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By J. Szekely, J. W. Evans

A formulation is given for radiant heat loss from the surface of molten steel held in a ladle and numerical solutions are presented for the resultant integrodif-ferential equations. The results are shown on plots of the net rate of heat loss against time, with the geometlry, emissivities, thermal properties of the walls, and Preheat as parameters. It was found that the rate of the vadiant heat loss from the exposed metal surface was comparable to the conductive losses from the Portion of the metal in direct contact with the walls. The radiant heat loss was markedly affected by the geometry and by the thermal properties of the walls the net radiant heat loss from the steel could be drastically reduced by providing a top cover and also by the provision of preheat. The results of this work are thought to be relevant to heat loss calculatious concerned with vacuum degassing and with operatzons in which molten metals are held in ladles. WhEN molten steel is held or transferred in ladles heat losses inevitably occur. The accurate assessment of these heat losses is of importance in process design considerations, as the temperature of the metal may have to meet rigid specifications in certain stages of the processing sequence. As shown in Fig. 1, the principal mechanisms responsible for heat loss are: i) Conduction into the walls and ii) Thermal radation from the top metal surface (possibly augmented by natural convection) The conductive heat loss may be readily calculated as much information is available in the literature on both the general theory1'' and on its particular applications to ladle heat loss calculations. Evaluation of the radiant component of the heat loss is less straight-forward. In two recent papers it has been shown that the presence of a slag layer 2 to 3 in. thick would prevent any significant heat loss for periods up to an hour,5'" however, should bare metal be exposed, constituting the radiant surface, substantial heat losses could occur. This latter case is of considerable practical interest in various degassing operations and in the vacuum processing of certain specialty steels, where the top surface of the metal is not covered by a protective slag layer. Under these conditions a substantial radiant flux is emitted by the top metal surface; part of this flux leaves the system, part of it falls in the ladle walls. The radiant flux incident on the ladle walls is in part absorbed and conducted away, and in part reflected and re radiated. The purpose of the paper is to present a general formulation of the problem, the resultant solution of which should enable computation of the net radiant heat loss from the metal surface. The principal variables, the effect of which will be investigated, include initial metal temperature, geometry, thermal and radiative properties of the wall, and various modes of preheat. FORMULATION Consider a cylindrical enclosure, shown in Fig. 2, with a diameter D, height H, and wall thickness W, the cover at the top of the cylinder having a wall thickness L. If the temperature of the base (representing the top surface of the metal) is kept constant, say, Tb, the problem is to calculate the net rate of heat loss from the base as a function of time, geometry, the initial temperature distribution, and the thermal properties of the system. As customary, the formulation will consist of the mathematical statement of the conservation of thermal energy within the system.

Jan 1, 1970

By Richard A. Dick

Underground blasting in permanently frozen gravel was studied in a 7-by 12-ft drift by running a nonreplicated 2 X 2 X 2 factorial experiment on the effects of type of cut, delay, and explosive on the fragmentation subsystem. Comparisons were made between a V-cut round and a burn-cut round, millisecond delays and half-second delays, and 40 percent special gelatin and 60 percent high-density ammonia dynamite. The number of large blocks in the muck pile) loading time, shuttle car operating time lost because of cleanup needs, length of advance per round, and length of muck pile were recorded and statistically analyzed. None of the blast parameters had a significant effect on the length of advance or length of muck pile, although the half-second delays tended to give a shorter muck pile than millisecond delays. The burn cut required less secondary breakage, less loading and cleanup time, and gave better overall fragmentation than the V-cut. The ammonia dynamite shots required less secondary breakage and less loading time than those using special gelatin. The half-second delays gave better overall fragmentation and required less cleanup time, but the millisecond delays gave a better loading rate. None of the differences between delays and explosives were notably significant.

