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By P. G. Shewmon, H. E. Collins

A study has been made to determine the sites at which sulfur adsorption occurs on copper surfaces. measurements were made of the relative torques, Ys, at the intersection of twin boundaries with surfaces near the three low-index orientations, i.e., (100), @lo), and 011), over a range of H2S/H2 ratios. HZS concerztvations j'ro~n 3 to 1500pp)n between 830" and 1050°C were used. It is concluded that sulfur adsorption occurved preferentially though not exclusively at edge sites near the (100) and (110) surfaces in the HzS range — 700 Ppm giving rise to negative torques near these orientations. Beyond this HzS range, adsorption occurred at all sites. Near the (111) surface, 7/y little with HzS concentration up to approxiwzately 75pptn. Above this range, the results indicate adsorption is occurring OH both terrace and edge sites. SCIENTIFIC interest in surfaces and their interactions with a gaseous environment dates back to the beginning of the 19th century. The scientific luminaries of that period—Faraday, Maxwell, Rayleigh, Dewar, and Gibbs—were already concerned about such processes. However, it has only been within the past several decades that adsorption on metal surfaces has been actively studied. This increased interest in adsorption has been brought about by the advent of new and improved experimental techniques and apparatus, e.g., ultrahigh vacuum, and field-emission and ion microscopes. However, most of the work done using these techniques has been carried out at low temperatures. When adsorption studies have been made at either low or high temperatures, they usually gave no indication of the particular surface orientations or type of sites on which adsorption was occurring. In the last few years, there have been a series of studies in which the surface tension, y,, and/or its derivative with respect to orientation, 7, have been studied as a function of orientation and atmosphere.'-7 Nearly all of the work on the relative torque,* ~/y, silver annealed in hydrogen and air.6 Recently Winterbottom and Gjostein" have used a modified and more accurate Mykurian method to determine the y plot of gold in hydrogen The only work in which T/~, has been measured over a range of chemical potentials for a given solute, p2, is that of Robertson and shewmon7 on the Cu-0 system. They measured T/Y, vs Po, (10"" to 10- l3 atm) at 1000°C in various mixtures of Hz0 and HZ. From this work they estimated the value of p2 at which one half of the surface sites are occupied with oxygen, pg, as being in the range 10- l6 to 10- l5 atm of oxygen. They also found that increasing Pa increased the magnitude of ~/y, near the (111) and (100) orientations. This indicates that oxygen is not adsorbed preferentially at step edges, but uniformly over all surface sites. In addition, they did one experiment on sulfur adsorption on copper surfaces, which indicated that sulfur adsorption decreases ~/y, near the (100) orientation, while not affecting ~/y, near the (111). This could be interpreted as indicating that sulfur adsorbs preferentially at step edges near the (100). In this paper the primary objective of the work has been to carry out a study of sulfur adsorption on copper surfaces over a range of temperatures and p,. In conjunction with this work, thermal grooving at grain boundaries has been examined as a method of determining the effect of sulfur adsorption on y,. METHODS Ideally, one would like to have information on the quantity of solute adsorbed on a surface and the types of sites at which it is absorbed as a function of p2. The total quantity adsorbed or the surface excess is given by the thermodynamic equation Thus data on the variation of y, with pz indicates the value of p2 at which adsorption becomes appreciable and the quantity adsorbed. The type of adsorption site is more difficult to deduce but information on this can be obtained from the variation of rz with 8, the angular deviation of the surface orientation. This is obtained from the thermodynamic equationlg Data on t and ys as functions of p2 have been obtained by the following methods. 1) Twin Boundary Grooving—By determining the effect of adsorption on the torque, 7, where T is the variation of surface energy, y,, with orientation, it is possible to obtain some indication as to the preferred sites of adsorption. Experimentally, the torque value measured is the relative torque, 7/ys The twin boundary grooving technique suggested by Mykura'' was used in this study to determine near the three low-index orientations— (loo), (110), and (111). Mykura's equation relates 7 /yS to measurements of the di-

