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By Jei Y. Choi, Paul G. Shewmon

The surface self-diffusion coefficient of copper (D,) has been measured between 847° and 1069 "C for six different orientations. These were the(111), (110, (100, and three higher index surfaces. The activation energy for Ds (designated Q s) was found to be about 49 kcal per mol for all six surfaces, and Do about 2 x 104 sq cm per sec. At any temperature Ds varied by no more than a factor of three over these orientations. It is shown that, if the free energy of a surface atom is uniquely determined by its number of nearest neighbors, it follows from the Principle of microscopic reversibility that Qs should have the same value for all surface orientations, and Ds should vary little with orientation. This model also suggests that for clean fee metals Qs ~ 2/3 AH, (heat of vaporization). This is true for copper. ALTHOUGH it has been appreciated for several decades that atoms can diffuse more rapidly on a surface than through the bulk of a crystal, it has only been in the last few years that reliable values of the surface self-diffusion coefficient (Ds) have become available. Tracer studies of Ds had been attempted prior to this period, but when a tracer is placed on a surface, an ever increasing fraction of it is drained off into the lattice. The correction for this loss involves a very difficult, and as yet unperformed calculation. Those who have worked with tracers have not corrected for this loss.1, 2 Thus their results indicate that Ds is greater than the self-diffusion coefficient in the lattice (Dl), but it has not been established that they give quantitative data on Ds. A procedure which avoids the problem of tracer loss is to study the rate of mass-transfer under the effect of surface tension. If the surface asperity being studied is very small, the mass transfer occurs entirely by surface diffusion. The kinetics at which a grain boundary groove forms on an initially plane surface is a well-studied case of this type. The smoothing of a slight scratch in an otherwise flat surface is another procedure that has been studied. If these grooves are up to 20 to 30 µ in width, the dominant mechanism for mass transfer is surface diffusion (at least in the case of metals with low vapor pressures), and the widths can easily be measured with an interference microscope. Of these two, mass-transfer techniques only in the case of grain boundary grooving has a rigorous mathematical treatment been given. This was done by Mullins.3,4 His analysis predicted that in the case of copper in an atmosphere of an inert gas, surface diffusion should be the dominant transport mechanism. This analysis gave an equation for the groove profile and predicted that the width of the groove would increase as (time)1/4. Mullins and Shewmon showed that both of these predictions agreed with experiments.5 Thus the validity of the values of Ds given by this procedure seems to be well established. Gjostein has used copper bicrystals and the grain boundary grooving technique to determine Ds and the activation energy for surface selfdiffusion (9,) in the [001] direction on surfaces ranging between the (100) and (110) planes.= He reported that Qs = 41 kcal per mole and Do = 6.5 x 102 sq cm per sec for all orientations studied. Since the results did not change with the dew-point of the dry hydrogen atmosphere or the type of refractory tube used, he concluded that the surfaces were clean, or at least that the results were not influenced by any impurities chemisorbed from the atmosphere. The work reported here reproduces and extends Gjostein's study in that D s and Q s were determined for copper over a wider range of orientations. To study the effects of impurities, two purities of copper were used as well as cathodic etching to remove any possible electropolishing film. Gjostein postulated that the diffusing atoms on a surface near a low index plane are the few atoms which are adsorbed on the smooth region between ledges or steps in the surface. A more rigorous derivation of the equation relating Ds to the concentration and jump frequency of these adsorbed atoms is given here. Using this treatment, our empirical observation that Q s and D s are essentially the same for all surface orientations can be shown to follow from the assumption that the free energy of a surface atom is uniquely determined by its number of nearest neighbors. The studies of D s using the scratch technique have been carried out by Blakely and Mukura on nickel,' and by Geguzin and Oveharenko on copper. The latter study using copper gives values of D s roughly

Jan 1, 1962

By Wolfgang Gartner

METALLURGISTS engaged in the pulling of single crystals of germanium and silicon, and their zone purification and zone levelling for transistor and diode production, have found that the lifetimes of minority carriers in low resistivity samples tend to be shorter than in high resistivity material, although equal care is taken in the crystal preparation. In other words, it is more difficult to obtain long lifetimes in single crystals of low resistivity semiconductors. It is the purpose of this note to point out that this phenomenon follows directly from the Hall1 and Shockley-Read' theories of lifetimes in semiconductors." In general, the recombination mechanism may be very complicated,' but experiments seem to indicate that the simple formula2 for the lifetime of excess carriers given by n0 + n3 Pn + P1 T = Tpo,------------------+ Tjpu ----------------------- [ 1 ] nu + pn na+ + Pa is a good representation of the situation prevailing in transistor grade semiconductors. In this formula, no and pa are the equilibrium densities of electrons 6+ - E./ET and holes, n1 = N,e is the number of electrons E1- E2/KT in the conduction band, and p1 - N,e is the number of holes in the valence band, both for the case in which the Fermi level falls at the trap level, E1. N,. is the effective density of states in the conduction band; E1, the recombination level; E1, the lower edge of the conduction band; k, Boltzmann's constant; T, absolute temperature; N,., effective density of states in the valence band; and E,., the upper edge of the valence band. t,.,, denotes the lifetime of holes injected into highly n-type material, and The indicates the lifetime of electrons injected into highly p-type material. Eq. 1 holds for nondegenerate semiconductors in which only one recombination level is active and the charge in the recombination centers is neglected. It is further assumed that the number of injected ex-