Jan 1, 1970

By R. J. Watson, A. H. Juch

About half a million sucker-rod pumps are installed in oil wells in the U. S. alone. In Venezuela, too, the system is widely used; some 5,000, or 90 percent, of Cia. Shell de Venezuela's wells produce a total of 400,000 BOPD by this method. Most of the crude pumped is viscous, gassy and contains relatively small amounts of free water. API gravities vary from 90 to 16O; dead oil viscosities vary from 10 to 10,000 cp at the pump; and GOR's range from 100 to 2,000 cu ft/bbl. Pumps are set at depths ranging from a few hundred to 6,000 ft; the average setting depth is about 2,500 ft. From the literature, it appears that although recent years have seen significant progress toward understanding the rod pumping system as a whole, relatively little attention has been paid to those key items, the sucker-rod pump and the subsurface gas separator or gas anchor. Perhaps because of proration in the U. S., pump manufacturers have seemingly concerned themselves more with the durability of their product, achieved mainly through robust design and metallurgical know-how, than with its working efficiency. In 1963, CSV commenced a major rehabilitation and expansion of its heavy oil fields along the Bolivar Coast. The advent of the more efficient gravel-packed completion and of large-scale thermal recovery (mainly steam soak) operations resulted in well potentials *Now with B. I. P. M., The Hague, The Netherlands. greater than pump capacities. Hence, an urgent need arose to improve over-all pump efficiencies and to attack those special problems related to the production of both the extremely viscous and the hot, steam-laden crudes that formed an increasing proportion of the total stream. There followed a detailed investigation and testing program, carried out in close cooperation with a major pump manufacturer. This culminated in the introduction to the oil industry of a new line of sucker-rod pumps. Early Investigations and Experiments Field Tests Extensive field tests were carried out in three primary Bolivar Coast wells with an in-situ dead oil viscosity ranging from 400 to 6,000 cp. In these installations provision was made to (1) monitor bottom-hole pressures below, in and above the pump by means of pressure transducers, and record casing- and tubing-head pressures continuously; (2) measure accurately the annulus gas, as well as measure the tubing gas and liquid production from the well; (3) take special PVT samples of the well fluid; (4) measure power consumption of the prime mover; and (5) measure the rod loads at the polished rod. A typical test installation is illustrated in Fig. 1. It was established from the pressure transducers that with viscous oils, there is considerable flow resistance across the pump and gas anchor assembly. Pressure surges were observed over each pump cycle,

Jan 1, 1970

By John J. Henn

As part of the U.S. Department of the Interior programs on rutile, authorized by the Office of Emergency Preparedness in June 1967 under provisions of the Defense Production Act, the Bureau of Mines reviewed available literature on major proposed processes for producing rutile substitutes. The processes are grouped according to the major processing step, and important operating features are described. Sixty-one references are cited.

Jan 1, 1970

By J. Douglas, W. T. Ford, G. E. Henderson, I. F. Roebuck

An implicit numerical method is presented for simulating the differential and algebraic relations governing one-dimensional three-phase flow in porous media. The method is based upon compositional representation of the hydrocarbon system. Variable physical properties and water-oil capillary forces are included in the formulation; however, the effect of gravity is ignored. The effects of changing composition and mass transfer are considered through the use of known phase behavior concepts and correlations. The differential and algebraic equations and the numeric approximations to these equations are presented, and the computing algorithm is discussed in detail. This method is used to simulate a single-phase, two hydrocarbon-component gas displacement laboratory experiment. The method is also applied in simulating a solution gas drive and a gas injection problem using a reservoir oil represented as a nine-component mixture. For comparative purposes, the latter two problems also are examined with a one-dimensional volumetric model. The results of the simulation of the laboratory experiment demonstrate the relevance of this method to problems wherein the effects of mass transfer significantly enter the displacement process. The comparison of the results of the volumetric and compositional methods applied to a reservoir system illustrates not only the advantages and benefits derived from examining the hydrocarbon system composition, but also the necessity of this approach in application to a general reservoir problem. INTRODUCTION The advent of large memory, high-speed digital computers enabled reservoir engineers and mathematicians to pool their knowledge in the development of sophisticated techniques for the prediction of oil and gas reservoir performance. These techniques have progressed from volumetric and trend analysis calculations to the development of "mathematical models", or reservoir simulators. These latter models, in general, utilize finite difference approximations to the rather complex partial differential equations that mathematically describe the physics and thermodynamics of fluid flow in porous media. Many forms of this "model" type are available today, and much of the recent literature has been devoted to either improving known methods or developing new techniques for use in these prediction methods. The more advanced techniques in use at this time consist of the solution of differential and algebraic relations that describe a reservoir geometry in one, two or three dimensions and that incorporate reservoir hydrocarbon and water fluid systems that obey specified physical laws, having properties that might easily be measured in the laboratory. This type of model utilizes formation volume factors and other volumetric data, expressed directly as functions of pressure, to represent the reservoir fluid system. Experience gained with this type of simulator, commonly known as a "beta-factor model", has indicated that the approach has many outstanding defects, most of them due to the assumption that those properties measured in the laboratory completely describe the behavior of the fluid system throughout the life of the project under study. The effects of varying hydrocarbon composition and mass transfer between the phases of this hydrocarbon system must, by definition, be ignored. These defects, which may often be ignored in

Jan 1, 1970

By M. B. Bransford

A calculation procedure was evolved by the Bureau of Mines for determining the heat-transfer characteristics of dilute gas-solid mixtures in an externally heated tube. The procedure accounts for differences in gas and particle velocities and covers a range of particle sizes. Heat transfer coefficients obtained by the calculation procedure are compared with values reported in the literature.