Jan 1, 1967

By Martin E. Chenevert

The early work of Terzaghi1 showed that the true stress state of a rock can be expressed by the principle of effective stress. This principle states that effective stress is equal to total applied stress minus the pore pressure. Since the introduction of this principle, a great effort has been made to measure the pore pressure of rocks so that the true stress state can be determined. For clean, permeable sandstones, it is usually found that the effective stress principle can easily be applied. Direct measurement of the pore pressure is achieved with a hydraulic pressure device and the effective stress state thereby computed. However, for fine-grained rocks which contain large amounts of clay (referred to herein as shales), pore pressure measurements are usually quite difficult because of the adsorptive forces of the clay platelets, which produce negative internal pressures. No suitable device is known for measuring internal pressures of dry shales; the effective stress approach is therefore not feasible and data are usually presented in another form. As an example, data from compressive strength tests are presented as a function of rock wetness, rather than effective confining stress. The work of Belopoloskii2 and Colback and Wiid3 are examples of such data. It was pointed out by Lambe and Whitman4 that a better way must be found to express the effective stress of argillaceous rocks. The information presented herein is an attempt to fill that need. Various authors have been able to measure moderate negative pore pressures (0-240 psi) within rather wet, argillaceous rocks by means of various pore pressure devices. In 1961 Lambe5 resented information which shows that pore pressures in argillaceous rocks are indeed negative ; he presented values of suction pressure as low as - 14 psi. Likewise,

Jan 1, 1970

Establishment of a Bureau of Mineral Research at the Michigan College of Mining and Technology, initiated by the State of Michigan with legislation in 1951, is moving toward realization. The Michigan Legislature appropriated $24,000 to cover preliminary costs of plans and specifications for "engaging in a broad, widespread study of the beneficiation of lowgrade ores, of ore dressing, and all the problems of metallurgy that enter into such a program." Ralph C. Calder, of Detroit, who designed Michigan Tech's campus buildings, is preparing plans for the proposed Ores Research Building. Members of the college staff, Professors F. J. Tolonen, W. E. Keck, and Research Engineer Paul Jasberg are assisting in preliminary planning. C. Harry Benedict, retired chief metallurgist of Calumet and Hecla and a member of Michigan Tech's Board of Control, is assisting with technical details. Professor Nicholas Manderfield, head of the department of Mineral Dressing, was assigned to visit other research installations and suggest plans for the Bureau.

Jan 1, 1952

By C. C. Nathan

Data are resented on the physical properties of five waxes obtained from fields in Texas and Louisiana in which "parafin" troubles are being experienced. The crude parafin was fractionated into three components, voluble in cold acetone, soluble in boiling acetone, and insoluble in boiling acetone. The acetone insoluble fraction was found to consist essentially of straight chain parafin hydrocarbons in the molecular weight range 525 to 700. Solubilities of the purified high molecular weight parafins were determined in a number of solvents. It was found that in hydrocarbon solvents, including crude oil, solubilities could be calculated satisfactorily by use of ideal solubility relations. In chlorinated, and oxygenated solvents, large deviations from ideal behavior were observed. These deviations could be partially correlated with the internal pressure of the solvent. INTRODUCTION A problem encountered in many producing oil fields is that of "paraffin" deposition. The problem refers to the deposition of material from the crude oil onto tubing, pumping rods, flow lines, or other material contacted by the crude. This problem has been recognized for nearly a hundred years, and numerous investigations have been reported on its causes and prevention or alleviation. One of the more comprehensive of such investigations was published by Reistle1 in 1932. A few of the salient findings of his report are briefly as follows: The term "paraffin" as used to describe this problem refers to the deposit of carbonaceous material which is not soluble or dispersible by the crude oil under the conditions where deposition occurs. The "paraffin" normally consists of high molecular weight paraffin hydrocarbons, both straight chain and branched, resins and asphaltic materials of undetermined nature, occluded oil and water, and possibly sand. In consistency, the deposit may vary from a soft, sticky material, to one which is hard and brittle. Deposits are usually black, although lighter colors are sometimes observed. Under the conditions of temperature, pressure, and crude oil composition occurring in the underground reservoir, the paraffin is in suspension or solution in the crude. As the oil flows to the surface, there is generally a reduction of temperature, pressure, and the amount of dissolved gases contained in the oil. Reduction of temperature and gas break-out were shown by Reistle to be factors causing reduced solubility of the paraffin in the crude. Thus, as the crude containing paraffin rises to the surface and flows to storage tanks at atmospheric temperature, the solubility of the paraffin may be exceeded. Deposition will begin at the point in the system where the temperature of the system falls below its cloud point, and continue as long as there is a further drop in the solution power of the crude for the paraffin. The severity of the deposition as well as the location of the bulk of the deposition, i.e., in subsurface or surface equipment, will depend on the amount of paraffin originally in the crude, the manner in which pressure and temperature of the crude

