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By R. Simon, D. J. Graue

This paper presents correlations for predicting the solu-lility, swelling and viscosity behavior of CO2-crude oil sys8i.m~. The correlations were developed from experimental data obtained by the authors. These data are also presented. The data were determined by measuring the properties of mixtures of CO, and nine different oils. Experiinental conditions covered a range of 100 to 250°F and pressures up to 2,300 psia. Properties predicted by the correlations have average deviations, expressed as per cent of experimental value, of 2 per cent for solubility, 0.5 per cent for swelling and 12 per cent for viscosity. INTRODUCTION Interest in CO2 injection as an oil recovery process has led to the development of performance prediction methods which can be applied to specific reservoirs.1 iS To use these performance prediction methods, it is necessary to know the solubility, swelling and viscosity properties of CO2-crude oil mixtures at reservoir conditions. Some information on these properties has appeared in the literature; however, this information did not cover the range of different oils and conditions needed to prepare generalized correlations for reservoir engineering purposes. Consequently, an experimental program was undertaken to collect the data needed. The data obtained and the correlations developed from the data are described in the following sections of this paper. SOLUBILITY OF CO2 IN CRUDE OILS CO2 solubility data in the literature come from six principal sources. The solubility prediction method of Welker and Dunlop3 is limited to 80F. The information in Ref. 4 is of two types: the first includes binary and ternary mixtures of CO, and light hydrocarbons (C1 to C6), and the second gives data for CO1 and heavy hydrocarbons for a temperature range of 40 to 90F. Ref. 5 contains a KCO2 chart for systems whose convergence pressure is 4,000 psia. The KCO2's are based mainly on CO2-natural gas mixtures. Poettmann's work covered CO2 solubility in one condensate and one crude oil6,7 Ja-coby and Rzasa measured CO? solubilities as a function of pressure and temperature for two natural gas-absorber oil mixtures and two natural gas-crude oil mixtures.'8 CO, concentration in these four systems was fixed at 5 mol per cent. The work reported in this paper extends CO, solubility data to a variety of different crude oil types in a temperature range from 110 to 250F and pressures up to 2,300 psia. The experimental procedure used by the authors to obtain the solubility data consisted of combining known amounts of pure CO, and crude oil in a visual cell at a fixed temperature and measuring the bubble point of the mixture. Measurements were made for a total of 40 different CO2-oil mixtures and the results are shown in Table 2. The mixtures included nine different oils (seven crude oils and two refined oils) whose properties are listed in Table 1. All nine oils had vapor pressures less than 1 atm at the experimental temperatures. Consequently, analysis of the bubble-point vapor showed a CO, concentration over 99 mol per cent. At no time during these experiments was a second, more dense, liquid phase observed. The solubility correlation which was developed from the data in Table 2 is presented in Figs. 1, 2 and 3. In these figures, solubility is expressed as xco2 the mol fraction of CO, in the CO2-oil mixture. Fig. 1 shows solubility as a function of CO2 fugacity6 and temperature. Fig. 2 shows the same solubility data expressed as a function of saturation pressure and temperature. The solubility shown in Figs. 1 and 2 is for an oil whose UOP characterization factor is 11.7. UOP characterization factors of crude oils can be determined from Ref. 10 if the viscosity and APT gravity of the oil are known. Fig. 3 gives the solubility correction factor for oils whose UOP characterization factors differ from 11.7. The solubility correlation in Figs. 1, 2 and 3 predicted

