifications that define the requirements in terms of heating value of the coal, expressed in British thermal units, and the composition as shown by proximate analyses. To these, when required, are added the ash-softening temperature, the free-swelling index, and the Hardgrove grindablity index. Under most of these specification contracts the bidders guarantee the quality of the coal, and that guaranteed by the successful bidder becomes the standard of his contract. The deliveries are sampled in accordance with instructions3 issued by the Bureau of Mines; the samples are analyzed in the Bureau laboratory to determine whether the coal is of the quality guaranteed by the contractor; if it is not, a price adjustment is made. Analyses of the delivered coal and tipple samples (samples collected at mine tipples as coal is being loaded into railroad cars or trucks) provide valuable data for use in evaluating future bids. In addition, the continuous of coal as delivered is a check on the practical results obtained in the coal.

Jan 1, 1967

By D. A. Elkins

This report is the second of a series of three that will evaluate, in order, the metallothermic, carbothermic, and electrolytic methods of magnesium production. The historical development of the carbothermic process is outlined. Production costs varying from 38.9 to 21.8 cents per pound of magnesium are estimated for different versions of the process. Additional suggested process modifications are listed. The technical and economic potential of the different versions are compared. Areas deemed most promising for future research on the process are delineated.

Jan 1, 1967

By H. G. Iverson

Solid state reactions of manganese with silica were investigated in high-temperature tests. Reactions of 0.5 to 4.0 moles manganese (Mn) with 1 mole silica (SiO2) at 1,100° C and of 2.0 Mn:SiO2 mole-ratio mixtures at 1,000° to 1,150° C yielded products consisting of a slag phase and a metallic phase. At 1,100° C, the slag phase from reactions of the low Mn:SiO2 mole-ratio mixtures was composed of SiO2 and rhodonite (MnSiO3), and the slag phase from the high Mn:SiO2 mixtures was composed of MnSiOs and tephroite (Mn2SiO4). The metallic phase from the corresponding low Mn:SiO2 mole-ratio reactants consisted of two manganese silicides, Mn5Si3 and Mn3Si; from the high Mn:SiOg mixtures, it was Mn and the manganese silicide (Mn5Si). For the higher mole ratios of MnSiO2 the manganese content in the metallic phase increased, while the manganese and silica contents of the slag phase remained nearly constant. The slags did not contain free or uncombined manganese oxide (MuO). For the 2.5 to 4.0 Mn:SiO2 mole-ratio mixtures reacted at 1,100° C, the maximum quantities of silica reduced and of the manganese in the slag appeared to become asymptotical at about 41 and 48 percent, respectively. A brominating procedure was developed that was highly selective in removing the metallic constituents from the reaction product, leaving the slag phase as residue. X-ray diffraction patterns were obtained on prepared silicides Mn5Si, Mn3Si, and MnSi.

Jan 1, 1967

By R. N. Orava, L. A. Rice

One of the difficulties encountered in the preparation of titanium specimens for transmission electron microscopy is the formation of a surface hydride phase during the thinning operation at ambient temperatures. This necessarily destroys contrast, obscures features of interest, and often leads to misleading results. By cooling the polishing solution to temperatures below 0°C this problem has been overcome in the past.' However, since the cooling procedure is somewhat inconvenient, a technique was developed at this laboratory for thinning titanium at room temperature. The material examined was A-70 grade commercial-purity titanium purchased from the Crucible Steel Co. of America. The mechanical and thermal treatments, described elsewhere,* yielded a recrystallized grain size of 4 to 5 p. A slice, 0.5 mm thick and 1.5 mm wide, was cut from a bulk specimen2 using a diamond cut-off wheel. The sample was then coated with paraffin wax. Two concentric holes, about 0.03 in. in diam, one at each broad face, were scribed through the wax to the surface of the metal. Subsequent polishing for several minutes resulted in a preferentially thinned or "dimpled" region. Thereafter, the wax was removed and the entire specimen polished to the point of breakthrough at the base of the dimple. Polishing was effected chemically in a solution comprised of 30 pct HF and 70 pct HN03 by volume, kept at room temperature (20" to 25OC). The specimens were mounted in a stereo holder and examined at 100 kv in a Philips l00 B Electron Microscope. A micrograph from a foil prepared in this way is shown in Fig. 1. Several points are noteworthy. This electron micrograph shows neither evidence for the formation of a hydride phase due to specimen preparation nor, moreover, any obvious surface contamination in electron-transparent areas of a freshly prepared foil. Localized variations in foil thickness observed in some specimens seem to be a characteristic of this chemical polish but do not seriously detract from foil quality. With care, the lifetime of a good specimen exceeded 2 hr in the beam. On the other hand, the exposure of a sample to air at atmospheric pressure, when still warm from the beam, clearly resulted in the deterioration of a formerly clean area just previously in the field of view. An example in Fig. 2 of a contaminated region reveals features, and "spots", not unlike those observed in much purer material by Yamane and Ueda. Consequently, one can conclude that: 1) titanium can be thinned satisfactorily in a solution at room temperature for transmission electron microscopy; 2) large-scale precipitates, >50A in diam, are absent in commercial-purity, recrystallized, furnace-cooled, A-70 titanium containing about 3800 wt ppm interstitials and the same amount of iron; 3) care must be taken not to attribute surface contaminants to precipitates. The authors are grateful to the Franklin Institute for financial support and permission to publish.