Jan 1, 1957

By M. Gensamer

IN applied mechanics and in metallurgy the transition from elastic to inelastic action is a matter of considerable interest and importance. Often the first inelastic deformation is apparently quite homogeneous; that is, uniformly distributed throughout the specimen. Sometimes this deformation is heterogeneous; that is, localized; inelastic deformation proceeds to some definite amount in restricted regions before adjacent regions of the specimen are inclastically deformed. In such cases the deformation does not become homogeneous until the whole specimen has been deformed the amount corresponding to that for each localized deformation. If the test is stopped before uniform extension sets in, the heterogeneous character of the deformation is apparent on the surface of the specimen through characteristic markings, which have been called "Lüders"' lines, "Hartmann's" lines, the "Piobert effect," or simply "flow figures." These markings are the source of considerable trouble in fabricating operations, particularly in the deep drawing of steel sheet. In many cases where the transition is of this nature, the stress developed at the upper limit of the elastic range is greater than the stress during the period of heterogeneous deformation, giving rise to the familiar "drop of the beam" effect in testing. The amount of the yield-point elongation, as well as the value of the stress at the lower yield point (the value to which the stress drops when yielding begins), are functions of the tempera-ture and the testing speed. Lower temperatures and faster rates of testing increase both the yield-point elongation and the yield-point stress. These matters have been ably discussed in a recent paper by Winlock and Leiter1 though, as brought out by the discussion of that paper, the phenomena are but little understood. The purpose of the present paper is to clarify the problem through the application of a simple principle, and to show that, through the application of this principle, a number of phenomena in the plastic deformation of metals become more read-ily understood.

Jan 1, 1938

By R. B. Tippin, J. S. Browning

Inasmuch as the higher grade potash deposits are rapidly being depleted, it is important that economic beneficiation techniques be developed for recovering potassium compounds from lower grade sylvite ores and deposits containing clay materials. The Federal Bureau of Mines has conducted research to develop processes for heavy liquid concentration of potash ores, This method of concentration is discussed, and results of tests made on potash ores from New Mexico are presented. The tests demonstrated the technical feasibility of producing near commercial-grade potash concentrates, with a high recovery of the contained sylvite. The concentration of minerals based on their differences in specific gravity dates back to the very beginning of mineral dressing, and the use of heavy liquids in the laboratory to achieve optimum mineral separations has been utilized for many years. With the advent of froth flotation and its success, the incentive to develop new processes has remained relatively dormant. However, flotation refinements in the nonmetallic ores have not progressed as rapidly as in metallic (sulfide) ores because of the complexity of the deposits and the chemical similarities of the minerals.

Jan 1, 1967

By J. M. Flaitz, A. S. Parks

OF the various methods of sampling gas-condensate wells, a method that secures a continuous representative sample of the well stream is desirable. Such a method, consisting of a sampling tube introduced into the well tubing, has proved satisfactory. The method is sufficiently accurate for operating and engineering problems A portable testing apparatus can be used with the sampling tube to obtain data useful in studying the economic and technical aspects of the development and operation of gas-condensate properties. Introduction The recent discovery and development of gas reserves that contain hydrocarbons that condense with reduction of temperature or Pressure, or both, to form a product known as condensate, has brought many new problems to the oil and gas industries. With further discovery of deep, high-pressure fields it is presumable that many more gas fields of this type will be added to the steadily increasing number. Such gas reserves are found either associated with oil as a gas cap or in separate formations. There seems to be no positive correlation between the physical or geological nature of the reservoir, and the chemical composition or phase characteristics of its contents. Knowledge of the chemical make-up and phase behavior of gas-condensate reserves is needed to cope with many problems. A knowledge of the chemical composition and phase characteristics of the reservoir material is necessary to properly design a gasoline or recycling plant, to estimate natural gas and condensate reserves, to enable the operator to study the economic and technical aspects of various methods of operation and development, and to carry Out the plan of operating subsurface and surface lease equipment. This information is often useful in questions of mineral ownership, proration, legal position, and taxation. It is the purpose of this paper to discuss methods used by the writers to determine the chemica1 composition and phase characteristics of the fluids produced from a condensate well. The scope of the paper includes a discussion and description of the method of sampling, the results of tests on the accuracy of the sampling method, a description of a portable testing apparatus used to examine the phase characteristics, typical results of tests on wells from several condensate fields, and some of the applications of these data to production problems. References to previous work on this subject are cited at the end of the paper. The Problem At reservoir conditions of temperature and pressure, the fluids produced from a condensate well exist in a homogeneous vaporous condition. The consequent reduction of temperature and pressure that occurs as this gas enters and flows up the well tube results in condensation of some of the hydrocarbon material to form a liquid. The relative amount of liquid condensed at any point in the flowing system