Jan 1, 1970

By C. S. Samis, J. C. Mitchell

Sodion activity data have been obtained for the Na-A1 system for sodium concentrations in aluminum between NN, = 25 . 10-and 300 x 10'. This concentration intert-a2 encompasses those sodium concentrations nor1)zally encountered in aluminum reduction cell operation. The sodium activity data were measured by a two-phase equilibration of sodium between a lead and an aluminam rich phase. The Na-Pb system was emplojed as a reference for the determination of the actiz7itj 0.f sodium. The activity of sodiin in aluminuwz exhibits large positi2.e deviations frorn ideality and a strong dependence, on concentration below NN, = 100 x 1K6. The inteated data indicate that the activity of aluminium is equal to its mole fraction over the range of miscibility of the Na-A1 sgstem. The data on the Na-A1 binary have been combined with experimental data on the cryolite-A1 system at 1025°C to obtain the activities of Na F and AlF, in liquid cryolite oz2er the cornposition 1-ange encountered in aluminum cell operation. The results are in agreement with activities calculated from the NaF-AlF, phase diagram. ALUMINUM is produced commercially by the electrolytic reduction of aluminum oxide dissolved in molten cryolite. There is considerable controversy over the actual mechanism of the discharge processes, but sodium potentials in the systems appear to play an important role in the reduction mechanism. The metal-salt reaction involving NaF and aluminum to produce A1F3 and sodium is responsible for the presence of sodium in the aluminum metal phase. Additional sodium may be produced from the simultaneous deposition of sodium and aluminum at the cathode as a result of a cathodic overvoltage. runert' has suggested that sodium gas at atmospheric pressure would be the result of reaction between cryolite and aluminum at 1000°C. Subsequent investigations have shown that production of sodium at atmospheric pressure does not occur. These later investigations can be conveniently separated into two categories. The first involves sodium, aluminum, and cryolite, in which the sodium activity was measured. The second includes a lead phase for sodium activity measurement. Jander and errmann,' studied the reaction: at 1090°C in alumina crucibles under an atmosphere of dry, oxygen-free nitrogen. The equilibrium constant for the reaction was expressed in terms of concentration. Their results in Fig. 1 show an increase in sodium content of the aluminum with increasing NaF/A1F3 weight ratio. Pearson and waddington3 performed similar experiments at 1000°C. Their results are included in Fig. 1. Dewing and ollinshead have measured the sodium content of aluminum as a function of the NF/AF, ratio at 1025"C, Fig. 1, and ewin' measured the sodium content of the aluminum in a system involving the solid reactants NaF, cryolite, and liquid aluminum. This reaction is different from those discussed above. Two solid phases, NaF and Na3A1F6, and a liquid aluminum phase were present. The sodium concentration in the aluminum was determined by the temperature. Dewing's measurements covered the temperature range 679" to 896°C. Omo, Matsushima, and 1t02" investigated the equilibrium 6NaF ential thermal analysis. Stokes and Frank6 determined sodium activities by

Jan 1, 1970

By J. A. Brierley, Roshan B. Bhappu, D. H. Reynolds, P. H. Johnson

Although the economic importance of recovering copper by leaching of mine work dumps from open-pit operations has been realized for some time, serious attempts to understand and to improve such operations through scientifi research has been made only in recent years. This progress report covers the results of chemical, physical, and biological studies pertaining to the dump-leaching process and discusses salient features and parameters that may be helpful in improving such operations. The dump leaching of low-grade copper ores, as an integral part of the open-pit mining operations in the Southwest, has been practiced for the last 50 years and is increasing in importance as one of the major sources of copper. The recent acceleration in dump leaching can be attributed to: (1) the greater tonnages of low-grade ores mined and dumped at newer mines as well as resulting from increased stripping ratios at the older mines, (2) the relatively small investment required for dump leaching facilities per pound of copper recovered contrasted with expansion of milling facilities to recover equal amounts of the metal by raising tonnage throughout, (3) low labor requirements needed for leaching, and (4) the simple and continuous nature of the process needing little close supervision of trained operators. In the past, the mining companies have not worried about efficiency in dump leaching but have been satisfied with whatever metal recoveries could be made without much effort. However, because of the huge amounts of metal accumulating in the low-grade waste dumps, compared to the relatively small amount recovered annually, an operator today cannot leave dump leaching to chance. What appears to be a simple, empirical process is actually a very complex one involving a large number of critical factors that encompass Several Scientific disciplines, such as physics, chemistry, geology, biology, and hydrology. It is imperative that