Jan 1, 1966

By S. Gilbert, G. R. Bailey

A further evaluation of the bomb-sampling method for determining the oxygen content of liquid steel is presented. The results of this study and their close agreement with the results of an earlier evaluation confirm the conclusion that the bomb-sampling method is valid for obtaining representative samples for the determination of the oxygen content of a liquid steel bath. WHAT constitutes the most desirable procedure for obtaining a sample suitable for determining the oxygen content of a liquid steel bath has been a controversial subject for several years. In 1952 Huff, Bailey, and Richards' described a modification of the bomb-sampling technique originated by McCutcheon and Rautio.' In both the modified and original techniques, a small cast-iron or steel mold containing aluminum wire and appropriately covered is inserted into the furnace, coated with slag, and then plunged into the metal bath. Upon entering the metal, the cover melts and a sample of the steel bath enters the mold. The data presented by Huff, Bailey, and Richards' indicated that reproducible samples could be obtained by their method. Furthermore, the oxygen analyses from samples obtained by their method agreed better with those from controlled laboratory experiments than did analyses from samples obtained by methods previously suggested for sampling large liquid-metal baths. Most techniques, other than bomb-sampling, require that a sample of liquid steel be removed from the furnace in a well slagged spoon and poured into an iron mold containing aluminum or into a massive copper mold for rapid chilling. Pouring in this manner requires that the sample pass through the air. The controversy, then, is somewhat as follows: Proponents of the spoon-sampling method and similar dip-and-pour methods feel that the introduction of a cold steel mold into a molten steel bath may result in a localized boiling condition that may deplete the steel of oxygen to a significant degree in the area where the bomb is introduced. Conceivably this boil could cause results that are, on the average, too low and nonrepresentative of the bath composition. On the other hand, samples that are spooned and then poured through the air may also be nonrepresentative because of oxidation by the atmosphere. The restrictions imposed in sampling with a spoon are much more stringent than those imposed when sampling with the bomb-type mold within the furnace. The spoon sample must be taken in a well slagged spoon, a requirement that depends on the condition of the slag in the furnace. Also, the samples must be poured as quickly as possible, without shaking the spoon and without allowing slag to enter the mold. The necessity of fulfill-

Jan 1, 1955

By B. M. Larsen, W. E. Shenk, T. E. Brower

Shortly after our previous paper on this subject was printed1 we located a source of uncertainty in the results arising from the unexpected fact that hydrogen slowly reduces silica at 1100" C. in presence of iron, even when the iron nowhere touches the silica, although in absence of iron it does not do so. This difficulty has been completely obviated by the use of a small high-frequency furnace, which enables us to heat the specimen for analysis without raising the temperature of the silica vessel to a point at which any appreciable reduction of the silica glass occurs. We now describe this modification of procedure, and present some typical results obtained with it. For any given specimen of steel, the results are entirely definite and reproducible, but their precise significance is still open to some question, as indeed is true of all methods of oxygen determination SO far developed. Further elucidation of this question is to be expected from the cooperative comparison of the several methods now under way under the auspices of the Bureau of Standards at the instance of the Iron and Steel Division of the A.I.M.E. Apparatus The final form of apparatus we have used is identical with that described and illustrated in our previous paper, except for the substitution for the Globar furnace of a small high-frequency furnace actuated by a vacuum tube oscillator2 0f about 1.5 kw. capacity, and for a slight modification of the containing vessel. This transparent silica vessel is illustrated in Fig. 1 of this paper. Its enlarged portion is about 5 cm. in diameter and 13 cm. long. The silica tube for inlet of hydrogen is fused into this bulb and ends beneath the metal "bucket" holding the steel sample. This sample is in the form of fine millings. The "bucket" is suspended by a platinum wire from the cap of Pyrex glass. The high-frequency

Jan 1, 1934

By Albert E. Wood, Edgar R Shepard

The interest of the Federal Government in improvement of waterways dates from 1820, when Congress appropriated $5000 for making a survey of the Mississippi and Ohio Rivers and assigned this work to the Corps of Engineers of the Army. Since that time the Government has gradually assumed increasing jurisdiction in the matter of improvement and control of inland waterways until, by the River and Harbor Act of Jan. 21, 1927, Congress assigned to the Secretary of War and to the Chief of Engineers the duly of making surveys, in accordance with House Document No. 308, 69th Congress, to formulate plans for the most effective improvement of the navigable streams of the United States and their tributaries, for navigation, development of water power, control of floods, and the needs of irrigation. Virtually all the preliminary investigations and surveys required by this act have been completed. The reports made to Congress have been published and often are referred to as ''308 Reports." The map shown in Fig. 1 is merely a skeleton distribution of the projects covered by these reports, but it serves to indicate the magnitude of the proposed undertaking. In many instances, a single character on the map stands for a major development involving several dams and reservoirs or many miles of canals or levees. The devastating floods of 1936, and the need for worthy public works to take up the slack in employment, gave further impetus to this program and in 1936 led to the enactment of a bill authorizing a large number of these projects. The National Flood Control Act of 1936 specifically authorizes some 270 flood-control projects in 31 states, and affecting nearly every state in the Union, with an estimated construction cost of about $300,000,000. In addition, the 1936 Act directs the Secretary of War to make preliminary examinations and surveys for flood control in some 230 additional localities, and to continue surveys and studies of 18 reservoir sites. The Corps of Engineers is proceeding rapidly with foundation investiga-