Jan 1, 1967

By E. R. Dean

A wire-feed mechanism has been employed to fabricute metal alloy film resistors to various sheet resistivities on oxidized silicon substrates. The effect of several thousand hours storage in air at elevated temperatures on the resistance and temperature coefficient of resistance is presented. Unprotected films of- sheet resistivity between 100 and 500 ohms per sq fabricated at 300°C substrate tenzperatures were unstable when stored at 150°Cfor extended periods. The higher sheet resistivity films exhibited the greatest instability; however, even the 100 ohms per sq films drijted excessively for device application. When stored at still higher temperatures, the normalized resistance increases to maximum, then decreases until a minimum value is obtained, then finally increases in resistance until open. The use of a protective overcoating of SiO has had considerable benejicial effects on the film stability, so that 250 ohms per sq films deposited on 300°C substrates are now stable after 1000 hr storage at 250°C and possess a temperature coefficient of resistance less than 200 ppm per C. The use of a low substrate temperature during depositon (100°C) enables the preparation oj resistors with very low tenperature coefficients of resistance (10 to 20 ppnl per 'C). However, these films are less stable than their higher substrate temperatuve counterparts. During extended storage, the resistance of the protected films always decreases with lower substrate films exhibiting larger normalized resistance decreases. This resistance decrease is accompanied by a linearly related increase in the temperature coefficient of resistance. The electrical behavior of these films may be explained by postulating That the structure of the films is in the transition region between thick continuous films and ultrathin island structure films so that the conductivity is the restlt of both electron scattering and tunneling-activated charge carrier creation between neighboring grains. The annealing behavior when thermally aged is the result of defect anneal, grain growth, and selective oxidation. TheRE is a considerable interest in thin metallic films for use as resistor elements in microelectronic circuits.1,2 These resistor films must be stable when exposed to elevated-temperature storage or operating ambient, possess low temperature coefficients of resistance (hereafter referred to as T.C.R.), and be of a high enough sheet resistivity to be useful. The resistivity and T.C.R. of a thin metallic film are determined by the structure and thickness of the film. Hence the stability of the film when exposed to stress would depend on the stability of the structure. The resistivity of a thin film is the result of the electrons' interaction with the lattice vibrations (electron-phonon scattering), scattering of electrons due to impurities, defects, and grain boundaries and specula reflection from the film surfaces.3' All of these effects serve to reduce the electron mean free path and result in a resistivity higher than the ideal bulk. In ultrathin films possessing essentially an island structure consisting of a planar array of aggregates separated by a few to a few tens of angstroms, conduction is dominated by a combination of tunneling and activated charge carrier reation. Thin films would be characterized by relatively low resistivity, positive T.C.R., and reasonable structure stability whereas ultrathin films possess unstable structures, negative T.C.R., and exhibit high resistivity. Feldman6 has investigated films intermediate between the two regions and postulates that the resistivity of a film in the transition region is composed of two linearly additive parts: that due to the resistance of the grains and that due to the gaps. The grain resistivity would represent the scattering of the conduction electrons by defects, surfaces, and phonon interaction while the gap term represents the tunneling contribution. For gold and platinum films, he found as the film structure becomes progressively less continuous, corresponding to thinner films, the absolute value of the T.C.R. becomes progressively smaller until negative values are observed with respective zero T.C.R.'s at about 35 and 150 ohm per sq, respectively. Recently the author7 investigated the behavior of a multicomponent alloy of nickel, chromium, and iron and found the T.C.R.'s of these films decrease with decreasing substrate temperature during deposition. The lower T.C.A. associated with lower substrate temperatures was attributed to an increased contribution to the total resistivity from the negatively temperature-dependent gap tunneling since it is well-known that thin films deposited on low-temperature substrates consist of a higher density of smaller grains than the same sheet resistivity films deposited on higher-temperature substrates. Under conditions of thermal anneal, the author found that, when various sheet resistivity films fabricated at 300°C substrate temperature are exposed to extended storage in air at 300°C, the thinner films increase in resistance until open, while the thicker films

