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By L. S. Darken

IT has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernst1 in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and Fuoss2 with results which have recently been confirmed experimentally by Harped and Nuttall.3 This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author 4.6 who pointed out4 that "for a system of more than two components it is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepticism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley11 in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion 0f acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 1050°C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1948

By E. T. Turkdogan, P. Grieveson

Experimental results are given for the rate of oxidation of ferrous iron to ferric iron in pure molten iron oxide by carbon dioxide + carbon moloxide mixtures at 1550°C. It is shown that the rate-controlling process is the interdiffusion of iron and oxygen atoms within the melt. The inter-diffusivity of iron and oxygen in the melt is obtained from the results and the value of (5.0 * 1.0) x 10-5sq cm per sec is recommended for the temperature of 1550°C. Similarly, it is also found that the rate of reduction of molten iron oxide is con -trolled by diffusion in the melt; however, apparent interdiffusivity values from these experiments are 10 to 20 pct higher than those obtained in the oxidation experiments, by virtue of convection arising from density difference. The results of the oxidation experintents are used to calculate an estimated self-diffusivity of iron in molten iron oxide of (1.5 * 0.5) x sq cm per sec. BECAUSE of the industrial importance of iron oxides, the study of the kinetics of both the reduction and oxidation of the solid oxides has received a great deal of attention. However, knowledge of the kinetics of similar reactions in the liquid state is very meager. Dancy 1 studied the kinetics of reduction of molten iron oxide by carbon in pig iron and found that the reaction is very fast. It was concluded from the results that the reduction of molten ferrous oxide is a first-order reaction up to 80 pct reduction, while

Jan 1, 1964

By A. G. Guy

Zinc vapor from a reservoir of liquid zinc maintained at lower temperatures was diffused into sets of copper-zinc alloys at 759° and 870° C and into sets of silver-zinc alloys at 650° and 700° C. Each set of ,four copper-zinc alloys consisted of pure copper and 90/10, 80/20, and 70/30 brass. Similarly the set of silver-base alloys consisted of specimens containing 0, 7, 15, and 20 pct Zn. Natural markers at the initial surfaces of the specimens ware "trapped" under a thin electroplate and their depth of burying was measured after diffusion. The ratio of diffusivities of the two components determined from these data and the chemical diffusion coefficient calculated by the Matano method agreed with previously reported results. The line of markers was irregular and was often discontinuous when a grain boundary was crossed. TECHNIQUES involving the vapor phase have been widely employed in studying diffusion phenomena in metals. Many investigators have evaporated the more volatile component from an alloy, but it is generally believed that the porosity created under these conditions interferes with adequate interpretation of the experimental results. The extensive work of Gertsriken6 has been criticized on this score. Accary1 found that the diffusion coefficient for de-zincification of brass is larger by a factor of five than that for zincification, although he attributed the difference to a higher vacancy concentration under conditions of dezincification. Balluffi and siegle2 thoroughly investigated the technique of adding a more volatile component to a less volatile base metal as a means for studying diffusion. They verified that no porosity forms in a brass under these conditions and that the diffusivities of the two components can be determined from observations of the motion of markers originally placed on the surface of the specimen. The mathematical analysis that they developed for treating the experimental data was modified in a later note, but essentially it involved using the graphical Boltzmann-Matano method that is customarily applied to solid-solid diffusion couples. The experimental method used in the present research was similar to that employed by Balluffi and Siegle except for two modifications. Balluffi and Siegle used alloy chips as the source of metal vapor. This procedure has the disadvantage that the concentration of solute at the surface of the specimen changes during the diffusion experiment as the alloy content of the chips is gradually decreased. This disadvantage was overcome by employing liquid zinc as the source of zinc vapor in a manner similar to that described by Herasymenko.9 There was then no limitation on the amount of solute usefully available, and several relatively large specimens could be diffused in a given experiment. The second modification was the use of natural markers on the surface of the specimen rather than larger, artificial markers, such as the alumina powder employed by Balluffi and Siegle. It was expected that the fine, natural markers would permit more precise measurement of the buried interface as in the case of ordinary sandwich specimens.10 EXPERIMENTAL The experiments were designed so that zinc from the vapor phase would maintain a constant zinc content at the surface of pure copper (or silver) and