Jan 1, 1940

By Albert E. Wood, Edgar R. Shepard

The interest of the Federal Government in improvement of waterways dates from 1820, when Congress appropriated $5000 for making a survey of the Mississippi and Ohio Rivers and assigned this work to the Corps of Engineers of the Army. Since that time the Government has gradually assumed increasing jurisdiction in the matter of improvement and control of inland waterways until, by the River and Harbor Act of Jan. 21, 1927, Congress assigned to the Secretary of War and to the Chief of Engineers the duly of making surveys, in accordance with House Document No. 308, 69th Congress, to formulate plans for the most effective improvement of the navigable streams of the United States and their tributaries, for navigation, development of water power, control of floods, and the needs of irrigation. Virtually all the preliminary investigations and surveys required by this act have been completed. The reports made to Congress have been published and often are referred to as ''308 Reports." The map shown in Fig. 1 is merely a skeleton distribution of the projects covered by these reports, but it serves to indicate the magnitude of the proposed undertaking. In many instances, a single character on the map stands for a major development involving several dams and reservoirs or many miles of canals or levees. The devastating floods of 1936, and the need for worthy public works to take up the slack in employment, gave further impetus to this program and in 1936 led to the enactment of a bill authorizing a large number of these projects. The National Flood Control Act of 1936 specifically authorizes some 270 flood-control projects in 31 states, and affecting nearly every state in the Union, with an estimated construction cost of about $300,000,000. In addition, the 1936 Act directs the Secretary of War to make preliminary examinations and surveys for flood control in some 230 additional localities, and to continue surveys and studies of 18 reservoir sites. The Corps of Engineers is proceeding rapidly with foundation investiga-

Jan 1, 1940

By A. D. LeClaire

This paper claims to provide a description of diffusion processes in solids which is said to be a reformulation of Fick's Laws and therefore, presumably, is supposed to be as general as those laws. In fact, it appears to provide no more than an atomic model of a rather restricted type leading even to results in conflict with experiment. The restriction lies in the assumption, carried throughout the paper, that even in a chemical gradient the jump frequency i of an atom of species i is a function only of the composition on the plane from which it jumps, i.e., ?i = ?i(cl, c2 ...). This means that atom jumps in opposite directions from a site would occur with equal probability. There would then be no tendency for atoms to migrate preferentially in one direction along the gradient, so the model is incapable of accommodating the well established phenomenon of atom drift in a chemical gradient.10-" A more general model that does not suffer this difficulty was discussed in a paper13 I wrote in 1958, and the results therein already contain as a special case those given by Dr. DeHoff. The simplest sufficiently general assumption is to suppose that ?i is a function ?i(a1 a2,...; wl, w2, ..-) of the concentration aj and ? ?j at the site from which and to which, respectively, a jump is made. Any such function can always be expressed as a function of the sum and difference of its arguments. Thus d is the jump distance and g a geometrical constant. Obviously this is zero, i.e., no drift, if ??ri/??j = 0. X is written in this form, revealing two components of the total drift, because it can be shown that only the second component, depending on ??'i/???(?j -aj), actually contributes to the net diffusion flux Ji. This component can be shown,13 by a straightforward ther-modynamic transcription, to be responsible for the so called "thermodynamic factor" in the Darken approximation for a chemical diffusion coefficient is the activity coefficient of i. Because the jump rate ?i in DeHoff's approximation has no dependence on the concentration gradient it does not seem possible to derive the Darken equation from his Eq. [6] without the further rather arbitrary assumption that ?i = const ri. It is to be noted too that the author's derivation of Eq. [12] is only valid when ?i is in fact a function only of the cj at the plane from which the atom jumps—for only then is ci?i a unique function of position and therefore of A. Author's Reply R. T. DeHoff I am indebted to Dr. LeClaire for his penetrating discussion of my paper, "A Reformulation of Fick's First Law". I concede that it does appear initially that the relationship presented in my paper could be derived from the detail atomic model of random walk and atom drift presented in Dr. LeClaire's approach. However, there are some important differences in concept and viewpoint which deserve further amplification. Dr. LeClaire's description is penetrating, detailed, and fundamental. His approach describes an extremely complex phenomenon, the displacement of atoms in a multicomponent gradient, at a sophisticated level. For precisely these reasons, his analysis has not proved to be useful for experimental studies that have practical objectives. For example, in order to obtain the information required to complete the analysis of the jump frequency distribution in a ternary system, the following series of experiments would, I believe, be required: 1) chemical (gradient) experiments, covering the composition range;