Jan 1, 1967

By Olav Mellgren

Part I. The interaction between potassium ethyl xanthate and lead salts has been studied thermo-chemically. It is shown that ethyl xanthate reacts with lead carbonate, basic carbonate, thiosulfate and sulfate according to principles of simple chemistry, whereas reactions with lead sulfite, metasulfite, basic thiosulfate and hydroxide at high pH are associated with secondary reactions. A new compound "xanthogen thiosulfate" is postulated. Part 11. Adsorption of ethyl xanthate on galena has been studied quantitatively and thennochemi-cally. It is shown that an ion-exchange mechanism governs the adsorption process and that the heat of adsorption of xanthate on galena is equivalent to the heat of reaction of ethyl xanthate with bulk lead salts. It is concluded that the entropy content of the surface "compound" on galena is different from that of a corresponding bulk lead salt. Alkali depression is in part shown to be due to the instability of the xanthate-galena system at high pH and to the formation of basic lead salts. Sulfate and carbonate ions are shown to have a stabilizing effect on the xanthate-galena system. PARTI. THERMOCHEMISTRY OF ETHYL XANTHATE AND OF ITS REACTION WITH LEAD SALTS In the past little attention has been paid to the chemistry of lead xanthate. It is known that xan-thates form slightly soluble compounds with lead and that suspensions of lead xanthates in alkaline solution decompose rather readily.' The solubility of lead ethyl xanthate is of the order of 2.6 x 10-6 moles per 1. At increasing pH the xanthate concentration of a saturated solution contains more xanthate. Thus at pH 11 this xanthate content is about 100-fold larger than at pH 7.1 Xanthates are known to be consumed when added to a suspension of slightly soluble lead salts such as lead sulfate and lead carbonate. It is unknown to what extent this xanthate consumption is due to a simple chemical reaction because, frequently, observations are made which reveal secondary reaction products in such reactions. Thermochemical study of the reaction between xanthate and lead salts offers a means to clarify the significance of these reactions as the enthalpy changes can be accurately predicted from heat of formation of lead salts in pure solution reactions. In the present work the heats of formation of lead ethyl xanthate from potassium ethyl xanthate and lead salts are determined and some thermochemical aspects of xanthate in solution are studied. The results of these investigations are presented in Part I. In Part II the heat of adsorption of ethyl xanthate on galena surfaces is presented. All enthalpy changes were measured directly in a microcalorimeter. Calorimeter: The calorimeter used for measuring enthalpy changes was similar to that used by Redinha and Kitchener2 which was based on a description by Derbyshire and Marshall.3 Other useful references4,5 are listed. A sketch of the calorimeter

