Search Documents

By K. C. Hong, R. B. Jensen

The problem of determining the optimum set of steam volumes and cycle lengths for a single well undergoing multicycle steam stimulation in order to maximize the cumulative discounted net income has been formulated mathematically and programmed for a digital computer. The mathematical fonnulation of the problem and the method for its solution are discussed in this paper. The oil production performance during each stimulation cycle was simulated by either a constant percentage or a harmonic decline. Using simple analytical expressions for production performance, the cumulative discounted net income and cumulative time of operation were related to the pertinent process and cost parameters and two principal process control variables (cycle length and steam injection volume). The discrete maximum principles was used to transform the equations for cumulative time of operation and cumulative discounted net income into a set of simultaneous equations. The simultaneous equations then were solved by trial and error on a digital computer to determine the set of cycle lengths and stem injection volumes that gives maximum cumulative discounted net income over the project life. INTRODUCTION Steam stimulation is a process for improving the oil recovery rate from wells producing high-viscosity crudes. The process is applied on an individual well basis and is executed in a series of cycles, each consisting of three phases: steam injection, soaking (steam condensation), and production. Significant increases in production rate following the stimulation operation result from heating the reservoir around the wellbore. As heat is removed with produced fluids and dissipated into nonproductive formations, the production rate declines, usually to near the prestimulation value. Typical production responses are given in case histories reported by Owens and Suter,l and are depicted in Fig. 1. Duration of the production phase is equal to the time for the oil production rate to decline to some specified value and is called the cycle length. (Cycle length is defined as the producing portion of the cycle and does not include the downtime required for steam injection and soaking operations.) Termination of the production phase coincides with the start of steaming for the next cycle. The process is continued, cycle by cycle, until it becomes unprofitable. Models 2-4 have been developed to simulate behavior of a single well during one cycle of steam stimulation and have been used to investigate the effects of system and operating conditions on the production responses. However, these investigations have not shown how the models can be used to determine a most profitable set of operating conditions for a multicycle stimulation project. Perhaps these models are too complicated mathematically to be adapted readily to an optimization study. This paper presents a method for optimizing a multicycle steam stimulation project based on simple production performance models. First, the performance of a steam-stimulated well during each cycle was simulated by either a constant percentage or a harmonic decline model. Using these simple analytical expressions for production performance, the cumulative discounted net income (before tax) and cumulative time of operation for each cycle were related to the pertinent process and cost parameters and two process control variables—the cycle length and the steam injection volume. Finally, the profit function to be maximized was formed. The analogy between the above problem and problems of optimizing multistage decision processes that have been reported extensively in the chemical engineering literatures5-10 in recent years has led this investigation to the use of the discrete maximum principle.5-7 This principle was used to transform the equations for cumulative discounted net income and cumulative time of operation into a set of simultaneous equations characterizing the optimum operating conditions in terms of the two control variables. These equations

Jan 1, 1970

By James A. Barr

The writer's first experience with flotation was during World War I, in the bene-ficiation of Alabama graphite schist ores. One plant used a cone with a peripheral overflow; dried ore was distributed by a rotating disk onto the surface of the water. No reagents were added' The flake-graphite film floated along with some fine silica. Dewatering screens separated the flake. Naturally unit capacities were low but results were satisfactory. Minerals separation mechanical flotation machines were used in another graphite mill. pine oil was added directly to the head cells, with very good results. All the graphite concentrates from both types of flotation were carefully refined after drying by passing through burr mills, followed by very close sizing on sifters. In March 1927, the writer ran a very successful flotation test on minus 28-mesh, deslimed, Tennessee brown phosphate "sand,"† using a mechanical laboratory machine built in the shops of the Anaconda Copper Mining Co., through the courtesy of Ernest Klepetko. The machine was soon converted to a subaeration type, with improved results. This phosphate research program was greatly enlarged and led to the formation of the phosphate Recovery corporation. The development of nonmetallic flotation followed rapidly. The first flotation machine for bene- ficiation of phosphate was installed in January 1928, in a pilot mill, by International Minerals and Chemical Corporation, at Mulberry, Florida. These machines were Minerals Separation, 24-in., sub-,,,tion types, with weir control of pulp between cells. The sand bleeders were very small—about 1¼-in. diameter. As the feed flake. Is to 25 per cent plus 28-mesh material, the cells choked up frequently. This was corrected by cutting a 2 by 6-in. bleeder opening above the impellers, at grid level, which short-circuited the coarse fractions directly into the feed of the next cell. The matter of size classification and grinding was a considerable problem, which does not come within the scope of this article. Because of the troubles noted above, cascade-type roughers were installed in the second flotation plant, built about 1930. Experimental cells had been tried in 1928. General plant layout is shown in Fig. 1 and details of the cascade construction in Fig. 2. The cascade installation in plant NO. 2 gave good results and eliminated troubles due to choke-ups and coarse feed. The capacities and metallurgical results equaled those of the modified 24-in. Minerals Separation flotation machines in plant No. I The objections to the cascade installation are the floor space and mill height required. In 1939 an improved Minerals Separation machine was tested in parallel with the cascades. Extensive tests indicated