Jan 1, 1970

By R. G. Bentsen, D. A. T. Donohue

The cyclic steam injection process has become the most widely applied and most successful thermal recovery technique in use today.1-4 Normally, steam stimulation is repeated several times during the life of a project. The problem is to select the optimum number and size of steam treatments so that the profits realized over the entire life of the project are maximum. Obviously, operating costs rise directly with the frequency and amount of steam injection. Operating efficiency, on the other hand, can be adversely affected if the amount and frequency of stimulation are insufficient. Thus arises a multistage decision problem; that is, a decision must be made at each sub-period (day, for example), as to whether steam should be injected, and, if so, how much. It is desirable that these decisions be made in such a way as to secure maximum net profit before taxes. This can be achieved by dynamic programming. To use dynamic programming, we must be able to predict not only the production rate-time curve resulting from a given stimulation, but also how changes in stimulation policy will affect this curve. In this study, the effect of steam injection on well performance is estimated on the basis of a simple model that takes into account both steady-state and transient flow. Oil production rate is calculated for both types of flow, and the larger of the two values is used. This allows the calculation to change to radial steady-state flow at such time as this mechanism becomes more effective than the transient mechanism. We propose to show how dynamic programming can be used to optimize the steam soak process with respect to net profit. For this, a mathematical representation of the steam soak technique is necessary. A further objective, therefore, is the formulation of a mathematical model capable of realistically simulating the physical process. Oil Production Response Model The advantage of using a mathematical model is its generality and ease of manipulation. However, the model must be an accurate representation of the physical process, for a solution derived from a model can be no better than the model itself. The question now arises as to how well the model should be expected to simulate reality. In general, the simplest model should be tried first, for additional accuracy is apt to require additional cost and time. Also, the search for a high degree of accuracy may yield only greater complexity and difficulty without yielding significantly better results. With this in mind, we kept our model as simple as possible, yet generally representative of the actual physical process. The number of state variables is limited to three, and stochastic variations in the parameters are ignored. As a consequence, use of this model should be restricted to cases in which the underlying assumptions are not severely violated. In

Jan 1, 1970

By Robert E. Wood

The temperature dependency of the low-density viscosity coefficients, ?°T, of helium and of nitrogen, 100° to 1,000° K, is correlated with empirical equations, and the temperature and composition dependencies of the low-density viscosity coefficients, ?°T, of helium-nitrogen mixtures are correlated with the Chapman-Enskog expressions by using the Lennard-Jones (6:12) potential function. The residual viscosity, ?T,P - ?°T (the difference between the viscosity of a compressed gas and the dilute gas at a given temperature), was found to be a function of the thermal pressure coefficient, (?P/?T)V, and two parameters, a and 1, which are characteristic of gas composition. The equation ?T, P = ?°T + a [(?P/?T)V]ß represented 1,340 higher pressure experimental viscosity values with a mean absolute deviation of 0.86 percent, and this equation was used to compute viscosities of the gaseous helium-nitrogen system for a range of temperatures and pressures including those encountered in Bureau of Mines helium purification processes and in a crude-helium conservation gas reservoir. Tabular viscosities for helium, nitrogen, and 13 helium-nitrogen mixtures are presented for 110 temperatures, 133° to 740' K, and 49 pressures in the range 1 to 240 atmospheres. The accuracy of the tabulated viscosities varies because correlation parameters were obtained from experimental data of unequal reliability. It is estimated that uncertainties in the computed viscosity values are ±5 percent for the region 325° to 740° K, ±2 percent for the region 183° to 325° K, and ±5 percent for temperatures below 183° K. The latter uncertainty may rise to y10 percent as critical conditions are approached.

Jan 1, 1970

By Paul Biggs

This Bureau of Mines report provides information on 138 waterflood projects in Wyoming. Injection was in 25 producing zones and 65 fields. Specific data presented include field location, discovery and development, water supply and injection, oil and water production, estimates of oil in place, and oil recoveries by primary and secondary methods. The 138 projects studied will, if successful, recover about 800 million barrels of secondary oil. Almost all of the injection water is from deep water wells.