Jan 1, 1970

By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.' The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.' The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968

By Theodore Simons

(Butte Meeting, August, 1913.) DURING the last half century a great amount, of ingenuity and energy has been devoted to the invention of appliances for the recovery of valuable minerals from very fine sands and-slimes. The reason for this is that in almost every, dressing plant the greatest losses of values, considered relatively as well as absolutely, occur in the treatment of slimes. The natural aim of mill operators to minimize these losses has in recent years received another impetus,, from the fact that the gradually diminishing occurrence of high-grade ores makes a more intense recovery of values from existing resources absolutely necessary for profitable operation. The results of such attempts are found in the appearance of a great number of machines and appliances which make it profitable to-day to rework old dumps, containing the tailings of older processes. A constantly growing difficulty of obtaining skilled labor and the increase in wages made it prohibitory to employ those types of machines which required much attention, and in the middle of the nineteenth century the various concentrating tables of the percussion type, which automatically discharge their products, began to take the .place of the intermittent tables, on which, when the bed had reached a certain thickness, operation had to be stopped in order to allow the skimming by hand of the separate layers formed on the table. In the course of. years, two general types of machines evolved for the treatment of fine sands and slimes :- The so-called concentrators and vanners, on the one hand, and the huddles and round tables on . the other.1 For the profitable treatment of the very finest slimes, round tables have as a last resort proved more satisfactory and economical than other machines.

Jan 7, 1913

By R. M. Leibrock, C. W. Ziemer, R. P. Vincent

The Stanolind flowmeter, which employs a hot-wire anemometer connected in a Wheat-stone bridge circuit, has proved useful for determining the relative productive ability of individual sand members of gas wells. The operation of this instrument in measuring gas velocities in the well bore above each producing member has provided both a direct and accurate means of analyzing reservoir performance. Results of tests conducted with the well flowmeter in the Hugoton gas field of western Kansas have indicated some rather unusual production characteristics. In two cases it was found that all or the greater part of the total gas produced was coming from one section in wells where four "pay" sections had been perforated individually. These actual measurements contradict in many instances the indications of data obtained from electric logs and from core analysis; the fact that these latter sources often give incorrect results, demonstrates the necessity of a method, such as is provided by the well flowmeter, for accurately determining the amount of gas coming from each producing member. Introduction In any gas well where a number of pay sections have been perforated individually and are producing to a common outlet, the question arises as to the relative amounts of gas being passed through each set of perforations. In the past it has been the policy to depend on core analysis to estimate relative productivities, or, where the sections were not cored, to obtain some idea of production characteristics from electric-log studies. The weaknesses in these methods are readily apparent and indicate the need for more reliable means of measuring gas flow from each zone. The Stano-lind flowmeter* was developed for this purpose. Preliminary tests were made with the instrument in the Katy gas field near Houston; however, the bulk of the routine work with the well flowmeter has been confined to the Hugoton gas field in western Kansas, where results obtained have been encouraging. A description of the instrument, the field technique employed in testing, and a few of the results obtained in the Hugoton area are discussed in this paper. Description or Instrument The well flowmeter is 1¾ in. od and 7 ft long; it is entirely self-contained, can be run through tubing as small as 2 in. id in wells with high pressure (4500 psi) and temperature (210°F) and is lowered on a wire line commonly used for other instruments of the bottom-hole type at falling rates up to 500 ft per minute. It will detect gas flow as low as 10 ft per minute linear velocity, and yet withstand and record velocities of 1000 ft per minute without damage to the detecting element. Killing the well is not required nor desirable for running a production profile when using the instrument, and it is necessary to stop flow for only a short time. The detecting element of the instrument is a hot-wire anemometer connected in a