Jan 1, 1947

By James A. Barr

The writer's first experience with flotation was during World War I, in the bene-ficiation of Alabama graphite schist ores. One plant used a cone with a peripheral overflow; dried ore was distributed by a rotating disk onto the surface of the water. No reagents were added' The flake-graphite film floated along with some fine silica. Dewatering screens separated the flake. Naturally unit capacities were low but results were satisfactory. Minerals separation mechanical flotation machines were used in another graphite mill. pine oil was added directly to the head cells, with very good results. All the graphite concentrates from both types of flotation were carefully refined after drying by passing through burr mills, followed by very close sizing on sifters. In March 1927, the writer ran a very successful flotation test on minus 28-mesh, deslimed, Tennessee brown phosphate "sand,"† using a mechanical laboratory machine built in the shops of the Anaconda Copper Mining Co., through the courtesy of Ernest Klepetko. The machine was soon converted to a subaeration type, with improved results. This phosphate research program was greatly enlarged and led to the formation of the phosphate Recovery corporation. The development of nonmetallic flotation followed rapidly. The first flotation machine for bene- ficiation of phosphate was installed in January 1928, in a pilot mill, by International Minerals and Chemical Corporation, at Mulberry, Florida. These machines were Minerals Separation, 24-in., sub-,,,tion types, with weir control of pulp between cells. The sand bleeders were very small—about 1¼-in. diameter. As the feed flake. Is to 25 per cent plus 28-mesh material, the cells choked up frequently. This was corrected by cutting a 2 by 6-in. bleeder opening above the impellers, at grid level, which short-circuited the coarse fractions directly into the feed of the next cell. The matter of size classification and grinding was a considerable problem, which does not come within the scope of this article. Because of the troubles noted above, cascade-type roughers were installed in the second flotation plant, built about 1930. Experimental cells had been tried in 1928. General plant layout is shown in Fig. 1 and details of the cascade construction in Fig. 2. The cascade installation in plant NO. 2 gave good results and eliminated troubles due to choke-ups and coarse feed. The capacities and metallurgical results equaled those of the modified 24-in. Minerals Separation flotation machines in plant No. I The objections to the cascade installation are the floor space and mill height required. In 1939 an improved Minerals Separation machine was tested in parallel with the cascades. Extensive tests indicated

Jan 1, 1947

By R. I. Jaffee, H. R. Ogden, D. J. Maykuth

Phase diagrams for the Ti-W and Ti-Ta systems were determined. The Ti-W system is characterized by a wide, two-phase region of ß plus tungsten which is derived from a peritectic reaction between the liquid and tungsten solid solutions. The ß field terminates in a eutectoid reaction between a titanium and tungsten terminal solid solution. Tantalum and ß titanium form a complete series of solid solutions. Other features of this system are the extensive a-ß field at low temperatures and an appreciable solubility of tantalum in a titanium. BOTH tungsten and tantalum were first thought to form ß-isomorphous systems with titanium as a result of early work' using powder-metallurgical techniques. Later work2 on arc-melted Ti-Ta alloys, made using a commercial titanium base, showed that, in the range of 0 to 10 pct, tantalum was soluble in ß titanium and that the a solubility extended to between 2 and 5 pct Ta at 790 °C. The present investigation covered the entire alloy range in both systems and was chiefly concerned with high-purity alloys at the titanium-rich end. The constitution of titanium-rich alloys made with a commercial titanium base was reported by Holla-day, Kura, and Jackson.3, 4 As will be shown in detail later, the early prediction of a isomorphism was true for the case of the Ti-Ta system, but not for the Ti-W system. The results of this investigation will be presented first. The experimental methods used are described in the Appendix. Ti-W System The entire Ti-W phase diagram is shown in Fig. 1. Details of the titanium-rich side are shown in Fig. 2. The chief features of the system are a ß eutectoid and a high-temperature peritectic between liquid and tungsten solid solution. Melting Range: Examination of cast structures of low and medium-tungsten-content ingots showed cored ß phase as the primary constituent. Fig. 3a illustrates a typical cast structure for alloys in the range of 20 to 30 pct W. From 30 to 72 pct W, coring was very severe. Alloys containing 72 through 88 pct W, however, showed definite evidence of a peritectic reaction between the liquid and a terminal solid solution of titanium in tungsten. Fig. 3b shows the cast structure for an 80 pct W alloy. A 95 pct W alloy, shown in Fig. 4, consisted primarily of primary tungsten solid solution plus a small quantity of ß probably rejected during cooling. Incipient-melting experiments located the peritectic temperature between 1850" and 1900°C and indicated that the reacting phases are liquid containing about 25 pct W and tungsten terminal solid solution containing about 8 pct Ti. Figs. 5 and 6