Jan 1, 1942

By J. M. Flaitz, A. S. Parks

OF the various methods of sampling gas-condensate wells, a method that secures a continuous representative sample of the well stream is desirable. Such a method, consisting of a sampling tube introduced into the well tubing, has proved satisfactory. The method is sufficiently accurate for operating and engineering problems A portable testing apparatus can be used with the sampling tube to obtain data useful in studying the economic and technical aspects of the development and operation of gas-condensate properties. Introduction The recent discovery and development of gas reserves that contain hydrocarbons that condense with reduction of temperature or Pressure, or both, to form a product known as condensate, has brought many new problems to the oil and gas industries. With further discovery of deep, high-pressure fields it is presumable that many more gas fields of this type will be added to the steadily increasing number. Such gas reserves are found either associated with oil as a gas cap or in separate formations. There seems to be no positive correlation between the physical or geological nature of the reservoir, and the chemical composition or phase characteristics of its contents. Knowledge of the chemical make-up and phase behavior of gas-condensate reserves is needed to cope with many problems. A knowledge of the chemical composition and phase characteristics of the reservoir material is necessary to properly design a gasoline or recycling plant, to estimate natural gas and condensate reserves, to enable the operator to study the economic and technical aspects of various methods of operation and development, and to carry Out the plan of operating subsurface and surface lease equipment. This information is often useful in questions of mineral ownership, proration, legal position, and taxation. It is the purpose of this paper to discuss methods used by the writers to determine the chemica1 composition and phase characteristics of the fluids produced from a condensate well. The scope of the paper includes a discussion and description of the method of sampling, the results of tests on the accuracy of the sampling method, a description of a portable testing apparatus used to examine the phase characteristics, typical results of tests on wells from several condensate fields, and some of the applications of these data to production problems. References to previous work on this subject are cited at the end of the paper. The Problem At reservoir conditions of temperature and pressure, the fluids produced from a condensate well exist in a homogeneous vaporous condition. The consequent reduction of temperature and pressure that occurs as this gas enters and flows up the well tube results in condensation of some of the hydrocarbon material to form a liquid. The relative amount of liquid condensed at any point in the flowing system

Jan 1, 1942

By S. T. Wlodek, John Wulff

Dense, adherent, and ductile coatings of chromium can be applied to Molybdenum by selectively freezing out the chromium solute from a supersaturated copper-or tin-rich liquid alloy. The successful exploitation of this technique depends on the control of variables common to any freezing process. Under the most favorable combimtion of supersaturation, nucleation, and mass-transfey, coatings as thick as 0.004 in. can be obtained. In exploratory experiments it was found that a coating of chromium may be applied to molybdenum by immersing the molybdenum body in a supercooled copper-chromium or tin-chromium melt and selectively freezing out the contained chromium onto the molybdenum body. Supercooling of the liquid metal plating bath can be achieved by cooling, or the maintenance of thermal or concentration gradients in the melt. The technique is similar to conventional dip-plating procedures where the sample is immersed in a molten bath of the pure plating medium, except that in these studies, the plating medium consisted of a dilute solution of chromium in liquid tin or copper. The success of this method requires that the base material to be plated be isomorphous with the coating and insoluble in the plating bath. In addition, the plating bath, while having an appreciable solubility for the coating component, must have negligible solid solubility in the solid plate. Such relationships exist in the molybdenum-chromium, chromium-tin, and chromium-copper systems. Liquid tin and copper are satisfactory as the plating solvent, because although chromium is appreciably soluble in both of these liquid metals, solid inter-solubility is almost negligible, and no compound formation occurs. The same relationships exist between molybdenum and copper or tin except that the solubility of molybdenum in liquid tin or copper is insignificant. It is this combination of solubility relationships, as well as the completely isomorphous nature of the molybdenum-chromium system, which allows the formation of a chromium coating on molybdenum by the selective freezing mechanism. Since the main deterrent to the widespread use of molybdenum for high-temperature structural applications is its poor oxidation resistance, the formation of a dense and ductile chromium coating on molybdenum may well be of commercial significance. In addition, the basic principle of coating formation by selective freezing should be applicable to other metallic or even nonmetallic systems. The precipitation of the solute from a liquid metallic solution, for the formation of a protective coating, has not been previously considered in the literature. Frequently, however, a similar phenomenon has been described in the corrosion of metallic heat exchangers by liquid metals1 wherein temperature gradients in the liquid metal heat-transfer medium result in the formation of layers or deposits of metallic residue2 in the cooler portions of the system. Impregnating techniques using liquid baths have been tried as a plating process. Semchyshen and Barr, for instance, have successfully diffused chromium into molybdenum by immersing the molybdenum specimen in a liquid tin-chromium or copper-chromium alloy. This simple holding technique fails to produce a layer of pure chromium and requires prolonged immersion to allow for the diffusion-activated enrichment of the molybdenum. During the course of this investigation, most of the phase relations published for the copper-chromium4 and molybdenum-chromium4 systems, were found reliable. It was necessary, however, to investigate the solubilities of chromium and molybdenum in liquid tin as well as the solubility of molybdenum in liquid copper. These determinations were made by a simpie weight loss technique on materials of the same purity as used in the plating studies. The results of these solubility studies are given in Tables I and I1 and indicate that although the solubility of molybdenum in liquid

Jan 1, 1961

By C. P. Proctor, J. B. Morrow

With numerous plans under consideration for coal classification, and with the advent of the Bituminous Coal Code, the intelligent sampling of coal has become increasingly important. To us it is rather significant that there have been very few fundamental studies of coal sampling in American technical literature since those of E. G. Bailey, which appeared in the Journal of Industrial and Engineering Chemistry in March, 1909. He covered the subject up to that time so thoroughly and in such an excellent manner that perhaps many other later students have felt that they could add very little to his findings. The recent studies of the British Engineering Standards Association have indicated the possibility of a somewhat different interpretation of Bailey's results, permitting the taking of smaller samples, and perhaps it will now be helpful to reopen this question. C. W. H. Holmes, in an informative series of articles on coal sampling recently published in Colliery Engineering, makes two rather interesting statements, as follows: It is scarcely surprising to find a lack of interest and knowledge regarding the sampling of coal not only in the mining industry itself but also among consumers of industrial fuel: at its best coal sampling is a dirty business, regarded as a nuisance and an expense by the commercial man, and usually as a nuisance and nothing else by the chemist. The writer can conceive only two classes of people who have never experienced any difficulty in obtaining representative samples of coal from wagons; those who have never tried to, and those who have never had the necessity or desire to check the accuracy of their work. The primary purpose of this paper is to present some tabulated data of the more significant results of a sampling investigation undertaken during the last four years to obtain certain fundamental data on the variables connected with coal sampling and to point out that often assumptions have been made that are not in accordance with the facts. One of the standard sampling methods states:

Jan 1, 1936

By C. P. Proctor, J. B. Morrow

With numerous plans under consideration for coal classification, and with the advent of the Bituminous Coal Code, the intelligent sampling of coal has become increasingly important. To us it is rather significant that there have been very few fundamental studies of coal sampling in American technical literature since those of E. G. Bailey, which appeared in the Journal of Industrial and Engineering Chemistry in March, 1909. He covered the subject up to that time so thoroughly and in such an excellent manner that perhaps many other later students have felt that they could add very little to his findings. The recent studies of the British Engineering Standards Association have indicated the possibility of a somewhat different interpretation of Bailey's results, permitting the taking of smaller samples, and perhaps it will now be helpful to reopen this question. C. W. H. Holmes, in an informative series of articles on coal sampling recently published in Colliery Engineering, makes two rather interesting statements, as follows: It is scarcely surprising to find a lack of interest and knowledge regarding the sampling of coal not only in the mining industry itself but also among consumers of industrial fuel: at its best coal sampling is a dirty business, regarded as a nuisance and an expense by the commercial man, and usually as a nuisance and nothing else by the chemist. The writer can conceive only two classes of people who have never experienced any difficulty in obtaining representative samples of coal from wagons; those who have never tried to, and those who have never had the necessity or desire to check the accuracy of their work. The primary purpose of this paper is to present some tabulated data of the more significant results of a sampling investigation undertaken during the last four years to obtain certain fundamental data on the variables connected with coal sampling and to point out that often assumptions have been made that are not in accordance with the facts. One of the standard sampling methods states:

Jan 1, 1936

By T. F. Kassner

The dissolution kinetics of type 304 stainless steel in the Bi-Sn eutectic alloy have been investigated under the well-defined hydrodynamic conditions produced by the rotating-disc sample geometry. In addition, the mutual solubilities of iron, chromium, nickel, and manganese from 304 stainless steel in the eutectic alloy were determined over the temperature range 450" to 985°C. The convective -diffusion model for mass transport from a rotating disc was used to interpret the experinlental dissolution data. The dissolution process was found to be liquid-diffusion-controlled under specific conditions of temperature and Reynolds number. Liquid penetration into the 304 stainless steel resulted in a reduction of the di,ffusion-controlled mass flux and thus precluded the calculation of the diffusion coeficients of the four components from 304 stainless steel in the Bi-Sn eutectic alloy. The convective-diffusion model for diffusional limitations of electrode reactions and mass transport at the tationssurface of a rotating disc set forth by Levich 1,2 has found wide applicability in the investigation of electrochemical and dissolution phenomena in aqueous systems. Riddiford 3 and Rosner have reviewed the model and also include numerous references on work of this nature. More recently the rotating-disc system has been applied to the investigation of hetereogeneous reactions in liquid-metal systems. Shurygin and Kryuk 5 have measured the dissolution rates of carbon discs in molten Fe-C, Fe-Si, Fe-P, and Fe-Ni alloys. Shurygin and shantarin6 also studied the dissolution kinetics of iron, molybdenum, chromium, and tungsten, and the carbides of chromium and tungsten in Fe-C solutions with a rotating-disc sample geometry. In these systems it was possible to distinguish between diffusion and reaction control mainly through experimental confirmation of the velocity dependence of the dissolution rate predicted by the model. However in the absence of dependable solubility data and the virtual lack of diffusion data in these systems, a quantitative check of the magnitude and the temperature dependence of the rate was not possible. In many instances, estimates of the activation energy for solute diffusion and the diffusion coefficient based upon the experimental dissolution data are not credible. A recent study by this author7 has resulted in a critical test of the model in a liquid-metal system. The solution rates of tantalum discs in liquid tin were measured over a wide range of temperature and velocity conditions. In addition, the solubility and diffusion coefficient of tantalum in liquid tin were determined as a function of temperature. The latter data were used with the model to predict both the magnitude and the temperature dependence of the dissolution flux. In that work it was also deemed necessary to reevaluate the solution to the convective diffusion equation to incorporate the effect of the lower range of Schmidt numbers encountered in liquid-metal systems. Good agreement between the model and the experimental dissolution data in the region of diffusion control was obtained in the Ta-Sn system. The Bi-Sn eutectic alloy is used as a seal between the reactor head and the reactor vessel in the Experimental Breeder Reactor-11. The alloy is fused periodically prior to fuel-handling operations. In that connection, it was necessary to investigate the compatibility of the liquid alloy with the type 304 stainless-steel containment material. The results of a rotating-disc study in this multicomponent system are presented. EXPERIMENTAL METHOD The 5.08-cm-diam discs were machined from 0.317-cm-thick plate. Chemical analysis information for the type 304 SS material is given in Table I. The discs were ground flat on metallographic paper and given a final polish on Linde B abrasive. A thin support rod was threaded into the disc and the region around the threads was fused under an inert gas. The support rod was fitted with a quartz protection tube and then was attached to a supporting shaft which passed through a rotary push-pull vacuum seal. The disc and supporting shafts were dynamically balanced prior to insertion into the furnace tube. The apparatus is shown schematically in Fig. 1. The 58 pct Bi-42 pct Sn eutectic alloy melts were prepared from 99.995 pct pure Bi and Sn by fusing the components in a 7-cm-ID Pyrex crucible. The system in which the melts were made was evacuated to a pressure of 1 x 10-6 Torr and back-filled with purified argon several times before melting the charge. The ingot was reweighed and placed in a slightly larger-diameter Vycor crucible used in the dissolution runs. A run was started by lowering the disc into the liquid