Jan 1, 1970

An assessment of methods currently available for the accurate determination of low concentrations of platinum in ores and mineral concentrates indicated that prior treatment of the sample by fire assay procedures is necessary. To enable rapid determinations to be carried out, instrumental methods applied to the metallic bead produced from the fire assay treatment have been evaluated, considering maximum flexibility for concentration variations, minimum chemical operations, and adequate sensitivity.Atomic absorption spectrometry proved suitable, giving solution determination limits of 0·4 p.p.m. Pt, 0·1 p.p.m. Pt, or 0·06 p.p.m. Pt under various extraction conditions using aqueous and organic agents. Thesedetermination limits related to 1 assay ton of sample (32·67 g) produced easily readable and accurate readings within the range of platinum contents (0·03-2·0 p.p.m.) of economic interest in deposit evaluation and prospecting. The technique shows promise of also being suitable for determination of palladium and gold.

Jan 1, 1970

By H. D. Jacobs

A process for recovering both iron and manganese from four manganiferous ores of the Cuyuna Range was evaluated. It comprised: (1) Low-temperature gaseous reduction to convert nonmagnetic iron minerals to magnetite and manganic minerals to manganous oxide, (2) acid leaching to extract manganese, and (3) magnetic separation to reclaim iron from the leach residue. Iron recoveries from the magnetic products ranged from 70 percent to 90 percent; manganese recoveries from leach filtrates ranged from 75 percent to 95 percent. Two ores, from the Hillcrest and South Alstead properties, yielded magnetic products considered adequate for use as blast furnace feed. Although good yields of manganese were attained on all ores, appreciable iron accompanied the manganese into solution. Previous work, however, has shown that this iron can be precipitated almost quantitatively under autoclave oxygen pressure with very little loss of manganese.

Jan 1, 1970

By Ted C. Briggs

Twenty-two compressibility runs were made with helium over the temperature range -5° to 80° C and at pressures to 800 atmospheres. A Burnett apparatus was used. Data from the runs were fitted to a fourth degree polynomial equation of state in the pressure and a weighting factor of Pr-3/4 was used. All data for a particular isotherm were treated simultaneously. A temperature function was found to represent the parameters B and C. Compressibility factors determined by this investigation are believed to be accurate to better than 0.05 percent.

Jan 1, 1970

By E. J. Bonet, P. B. Crawford

It is fairly common practice to reinject water into the aquifer near the oil-water interface in water-drive reservoirs. There have been many studies of aquifer behavior without reinjection,l-5 but apparently no analytical studies have been made to indicate performance when injection wells are present in the aquifer. The diffusivity equation may be used to describe the pressure behavior in an aquifer. When sources are present it can be written as A general solution of Eq. 1 may be obtained as the sum of two solutions. One is a general solution of the homogeneous equation, obtained by dropping the source term in Eq. 1 and still satisfying the required boundary conditions. Another is a general solution of Eq. 1 satisfying homogeneous boundary conditions.1° The first solution, which corresponds to the aquifer without reinjection, has been given quantitative and qualitative treatment in the literature.l-5,8,9 The latter solution will be treated here. Solutions with variable injection rates are obtained by superimposing solutions with constant rates, so we have considered only the latter. Five cases have been treated here: 1. A linear aquifer of finite width and extent. Water is injected into the aquifer at point xo, yo at constant rate. The pressure along the line x = 0 is maintained at zero pressure. (See Fig. 1.) Equations showing the pressure distribution, rates, velocity and cumulative influx have been developed. Certain numerical results are shown. 2. A linear aquifer of finite width and extent. Water is injected into the aquifer at point xo, yo at constant rate. The rate of production along the oil-water water contact is maintained constant. Equations showing the pressure distribution inside the aquifer are presented. 3. A linear aquifer of finite width and extent. Constant pressures are maintained at opposite ends of the aquifer. Water is injected at constant rates at point xo, yo. Equations showing the pressure distribution are shown. 4. A linear aquifer of finite width and infinite extent. The pressure is maintained constant at the oil-water contact. Water is injected at a constant rate at point xo, YO. 5. A linear aquifer of finite width and finite extent. The pressure at the oil-water contact is maintained constant. Water is injected at constant rate per unit length along a line x,. The Linear Aquifer The linear closed aquifer, performing at constant terminal pressure was selected as the first case to be analyzed. The development of the equations is based on uniform injection per unit of thickness, and gravity effects are neglected. In practical application this condition is probably most closely achieved when the

Jan 1, 1970

By N. N. Moebs

The Bureau of Mines air-sealed a 77-acre) above-drainage coal mine to evaluate sealing as a means of reducing the acid and metallic salt contents in drainage from abandoned mines. An approximate reduction in acidity of 150 ppm (equivalent to 193 pounds per day) and in iron of 98 ppm were directly attributed to sealing. The topographical, hydrological, and other factors involved in air-sealing are discussed, and the construction used to seal the mine is described.