Jan 1, 1954

By Verne E. Hooker, Robert M. Becker

The evaluation of in-situ rock stresses from measurements of the change in diameter of a borehole that is stress-relieved by overcoring has become a common practice. Generally the stress evaluation has been based on isotropic relations whereas rock in varying degrees is aniso tropic. A plane elasticity solution fora circular hole along one axis of an orthotropic medium has been adapted to evaluation of in situ stress. The necessary elastic parameters for this evaluation may conveniently be obtained from static tests on the overcore in conjunction with a consistent orthotropic thick-wall cylinder solution. The method and equations for the laboratory and field evaluations are summarized and illustrated. The determination of in-situ rock stresses from boreholc deformation measurements has gained widespread acceptance. Hastl measured the change in diameter of a borehole that was stress-relieved by drilling a larger concentric core; this overcoring method has produced a major portion of the field data for recent stress evaluations in rock. These evaluations are based on the elastic properties of the rock, which are conveniently determined by testing the overcore.6-8 The stress evaluation and the overcore testing procedures generally assume isotropic relations whereas rock is anisotropic in varying degrees. Recently, an anisotropic plane stress solution was adapted for evaluation of in-situ stress9 and a related plane strain solution was developed for the testing of stress-relief core. 10 The present paper unifies the stress evaluation and overcore testing procedures for a general class of anisotropic rock. Equations are presented for calculating the state of stress in a plane normal to the borehole, and a consistent thick-wall cylinder solution is given for determining the necessary elastic properties. In addition, a complete example of stress evaluation from laboratory and field data is presented, and the order of error in computing the state of stress from isotropic relations is illustrated. Several limitations of the results should be emphasized. All results assume small linearly elastic deformations of a homogeneous medium. Rock characterized by orthotropic, transversely isotropic, and isotropic elasticity is considered; however, the anisotropic results assume a special relation among certain elastic constants in addition to geometric orientation with respect to a plane of elastic symmetry. For some stress determinations in rock, these may be severe limitations. On the other hand, the anisotropic evaluation procedure involves little additional effort and is much more flexible than the corresponding isotropic evaluation procedure. The collection of field data is identical. The laboratory determination of elastic parameters is no more difficult and time-consuming for the anisotropic than for the isotropic model. Only the calculations require some additional effort for the anisotropic evaluation, and this additional effort is eliminated by use of a small computer. The flexibility of the anisotropic procedure is greater because more than two independent elastic constants are available in fitting rock data. For the special relationship assumed among orthotropic constants, five independent elastic constants are available for the determination of in-situ secondary principal stresses as compared with two independent elastic constants for the isotropic model. Much of the material presented is either directly from the literature or adapted from the literature through superposition or the usual transformations. Consequently, only enough detail for clarity of presentation is included. RELATIONS FROM ANISOTROPIC ELASTICITY Materials that have three mutually orthogonal planes of elastic symmetry are called orthotropic. By directing the axes of the coordinates perpendicular to these planes, Hooke's law for an orthotropic solid 11 is

Jan 1, 1970

ORE at the Jeffrey mine of Canadian John Mansville at Asbestos, Que., is hoisted by two 12 1/2 - ton capacity aluminum skips, counterbalanced. When the loaded skip reaches the surface it empties, via its sliding door, into a bin. Simultaneously, the skip tender, who operates at the 940 level, loads ore into the alternate skip from a 12 ½ -ton measuring pocket. This done, he sets the skips in motion. Problem: When moisture content of the asbestos ore is high, the ore, unknown to the skip tender, some- times sticks in the dumping skip, preventing complete discharge. Moreover, the sliding skip doors sometimes jam and stay open after the ore is discharged. If a skip in this condition is lowered, the result is either an overflow of ore, or the ore discharges through the open skip door, down the shaft. Spilled ore must then be mucked out of the spill pocket and hoisted in 2-ton cars. Cost is high, time is lost, and the shaft is sometimes damaged. Solution: A television apparatus was installed so that the skip tender might quickly spot improper door operation or hang-ups at the dumping station.

Jan 8, 1958

By K. O. Stamm, B. A. Rogers

Because it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,l which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has devel oped recently concerning the reversibility of the transformation. From thermo-dynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912" for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9I8° and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rater of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°C. and concluded that a change occurs reversibly between 907' 3" and 910" 3°C., probably between 907" and 910°C. Wells, Ackley, and Meh16 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, ½°, and .?°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909. 5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien eiements were low enough, the A3 transformation would be completely reversible at 909.50 + 1°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1942

By B. A. Rogers, K. O. Stamm

Because it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,l which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has devel oped recently concerning the reversibility of the transformation. From thermo-dynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912" for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9I8° and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rater of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°C. and concluded that a change occurs reversibly between 907' 3" and 910" 3°C., probably between 907" and 910°C. Wells, Ackley, and Meh16 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, ½°, and .?°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909. 5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien eiements were low enough, the A3 transformation would be completely reversible at 909.50 + 1°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1942