Jan 1, 1967

By J. M. Tobin, L. H. Cadoff, L. M. Adelsberg

The reaction between liquid zirconium and graphite at temperatures above 2000 °C has been investigated. The reaction products were found to be carbon-saturated zirconium metal and ZrC which formed between the graphite and the metal. Parabolic growth behavior was observed for the ZrC Phase at all temperatures of this investigation. The parabolic growth constant at temperatures between 2000° and 2860°C was measured to be 1.83 exp 84,300/RT) sq cm per sec. The reaclion mechanism was proposed to be the rapid carbon saturation of the liquid metal and the formation of ZrC at the metal-carbide interface with diffusion of carbon through the ZrC, the "rate - determining step" of the reaction. The concentration-independent diffusion coefficient of carbon in ZrC, (DZrC), was expressed as 0.95 exp? 78,700/RT) sq cm per sec. This value mas calculated using the temperature-invariant ZrC phase fields proposed in the literature. The [ZrQiq)] — [ZYQiq) + ZrC] phase boundary over the temperature range 2000° to 2800°C was determined and the ZrC + C eutectic temperature was found to be 2890° ± 50°C. ThE Group IV and VB transition-metal refractory carbides are of interest because of their high melting points, high temperature strength properties, and relative inertness in certain corrosive environments. The present-day understanding of these materials, however, is limited by the general unavailability of accurate and reliable physical and chemical property data. This is due primarily to the difficulties associated with the preparation of suitable, high-density, high-purity carbide samples, and the achievement and control of uniform high-temperature environments. Accurate measurement of temperature is also an important factor limiting the reliability of reported data. The Zr-C reaction was selected for investigation because of the high melting point (>34000C) and favorable nuclear properties of the reaction product, ZrC. The direct reaction method afforded an opportunity to obtain kinetic data on the fully dense carbide. In this paper, layer-growth techniques were used to estimate the diffusivity of carbon in ZrC and to investigate the phase equilibria in the Zr-C system at temperatures above 2000°C. EXPERIMENTAL PROCEDURES AND DATA Crystal bar zirconium (99.9 pct Zr), purchased from the Nuclear Materials and Engineering Corp., and ZTA graphite (99.9+ pct) were used in this study. The analyses of the materials are listed in Table I. A schematic of the high-temperature carburization apparatus is shown in Fig. 1. The sample was a zirconium metal charge in a 1/2 -in.-ID graphite crucible which was capped with a tightly fitting graphite stern. The crucible and stem were designed to closely approximate black-body conditions. The graphite crucible was packed in lampblack (outgassed 1 hr at 2100°C) which provided insulation and thermal stability to the system. The inert atmosphere was maintained by a constant flow of high-purity argon or helium gas. The nozzle-diffuser section on the top flange was sufficient to prevent back-diffusion of air into the system. Chemical analysis of the carburized samples revealed oxygen and nitrogen concentrations of less than 44 and 20 ppm, respectively. The sample was heated by induction with a Westing-house 5 kw-450 kc power source. Temperature was measured with a Milletron two-color pyrometer which was sighted into the crucible by reflection from an overhead front surface mirror. Optical losses due to glass absorption and light reflection at air-glass interfaces were minimized by the employment of the dynamic-gas seal. It was found that no correction was required for the front surface reflector. The pyrometer was calibrated periodically against a U.S. Bureau of Standards tungsten ribbon secondary standard. Temperatures inside the crucible were also calibrated against the Zr-ZrC eutectic (1850°C)1 and the Nb-Nb2C eutectic (2335°C)2,3 temperatures and agreed to within ±10°C of these values. The temperature was controlled by manually adjusting the power input; variations of