Jan 1, 1948

By R. M. Leibrock, R. P. Vincent, C. W. Ziemer

The Stanolind flowmeter, which employs a hot-wire anemometer connected in a Wheat-stone bridge circuit, has proved useful for determining the relative productive ability of individual sand members of gas wells. The operation of this instrument in measuring gas velocities in the well bore above each producing member has provided both a direct and accurate means of analyzing reservoir performance. Results of tests conducted with the well flowmeter in the Hugoton gas field of western Kansas have indicated some rather unusual production characteristics. In two cases it was found that all or the greater part of the total gas produced was coming from one section in wells where four "pay" sections had been perforated individually. These actual measurements contradict in many instances the indications of data obtained from electric logs and from core analysis; the fact that these latter sources often give incorrect results, demonstrates the necessity of a method, such as is provided by the well flowmeter, for accurately determining the amount of gas coming from each producing member. Introduction In any gas well where a number of pay sections have been perforated individually and are producing to a common outlet, the question arises as to the relative amounts of gas being passed through each set of perforations. In the past it has been the policy to depend on core analysis to estimate relative productivities, or, where the sections were not cored, to obtain some idea of production characteristics from electric-log studies. The weaknesses in these methods are readily apparent and indicate the need for more reliable means of measuring gas flow from each zone. The Stano-lind flowmeter* was developed for this purpose. Preliminary tests were made with the instrument in the Katy gas field near Houston; however, the bulk of the routine work with the well flowmeter has been confined to the Hugoton gas field in western Kansas, where results obtained have been encouraging. A description of the instrument, the field technique employed in testing, and a few of the results obtained in the Hugoton area are discussed in this paper. Description or Instrument The well flowmeter is 1¾ in. od and 7 ft long; it is entirely self-contained, can be run through tubing as small as 2 in. id in wells with high pressure (4500 psi) and temperature (210°F) and is lowered on a wire line commonly used for other instruments of the bottom-hole type at falling rates up to 500 ft per minute. It will detect gas flow as low as 10 ft per minute linear velocity, and yet withstand and record velocities of 1000 ft per minute without damage to the detecting element. Killing the well is not required nor desirable for running a production profile when using the instrument, and it is necessary to stop flow for only a short time. The detecting element of the instrument is a hot-wire anemometer connected in a

Jan 1, 1948

By P. Schwarzkopf, J. H. Brophy

A modification of the Mendenhall wedge blackbody1 has been used to determine solidus temperatures and to anneal alloys in the tantalum-rhenium binary system. The technique has proven to be simple and accurate with modest power requirements. For temperatures up to 2800° C a piece of 10-mil tantalum sheet was folded double and formed as shown in Fig. 1. The middle of the resulting ribbon filament was a cylindrical-shaped crucible with less than a 1/8-in. opening. After inserting a specimen in the cavity, the filament was clamped between molybdenum electrodes in a high vacuum chamber. A representative filament 2 in. long and % in. deep was heated to 2800°C with a current of 700 amp at 4 v. The specimen temperature was determined by sighting into the cavity with a Leeds and Northrup optical pyrometer. The twisted filament shape was necessary to avoid serious geometric changes during thermal expansion. For temperatures between 2800" and 3000°C a 4-mil tungsten filament was employed. To facilitate fabrication it was warm-folded, and a twisted segment of 10-mil tantalum was used to support one end to absorb thermal expansion. This element assembly required about 700 amp at 10 v to reach 3000°C. Two geometric modifications of the filament were helpful for solidus temperature determinations. A shallow chamber, with depth to opening ratio of 3 to 1, permitted direct observation of the specimen through the optical pyrometer. The fact that the specimen was visible permitted the melting point to be determined when sharp features on the specimen surface became rounded; it also indicated that blackbody conditions did not prevail. By standardizing against the melting point of molybdenum, the observed melting temperature was corrected by the following form of Wien's Law: in which T is the true temperature, To is the observed temperature, and K is a constant characteristic of the filament geometry and determined experimentally for the molybdenum standard. The resulting corrected melting point for each alloy served as a reference temperature for the second more precise filament geometry. With a 6 to 1 depth to opening ratio, the specimen was indistinguishable from the filament interior, indicating good blackbody conditions. Using this technique, a series of specimens was isothermally treated at temperatures above and below the corrected direct reading. Incipient melting was detected by visual or micrographic examination of the specimen after cooling. This procedure was checked with specimens of pure chromium, molybdenum, and tantalum. Table I represents the values obtained, together with the solidus temperatures in the tantalum-rhenium binary system determined by the same technique. The alloy specimens were approximately 1/8 in. in diam. They were pieces of 10-g buttons melted four times in a nonconsumable tungsten electrode arc furnace on a water cooled copper hearth in 2/3 atmos of titanium gettered helium. Several sources of error are possible in such temperature measurements. Within the accuracy of the pyrometer no gradients were detectable near the specimen, and element distortion was virtually eliminated by twisting the tantalum. Compensation was made for the 1/8-in. sight glass by inserting several identical thicknesses and extrapolating to zero thickness. As a result an additional 10°C correction was added to all observations in the temperature range of 2500" to 3000°C. The principal source of error was then in the operation of the