C. P. SANDBERG, LONDON, ENG : † I think we should all be grateful to the Pennsylvania Railroad Company, and to their chemist, Dr., Dudley, for spending so much time and money in order to solve an important question ; nor are we less indebted to the public spirit which leads them to impart the experience thus gained. In Europe nothing similar has hitherto been done, either by a company or by any private individual. In England the great railway companies employ their engineers in other ways, and do not keep a chemist or specialist to study rails; but even if they did they would probably not publish the results. The chief professional engineers are so occupied with their private practice of railroad construction generally, that they cannot be expected to devote their time and energies to so special a question. The German Railway Union has, in my opinion, missed the real object of its elaborate researches by falling into the error of specifying costly, impracticable tests for rails-tests at the same time which do not infallibly expose the impurities that may be in the rails under examination. There has, therefore, been nothing done on this side of the Atlantic in the way of exhaustive study to determine the best composition for steel rails. America should consequently have full credit for the enlightened example which she has set. I wish, however, to make a few remarks on Dr. Dudley's second paper, a paper which follows very much upon the same lines of argument as the first read three years ago, upon which I have previously touched in my paper on the same subject read at the meeting in August last. If Dr. Dudley had discovered a new metal he could hardly, I think, have taken more pains to prove that he was correct in his first formula for the best chemical composition of steel rails. But I have seen so much done in the way of proof by experiment that I am inclined to think that almost anything can be proved by experiments and by samples. If Dr. Dudley would only give up his formula, which would not suit any country-not even America- * For the convenience of members it has bees thought best to insert the continuation of this discussion at the Virginia meeting in tide place, rather than to delay its permanent publication until the issue of Volume X, Transactions, where it would properly belong. T. M. D., Sec'y, † Sent to the secretary in manuscript.

Jan 1, 1881

By R. V. Smith

The theory for unsteady radial flow of gas, as simplified by Aronofsky and Jenkins, has been reviewed and compared with actual well performance. This study indicated that the theory should be modified by the introduction of an empirical "rate of flow" function "Y(q)". The expansion of the theory on the flow of gas to include a Y(q) term bridges the gap between the theory of unsteady-state flow of gas and actual gas-well behavior. Apparently, the Y(q) term is a function only of the rate of flow for a given well. The completion factor or skin effect is associated with the Y(q) function in such a manner that at least two or more sets of drawdown or pressure build-up tests are needed to separate the Y(q) function and the completion factor. Since the Y(q) function used in this report represents an energy loss dependent on rate of flow near the well-bore of a gas well which is in addition to the loss required by Darcy's law, the Y(q) function is related to the exponent of the back-pressure curve for a gas well. Techniques and equations are presented which permit the estimation of stabilized and "short-time" deliver-abilities. INTRODUCTION The published theory of radial unsteady-state flow of gas through porous media may be divided into papers1-" which use Darcy's law as a premise and other papers4-7,16-10 which recognize that Darcy's law may not hold for flow into gas wells. Miller8 compared theory based on Darcy's law with actual gas-well behavior and concluded that flow into gas wells deviates from Darcy's law. Houpeurt4,5 in a thorough investigation of flow into gas wells concluded that the flow rate into a gas well is proportional to the difference between the squares of upstream and downstream pressures elevated to a power between 1.0 and 0.5. Houpeurt also concluded that the deviation from Darcy's law is caused by irreversible, kinetic energy exchange between the flowing gas and the porous media. Tek9 presented a complete evaluation of the flow problem in gas wells. Several investigators state that the inclusion of gas compressibility into flow equations based on Darcy's law does not begin to explain the flow problems suggested by gas-well behavior. For many years, natural-gas engineers have realized that gas wells by actual test exhibit behavior which cannot be explained entirely by Darcy's law. Many tests on gas wells have indicated that a value of 0.85 for the exponent in the back-pressure equation is a fair average for many wells. However, Darcy's law either for steady or unsteady-state conditions indicates that the exponent should be 1.0. The purpose of this paper has been to examine this deviation from Darcy's law and to present a reasonable mathematical means of evaluating the deviation. The method presented in this paper combines previous theory with an empirical function to provide a description of gas-well behavior. All equations in this report are for constant terminal-rate-of-flow conditions. While present methods of testing wells usually are not based on this concept, they are believed to approach the constant terminal-rate conditions closely in many tests. However, several gas wells were tested by holding the rates of flow constant in order to approach more closely the constant terminal rate of flow; the results confirm the concepts presented in this paper. REVIEW OF THEORY FOR UNSTEADY-STATE FLOW OF GAS The basic partial differential equation for the flow of natural gas has been given in technical literature; the equation for a cylindrical reservoir with the well in the center is