Jan 1, 1956

C. H. WILSON,* New York, N. Y. (written discussion?).-On page 2680, under the heading Junction Box and Zone Box, the authors say, with reference to the zone-box principle of connections between primary couple, compensator couple, and copper leads, which method in its appli-cation to a single couple is shown in Fig. 34, that if this principle is adopted for a multiple installation, so as to save compensating leads; a selective switch may be (and the inference is that it must be) inserted between the zone box and the different couples, putting the switch at an inconvenient point, or putting up with some complicated interlacing of connections.. Wilson-Maeulen Co. has employed the zone-box method extensively for several years and in none of the many multiple installa-tions has either of those alternatives been resorted to. Instead there has been used a method of wiring with the switch at the indicator and involv-ing no more complications than the junction-box method shown III

Jan 11, 1919

The mines of the country are called upon to bear a very large part of the enormous taxes to be raised for 1917 and later years. The Internal Revenue Bureau, which is charged with the assessment and collection of these taxes, desires that the taxation laws shall be administered in a fair and business-like way. The application to mines, however, which have wasting assets, involves questions of particular complication and difficulty. To meet this situation, there has been established in. the Income Tax Branch, a Section of Mine Valuation in which these specific problems of the industry will be handled by competent engineers. But it is realized that something more than this is required for the satisfactory application of the tax laws to the mines, namely, as complete understanding as possible between the Government and the taxpayer, a spirit of cooperation as between the two and every possible assistance and advice from mine owners and mining engineers.

Jan 9, 1919

By J. Kinkead, R. M. Sherman, E. M. Frizzel

A recent research study performed under US Bureau of Mines Contract No. J0199088 "Modular Irrigation Equipment for Reclaimed Strip Mined Lands" investigated the feasibility of irrigation as a reclamation tool in the arid and semi-arid regions of the Western United States. Review of mined land characteristics, evaluation of irrigation systems, and assistance from the mining industry resulted in the design of two strategies for the implementation of reclamation irrigation using solid set systems. It is not the intent of this paper to suggest the generalizations made on the basis of a six state area can extend to the design of an irrigation system for a specific mine site. The purpose is to present two irrigation strategies that may be implemented with solid set irrigation in this six state area. The reader should note that the following is the result of research and, therefore, original concepts were presented. The ultimate validity of these concepts will be determined by future field tests.

Jan 1, 1983

Nature: Man is but one of the creatures which in- habit the earth, a dust speck in the universe. Thinking man has been concerned with his place and purpose in the universe since the earliest Egyptian and Chinese philosophers. Ancient creeds, as well as modern religions and philosophies of life, were concerned with the same problem. While such considerations and concepts have been valuable, theoretical philosophizing and dogmatic concepts are inadequate for a satisfactory solution of world problems of today. The concepts of man and life and their ultimate purpose should be sought in the relations of intelligent man to man and their relation- ship to the physical world. The quintessence of nature's accomplishment-man- is also the greatest disturber of nature and the greatest enemy of his own kind. While his spirit and mind defy and overcome natural limitations, his physical self is controlled by the same basic biochemical laws that govern any other form of living matter. This paradoxical duality of human voluntary and involuntary relations to nature is the source of the perpetual conflict between mind and matter. Therefore, the higher the spiritual evolution and perfection of the individual's mind, the greater and deeper the conflicting elements in their expression; and conversely, the simpler the mind or the mental and spiritual heritage, the less is the individual concerned with the conflicting elements.

Jan 1, 1950

Last spring the suggestion was made that the national engineering societies offer to assist the War Department in the formation of an engineer reserve in the United States Army. The suggestion was brought to the attention of some of the officers of the Army, who commended it and confirmed the belief that the need of such a reserve was a real one; that the European war had distinctly shown that engineers in time of war are required on a scale never before realized and of great varieties of experience. In our own army no adequate provision is made for great numbers of engineers, for although the corps of engineers is composed of men of the very highest professional proficiency in certain lines it is greatly short of the numerical strength that would be immediately required. Acting on this suggestion, the American Society of Civil Engineers, the American Institute of Mining Engineers, the American Society of Mechanical Engineers, the American Institute of Electrical Engineers and the American Institute of Consulting Engineers appointed committees authorized and directed to take such steps as might be advisable to urge the organization of such a reserve corps as part of the. regular army, and so assist in putting the United States in a better condition of prepared-