Jan 1, 1968

By Ernest Hersam

THE rate of output of a rock crusher is based upon a certain space relation, the calculation requiring that the size and position of the jaws, the principle of motion, and the speed of the machine be known. The result is a calculated maximum output. The purpose of this paper is to develop a method of calculating this maximum output, to judge the general applicability A utility of such a calculation, and, so far as possible, to record calculated values as a basis for the comparison of actual results, or for estimating the capacity of a new crusher or of a standard crusher working under new conditions. A method for calculating the capacity of crushing rolls, which has been in common use for a long time, is well presented by R. H. Richards.1 The output is conceived as a ribbon of rock, of which the breadth, thickness and length are governed respectively by the width of the rolls, the space, between them, and their peripheral velocity. The weight of the rock thus crushed in a given time can be calculated from its specific gravity, after applying a factor representing the percentage of voids in the hypothetical ribbon. The calculation of crusher capacity is made in a somewhat similar manner. While the action of rolls is simple, with few irregularities in operating conditions, in rock crushers the material advances intermittently, usually under the force of gravity alone, and is subjected to a variety of variable conditions. The effect of these variable influences upon' the calculation of capacity is now to be shown. In this paper, capacity will be discussed quite apart from any consideration of mechanical efficiency; that is, results will be stated not in terms of output per horsepower, but of output for a given machine when operated at a known speed, constructed and adjusted to receive material of a known size, and to yield a product having a definite maximum coarseness.

Jan 7, 1922

By Frederic Benard

The treatment of Balbach-Thum slimes at Copper Cliff by the Ontario Refining Co, is of interest because it differs considerably from methods usually employed for the recovery of fine gold from parting-plant slimes. Owing to the comparatively high percentages of palladium and platinum, wet methods are used to remover the greater proportion of these metals before electrolytic refining in the Wohlwill cells. The Plant The platinum-metals department, Wohlwill room, and gold-melting room extend along the north side of the silver refinery and are separated from the parting plant by a glass partition (Figs. 1 and 2). The platinum-metals department resembles a laboratory built on a large scale, with the various pieces of equipment laid out on terraces to facilitate handling. Because of the corrosive nature of the solutions, chemical stoneware is used throughout. Elevation of acids is accomplished by means of Mariotte bottles. On the top level are three steam-jacketed stoneware kettles of 50-gal. capacity, also a packed tower. One kettle is used for digesting the slimes while the remaining kettles are used for precipitating the gold. The dissolver is equippcd with a treated concrete hood, which is connected to the flue system. Gases are drawn off through the packed tower by means of a 6-in. stoneware exhaust fan. A 15 per cent solution of sodium carbonate is continually circulated through the tower. On the intermediate level are two suition filters, one for removing silver chloride and the other for the gold sand. The filter medium consists of an asbestos pad covered with a filter paper on which is a layer of twill. On the bottom level are two rectangular cementation tanks, 24 by 48 by 24 in. deep, and a suction filter used for removing the platinum-metal concentrates. The circulating pump for the packed tower is also here. Suction is provided by a vacuum pump having a capacity of 8 cu. ft. at 20-in. vacuum.

Jan 1, 1944

Frontino operates three underground lode mines at Segovia in the area of northwest Antioquia, Colombia, which has been an important gold producing district since the late 1800s. Auriferous pyrite, the pre-dominent sulfide, carries very finely disseminated gold. Other minor sulfides are galena, pyrrhotite, and sphalerite in quartz gangue with the host rock being granodiorite. Silver is associated with the galena and also occurs as a sulfo-salt. In 1.973 and 1974, at an annual milling rate of 145,000 mt (160,000 st), average mill heads were 7.80 g per mt (0.23 oz per st) Au; 20.0 g per mt (0.58 oz per st) Ag; and 0.37% Pb; with a production of 1,150 kg (35,700 oz) Au and 4,500 kg (141,000 oz) Ag. Over 300 mt (330 st) of Pb concentrate were shipped. The ore is crushed to minus 16 mm (5 18 in. ) and fed to a rod mill with the discharge passing over a 1.07 m by 1.07 m (42 in. by 42 in. ) jig operating in closed circuit with the underflow from a cyclone in closed circuit with two ball mills. Cyclone overflow is bulk-floated for sulfide recovery from which the tailings are sent to the river as waste with the flotation concentrate joining the jig concentrate for cyanidation. The combined gold bearing concentrates, after cyclone classification, are reground to a very fine mesh in closed circuit with cyclone classification, with the overflow going to the primary thickener. Regrinding, classification, and thickening is done in cyanide solution, and the primary thickener produces a pregnant solution for Merrill -Crowe precipitation. The thickener underflow is the feed to the agitators, thickener, and filter from which the overflow and filtrate are sent to precipitation. The washed filter cake is repulped and floated for the recovery of a galena concentrate for shipment. About 40% of the recovered silver is in this concentrate. In the refinery the precipitate is melted into a dore bullion. This 600 mt (660 st) capacity mill employs several interesting techniques. Gold recovery of 85% to 90% from a complex sulfide denotes good practice. While total power at 42 kwh per mt (46 kwh per st) is high, it would be recognized that the grinding units are small in size and the flowsheet is complicated due to the gold occurring in the sulfide minerals. The extremely low-cost electric power is generated by