By A. M. McQueen

Activity in the oil industry in Peru was somewhat above normal in 1928. Probably the most significant feature was the interest displayed in the oriental region in the northeast part of the country (Fig. 1). This region, though little known, has long been considered potentially rich in oil! gold, coal and other minerals, lacking only transportation to make it the country's most valuable source of income. The Standard Oil Co. of New Jersey, through its recently formed subsidiary the Standard Oil Co. of Peru, has acquired various tracts along the Maranon and Ucayali rivers in the neighborhood of the Brazilian border. Standard Oil Co. interests have had geological and surveying parties in this part of Peru since 1921, and as a result of the work done, we understand they have under lease at the present time some 2,500,000 acres of prospective oil lands. Development in the coastal region continued along normal lines during the past year. Production figures for both the International Petroleum Co. and Lobitos Oilfields show a small increase over the last few years. Total production figures since 1924 for the International Petroleum, Lobitos Oilfields and Zorritos companies, only in a minor degree estimated, are as follows: 1924, 7,924,700 bbl.; 1925, 9,138,042 bbl.; 1926, 10,750,676 bbl.; 1927, 10,110,696 bbl., and 1928, 11,969,677 barrels. International Petroleum Co., Ltd. Operations on the La Brea-Parinas Estate during 1928 continued with satisfactory results; nearly all branches showing improvement over the previous year. The average daily production for 1928 was 25,966 bbl., compared with 21,282 bbl. for 1927, an increase of 22 per cent. During the last two or three years, production methods on the company's property have been improved in line with the advance in scientific technique throughout the oil fields of the United States. Extensive investments were made in compressor equipment for handling surplus gas with the result that the gas-lift and repressuring operations are in no small way responsible for the increase in the 1928 production. In addition, the company's three casinghead plants produced 24,847,708 gal. of gasoline compared with 17,240,865 gal. in the previous year.

Jan 1, 1929

By John L. Miles

John L. Miles (Arthur D. Little, 1nc.)—Pollack and orris" have reported measurements on electron tunneling through A1-A12O3-A1 sandwiches in which the oxide was formed by gaseous oxidation in a glow discharge. From these measurements they deduced the asymmetry of the barrier and, since this is small, conclude that the mechanism suggested by Mott19 for the growth of oxide in thin A12O3 films is inapplicable. In earlier papers20 Pollack and Morris report similar work for oxide films grown thermally. In this case they find a greater asymmetry and conclude that the Mott mechanism is valid. I would like to point out that both these conclusions are quite unjustified. Mott suggests that the growth of the oxide film on aluminum results from the passage of ions through the already present film of oxide under the action of an electric field. This field results from a constant voltage which is in effect a contact potential between metal on one side of the barrier and adsorbed oxygen ions on the other side of the barrier. The theory does not require that the oxide grown is nonuniform either in stoichiometry or structure. It does however specifically assume that the partial layer of ionized oxygen on the surface remains adsorbed on the surface of the growing oxide. In other words, the so-called "built-in field" remains in the oxide only as long as the ionized oxygen is present. When a counter electrode of aluminum is deposited on the oxide, it will react with the adsorbed oxygen on the surface of the oxide, thus forming a small additional amount of oxide. It is clear, then, that there is no requirement in the Mott theory of oxide growth which would necessitate tunneling currents through an Al-A1203-A1 sample to be different when the polarity is reversed. Neither does the theory eliminate the possibility that some additional mechanism could cause the tunneling barrier to be asymmetric and hence tunneling currents to be a function of polarity in such a sandwich. Thus these tunneling-currents measurements are not germane to the question of whether the Mott mechanism is the true method of growth of aluminum oxide films. In fact, it is not surprising that there should be a difference between the oxide properties at the two interfaces (with resulting asymmetry in the tunneling barrier) since the growth conditions and growth rates must have been quite different at these two positions. S. R. Pollack and C. E. Morris (authors' reply)— The point raised by Miles above is one has caused some confusion in the past. The following is an attempt to clarify this point. The built-in field which is responsible for the growth of the thermal oxide at low temperatures arises, according to Mott, because of the passage of electrons from the Fermi surface of the oxidizing metal to surface states introduced by the adsorbed oxygen. It is assumed that the energy of these surface states lies below the Fermi energy of the metal. Electrons therefore continue to flow from the metal to the surface until the built-in electric field raises the potential energy of the surface states to the value of the Fermi energy in the metal, at which time equilibrium is obtained between the surface states and the metal. That is in equilibrium as many excess electrons pass from the metal to the surface per unit time as vice versa. The surface of the oxide prior to deposition of a metallic counterelectrode can then be pictured as follows. The Fermi energy lies in the energy gap of the oxide and is essentially pinned at the energy of the oxygen surface states. The vacuum work function of the oxide is then given by the sum of the electron affinity of the oxide (i.e., the difference in energy between the vacuum and the conduction-band minimum) plus the energy difference between the conduction-band minimum and the Fermi energy. The deposition of a metal onto the surface of the oxide can result in a transfer of electrons across the extremely thin oxide only if there is a contact potential difference between the deposited metal and the parent metal or oxide. That is if the vacuum work function of the deposited metal differs from that of the parent metal, then charge can be redistributed across the oxide in order to equilibriate the Fermi energy across the structure. (It should be