Jan 1, 1967

By K. H. Kilgren

At high formation pressures the distillate produced from a gas-condensate reservoir may be black in color. In this event the dense gas phase existing above the dew point is correspondingly dark. Volumetric phase data and an analysis of a reservoir fluid exhibiting these characteristics, together with a description of the visual equilibrium cell in which these observations were made, are presented in this paper. INTRODUCTION Previously the author, like many others in the oil and gas industry perhaps, tacitly assumed that the expressions black or dark oil system, crude oil system and bubble-point system were synonymous. Crude oil reservoir fluids are bubble-point systems and yield a black or dark stock-tank oil of relatively low API gravity. Conversely, a clear or amber colored trap distillate of high API gravity is assumed indicative of a dew point system or a gas-condensate reservoir fluid. This broad classification appears satisfactory for shallow reservoirs, but as the following study demonstrates, may be misleading when applied to deep reservoirs. Theoretically, there is no reason to exclude the possibility of producing a dark, low-gravity distillate from a gas-condensate reservoir. At sufficiently high values of pressure and temperature, heavy, dark-colored hydrocarbons may exist in the vapor state of a multi-component system. If enough dark-colored components are present in the reservoir vapor phase, the resulting condensate will be dark. The reservoir fluid investigated in the present study supports this contention. Stock-tank production was black in color and measured 29" APT gravity. From outward appearances, the liquid closely resembled a medium gravity crude oil. Experimental measurements proved the reservoir fluid was in reality a gas-condensate system. Volumetric phase data for this high-pressure system and a description of the visual cell in which the study was conducted successfully are presented in this paper. THEORY Phase behavior of a reservoir fluid can be predicted accurately with reference to a pressure-temperature phase diagram. If the reservoir temperature is lower than the critical temperature of the hydrocarbon fluid in place, bubble-point behavior will be observed. If the reservoir temperature lies between the critical and cricondentherm temperature, dew point behavior and retrograde condensation will occur. For reservoir temperatures above the cri- condentherm, only a single gas phase can exist in the reservoir regardless of pressure. Providing the composition of the reservoir fluid were known, it would be possible to predict the critical temperature and estimate the phase behavior from equilibrium relationships. However, the usual practice is to obtain a sample of reservoir fluid, subject it to varying pressures at the reservoir temperature and observe the phase behavior experimentally. The latter method was used to obtain the data reported here. WELL AND TRAPPING INFORMATION A summary of pertinent data for the well from which the reservoir fluid was sampled is presented in Table 1. This well is located offshore Louisiana. Except for the pressure which substantially exceeds hydrostatic pressure, the information does not appear unusual. Prior to the sampling program, the well was produced for 22 hours at a stock tank oil rate of 139 B/D. Average trapping conditions and gauging data for the six-hour test period that followed are summarized in Table 2. Samples of the first-stage trap gas and liquid were obtained during the latter portion of the test period. Ambient temperature remained 5 to 10F below trap temperature and presented no problem for sampling. Surface wind and moderate foaming of stock-tank oil presented some difficulty in obtaining accurate stock-tank gauges. SAMPLE ANALYSIS Compositions of the gas and liquid samples are shown in Table 3. The trap gas was analyzed by isothermal chromatography which revealed only a trace of heptane in the stream. The trap liquid was initially analyzed by low-temperature fractional distillation, yielding a bottom product of heptane and heavier components. Specific gravity of this fraction was measured and the mol weight was determined by freezing point depression. The hexane and lighter overhead gas collected during distillation was

Jan 1, 1967

By Robert E. Barieau

General expressions for evaluating practically all the thermodynamic properties of a fluid from a single equation of state are derived. Most of the formulas are expressed in terms of the compressibility factor, with this factor being an explicit function of the temperature and the molal density. Similar expressions are given using reduced variables.

Jan 1, 1967

By Manuel Gomez

This, report presents correlative data on ash and sulfur forms for Pittsburgh seam coal from Greene County, Pa. Prediction equations were developed for sulfur form distributions and washability characteristics. The equations developed were evaluated with an independent set of exploration core samples. It was demonstrated-that both sulfur distributions and washability characteristic's can be predicted from exploration core data ahead of mining. This information can improve the efficiency of selective mining techniques for the production of a uniform metallurgical coal product.

Jan 1, 1967

By D. R. Corson

The Bureau of Mines instrumented an operating stope in a deep vein mine to determine the amount of wall closure and the magnitude of loads imposed on a backfilled stope. Hydraulic pressure cells used to monitor pressures in the fill) with bolt closure points to measure vein-wall movement and the procedure for their installation) are described) and the results of the laboratory calibration analysis of the reliability of these cells are given. An attempt to monitor density and moisture changes in the backfill with a nuclear density-moisture device was only partly successful) owing to either deformation of access tubing or relative displacements of the vertical vein walls relative to the emplaced tubes. Data from the instrumentation indicate vein-wall closure in excess of 20 inches and pressures within the fill approaching 600 psi. Analysis) incorporating field data with results of laboratory tests of the compressibility of timber and tests defining the constrained moduli of the fill) points out the limited restraint to vein closure offered by timber sets. Ground movement induced by mining activity could be more effectively con-trolled by the use of densely compacted backfill.