Jan 10, 1915

By F. Julius Fohs

With portions of two coal basins within its borders and a few scattered fields already developed, the question arises: What is the future of Kentucky as an oil-producing State? Is the long list of failures due to lack of commercial pools, or unintelligent prospecting? A study of its beds and irregularities of structure points not only to a large waste of development money on unpromising areas, but also to the presence of a few structures well worthy of development. The surface rocks of Kentucky show in succession more than 4,000 ft. of Paleozoic sediments and more than 2,000 ft. of Cretaceous, Tertiary, and more recent deposits. Folding and erosion have brought these beds to the surface, where they have been observed and studied in detail by my associate, James H. Gardner, myself, and others. This has given opportunity to observe the beds offering suitable reservoirs and having the proper impermeable covering; also the mapping of outcrops and outcrop lines, taken in conjunction with available well records, indicates that certain areas are worth testing, and with even greater definiteness shows areas which should be excluded, as devoid of possibilities. West of the Tennessee River, Cretaceous, Tertiary, and Quaternary sediments occur so that all trace of ancient folding is obliterated, the sediments overlapping unconformably Mississippian rocks. This area embraces 2,000 square miles, or one-twentieth of the area of the State, the Paleozoic rocks covering the remainder. Since there is nothing upon which to base the location of tests for oil and gas in the Cretaceous-Tertiary beds of Kentucky, the Paleozoic area will be chiefly considered. The distribution of Paleozoic rocks in Kentucky is centered about the north-northeast striking Cincinnati geanticline, bringing to the surface on the Jessamine dome the oldest rocks exposed in the.State, those of the Devonian, Silurian, and Ordovician systems. On either flank of this great earth-arch are the Mississippian rocks, sloping gradually beneath the coal-measure basins to the west and to the east. West of the western coal basin, and. between it and the Cretaceous-Tertiary rocks further west, is a high area of Mississippian rocks. Crossing the State

Jan 1, 1915

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 H. J. Maguire

Those familiar with mill-practice understand the work required of an average bucket-elevator, but I wish to call special attention to the wear on the buckets. I have been studying in what manner the life and service of the bucket might be improved, and I feel that an adjustable lip, attachable to each bucket without the aid of rivets, will be of material advantage. For illustration, consider the feed-elevator of a typical mill in the Cæur d'Alene district. The ore is carried by water in a launder from the feed-rolls and dumped in the " boot" of the elevator, directly in front of the ascending bucket. Middlings from the return-rolls are similarly handled. Under this condition the bucket not only carries the ore, but also picks it up, and this latter requirement determines the life and service of the bucket. It might be said that it would be better practice to convey the feed to the elevator and dump it directly into the bucket, but at one mill at which this plan mas tried the results were disappointing and the rubber belt was badly worn. The wear of the bucket is confined to the lip and the corners which have to pick up the material. When the lip on a corner of a '7- by 12-in. malleable cast-iron bucket is worn down about 3 in., the bucket is of no further value as a carrier and has to be replaced. The worn bucket, containing about three-quarters by weight of the metal of the original bucket, has a scrap value of about 10 per cent. of that of a new bucket. To the cost of the bucket, however, should be added the time-

Jan 1, 1913

By Hans Rumpf

INTRODUCTION Agglomeration is based on adhesion between particles. Production of agglomerates of specific strength, strain properties, size, porosity and structure necessitates the activation of the adhesive forces. To achieve this, it is important for us to know details of the various systems of adhesion. Reports on the work of our Institute for the investigation of systems of adhesion were published on various occasions. A reference to those publications is made in the following abstract, and the findings previously published are presented only to the extent necessary for a better understanding of more recent test results, or of changed ideas. 1. MECHANISMS OF ADHESION We must distinguish between various "mechanisms of adhesion". By "mechanism of adhesion" we understand the interaction between a particle and a substrate resulting from a clearly definable physical or physico-chemical process resulting in a definite mathematical interrelation- ship between the decisive variables.