Jan 1, 1965

By Karl J. Benecke

Though the first patent on a bucket wheel excavator (BWE) was granted in 1881 in the US, this technology was developed in Germany to the high standards of today. However, this development was only possible in parallel with development of shiftable belt conveyors and boom stackers. The combination of these three types of equipment in the open pits of the Federal Republic of Germany has made lignite the cheapest energy source for power generation, despite the low heating value of German lignite on the order of 8500 kJ/kg (3600 Btu/lb) only. Comparing the costs for fuels used in power generating on the basis of their heating value, the relation between lignite, high quality black coal, and imported crude oil is on the order of 1 to 1.5 to 2.5, hence highly in favour of lignite. These cost advantages for lignite in Germany are due mainly to the concentration of lignite mining in a few high-output mines. The largest one, Fortuna mine in the Cologne district, produced a total of 45 million tons of lignite in 1976. That equals the annual fuel need of a 5750 MW power plant running 7000 hours per year at full capacity. Altogether 95.2 million bank m3 equal to 200 million tons of overburden had to be removed to accomplish this lignite output. The largest BWE ever built is working in the Fortuna mine [(Fig. 1)]. At a digging height of 51 m above crawler level, the total vertical reach in relation to the face conveyor level is 98 m by means of its conveying bridge and loading unit. The hourly output is 10 400 bank m3. Its weight in operation is 13 000 tons and its wheel diameter 21.6 m, as high as a seven-story building. Major reasons for the development of BWE technology in Germany were: ? Lignite deposits with moderately consolidated, alluvial-type overburden (gravel, sand, loam, marl, clay, etc.) ? Great overall depth of the deposits, ranging far beyond 100 m, requiring a wide opening of the mine, hence not permitting direct overcasting of overburden. ? Multiple-seam deposits of poor-quality coal divided by reject partings, which demand a perfectly selective digging tool for clean separation. In general, these conditions are almost identical to those prevailing in the lignite deposits of Texas and neighbouring states: The type of overburden suitable for BWE digging, the overall deposit depth ranges down to around 100 m, and finally, the multi-seam occurrence with partings between seams, the latter ranging from just 1 m to a few meters in thickness. Technique As the Texas-type lignite deposits come into focus more and more as a possible fuel source in power plants to replace natural gas and crude oil, the following will deal with the BWE technology for mining a typical Texas lignite deposit under the aspect of producing enough fuel for a 500-MW power plant located at the mine mouth.

Jan 1, 1980

By William R. Patterson

ACCORDING to the phase diagram for the Mn-Ni system,' the high-temperature, fcc y-manganese solid solution is stabilized to below room temperature, in the range approximately 22 to 28 wt pct Ni. However, pearson2 cites evidence in the literature showing that for manganese contents greater than about 75 wt pct the quenched phase in Mn-Ni alloys is fct. This is in keeping with zener's3 suggestion that in manganese-rich alloys the fcc high-temperature phase undergoes a diffusionless or martensitic transformation to a fct structure upon quenching. Work by Basinski and christian4 on manganese-rich compositions in the similar alloy system Mn-Cu established that in alloys of greater than about 82 wt pct Mn the y-manganese phase underwent a fee fct martensitic transformation upon quenching to room temperature. Striking evidence for this martensitic transformation was the highly twinned or banded microstructure, an example of which is shown in Fig. 1. Similar microstructures have also been found in quenched Mn-Cr5 and Mn-Au6 alloys. In the present investigation, we attempted to obtain similar evidence of a fcc — fct martensitic transformation in manganese-rich Mn-Ni alloys. Manganese alloys in the range 10 to 30 wt pct Ni were prepared by arc-melting, under argon, at atmospheric pressure. The alloys all were 50 g in size, and negligible weight loss occurred during melting. The starting materials were electrolytic manganese and nickel, both of 99.9+ pct purity. The alloys were subsequently homogenized 48 hr at 1750°F, hot-rolled 50 pct at 1700°F, annealed 2 hr at 1700°F, and water-quenched to room temperature. All heat treatment was done in purified argon. Both X-ray and metallographic techniques were used to examine the structures of the quenched alloys. X-ray diffractometer studies were conducted on powder specimens obtained from filings rean-nealed 2 hr at 1700°F in argon and water-quenched. Identification of the intensity peaks from the diffractometer counter traces showed that below about 10 to 12 pct Ni the y phase decomposed partially upon quenching to give an a- + ?-manganese structure. In the range approximately 12 to 25 pct Ni, the structure was found to be fct ? manganese with a c/a ratio approaching 1.0 at 25 pct Ni. Beyond approximately 25 pct Ni, the structure remained fcc. These results, including lattice-parameter determinations, are given in Table I. Metallographic examination. was carried out on specimens polished and etched after quenching, and also on polished specimens reannealed and quenched. In the first case, the distinctive twinning or banding so prevalent in Mn-Cu alloys was sought, while in the second, the surface relief effect generally regarded as being truly characteristic of a martensitic transformation was sought. The microstructure of representative alloys in the range 12 to 25 pct Ni is shown in Fig. 2. The structure of the Mn-15 pct Ni