Jan 1, 1970

By L. T. Larson

The spectral reflectivity of zirconium in light of 441 to 668 nanometers (nm) wavelengths and air immersion has been determined. Bireflectance and apparent-angle -of-rotation measurements show zirconium to be optically isotropic when examined in light of approximately 484 nm wavelength. There is a direct relationship between bireflectance and the tilt of the basal pole of zirconium from the surface normal. This relationship allows the determination of the spatial orientation of the basal pole of an individual single crystal within a coarse-grained poly crystalline section to within± 2 to 3 deg for angles of basal pole tilt from 0 to 90 deg. In recent years considerable attention has been given to the quantitative determination of optical properties of opaque minerals by use of vertically incident, plane-polarized light. In particular, Cameron' and Cameron et a1.2 have developed criteria for the identification of a large number of anisotropic ore minerals based upon measurement of the apparent angle of rotation and the ellipticity or phase difference of the reflected light. It was shown by Larson and Pickle-simer3 that apparent-angle-of-rotation measurements may also be used to determine crystallographic orientations of grains of noncubic metals. In particular, it was shown that the basa.1 pole orientation in space of zirconium grains can be determined to ±3 deg for those grains with basal pole tilts of 10 to 90 deg from the plane of the section. Another, even more widely studied, optical property is reflectivity. cameron4 has commented upon measurement of the reflectance of plane-polarized, vertically incident light and Bowie and Taylor5 have made such measurements an integral part of their system of ore-mineral identification. Leow6 has reported on the spectral reflectivity of molybdenite and has used reflectivity values to calculate refractive indices and absorption coefficients. Cameron7 has made use of reflectivity values to ascertain aniso-tropic ore mineral symmetry and Piller and v. Gehlen8 have evaluated sources and importance of errors in reflectivity measurements as applied to calculation of optical constants. cambon9 has shown that reflectivity measurements using vertically incident, plane-polarized light are useful in the investigation of metals and in the identification of phases present in alloys. Bronson10 has made preliminary measurements on the optical anisotropy of beryIlium and Mott and Haines11 have published qualitative data on the intensity of light reflected from sections of bismuth, tin, and aluminum when these metals are microscopically examined under crossed polarizing plates. Koritnig12 has correlated the reflectivity of homogeneous solid solutions with their chemical compositions. From the above work and investigations in progress by this author, it is apparent that accurately determined values for the reflectance of vertically incident, plane-polarized monochromatic light from carefully polished surfaces of noncubic metals can prove useful in identification, composition determinations, and crystallographic orientation applications. Finally, reflectivity values, when measured in two media of differing refraction index and related to standards whose spectral reflectivities in these media are known, can be used to calculate optical constants such as refractive index and absorption coefficient. These constants may prove of use to those concerned with problems of electron band configuration. This paper reports the spectral reflectivity of zirconium measured in light of 441 to 668 nanometers (nm) wavelengths and air immersion. It also gives maximum bireflectance values for a prism section of zirconium in these wavelengths and shows how bire-flectance may be used to determine the crystallographic orientation of zirconium single crystals. Because of the lack of information on the reflectivities of the standards in oil immersion, no attempt is made to calculate the refractive indices or absorption coefficients although it is recognized that such values may be of fundamental importance. METHOD Single crystals of zirconium were cut by electro-discharge machining from a single-crystal rod grown from iodide bar by an electron-beam zone-melting process.13 The crystal sections were mounted in cold-setting epoxy resin and mechanically polished to a plane, uniform, bright surface. Each crystal was then chemically polished in a 26/26/43/5 mixture (by vol) of water, nitric, lactic, and hydrofluoric acids to remove the mechanically damaged and smeared surface layer. Final polish was obtained by electropolishing at 30 v in a bath of methyl alcohol and perchloric acid (98/2 by vol) at -70oc.14 Reflectivity measurements were made using a photometer system designed and developed at Oak Ridge National Laboratory and described in detail by Larson.15 Briefly, the reflectivity measuring system consists of a reflecting microscope; a double-beam, null-balancing photometer array; a mechanically driven microscope stage; and a direct X-Y readout of the reflectivity of the specimen relative to its orientation on the microscope stage. The measuring photometer receives its signal from the specimen through a slotted Wright occular placed on top of the photovisual head of the microscope. The reference photometer receives light through a flexible glass "light pipe" from a mirror in the reflecting system of the microscope. Monochromatic light is attained through use of interference filters (15-nm half-peak width pass bands) placed in front of a stabilized Vickers 12 v, 100 w, tungsten-filament, quartz-iodide lamp.