Jan 1, 1977

By John J. McCabe

INTRODUCTION Over the years, Congress has written into the Internal Revenue Code various provisions aimed at lessening at least one financial burden faced by taxpayers in the mining industry - the federal income tax burden. These provisions include the election to deduct exploration expenses, the election to defer deduction of development expenses, and the percentage depletion deduction. Careful tax planning from the very beginning of a mining venture is essential in taking maximum advantage of these tax benefits. A major decision to be made is the choice of organizational structure. (For a more detailed discussion of this subject, see McCabe, John J., "Developing Structures for Investments in Mineral Property," New York University Institute on Federal Taxation, 42 NYU 24, 1984). One such structure is the use of multiple corporations, with mining activities conducted by one corporation and nonmining activities, such as manufacturing, financing and administration, conducted by the other corporation. This technique, which will be discussed in detail below, can be particularly advantageous in delaying recapture of previously deducted exploration expenses and in maximizing depletion deductions. TAX BENEFITS IN MINING Exploration Subject to certain restrictions discussed below, exploration expenditures (i.e., expenditures paid or incurred during the taxable year for the purpose of ascertaining the existence, location, extent, or quality of any deposit of ore or other mineral, and paid or incurred before the beginning of the development state of the mine are deductible at the election of the taxpayer (Section 617(a)).* Were it not for this option, exploration expenditures would be required to be capitalized and recovered through depletion, after production begins. Exploration of a mineral deposit can be very costly and may not result in commercial production for some time. If the taxpayer has income to he offset by the deductions, a mining venture can usually be structured in such a way as to allow the offset of mining losses against the other income. With today's high interest rates, this election can be quite valuable in present value terms. Corporate and noncorporate taxpayers are subject to different restrictions on this tax benefit. Corporations may elect to deduct only 85 percent of eligible exploration expenditures (Section 291(b)). (The Tax Reform Act of 1984 reduced this to 80 percent effective for expenditures after December 31, 1984, in taxable years ending after such date). The remaining 15 percent (20 percent after December 31, 1984) is capitalized and recovered at the same rate as five-year ACRS property (Section 291(b)). Individual taxpayers are not subject to this 85 percent rule; however, any amount deducted in excess of ten-year straightline amortization is a tax preference item for individuals (Section 57(a)(5)). Individuals may avoid the tax preference by electing to capitalize exploration expenditures and amortize them over ten years (Section 58(i)). In order to prevent the taxpayer from, in effect, converting ordinary income into capital gain by selling property that has given rise to exploration expense deductions, the Code requires recapture of such deductions upon the occurrence of certain events (Section 617): 1. Upon disposition of the property, adjusted exploration expenditures are recaptured to the extent of gain realized on the disposition (Section 617(d)). 2. If the property is leased, the lessor is disallowed any depletion deduction until his adjusted exploration expenditures have been recaptured in the form of foregone depletion deductions (Section 617(c)).

Jan 1, 1985

As a service to its readers, MINING ENGINEERING is publishing the mineral industry portion of the 1952 list of "Accredited Undergraduate Engineering Curricula in the United States." This list, revised annually, is issued by the Education Committee of the Engineers Council for Professional Development, and covers all phases of engineering education. The AIME is actively represented on ECPD, which was jointly organized by the Founder Societies and various other groups interested in the professional recognition of engineers.

Jan 4, 1953

By Enid C. Plante

This paper deals with the flotation of the mineral fluorite (calcium fluoride) and of two associated gangue minerals, calcite and quartz. The aim of the investigation was to produce "acid-grade" fluorite, which must contain less than one per cent of silica. Several reagents are used successfully in practice for floating fluorite from its ores. Oleic acid is the most widely used collector, usually at temperatures above 60°C, with sodium silicate as a dispersant for quartz and quebracho or tannin to depress calcite. Sulphides (e.g., galena) are often removed first by xanthate flotation. Many investigators23 report results in which more than 80 pct of the fluorite is recovered in a concentrate assaying 96 pct or more of fluorite and less than I pct of silica. This investigation was undertaken with the intention of floating the gangue, which is the minor constituent of the ore, from the fluorite. Hence emphasis was first placed on the cationic compounds that float quartz. No satisfactory separations were obtained in this way, and other reagents were investigated to discover whether these were more effective than oleic acid in floating fluorite from quartz in the usual way. The first part of the paper describes experiments with several long-chain collectors available commercially. Most of this work has been by captive-bubble and cylinder flotation tests, with some batch tests in a flotation machine. The second part describes the use of sodium cetyl sulphate as a collector for fluorite and includes laboratory tests and extension of the work to batch tests in the flotation machine. A method for determining the adsorption of sodium cetyl sulphate on fluorite has been developed and is described. Theory of Collection by Paraffin-chain Salts It may be assumed that these compounds are adsorbed at the mineral surface in one or more of three ways outlined by Kolthoff:12 1. Exchange adsorption between lattice ions in the mineral surface and collector ions in solution. Closely related is adsorption by the collecting mechanism postulated by Taggart,17 in which there is metathesis between the collector and the mineral cation or anion. 2. Exchange .adsorption between adsorbed gegen ions (p. 67, ref. 19) and collector ions in solution. 3. Adsorption of nonelectrolytes (polar-nonpolar) without displacement of adsorbed ions. With cationic collectors, inorganic cations in the solution (e.g., hydrogen ion) compete with the collector ions and therefore act as depressants, while inorganic anions have the same effect with anionic collectors. From this follows the general conclusion that ions of the same charge as