Jan 1, 1967

By S. H. Gelles

Samples of poly crystalline zinc of 99.999+ pct purity were observed metallographically after having been exposed to hydrostatic pressures of up to 27 kbars. The deforrnation produced by this treatment was analyzed using X-ray and metallogaphic techniques. Basal-plane slip occurred universally in all grains exumined at the lowest pressure used (8 kbars). At pressures of >23 kbars, {1012} twin nucleation and growth were noted as well as slip. Formation of bend planes, complex kink bands, and recrystallization at the gain boundaries were also observed in this pressure range. These observations are discussed in reference to the expected deformation behavior of zinc under high hydrostatic pressure. It has been shown over the past few years1'3 that anisotropic, poly crystalline metals can be made to deform plastically by the application of a hydrostatic pressure. The effect is greater 1) the larger the anisotropy of linear compressibility and 2) the smaller the stress level needed to produce plastic deformation. Zinc having both very anisotropic linear compressibilities and a very low critical resolved shear stress (CRSS) for basal-plane slip has been shown to exhibit large amounts of plastic deformation when subjected to a hydrostatic pressure.2,3 At pressures up to 15 kbars, grain boundary migration and slip on one set of glide planes have been reported.' After exposing samples to 20 kbars pressure, grain boundary migration, single slip, multiple slip, and twinning have been noted.' The identification of the deformation modes operative under these conditions has not been reported. It was the purpose of this research to identify the deformation modes induced in poly crystal line zinc by the action of a hydrostatic stress and to study the strain accommodation at grain boundaries. Hydrostatic pressure could affect the operational modes of deformation by altering the Peierls-Nabarro stress. This may be roughly approximated by the relationship4

Jan 1, 1967

By L. C. George

The Bureau of Mines measured vapor pressures of selected mixtures in the binary system SnCla-ZnC12 by the static pressure method. Equations expressing the vapor pressure) and the heat and free energy of vaporization) as functions of temperature were developed by numerical analysis based on the sigma-plot method. It was found that the vapor pressure of any SnCl2-ZnCl2 mixture) at any temperature within the range of this investigation) could be accurately calculated from the derived values for the heat and free energy of vaporization for the mixture, with a probable error of 0.01 cm Hg or less.

Jan 1, 1967

An extensive series of tests was carried out on a ball mill-rake classifier circuit in the New Broken Hill Consolidated Ltd. concentrator. The data were used to develop a mathematical model of the operation of a rake classifier and this model has been used in the simulation of the performance of a ball mill-rake classifier circuit on a digital computer. As a result of this simulation it has been possible to develop a technique for the optimization and control of a circuit which includes these units.

Jan 1, 1967

By Graham A. Brown

Activities in offshore mineral exploration In Australia are increasing almost daily, at such a rate that this report will rapidly become out of date. At the time of writing, February 1967, there were no commercial discoveries of offshore minerals reported in Australia, although there has been definite encouragement in many fields. While this initial encouragement has not revealed any commercial mineral deposits offshore hopes are running high in Australia for success in 1967. Why should mineral deposits be expected offshore in Australia in the first place? The reasons are many. The minerals to be discovered also are many. The reasons are based on the history of alluvial and beach mining activities in Australia's past and at the present time, and on the physical environment of the vast Continental Shelf which surrounds the continent. A brief examination of the two primary features which are necessary before offshore mineral exploration can be contemplated should be, undertaken. Two favourable environments are necessary; firstly a Continental- Shelf to form a physical environment for the accumulation of the mineral deposits, and secondly a favourable political-legal environment to give the exploration companies adequate protection during exploration, and suitable long term arrangements for the exploitation of the deposits after discoveries have been made. Australia is well endowed with both of these.

Jan 1, 1967

By K. E. Brown, J. P. Brill, A. R. Hagedorn, T. C. Doerr

A recent correlation for multiphase vertical flow by Hagedorn and Brown1,7 has been used to examine the effect of numerous variables such as pipe size, gas-liquid ratio, liquid flow rate, liquid viscosity, liquid surface tension, oil API gravity, water cut, etc., on flowing pressure gradients. Most previous correlations were derived by using a form of the general energy equation which assumed negligible changes in kinetic energy. Under certain flow conditions this can lead to serious errors in predicting pressure traverses. Examples of traverses calculated both with and without the kinetic energy term are included here. The Chew and Connully correlation for calculating changes in viscosity with changing pressure and temperature has been extended so that the effect of a changing viscosity with depth on pressure gradients can also be predicted. Examples illustrating the effect of tubing size show the importance of this correlation in determining pipe sizes for initial well completions. Limitations on production rates in small pipe sizes from excessive friction losses can be predicted with greater accuracy. The combined use of a vertical-flow correlation with a horizontal-flow correlation provides a method for determining the maximum flow rate possible from both flowing and gas-lift wells. Examples are included to illustrate application of the combined use of vertical and horizontal-flow correlations in optimizing production rates and minimizing excessive costs from over injection of gas in gas-lift wells. INTRODUCTION The problems of multiphase vertical and horizontal flow are immediately encountered in any producing well. Fig. 1' shows three stages of production: flow in porous medium, vertical flow and horizontal flow. All three stages affect the production rate from a well. If we are confronted with a particular well and consider only the variables involved in the vertical and horizontal stages of Fig. 1, we should be capable of calculating the flowing bottom-hole pressure necessary to produce a particular flow rate. A change in any of the variables results in a new solution to the problem. Recent approaches in developing horizontal and vertical-flow correlations have improved to the extent that the solution can now be obtained with more confidence than previously. VERTICAL AND HORIZONTAL FLOW CORRELATIONS Since Poettmann and Carpenter's' original work in multiphase vertical flow, there have been many additional vertical-flow correlations developed which have greatly improved the accuracy of pressure-loss calculations. These