Jan 1, 1970

By Karl A. Bauer, Cornelis Bezemer

The deposition of calcium carbonate scale on surface and subsurface production equipment creates an operation problem in many oil fields. The formation water in which the carbonate-scale-forming components are initially dissolved becomes supersaturated with calcium carbonate as a result of the drop in pressure during production. The continuous flow of a supersaturated solution through the production equipment results in the growth of a dense layer of calcium-carbonate crystals. For a scale layer to be built up, the supersaturated formation water should contact the walls of the production equipment. The tendency for scale to be deposited, therefore, will be low, if the crude has a low water cut and if the water is finely dispersed in the oil. A scale problem will occur, if at a high water cut part of the water is present as free water. The rate of scale deposition will then be approximately proportional to the rate of free water production. Depending upon where the formation water becomes supersaturated, scale may be deposited in the flow line only, in both flow line and tubing, and in some cases even in the perforations and in the formation near the wellbore. In the South Sumatran fields (Indonesia) the main difficulties encountered due to the deposition of calcium-carbonate scale have been restriction of flow through tubings and flow lines, wear and abrasion of plungers and liners, and stuck plungers or wellhead valves. So far, the only methods of combating the *Presently associated with Brunei Shell Petroleum Co., Ltd.. Seria. scale problem have been routine acidizing and additional well pulling. As for the pumping wells, it was estimated that some 50 percent of the total well-pulling effort was directly attributable to scale deposition. The most promising alternative was to prevent the deposition of calcium carbonate scale by means of chemicals. Inorganic polyphosphates such as sodium hexametaphosphate and trisodium polyphosphate are known to retard the formation of scale by the "threshold action". They are adsorbed on specific faces of the crystal nuclei and thus prevent crystal growth, thereby stabilizing supersaturation. Polyphosphates are effective at very low concentrations ( a few ppm), and far less than stoichiometric quantities are required to keep the scaling ions in solution. Recent investigations on barium sulfate scale1 have confirmed this mechanism. The types of polyphosphate mentioned can be applied as concentrated aqueous solutions either squeezed into the formation, lubricated down the annulus or injected via macaroni string. Several squeeze jobs with polyphosphate solutions have been carried out in the South Sumatran fields, however, with disappointing results. Lubrication down the annulus and injection through a macaroni string were not considered attractive in this area because of the kind of equipment and the degree of supervision these techniques require. Polyphosphates are also available in a granular, glassy form, which, in contrast with the readily soluble types already mentioned, show an extremely low