Jan 1, 1949

By Enid C. Plante

THIS paper deals with the flotation of the mineral fluorite (calcium fluoride) and of two associated gangue minerals, calcite and quartz. The aim of the investigation was to produce "acid-grade" fluorite, which must contain less than one per cent of silica. Several reagents are used successfully in practice for floating fluorite from its ores. Oleic acid is the most widely used collector, usually at temperatures above 60°C, with sodium silicate as a dispersant for quartz and quebracho or tannin to depress calcite. Sulphides (e.g., galena) are often removed first by xanthate flotation. Many investigators23 report results in which more than 80 pct of the fluorite is recovered in a concentrate assaying 96 pct or more of fluorite and less than I pct of silica. This investigation was undertaken with the intention of floating the gangue, which is the minor constituent of the ore, from the fluorite. Hence emphasis was first placed on the cationic compounds that float quartz. No satisfactory separations were obtained in this way, and other reagents were investigated to discover whether these were more effective than oleic acid in floating fluorite from quartz in the usual way. The first part of the paper describes experiments with several long-chain collectors available commercially. Most of this work has been by captive-bubble and cylinder flotation tests, with some batch tests in a flotation machine. The second part describes the use of sodium cetyl sulphate as a collector for fluorite and includes laboratory tests and extension of the work to batch tests in the flotation machine. A method for determining the adsorption of sodium cetyl sulphate on fluorite has been developed and is described. Theory of Collection by Paraffin-chain Salts It may be assumed that these compounds are adsorbed at the mineral surface in one or more of three ways outlined by Kolthoff :12 I. Exchange adsorption between lattice ions in the mineral surface and collector ions in solution. Closely related is adsorption by the collecting mechanism postulated by Taggart,17 in which there is metathesis between the collector and the mineral cation or anion. 2. Exchange adsorption between adsorbed gegen ions (p. 67, ref. 19) and collector ions in solution. 3. Adsorption of nonelectrolytes (polarnonpolar) without displacement of adsorbed ions. With cationic collectors, inorganic cations in the solution (e.g., hydrogen ion) compete with the collector ions and therefore act as depressants, while inorganic anions have the same effect with anionic collectors. From this follows the general conclusion that ions of the same charge as