Jan 1, 1981

By F. D. Rosi, C. A. Dube, B. H. Alexander

WHEN a deformed polpcrystalline metal is heated to a sufficiently high temperature, a recrystallized structure develops which consists of small, essentially stress-free grains. This transformation is referred to as primary recrystallization. Under certain conditions, on prolonged annealing of the specimens, a type of grain coarsening occurs in which a small number of grains commence to grow at various points by devouring the neighboring finegrained primary structure, which, in itself, exhibits a marked stability toward normal grain growth. This grain coarsening process has been referred to by Burgers' as "secondary recrystallization" or "exaggerated grain growth." Although much work has been done on recrystallization and growth processes, present knowledge of the factors which determine the occurrence and growth of secondary grains is inadequate for the advancement of a theory which accounts for the observed characteristics of this recrystallization phenomenon. In this respect, it would be important to make measurements of the velocity of growth of these large secondary grains. The early work of Feitnecht2 on aluminum showed that the size of secondary grains increased with temperature and time, suggesting that such measurements would be possible. More recently, Burgers1 found that the growth velocity of these grains in aluminum was constant over a large time interval, as is generally found for the growth velocity of primary grains in a uniformly deformed test piece.3-5 It is reasonable to expect that the determination of the activation energy of the secondary growth process might lead to a better understanding of the underlying atomic mechanism. This investigation, therefore, is one of a series primarily designed to measure the growth velocity of secondary grains at various temperatures for silver, copper, and aluminum. It is hoped that these studies along with those of orientation relationships, will establish a sound basis for theorizing as to the origin and nature of the secondary transformation. Experimental Procedure The metal used in the present investigation was high-purity silver (999.9 fine), which was supplied in the form of cold-rolled plates 0.250 in. thick. These plates were annealed at 500°C for 1 hr and then straight-rolled to a thickness of 0.04 in. in three reductions of approximately 45 pct, followed in each case by an anneal at 450°C for 1/2 hr. The 0.04 in. sheets were given a final reduction of approximately 50 pct, which resulted in a thickness of 0.02 in., thereby insuring two-dimensional crystal growth. Individual specimens of this material about 1x3 cm were used for all heat treatments, unless otherwise noted. The annealing was carried out under an atmosphere of argon in an Inconel tube furnace whose temperature was controlled to within -+2°C. Metallographic examination of the secondary transformation was accomplished by mechanically polishing the specimens on one side to approximately one half their thickness through 2/0 metallographic emery paper, and then electrolytically polishing in a solution of potassium ferrocyanide and sodium cyanide. With a current density of approximately 20 amp per sq dm, the time required to obtain a satisfactory surface varied from 3 to 5 min. Standard potassium bichromate was used to etch the electrolytically polished surfaces. A heavy etch with this solution produced a sharp contrast between the secondary grains and the fine-grained primary structure, darkening the latter while leaving the large secondary grains bright. All area measurements of the secondary crystals were made with a planimeter on enlarged tracings of the grains.

Jan 1, 1953

By L. Douglass Anderson

Fox some years past the annual reviews of the metallurgy of lead have almost uniformly stated that there have been no great changes, such as there were, being more particularly noticeable in the refinement of details. While this is quite true, nevertheless these changes in details are gradually bringing about a condition that, taken as a whole, constitutes a considerable advance in the art. Local circumstances have often -compelled metallurgists to adopt certain peculiarities of practice which -upon trial have been found advantageously applicable to more than the restricted district f origin. This paper will deal ' with some of the more novel features developed in recent years at the United States smelter, Midvale, Utah, particularly with reference to the influence of the bag house. The plant is equipped with six blast furnaces, 48 by 160 in., mechanically fed; four Wedge furnaces for roasting matte and sulphide ores; four Dwight-Lloyd sintering machines; 20 converter boxes for blast roasting; storage bins for ore, fuel, and fluxes; "oxide" and "sulphide" sampling mills; bag house taking all the gases of the plant; arsenic plant for treating the dust gathered there; laboratory, shops, etc. The most marked feature of the plant is its complete bag-house system. Of the many schemes thus far tried for preventing damage to surrounding agricultural interests the writer is aware of none as yet quite as efficient as the bag house. A common remark of visitors upon approaching the plant and viewing the clear stacks is that it appears to be shut down, whereas once inside all the evidences of industry are found.

Jan 7, 1914

By L. Douglass Anderson

Fox some years past the annual reviews of the metallurgy of lead have almost uniformly stated that there have been no great changes, such as there were, being more particularly noticeable in the refinement of details. While this is quite true, nevertheless these changes in details are gradually bringing about a condition that, taken as a whole, constitutes a considerable advance in the art. Local circumstances have often -compelled metallurgists to adopt certain peculiarities of practice which -upon trial have been found advantageously applicable to more than the restricted district of origin. This paper will deal with some of the more novel features developed in recent years at the United States smelter, Midvale, Utah, particularly with reference to the influence of the bag house. The plant is equipped with six blast furnaces, 48 by 160 in., mechanically fed; four Wedge furnaces for roasting matte and sulphide ores; four Dwight-Lloyd sintering machines; 20 converter boxes for blast roasting; storage bins for ore, fuel, and fluxes; "oxide" and "sulphide" sampling mills; bag house taking all the gases of the plant; arsenic plant for treating the dust gathered there; laboratory, shops, etc. The most marked feature of the plant is its complete bag-house system. Of the many schemes thus far tried for preventing damage to surrounding agricultural interests the writer is aware of none as yet quite as efficient as the bag house. A common remark of visitors upon approaching the plant and viewing the clear stacks is that it appears to be shut down, whereas once inside all the evidences of industry are found.