Jan 1, 1970

By G. S. Cole, G. F. Bolling

A series of Al-Cu alloys has been cast from constant superheat to solidify either with a hot top or with a free liquid/air interface. All the other variables which affect relative fluid motions were kept constant except the imposition of slow rotations m oscillations of the mold. Depending upon the exact circumstances, evi-dence could be found for the nucleation of equiaxed grains from dendrite bits detached from the columnar zone, or from the free surface, or from solid bits induced at pouring; a special experiment showed the solute buildup during ingot solidification and by inference the reality of constitutional supercooling. All methods of grain nucleation are thus supported. When solidification is arranged in a static mold the columnar- to-equiaxed transition occurs by one of these nucleation paths, subject to the natural decay of temperature gradients which promotes nucleation or the survival of nuclei. But when solidification is forced under special fluid flows it may display odd transitions. In one of these the equiaxed zone is synihesized from. dendrite bits detached from the solid/liquid interface. These survive under the concurrent lowering of temperature gradients and eventually cause transition by impeding columnar growth. GRAIN structure control is desired because real experience shows that specific properties are associated with specific cast grain structures. But since control is thus a matter of need and does not require understanding, much of casting remains art. For example, the manipulation of relative fluid motions in simple ingots provides a control of grain structure development,1-4 but theoretical insight is not required in order to broaden its potential applicability. Fortunately, however, once a variable like fluid flow is recognized it can also provide paths toward new insight. New observations using this variable have provided an insight which is curious. All the theories or descriptions of the columnar-to-equiaxed transition (CET) seem to be supported as long as the appropriate experiment is carried out. In order to develop this idea, let us ignore segregation, the chill zone (until a later section of this paper), and the origin and development of the columnar zone.= The details of questioning how equiaxed material forms in a casting may be divided in two. The first part is simply a questioning of the origin for equi-axed grains: are there fresh nuclei from heterogeneous nucleation, or dendrite bits broken off or melted from the columnar zone or elsewhere,6 or other solid bits surviving from the outset of freezing? The second is more complex, a questioning of the CET: does columnar growth slow down and allow the dominance of equiaxed grains, however they are formed, or do equi-axed grains take over and force columnar growth to stop? This "chicken-or-the-egg" second question can be quite useful, especially because it allows us to delineate the ordinary or NATURAL EQUIAXED ZONE and the induced or SYNTHETIC EQUIAXED ZONE. A natural equiaxed zone occurs if solidification proceeds in the absence of disturbances or extraneous forces such as ultrasonics, stirrings, and so forth. Both the CET theory proposed by Winegard and Chal-mers, 7requiring constitutional supercooling, and the CET theory suggested by Chalmers,8 requiring nuclea-tion only on pouring, pertain to the natural equiaxed zone. The best collating evidence to date for both these theories is contained in the work by Biloni and Chal-mers;9,10 the former theory7 is supported by special versions of the unidirectional growth experiment performed by Plaskett and winegardl1 and the latter theory' is supported in detail for the solidification of small ingots. An equiaxed zone can be synthesized when disturbances caused by forced fluid flows2-4 or other artificial means9,10 break off or melt off dendrite tips from an advancing solid/liquid interface,* if (and only if) temperature gradients in the melt are (forcibly) reduced enough to ensure the survival of these bits of dendrites, 2'3 Willful disturbances even so trivial as those produced by rapping a mold might be included here; as will be shown for example, this follows Southin's suggestion that the free liquid/air interface

Jan 1, 1970

By J. Szekely, V. Stanek

Heat and gas flow interactions in nonisothermal packed beds were examined in the paper. A study was made of the response of the system to a step or pulse change in the inlet gas temperature, with a fixed value of the overall pressure drop across the bed. Under these conditions the heat flow and fluid flow transients are coupled because the convective heat transfer rate is alfected by the mass flow rate of the gas which, in turn, for a fixed pressure drop will depend on the temperature profile in the system. The Problem was stated in terms of differential equations, which were integrated numerically. The parameters used in the computation were so chosen to reflect the operation of the stack region of blast furnaces and sinterbeds. The computed results showed that the pressure drop-flou1 relationships and the rate of progress of the temperature fronts (waves) were strongly interrelated and were also markedly affected by variations in particle size and in void fraction. MANY metallurgical processes involve the contact of solid particles with a gas stream in a packed bed arrangement under nonisothermal conditions. Examples are shaft furnaces, regenerators, pebble heaters, and the sinter process. Although the heat and mass transfer aspects of packed bed processing have been extensively studied, the associated flow phenomena and in particular the effects of nonisothermality on the flow, have received little attention to date. :In fact, most of the previous workers considered the flow rate of the carrier gas time invariant and independent of the heat or mass transfer processSzekely and carr2 have shown that the pressure drop-flow relationships in nonisothermal packed beds may be strongly affected by the temperature profile within the system. These authors have devised a method for relating the pressure drop to flow for a given temperature profile. thus providing an extension of the Ergun equation to steady nonisothermal systems. Finally, in a recent paper willmot3 examined the response of regenerators to externally imposed changes in the gas flow rate. Both these investigations were somewhat specialized since, in general, neither the temperature distribution nor the gas flow rate may be regarded as truly independent variables, thus the heat transfer and the fluid flow problems have to be solved simultaneously. The work reported here is divided into two parts: in Part 1 the general formulation is given and a detailed discussion is presented of fixed bed systems. Part is devoted to systems in which a gas and particulate solids are contacted in a counter flow arrangement. FORMULATION Consider a nonisothermal fixed packed bed, extending from through which a gas is flowing. The problem is to develop a relationship between pressure drop and gas flow (with the gas flow being the dependent variable) and to evaluate the rate at which a change in the gas temperature, imposed at the inlet, travels through the system. Let us consider an infinitesimal section of the bed and establish differential heat, mass, and mechanical energy balances over this region. In addition, relationships are needed describing the temperature dependence of gas density (equation of state) and the temperature dependence of viscosity. These may be written as: where c, and are constants. It is noted that in this formulation we neglected any temperature gradients within the solid particles, thus assuming these to be either sufficiently small or of sufficiently high thermal conductivity to meet this condition. The justification and consequences of this assumption will be mentioned in the discussion.

Jan 1, 1970