Jan 1, 1961

By C. G. Dunn, P. K. Koh

Microstructure, magnetic torque, and texture data before and after grain growth were obtained on two 3.25 pet Si-Fe specimens having initially the same cold-rolled textures and the same primary recrystallization textures. The latter textures consisted of four components, two only of which were strong; the strong components were near (120) [001] and (320) [001]. The textures of the two specimens obtained by grain growth were different. In one specimen the two weak components were converted into strong components by a secondary recrystallization process; in the other specimen the primary recrystallization texture was retained by a normal grain-growth process. The difference in behavior of the two specimens was interpreted in terms of a difference in the relative grain sizes between weak and strong components; i.e., in terms of a geometrical factor that would alter the early growth rates of grains belonging to the two weak components of the texture. Specifically the growth rate was considered as the product of two terms: a driving force and a boundary mobility. The texture changes observed are considered to favor the oriented-nucleation growth-selectivity theory more than the oriented-growth theory. WHEN primary recrystallization and grain-growth textures form as a result of annealing deformed metals or alloys, the fundamental processes involved are nucleation and growth. Knowledge, therefore, about nuclei and the factors influencing their growth is required not only for the understanding of texture development but also for its control. In the oriented-growth theory of texture formation1, 2, 3 the problem of nuclei is generally disposed of by the assumption that nuclei are available in all orientations; the theory then has to explain the final texture from the initial texture and the way boundary mobility depends on orientation. In the oriented nucleation theory of texture formation"' nuclei are considered to be present only in certain orientations but the importance of growth selectivity is still recognized. For example, the mobility of boundaries of approximately the same orientation and of the coherent type in twins is believed to be low while that of high-angle boundaries, in general, is high. Because of this the theory may be described as an oriented-nucleation growth-selectivity theory. The main feature of the oriented-nucleation theory, however, is the importance given to nuclei; i.e., how they form in specific orientations and how they grow. In the present investigation two cold-rolled single crystals were used to study the effects of growth after primary recrystallization. The cold-rolled textures and the primary recrystallization textures were determined from portions of these specimens and reported earlier.",' The two cold-rolled crystals were in the (111) [112] stable end orientation, the recrystallization textures were nearly identical and consisted of two strong components, designated M and M', which were near (120) [00l] and (320) [00l], respectively, and also some specific weak components near (111) [110] and (111) [110]. It is well recognized that a single strong component in the primary recrystallization texture may be needed for secondary recrystallization3, 5, 8 but unfortunately when this is the case the amount of material left in deviating orientation may be too small either for growth or for positive identification. The present samples proved to be almost ideal for the study of minor components and their influence on texture changes produced by growth after primary recrystallization. The results obtained are interpreted in terms of present knowledge of grain-growth processes. Experimental Procedure Two lots of silicon-iron alloy of essentially the same composition, namely, 3.25 pet Si, 0.004 C, 0.009 P, 0.010 S, 0.035 Mn, 0.070 Ni, 0.090 Cu, 0.009 Sn, with traces of A1 and Cr and the balance Fe, were converted into single crystals 0.025 in. thick and 1.25 in. wide. The orientations were predetermined by the method of reorienting a seed crystal as described elsewhere.3 pecimen 1 from one lot had the (335) [556] orientation while specimen 2 from the second lot had the (111) [112] orientation.* Both crystals were cold rolled to a reduction in thickness of 70 pet while widening approximately 20 pet. Samples of each were selected for determining 1) the cold-rolled texture, 2) the time required at