Jan 1, 1967

By R. Al-Hussainy, P. B. Crawford, H. J. Ramey

The effect of variations of pressure-dependent viscosity and gas law deviation factor on the flow of real gases through porous media has been considered. A rigorous gas flow equation was developed which is a second order, non-linear partial differential equation with variable coeficients. This equation was reduced by a change of variable to a form similar to the diffusivity equation, but with potential-dependent diffusivity. The change of variable can be used as a new pseudo-pressure for gas flow which replaces pressure or pressure-squared as currently applied to gas flow. Substitution of the real gas pseudo-pressure has a nrtmber of important consequences. First, second degree pressure gradient terms which have commonly been neglected under the assumption that the pressure gradient is small everywhere in the flow system, are rigorously handled. Omission of second degree terms leads to verious errors in estimated pressure distributions for tight formations. Second, flow equations in terms of the real gas pseudo-pressure do not contain viscosity or gas law deviation factors, and thus avoid the need for selection of an average pressure to evaluate physical properties. Third, the real gas pseudo-pressure can be determined numerically in term of pseudo-reduced pressures and temperatures from existing physical property correlations to provide generally useful information. The real gas pseudo-pressure was determined by numerical integration and is presented in both tabular and graphical form in this paper. Finally, production of real gas can be correlated in terms of the real gas pseudo-pressure and shown to be similar to liquid flow as described by diffusivity equation solutions. Applications of the real gas pseudo-pressnre to radial flow systems under transient, steady-state or approximate pseudo-steady-state injection or production have been considered. Superposition of the linearized real gas flow solutions to generate variable rate performance was investigated and found satisfactory. This provides justification for pressure build-up testing. It is believed that the concept of the real gas pseudo-pressure will lead to improved interpretation of results of current gas well testing procedures, both steady and unsteady-state in nature, and improved forecasting of gas production. INTRODUCTION In recent years a considerable effort has been directed to the theory of isothermal flow of gases through porous media. The present state of knowledge is far from being fully developed. The difficulty lies in the non-linearity of partial differential equations which describe both real and ideal gas flow. Solutions which are available are approximate analytical solutions, graphical solutions, analogue solutions and numerical solutions. The earliest attempt to solve this problem involved the method of successions of steady states proposed by Muskat.' Approximate analytical solutions' were obtained by linearizing the flow equation for ideal gas to yield a diffusivity-type equation. Such solutions, though widely used and easy to apply to engineering problems, are of limited value bemuse of idealized assumptions and restrictions imposed upon the flow equation. The validity of linearized equations and the conditions under which their solutions apply have not been fully discussed in the literature. Approximate solutions are those of Heatherington et al.. MacRobertsl and Janicek and Katz.' A graphical solution of the linearized equation was given by Cornell and Katz. Also, by using the mean value of the time derivative in the flow equation, Rowan and Clegg' gave several simple approximate solutions. All the solutions were obtained assuming small pressure gradients and constant gas properties. Variation of gas properties with pressure has been neglected because of analytic difficulties. even in approximate analytic solutions. Green and Wilts8 used an electrical network for simulating one-dimensional flow of an ideal gas. Numerical methods using finite difference equations and digital computing techniques have been used extensively for solving both ideal and real gas equations. Aronofsky and Jenkins"I " and Bruce et al.11 gave numerical solutions for linear and radial gas flow. Douglas et al." gave a solution for a square drainage area. Aronofsky 13 included the effect of slippage on ideal gas flow. The most important contribution to the theory of flow of ideal gases through porous media was the conclusion reached by Aronofsky and Jenkins" that solutions for the liquid flow case'" could be used to generate approximate solutions for constant rate production of ideal gases. An equation describing the flow of real gases has been solved for special cases by a number of investigators using numerical methods. Aronofsky and Ferris 10 onsidered linear flow, while Aronofsky and Porter 17 considered radial gas flow. Gas properties were permitted to vary as linear functions of pressure. Recently, CarteP 18 proposed an empirical correlation by which gas well behavior can be estimated from solutions of the diffusivity equation using instantaneour values of pressure-dependent gas