Jan 1, 1965

By R. S. Wagner, R. G. Treuting, W. C. Ellis

Use of the Weisseizbevg goniometer for the study of the morphology of whisker crystals and transfer of the results to a stereograplzic projection are described. While in almost all instances a complete and rapid solution is obtained with a purely gaphical treatment, an absolute analytical treatment applicable to difficult cases is given. Examples are given for determination of growth direction and external features of a crystal, for detection of 'twintzittg, and for establislting the orientation relntionships in a kinked whisker crystal. We give here a method for the use of the Weissen-berg goniometerl" in the study of orientation relationships in "whisker" (micro) crystals3-8 and direct transference of the data to the stereographic projection. The operations are straightforward and require no involved calculations: in almost all cases solely graphical treatment is adequate. In a few complex instances, a more exact analytic method may be required. In the method, not only are equatorial reflections of an oscillation photograph used, but also those on higher layer lines, or those not occurring on a recognized layer line. Such reflections off the zero level are often essentialy to detect the presence of twinning. The method is particularly suitable for examination of whisker crystals since the axial or growth direction is almost always one of high symmetry, permitting a more restricted oscillation range to obtain the necessary reflections and an accordingly shorter exposure time. The method is also applicable when there is no lattice-related external symmetry, and is as well able to identify external crystal surfaces, when such exist, with the aid of an optical beam. Thus growth direction, identification of lateral faces, twinning, and orientation relationships in a kinked crystal can be established. A test for the Eshelby twist6-8 can readily be made. The method can be used for orientation, for structure analysis, and as an aid in the identification of an unknown crystal. Moving-film techniques have previously been employed variously for crystal-orientation studies.1,2,9-13 In particular, use of the Weissenberg method for orientation determination has been reported by Wooster and wooster.14 While their method derives the same data as here described, it differs in depending on the tracing of constant p streaks, a less than dependable phenomenon with small specimens, a few microns or less in cross section. The Laue method can and has been used for orientation studies of microcrystals,15 e.g., 2 p in cross section, but requires the extreme intensity and concentration from a microfocus tube to obtain reasonable exposure time. PRINCIPLES OF THE PRESENT METHOD Consider a crystal of random orientation with respect to the oscillation axis in a Weissenberg goniometer. Its diffraction pattern need not necessarily result in recognizable layer lines. In Fig. 1, a stereo-graphic projection of the reference sphere is given with the equatorial plane XZ normal to the oscillation axis Y, and the X-ray beam directed from X towards 2. The great circle ZZ is then normal to the beam, and the axes are right-handed. Thus the reflected X-ray beam lies at the intersection R of small circle ARB of radius 28 from 2, and of small circle RE of radius a from the rotation axis Y. a is the conventional semiapex angle of a cone of diffracted rays from the atoms aligned in the direction

Jan 1, 1967

FRank FirmstoNe, Easton, Pa.: The effect of lead on brass seems to have been recognized by Berthier, and the facts published by him as early as 1818 (Ann. des Mines, 1st ser., iii., 1818, p. 347 et seq.). He there says expressly that copper containing lead makes " dry " (see) brass, and that, for the same reason, blast-furnace

Jan 1, 1898

By F. H. Kihlstedt

THE Larap iron deposits, 125 miles east of Manila, are the biggest high-grade iron deposits in the Philippines, and have in seven years produced nearly 4 million tons of 6o per cent ore. Magnetic surveying followed by churn and diamond drilling cheaply developed a score of million tons. The ore zone is a wedge of metamorphic rocks in fresh, Miocene sediments overlain by agglomerates, which seem to have filled a river valley eroded in the sediments. A mild overthrust of the competent agglomerates crumbled the shale in front. Solutions gradually turned it into more competent hornfels and deposited pyrite, then magnetite and pyrite in the pores. As the temperature rose large bodies of magnetite with some pyrite were deposited by replacement and in open cavities in tensional areas of overthrust shears. At still higher temperature magnetite and calcium-magnesium silicates formed other bodies in similar cavities, and finally the thrust zone was invaded by syenite porphyry, causing high-temperature alteration products. Possibly, as temperature abated, more high-grade ore was deposited. The complicated faulting indicates dynamic, chronological and spatial changes of mineralization rather than zoning in a static system. Noncommercial copper, molybdenum and some gold accompanied the iron mineralization. In the thirties the Philippines gained a justified reputation as a country of considerable mineral wealth. Traces of Chinese workings show that these earliest travelers and traders had in a small way exploited the latent gold resources in the Islands. The Spaniards continued this for centuries, but did not succeed in establishing any steady mining industry. Modern technology was required to get it started. The rapid development in the last decade before the war got its impetus from several financial factors, the return to sugar growers of previously collected taxes, the influx of Spanish capital during the civil war in [ ] Spain, the influx of Chinese capital when the Japanese started their "China incident," and others. Directly or indirectly much of this capital reached the mining industry; in particular, gold mining. Out of the turmoil of an exceptional mining boom emerged a sufficient number of good and well managed gold properties to send the production to a level above that of any single state in the United States at the time. Other ore deposits besides those of gold also received their share, and for a country without any heavy industries at