Jan 1, 1959

By F. M. Stewart, F. H. Callaway, R. E. Gladfelter

In this paper oil initially in place is calculated by the various methods commonly used for analysis of water drive fields using data available as time progresses. Rate and pressure are predicted by means of the same methods using data available at the end of two years' history. These predictions are then compared with subsequent performance permitting an evaluation of the methods, which are Modified Schilthuis, Simplified Hurst, van Everdingen et al (1952), and the Electric Analyzer. INTRODUCTION Several variations of the material balance equation, differing in the term used to evaluate water influx, are in common use for estimating oil in place, predicting rate and volume of water influx, and forecasting producing rates and reservoir pressure in water drive reservoirs. The electric analyzer with an electrical network set up to simulate the oil reservoir and aquifer and their contained fluids may be used for the same purpose. Examples of the application of one or another of these methods have appeared in the literature. The accuracy and reliability of the material balance for calculating oil in place have been covered.' However, there have been few articles in which more than one method has been applied to an actual field allowing a comparison. It is felt that a field example, simple in nature, where the Modified Schilthuis, Simplified Hurst, van Everdingen et al (1952), and the Electric Analyzer have been applied would be of benefit in providing an evaluation of these methods as to their comparative usefulness and reliability in calculating initial oil in place and predicting performance. The Torchlight Tensleep reservoir is a small field in a large aquifer. The reservoir oil is greatly under-saturated, having a bubble point of only 55 psi and 2 cu ft/bbl of gas in solution. Changes in the reservoir volume factor in the range of pressures encountered are small, meaning little error in converting production to reservoir conditions. The pressure has declined from 1,618 psi initially to 137 psi during the first four and one-half years. Water production has been negligible. For Torchlight, the material balance equation as discussed later is considerably simplified by the omission of terms having to do with free gas. Thus with simpler equations, less variables to consider, the large pressure drop, the absence of a gas phase, and rapid pressure-rate adjustments, which mean an unusual amount of history in a short time, the reservoir appears suitable for comparing the methods listed above. GENERAL INFORMATION ON THE FIELD The Torchlight field is located on the eastern side of the Big Horn Basin, Big Horn County, Wyo., approximately 3 miles east of the town of Basin. The Tensleep reservoir was discovered in September, 1947. It lies at a depth of about 3,000 ft and produces oil of 35" API gravity. A total of five wells have been completed in the Tensleep, but only four are now producing. The reservoir is well defined in areal extent in that a total of 13 wells have penetrated the Ten-

Jan 1, 1955

By R. R. Webster, H. T. Clark

I. A. Sirel—I would like to ask Mr. Sims what would the preferred hot metal analysis be as far as manganese and silicon are concerned if you used specially made iron for this process instead of basic iron. C. E. Sims (authors' reply)—A preferred composition would contain somewhat less silicon than the basic pig iron used in these experiments. High silicon requires a large lime addition. Lime must be added in sufficient quantity to neutralize the silica formed and to leave an excess for dephosphorization. Manganese presents almost no problem in operation. It is almost completely oxidized and, in burning, develops considerable heat. The evidence indicates, however, that, in continuous commercial operation, there will be an excess of heat produced, and the bath will need to be cooled in some manner as by the addition of scrap or by utilizing the energy for the direct reduction of ore. There do not seem to be any serious limitations on composition of pig iron. One heat was made with an iron containing 2.27 pct silicon and the phosphorus finished at 0.007 pct. In another, the iron contained 0.45 pct phosphorus which was lowered to 0.019 pct. This indicates considerable leeway in composition. D. R. Loughrey—We are all very much interested in the recent discovery of very large deposits of iron ore both in Labrador and in Venezuela. I would like to ask Mr. Sims if the iron ore at either or both of these places is such that it would lend itself to the manufacture of iron suitable for use in the turbohearth. C. E. Sims-—According to my information, those ores are not essentially different from ores now used in this country for making basic pig. They should, therefore, be adaptable to this process. D. I. Brown—You have spoken about the leeway, or spread in analysis of the various irons you can use in the vessel. I would like to have you tell us, if you can, about the different kinds of steels which can be made in such a vessel. The turbohearth process, or it might more aptly be called pneumatic openhearth, is a little different from that used in most Bessemer shops and in the one in which I worked. If we had a blow in the air over 10 min, the boss was in the pulpit in a hurry