Jan 1, 1967

By M. W. Dumais, E. P. Abrahamson

In a paper by Abrahamson and Alexander concerning a series of correlations between electronic structure and property changes, it was hypothesized that each solute atom in a dilute solution had a characteristic volume of solvent atoms over which some form of electronic interaction occurred. From this description it is possible to picture the solute atoms as occurring in an ordered array for the most efficient arrangement. A recent review article2 has shown that some form of anomaly exists for a whole series of properties when dilute additions of tungsten are made to iron, of. Fig. 1. Any mechanism to fit one property must also be amenable to mechanisms for the other properties. The possibility of some structural change in this region appears to offer the best hope. The system chosen for investigation was the iron tungsten system. Zone-refined iron with zone-leveled tungsten additions were supplied by Materials Research Corp. as 3/8-in.-diam bars. Transmission electron microscopy was used to study the structure. One-quarter inch specimens of each alloy were cold-rolled to 10-mil sheets, cleaned, punched to electron-microscope specimen-holder size, and annealed in vacuum for 2 hr at 800°C and 2 hr at 700°C followed by a furnace cool. The specimens were attached to a platinum wire and the specimen edge and wire were painted prior to thinning in a solution of 10 pct perchloric acid in glacial acetic acid. It was believed that if ordering were present due to electronic interactions the polishing procedure chosen would provide a simultaneous combination of chemical attack and electropolishing to exhibit the ordered structure. The chemical attack would be expected to penetrate those areas equidistant from the tungsten atoms, while the electropolishing would serve to "plane off" the volumes where the chemical attack had taken place. If one of the ordered tungsten planes were parallel to the specimen face at the edge of the thinned hole, a plate or micalike structure would be expected. A typical result of this polishing is shown in Fig. 2. Here a series of plates can be seen lying one upon the other. In several other specimens the plates parallel to the electron beam have been observed, behaving like slices of bread in a loaf. These edge views coupled with moire patterns indicate that the minimum plate thickness is 37 to 42A. This is equivalent to a concentration of 455 at. ppm of W if a simple cubic superlat-tice exists, or one tungsten atom every twelve iron atoms on the ordered plane. It was further noted that the base iron exhibited no signs of platelike structure. As the concentrations increased above 100 at. ppm W the amount of plate material increased. Among the specimens investigated was that shown

Jan 1, 1967

By W. C. McClain

The amount of vertical subsidence occurring over a longwall operation is a function of the thickness of material removed, the quantity and quality of any fill material, the width of the extraction, and the depth. The relationship between these variables is empirically determined, and subsidence can be predicted using only a few easily established constants which are subject to local conditions, such as the angle of draw. Associated with the vertical subsidence are both tensional and compressional horizontal strains. The component of strain in the direction of face advance is temporary, while the component perpendicular to the direction of working is permanently retained by the ground. It is these horizontal strains and the vertical strain (tilt) which result in damage to surface structures. It is possible to ameliorate the consequences of mining subsidence by utilizing the well-proved techniques described in this paper in the underground operations and on the surface. INTRODUCTION In the past, American mining practice in stratified deposits has been mostly restricted to production by the room-and-pillar system where a sizable percentage of the salable product is left in place as pillars. These pillars are usually regularly spaced and provide a permanent support for the roof of the mine and the surface above. The longwall system employs an advancing face which may be as much as several hundred yards long and some sort of breaking and loading machine which moves back and forth along the length of the face. The roof is supported behind the face only to a distance required to provide working space for the production machine. The supports are then withdrawn and the roof is allowed to cave. The longwall system therefore possesses the various advantages of complete extraction, thus effectively increasing reserves, while at the same time eliminating the necessity and cost of installing artificial supports such as roof bolts and heavy steel girders over large areas. Longwall mining has long been practiced in Europe, where it has undergone an involved development, culminating in the recent perfection of powered-loading machines and automatic self-propelled supports, offering high productivity. With ever-in creasing

Jan 1, 1967