Jan 1, 1946

By H. W. Hitzrot, R. H. Limons, L. V. Fegan

The testing of a new method for measuring pellet-bed temperatures in the traveling-grate or shaft furnace is presented in this paper. This method, using silver-palladium alloy wires as indicators, overcomes disadvantages existing in the methods based on the use of thermocouples which are costly and time-consuming. The authors have developed and tested a new method for measuring pellet-bed temperatures in the traveling-grate or shaft turnace through the use of silver-palladium alloy wires as indicators. This method overcomes the disadvantages of existing methods, which, based on the use of thermocouples, are generally costly and time-consuming. For example, in the case of the traveling-grate furnace, the installation of an instrumented pellet, together with its attached thermocouples, requires stopping the furnace, with resulting loss of production time. As for temperature measurement in the shaft furnace by the existing method, the movement of the shuttle-car feeder seriously interferes with both the actual insertion and the resulting distribution of continuously fed thermocouples. The authors have overcome these difficulties by using, as temperature indicators, a range of silver-palladium alloy wires that can be easily recovered, after firing at any desired location in a pellet furnace. Silver-palladium wires having specific melting points from 2000°F to 2500°F are enclosed in ceramic capsules. Each capsule is placed in a ni-chrome wire basket filled with a sample of green pellets, the baskets being the means for recovering the capsule after firing. After the encapsulated wires have been exposed to the firing cycle, the alloy wires are examined to determine the maximum temperatures attained by the pellet sample. This method gives accurate, rapid determinations of maximum temperatures attained during pellet induration in either the traveling-grate or shaft furnace The new method has the following advantages over existing methods: 1) it is less expensive; 2) no furnace downtime is required; 3) the testing units can, be made in quantity in advance; 4) measurements can be made in rapid succession at all desired locations; 5) measurements of maximum firing temperatures are more accurate; 6) on the basis of points 4 and 5, the new method gives a more reliable picture of the correlation of pellet quality, petrographic textures and maximum temperatures, thus providing a more effective quality-control tool. A disadvantage of the method is, of course, that the measurements are not continuous and only maximum temperatures are determined. TEST PROGRAM Preparation of Materials: CALIBRATION OF ALLOYS - In the following discussion the term "bead point" (see Fig. 1) refers to the temperature at which each alloy begins to melt and form a bead. Fig. 2 gives the bead point curve for silver-palladium alloys. Before the alloys are used in plant tests, the bead point of each alloy should be determined in the laboratory to verify the alloy compositions. Once a given alloy has been calibrated, it can be

Jan 1, 1965

By Axel Sahlin

Having no business interest in any of the various machines used for granulating ores, my remarks on the subject are prompted solely by my desire to contribute towards the determination of the best apparatus such information, as I have been able to gather,

Jan 1, 1893

By M. D. Hassiallis

The claim is made in a number of patents1'2'3'4 that some compounds of the class known as aryl sulphides have collector properties. One of these patents generalizes the claim to include all aryl sulphides, whose generic formula is R-S2-R' (where x = 1,2, . . . ), with the restriction that if the aromatic radicals R, R' contain substituent groups these groups may not contain nitrogen or oxygen. Moses, Hess, and Perkins cite as evidence for their claims the results of flotation tests on Anaconda and Miami copper ores using diphenyl sulphide, ditolyl disulphide and dinapthyl disul-phide as collectors. The use of alkyl sulphides as collectors has also been reported5 with the conclusion that the alkyl sulphides are better collectors than the corresponding aryl sulphides. The experimental work cited appears to confirm this contention. In order to test these claims with respect to diphenyl sulphide, a sample, purchased from the Eastman Kodak Co., was tested against Anaconda ore. The procedure followed. was that of Moses, Hess, and Perkins. A sample of ore weighing 500 • grams was placed in a laboratory ball mill. To this was added 220 grams of water, 0.06 grams of commercial diphenyl sulphide (1/4 lb. per ton of ore), and 0.8 grams of lime (3 lb. per ton of ore). The material was ground until 93 per cent passed a 65-mesh screen. This pulp was diluted to 16 per cent solids. A sample of the diluted pulp was placed in a Minerals Separation type of laboratory flotation cell. After a a-min. agitation period, pine oil was added and the froth collected for a period of 15 min. This test recovered 68 per cent of the copper, with a ratio of concentration of 6.8:I. The tailing assay was 0.3 per cent Cu. Moses, Hess and Perkins attained a recovery of 75 per cent, with a ratio concentration of I2:I. Although these results do not compare too well with those of Moses, Hess and Perkins, subsequent tests showed an improvement, as judged by vanning of the tails. It is concluded, therefore, that the patent results are confirmed. Contact-angle Tests In order to study the response of the various minerals, found in Anaconda ore, to commercial diphenyl sulphide, some contact-angle tests were made. Polished particles of bornite, chalcodte, chalco-pyrite, pyrite and quartz were conditioned for 15 min. in a suspension of diphenyl sulphide in water. The concentration of this suspension was 0.284 grams per liter, this being the concentration of this reagent in the ball mill. The conditioned particles were rinsed with water (not rubbed with filter paper or boiled linen) and then tested against an air bubble in the bubble machine, with the following results: born-

Jan 1, 1943