Jan 1, 1947

By Akinobu Kasami, Keiji Maeda, Makoto Naito, Masaharu Toyama

Gap electroluminescent diodes have been prepared by the vapor phase diffusion of zinc into n-Gap crystals which were grown from a gallium solution (10 wt pct Gap) doped with tellurium and Ga203. A marked improvement in the efficiency of the red electrolumines -cence has been achieved by heat treatment after diffusion. External quantum efficiencies of diodes annealed under optimum conditions are 0.2 to 0.6 pct at room temperature, or about 200 times higher than the efficiencies of diodes quenched after diffusion. The optimum dopant concentrations in the gallium melt from which the crystals were grown are 3to6 x at. pct Te and 4 to 8 x 10-2 mol pct Ga203. The efficient diodes are characterized by linearly graded junctions with an i-layer 0.1 to 0.2u thick. Annealing increases the emission intensity by a factor of 20 to 50 and decreases the current density to 1/3 to 1/8 that of quenched diodes at a given bias. The decrease in current is attributed to an annihilation of deep recombination centers in the depletion layer. The increase in emission intensity is interpreted in terms of an increase in lifetime of minority carriers and an increase in the relative intensity of red-to-infrared emission. The dependence of these quantities on the tellurium and oxygen doping levels is also discussed. A number of studies have been made of the red light emission from for ward-biased Gap diodes.' At room temperature this emission band is centered at 7OOO? with a spectral width of nearly 1000?. Low-tempera-ture photoluminescence indicates that this emission is due to either the radiative annihilation of an exciton bound to a pair of zinc and oxygen atoms substituting on nearest neighbor lattice sites2,3 or the radiative recombination of an electron bound to this Zn-O pair with a hole bound to an isolated zinc shallow acceptor.3 An emission band is also observed with a spectral peak at 9800?. This infrared emission has been shown to be due to the recombination of an electron trapped at an isolated oxygen deep donor with a hole trapped at an isolated zinc acceptor.4 The red emission from Gap diodes is fairly efficient at room temperature because the nearest neighbor Zn-0 pair forms a deep electron trap at 0.3 to 0.4 ev below the edge of the conduction band.2'4 In diodes grown by liquid epitaxy an external quantum efficiency of 2.1 x 10-2 (photon/electron) has been attained by heat treatment at relatively low temperatures.5 This heat treatment was found to increase the efficiency by a factor of 3 to 6. However, no detailed studies have-been reported on the effects of heat treatment. We can only cite Onton and Lorenz's work6 on the change ; in the relative intensity of red-to-infrared emission. Heat treatment has also been tried on junctions built in during growth, but contrary to expectations the efficiency decreased. In-diffusion is a simple and controllable method of fabricating p-n junctions. For Gap, zinc is generally used to form a p-type layer on n-type crystals. The emission efficiencies of in-diffused diodes are, however, extremely low in comparison with liquid epitaxial diodes.' Although efficiencies as high as 2 x 1O-3 have been reported, values from 10-6 to 10-4 are generally obtained by typical diffusion techniques. Out-diffused diodes are known to be a little more efficient than in-diffused diodes. Nevertheless, the quantum efficiency is at most 7 x 10- 3 and ordinarily of the order of 10-4.8 NO results have been reported on heat treatment of either in-diffused or out-diffused diodes. This paper reports a marked improvement in the efficiency of the red emission observed for in-dif-fused diodes as a result of heat treatment after diffusion. The method described reproducibly yields diodes with external quantum efficiencies of 2 to 6 x 10-3. The observed dependence of efficiency on annealing time and on doping level will be discussed in terms of the lifetime of minority carriers and the formation of Zn-O complex pairs. EXPERIMENTAL A) Diode Fabrication. The n-Gap crystals used in this study were grown from a saturated gallium solution by a slow cooling method.8 The Gap content in the gallium melt was fixed to 10 wt pct corresponding to a growth temperature of about 1100 Tellurium was chosen as the n-type dopant and added to the melt in concentrations ranging from 0.001 to 0.06 at. pct. Oxygen was added in the form of Ga2O3, whose concentration was varied from 0.004 to 0.2 mol pct. The resulting crystals were platelets with well-developed (111) surfaces. Typical electrical properties were Hall mobilities of 130 to 30 sq cm per v-sec and carrier concentrations of 1016 to 10" cm-3 at room temperature. Diodes prepared from crystals with relatively low doping levels, in which u = 130 to 100 sq cm per v-sec and n = 0.6 to 6 x 1017 Cm-3, were examined in detail. The p-n junctions were produced in these n-Gap crystals by the diffusion of zinc from the vapor phase by the following procedure. The platelets were carefully lapped on both sides to a thickness of 150 to 200 u while maintaining the (111) orientation. After being etched in hot aqua regia, the crystals together with the zinc were sealed in an evacuated 12 mm ID quartz ampoule 20 cm long. The crystals and the zinc were then separated from each other at opposite ends

Jan 1, 1970

By Toshimi Yamane

The internal friction of cold-worked titanium iso-thermally annealed at temperature below the recrystallization temperature was measured. The internal friction was calculated from the half width of a resonance curve of the specimen which was vibrated transversally by the electromagnetic method. The experimental results were as follows: 1) The specimens annealed for a long time at temperature below the re crystallization temperature after cold working have the strain-amplitude dependent internal friction. 2) The internal friction increased by the cold working was decreased during the isothermal annealing. The reason of decrease of the internal friction is considered to be caused by the annihi-lation of lattice defects. 3) There is a linear relation between logQt-1/Q0-1 and (1/T)2/3 below the recrys-tallization temperature, where Q0-1 is the internal friction standing 24 hr at the room temperature after cold rolling, Qt-1 is the internal friction annealed at T°K for t min. 4) The hardness of the cold-worked titanium does not change by the annealing at 300°C for a long time but decreases by annealing at 400ºand 460°C. METALS, when cold worked, show sharp changes in physical and mechanical properties' The internal friction of cold-worked metals increases sharply and has a maximum value1,2 connected with working de- grees. The increased internal friction of cold-worked metals is recovered by annealing. This phenomenon is the well known effect called Köster effect. The recovery of the internal friction occurs earlier than the changes in tensile properties, hardness, or X-ray diffraction, and is very sensitive to the structure of a metal. The mechanism of the recovery at a temperature lower than the recrystallization temperature is being considered variously by many investigators: there are such views as the annihilation of dislocations by smith,' the rearrangement of dislocations mentioned by Nowick,4 and interaction of dislocation with point defects.5 Smith and Nowick also considered the interaction but it is so difficult for them to explain the rearrangement mechanism systematically, it being not considered a special model; therefore, we do not explain it quantitatively. Experiments measuring the recovery of the internal friction of cold-worked metals were performed by Gordon and Nowick6 on NaCl, and by Smith on copper. In addition, there are many studies, particularly those of measurements on copper by other investigators. There are comparatively many investigations on aluminum and iron which are the cubic system,'-' but only a few on metals of the hexagonal system.10 In view of this, I investigated cph titanium at room temperature and measured the internal friction after annealing isothermally at temperature lower than the recrystallization temperature. SAMPLES AND EXPERIMENTAL METHOD samples for the experiment were cut from a 6-mm titanium plate. The long direction of samples was