Jan 7, 1914

By Norman Pilling

THE solubilities of a series of experimental alloys covering the range 0 to 100 per cent. Ni, 0 to 30 per cent. Cr have been studied under conditions of complete submersion in several fully aerated acid solutions, and in solutions containing sulfurous acid. In nonoxidizing, hydrogen-discharging acids, if the nickel content is below a certain critical amount, chromium increases the rate of solution and nickel decreases this rate; this critical content of nickel is about 13 per cent. Alloys containing more than this corrode at a constant minimum rate independent of iron, nickel or chromium contents. Austenitic chrome-nickel steels may thus have a resistance to these acids equal to that of nickel-chromium alloys. In nitric acid and in unaerated sulfurous acid rather sharp limits of attack occur which are principally dependent on chromium content. In the former the limit of attack is not related to a particular chromium content but varies continuously with acid concentration. The action of sulfurous acid on these alloys is highly dependent on the presence of small amounts of other substances in solution, and many sulfurous acid mixtures rapidly attack alloys to which the pure acid is wholly inert. The observed effects are. not compatible with Tammann's theory relating corrosion resistance to lattice structure but are believed to be concordant with current views of the electrochemical nature of corrosion.

Jan 1, 1929

By R. F. Krueger

Results are presented from tests of dynamic fluid-loss rates to cores from clay-gel water-base drilling fluids containing different commercial fluid-loss control agents (CMC, polyacrylate or smt,ch), organic viscosity reducers (quebracho and complex metal lignosulfonate) and oil at several different levels of concentration. In the dynamic system the most effective individual additives to the clay-gel drilling fluid, based on cost-equalized concentrutiom, were found to be starch and the viscosity reducers. These results do not conform with the rankings determined by API fluid-loss rests, which indicate CMC, polyacrylate and starch to be the most effective and comparable. Generally, minimum dynamic fluid-losr rates were attained at cost-equalized concentrations of additive (including thinner) of about $1.00/ bbl, or less. For chernically treated clay-gel drilling fluids, both the standard and the high-pressure API filter-loss tests were found to he inaccurate indicators of trends in dynamic fluid-loss rates under the test conditions used, particulurly for drilling muds containing viscosity reducers. From a practical field viewpoint, restrictions on the applicability of the API fluid-loss test are such that it is open to question whether or not results of this test can be used routinely with confidence as an indicator of control of down-hole fluid loss under field treating conditions. INTRODUCTION The petroleum industry spends large sums of money during drilling operations to control the fluid-loss properties of drilling fluids based on the standard API filter-loss test,' which is a static filtration system. Laboratory studies' ' of dynamic filtration have shown that in a given time period filtrate loss from a circulating mud stream is greater than from a static system and that it is a function of linear mud velocity, pressure and the properties of the drilling fluid. Ferguson and Klotz' and Horner, et al," observed that (I) the dynamic fluid-loss rates for the drilling fluids used were not related to the extrapolated API filter loss and (2) the drilling fluids with the lowest API filter losses did not have the lowest dynamic fluid-loss rates. However, there has been no published information on the relative effects on dynamic fluid-loss rate as a given drilling fluid is treated with increasing amounts of chemical additive to reduce the API filter loss. Such information is economically important because drilling-fluid costs rise rapidly as chemical requirements increase. This paper presents the results of a study of dynamic filtratioi rates to cores from a clay-gel water-base drilling fluid treated with various commercial viscosity reducers and chemical fluid-loss control agents. The dynamic fluid-. loss rates to cores are compared with the standard API filter-loss values at several different levels of additive concentration. Dynamic filtration rates were obtained in each experiment under two different simulated wellbore conditions: (1) filtration just above the bit through a new mud cake laid down dynamically on a freshly drilled formation and (2) filtration up-hole through a mud cake formed by deposition of a static filter cake on top of the initial dynamically formed cake. The latter case corresponds to the bottom-hole conditions existing above the bit when mud circulation is restarted after a stand of pipe has been added or a round trip has been made to change the bit. Except for the short-duration, high-rate filtration beneath the bit where no mud cake can form, these two conditions probably represent the two extremes of dynamic filtration. Because thickness of a dynamic mud cake formed on freshly exposed formation is limited by the shearing action of the mud stream, the filtration rate for this condition is high. On the other hand, once circulation is stopped and a static mud cake forms on top of the dynamic cake, re-starting circulation has only a small effect on the cake properties and filtration rate is much lower thereafter. A discussion of the mechanics of mud-cake deposition and dynamic filtration is outside the scope of this paper but may be found in more detail in publications by prior investigators. APPARATUS AND EXPERIMENTAL CONDITIONS The test equipment used to simulate the dynamic flow conditions existing during drilling was a modification of that described previously by Krueger and Vogel: A schematic flow diagram is shown in Fig. 1. In general, a power-driven, high-pressure mud pump capable of delivering up to 60 gallmin was used to circulate drilling fluid parallel to the faces of 1-in. diameter sandstone cores mounted in a 2 3/4-in. ID high-pressure test cell. Pump rates were controlled by means of a magnetic clutch to maintain an average axial fluid velocity of 110 ft/min in the annular space between the cell wall and a 1 1/2-in. rod positioned on the center line of the cell. The core specimens were Berea sandstone plugs sealed with plastic inside 1 1/8-in. OD tubes and were fluid-saturated prior to use. Burettes were used to accumulate fluid discharged from the cores. The mud sump shown was used for treatment and storage of the drilling-fluid samples during a particular test. The valve arrangement permitted either (1) circulating drilling fluid through the by-pass line while treating with