Jan 1, 1951

By R. L. Schmidt, J. D. Verhoeven

The diffusion coefficients and electrotralzsport mobilities of aluminum, gallium, and arsenic have been determined in molten germanium with the capillary reservoir technique. The diffusion coefficients are slightly higher than those determined by the solidification technique of Brirton et a1.1 It was found that aluminium and gallium migrate to the cathode in molten germanium) whereas arsenic migrates to the anode under an electric field. A possible technique for producing p-n junctions by means of electric field freezing is discussed in view of the experimental data. In the past decade or so the literature has abounded with articles concerning the solid-state properties of the semiconducting elements germanium and silicon. It is surprising by comparison how little has been published concerning the liquid-state properties of these materials. In the production of doped germanium or silicon the diffusion coefficient of the dopant in liquid germanium or silicon is an important quantity. Yet, to the best of our knowledge, no one has ever made a direct measurement of the diffusion coefficient of solutes in either molten germanium or silicon. A number of authors'-4 have determined some diffusion coefficients by the indirect technique developed by Burton et al.1 This technique appears to give numbers of the correct order of magnitude but it does depend upon a number of assumptions in the analysis and also requires prior knowledge of the viscosity of the melt. In the present work a more direct measure of the diffusion coefficients of arsenic, gallium: and aluminum in molten germanium has been made. It has been shown independently by two groups of authors5, 6 that, when an electric current is passed through the interface of a solidifying metal containing an impurity, the resulting electrotransport in the liquid boundary layer at the interface offers a mechanism for control over the redistribution of the impurity accompanying the solidification. These authors show that the degree of control is proportional to the mobility, U of the impurity atoms in the liquid boundary layer, where the mobility is defined as the drift velocity relative to the solvent per unit electric field. In principle the results apply to the solidification of a doped semiconductor and offer an interesting technique for control of the doping of a semiconductor. In the present work the mobilities of aluminum, gallium, and arsenic were determined in molten germanium in order to evaluate the potential usefulness of electro-transport as a technique for solute control when applied to the solidification of doped germanium. EXPERIMENTAL PROCEDURE Both the diffusion coefficients and the mobilities were measured using high-purity alumina capillaries and a resistivity technique for analysis. A schematic diagram of the electrotransport apparatus is shown in Fig. 1 and the details of the cell design are shown in Fig. 2. For the mobility experiments electrical contact with the bottom of the capillary was made with graphite, as shown in Fig. 2. In order to prevent electrical contact with the melt the graphite was coated with a thin layer of alumina using a plasma spray torch. The cell assembly, a graphite electrode, and another assembly containing two blank capillaries were fastened to the lavite disk shown in Fig. 1. To make a run the system was evacuated and the doped germanium was outgassed at the operating temperature of 1030°C. The cell and blank capillaries were then submerged beneath the melt and a slightly positive pressure of helium was introduced to fill them. After passing current through the cell for a given time the cell and blank capillaries were raised from the melt and the furnace was shut off. The temperature of the cells dropped below the freezing point of germanium within 1 to 2 min after the furnace was shut off.

Jan 1, 1968

By Chi-shing Wang

Recently the U.S. Bureau of Mines has undertaken a research project to develop the mechanical roof pulling technique as a method for evaluating the effectiveness and the comparative advantages and disadvantages of various roof bolting systems for underground coal mines, based on the characteristic responses of bolted mine roofs to a prescribed external loading system. Two preliminary experiments of the test method were conducted in the Bureau's Safety Research Coal Mine (SRCM) at Bruceton, Pa., and further trials are underway. The fundamental concept of the test method, the design of test rigs, and the experimental results are summarized in this progress report.

Jan 1, 1976

By N. Rowlands, J. A. Finch, R. Espinosa-Gomez

The sulphation roast-leach process for complex sulphides results in phase changes due to roasting and leaching. The phases in the calcine, and in the neutral and hot acid leach residues were identified and their degree of liberation determined in order to design and Interpret separation tests on the residues. The hot acid leach residue was composed of hematite, silica, and lead sulphate with some associated silver. Magnetic separation was selected as the process for producing a lead concentrate, as the non-magnetic product. Separation was limited by -1 pm hematite reporting to the product, and hematite/lead sulphate agglomerates reporting to the magnetics.

Jan 1, 1984

By Robin P. Gardner

A radioisotope tracer method combined with a suitable back-calculation method is proposed and evaluated for the determination of model simulation parameters in open-circuit continuous ball mills. The method essentially consists of using impulse and/or step injections of short-lived radioisotopes of the naturally occurring trace elements manganese and sodium. It is evaluated here on the basis of the minimum standard deviations of the product weight-size distributions. These minimum standard deviations are taken as those predicted by a Poisson distribution of the number of particles present in size fractions of the samples taken for analysis. Previously developed tanks-in-series lumped parameter models are used in the evaluation. The results indicate that the method is very promising.

Jan 1, 1976

By Herbert H. Kellogg

Deposits of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine ( — 325-mesh) sand assaying 95.5 per cent SiO2, and a very fine (—3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. Experimental Procedure The Sample.—The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotalion Feed.—By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine frac- . tion was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper. A size separation of this type can be

Jan 1, 1948

By Herbert H. Kellogg

Deposits of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine (— 325-mesh) sand assaying 95.5 per cent SiO2, and a very he (—3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. Experimental Procedure The Sample.—The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotation Feed.—By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine fractioh was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper. A size separation of this type can be

Jan 1, 1947