Jan 1, 1963

By C. Feng, I. R. Kramer

A study was conducted to determine the influence of the surface on the yield point of fcc metals and high-purity iron. For the high-purity fcc metals, the yield Point produced by restraining a specimen may be eliminated by removing a sufficient amount of the layer. A yield point similar to that in fcc metals was found when iron specimens were pre-strained after a prior deformation. This yield point is not due to an aging effect but is associated with the surface layer. The yield points in age-hardenable aluminum alloy and those connected with "work softening" are not affected by a surface-removal treatment and are, therefore, caused by bulk-type dislocation reactions. The yield point which appears in previously strained fcc metals has been the subject of numerous studies. Several theories have been advanced to explain this "unloading-reloading" yield point. Cottrell and stokes,' from their study on the effect of temperature on plastic properties of high-purity aluminum, considered that it was the result of an avalanche "breakdown" of Lomer-Cottrell sessile dislocations. Haasen and Kelly2 extended this concept of dislocation-dislocation interaction to account for the yield point when unloading and reloading was carried out at the same temperature. On the other hand, strain aging was found to be responsible for the yield point in A1-Mg alloy by Westwood and Broom,3 and in aluminum alloys containing various amounts of alloying elements by Smallman, Williamson, and Ardley.4 In these cases, the yield point is considered to be associated with the locking of dislocations by impurity atoms. Birn-baum and filer5,6 and Takamura and muira7 reported that, when a high-purity copper specimen was prestrained, then held at a lower stress, and finally reloaded at the prestrain temperature, a larger yield point was observed. Such an increase was attributed to the locking of dislocations by point defects. In addition, Bolling8 suggested that both mechanisms, i.e., dislocation-dislocation interaction and strain aging, are responsible for the yield phenomenon, at least in a brass. Thus, there appears to be experimental evidence for both the strain aging and dislocation-dislocation interaction theories to explain the yield point in the fcc metals and alloys. In a previous article,9 one of the authors observed that, if sufficient amounts of metal were electrolti-cally removed after deformation of a high-purity aluminum single crystal, the yield point did not appear upon reloading. Continued pursuit in this area revealed that the effect of the surface on the yield-point phenomenon is not limited to one metal but affects a variety of metals of different lattice structures. Nor is the effect limited to the yield points produced by simple unloading-reloading at constant temperature; the surface exerts an important role on the yield point even when the temperature is changed at some stage during the test. It is the intent of the present article to give additional information regarding the effect of the surface on the yield-point phenomenon and to show the association between the yield point in both fcc and bcc metals and the existence of a heavy concentration of dislocation in the region near the surface of a deformed specimen.10 EXPERIMENTAL Materials. The single crystals used in this study had a nominal cross section of 0.125 by 0.125 in. and a 3-in. gage length and were prepared by a modified Bridgman technique. The initial purity for the metals was 99.997, 99.999, and 99.999 pct for aluminum, copper, and gold, respectively. Bar stock of these same materials was used in the preparation of the polycrystalline specimens of aluminum and copper. The iron specimens were machined from rods of "ferrovac", reported to have a purity of 99.98 pct. In addition, a precipitation-hardening aluminum alloy, containing 1.5 pct Cu, 2.5 pct Mg, and 5.5 pct Zn, was used. The polycrystalline specimens of iron, copper, and the aluminum alloy had a diameter of 0.17 in. and a gage length of 2 in. while the high-purity aluminum specimen had a nominal rec-

Jan 1, 1965