By P. J. Dean

This Paper contains a comprehensive survey of the known electron-hole radiative recombination mechanisms in the family of III-V compounds. Because of space limitations, the luminescence properties of each III- V compound are not reviewed separately and exhaustively. Instead, the different known types of recombination processes are discussed in turn and exemplified with reference to the III- V compound in which they were first recognized, or are best understood. Electron-hole recombinations usually occur predominantly at impurities or lattice defects either introduced de1iberately or inadvertently present, but radiative intrinsic interband electron-hole recombinations, which occur in perfect crystals, have been observed. Recombination processes which involve the participation of impurities or lattice defects ("extrinsic" recombinations) considered include transitions in which a) free carriers recombine with carriers trapped at impurities ("free to bound" transitions) , b) electrons bound at donor impurities recombine with holes trapped at acceptor impurities ("donor-acceptor pair" recombinations), C) excitons bound to charged or neutral donor or acceptor impurities recombine radiatively (both "resonance" and "two-electron" "bound exci-ton" transitions have been observed), d) excitons bound to neutral donor or acceptor impurities recombine non-radiatively (an example of an "Auger" recombination), and e) excitons bound to impurities with the same number of valence electrons as the host atom which they replace ("isoelectronic " traps) recombine radiatively. In addition, Auger recombination processes involving one or more free carriers have been observed. These extrinsic processes all involve impurities which are present as point defects. Some apparently well-authenticated examples of the recombination of excitons bound to complex impurity-lattice defect centers including nearest-neighbor donor-acceptor pairs are also discussed. Identificalions of the transitions involved in stimulated emission from the direct gap III-V compounds are briefly reviewed. Although the examples of these recombination mechanisms are selected from the III-IV compounds ia this review, these processes have quite general relevance in semiconducting crystalline solids; irrdeed most of them have also been identified in the 11- VI compounds and elernental semzconductors. THE development of crystal growth and purification techniques in recent years and concurrent advances in the understanding of physical processes in solids has accelerated the development of a wide variety of solid-state electronic devices of proven utility. These de- vices are generally used for switching or amplifying operations in electrical circuits. Most solid-state circuit elements are very photosensitive. This photo-sensitivity is generally undesirable and the single-crystal chip forming the active portion of the solid-state device is mounted in an opaque container. The photosensitivity is made use of in phototransis-tors and photodiodes, which are among the most sensitive detectors of electromagnetic radiation particularly in the near infrared.' In these devices, light is converted into electrical power. The solid-state lamp utilizes the inverse effect, namely the conversion of electrical power into light. There is an increasing tendency to use single-crystal diodes rather than the earlier electroluminescent cells in which the active material is present as a powder embedded in a suitable dielectric.' The radiation is emitted at a rate far in excess of the thermal equilibrium rate for the frequencies and temperatures involved; i.e., luminescence occurs. The development of practically efficient solid-state lamps is at an early stage compared with solid- state circuit elements or even photodetectors. Considerable progress has been made in recent years, however.3 The present review is devoted to a survey of the radiative recombination processes in the semiconducting compound crystalline solids formed from elements in groups I11 and V in the periodic table. These materials exhibit the full range of known recombination processes in solids. In fact many of these processes were discovered in 111-V semiconductors. Nonradiative recombination processes, which control the lutninescence efficiency, are also discussed. Luminescence is efficiently excited in semiconductors through processes which produce large excess concentrations of free electrons and holes in the energy bands of the crystal. Transitions induced by lattice defects or impurities usually predominate in the recombination process. By contrast, luminescence in the conventional fluorescent lamp is excited by optical absorption at the luminescent impurity center itself (the activator) and/or at a second type of impurity center (the sensitizer). This latter type of photoluminescence process, occurring in doped ionic crystals with wide band gaps, is outside the scope of this review.4 I) ENERGY BAND DESCRIPTION OF ELECTRON STATES IN CRYSTALS The energy band description of the energy states available to an electron in a crystal forms the basis of our understanding of the empirical division of crystalline solids into metals, semiconductors, and insulators in accordance with their electrical and optical properties.' Nonmetallic crystals have a finite energy gap between the highest energy band which is

Jan 1, 1969

By D. R. Walker, M. C. Shaw

THE laws of comminution of Kick and Rittinger have been debated for many years. Certain data obtained from ball mill and drop tests are found to be in approximate agreement with Rittinger's law while other data would seem to support Kick's law. In all these tests the energy required to produce a wide variety of particle sizes has been studied. Surface area has also been measured with considerable difficulty, at first because it was thought that the energy associated with crushing was that required to create new surface, later because of precedent and because a more fundamental variable was unknown. Tests made with the machine shop type of grinding process show that normally brittle materials that are usually crushed can behave like the more ductile metals. Brittleness is then a relative property largely dependent on specimen size and stress state. The machine grinding operation offers a convenient means for studying the comminution of materials in which the important size variable retains its identity. The energy required to grind a certain volume of material is shown to be strongly de- pendent on size. Kick's law is found to hold very well for particles below 1 micron in size, while Rittinger's law holds approximately in the comminution of larger particles. While a physical origin of Kick's law is established in terms of the theoretical strength of materials having a perfect lattice structure, there is found to be no physical basis for Rittinger's law.

Jan 3, 1954