Jan 1, 1960

By L. S. Castleman, R. K. Hotzler

We are currently studying the effects on recrys-tallization of impurities diffused into dispersion-hardened alloys. Our interest in this phenomenon was originally aroused by the observation that the recrystallization temperature range of tungsten "doped" with alumina and silica, or with thoria, is lowered drastically if nickel is plated onto the tungsten prior to heat treatment.' In this note, we report a similar effect that sulfur has on the recrystallization behavior of thoriated nickel. The experimental procedure for this exploratory phase of the investigation has consisted simply in heating commercially obtained stress-relieved samples of thoriated nickel for varying temperatures and times in sealed capsules containing air and small quantities of sulfur. The samples contain 2.4 vol pct thoria and initially less than 18 ppm S by weight; they are prepared either from 0.5-in.-ciiam rod stock or from 0.092-in. sheet and are in the "as-received" (stress-relieved) condition prior to exposure. In an atmosphere free of sulfur, such samples do not show evidence of recrystallization after being annealed for 1 hr at a temperature of 2500°F (1372C).2 The photomicrograph in Fig. 1 shows the microstructure of one of our samples annealed for 75 hr at 1000° C (1832°F) in a sulfur-free capsule. The grain structure is hardly evident (if at all) at 465 times magnification. In contrast, the photomicrograph of Fig. 2 shows the recrystallization that has taken place in a sample exposed to sulfur for 5 hr at 1000°C (1832°F). A nickel sulfide phase is visible at the grain boundaries of the light-appearing grains. We have also observed recrystallization to occur in a sample annealed at 600°C (1112°F) for 25 hr. This temperature is below the 637°C (1178°F) eutectic in the Ni-S system. In the latter case, no nickel sulfide phase is evident in the microstructure. Moreover, we have noticed the occur-

Jan 1, 1969

By Brown, R. W., G. H. Neill, R. G. Loper

All facets of ball sealer behavior must be known and understood to design for their optimum use in well treatments. The down-hole factors including the inertial forces, drag forces and holding forces have been discussed. Equations have been developed and presented for these forces. The use of these equations in this process will contribute to the most efficient use of an economical and proven ball sealer process. The urocedure presented has been used to successfully analyze field results indicating problems involving the use of ball sealers. These problems have been isolated and corrected in future treatments by using the procedure presented to revise the perforating program, the injection rate, the design of ball sealer stages and/or the type and size of ball sealers. The procedure presented also indicates that dislodgement of ball sealers occurs primarily in ultra slim-hole completions. INTRODUCTION The perforation sealing process has been proven highly successful and economical since it was introduced to the oil and gas industry in early 1956.' Since it has proved so successful in multistage fracture treatments at a much lower cost than conventional packers, the ball sealer process has become a byword in well completions.' Not only has it changed the design of fracture treatments, it has changed the concepts of selectively perforating and has greatly aided the success of the single-point and limited-entry techniques." Yet with all the advantages, there are still facets of ball sealer behavior that are not widely recognized. These must be known and understood to better design and execute the optimum ball sealer treatment. The down-hole behavior of ball sealers is influenced by a number of factors including an "inertial force", a "drag force" and a "holding force". These are considered in two phases—the initial seating of the ball and the forces tending to unseat the ball after contact has been made (see Fig. 1). This paper presents a theoretical study of these factors and formulas for predicting their influence. The authors acknowledge the fact that the flow equations presented herein describe the behavior of Newtonian fluids and do not cover the so-called power-law fluids. The assumptions made, however, are reasonable and well within practical limitations of the conditions encountered during field application. For example, it is assumed that the perforations are round with a discharge coefficient of 0.82. While this may not be exactly true, it has been verified within practical field limitations.' The discharge coefficient would not vary significantly even if the perforation size or configuration varied pronouncedly. The approach of assuming uniform perforation size is not as strained as it might first appear. Normally, a perforator contains charges equally spaced with the same number in each vertical (or horizontal) plane. If the perforating gun is not centralized, the holes in one plane will be smaller than average, while the holes in opposing planes will tend to be larger than average. The net result is that the two effects tend to balance. FACTORS AFFECTING CONTACT WITH PERFORATlON Ball sealers are injected into well treating fluids for the purpose of contacting and sealing those perforations which are accepting the fluid flow. The efficiency of the sealers is primarily influenced by: (1) the velocity of the balls down the pipe, and (2) the fluid velocity through the perforations. To divert the sealer to the perforation, the inertial force of the ball must be overcome by the drag force created by the fluid velocity through the perforation. BALL VELOCITY The final, or stable, velocity of the ball is the sum of the actual fall velocity and the fluid velocity. This will be

By R. I. Parsons, M. B. Standing, E. N. Lindblad

The recovery of the heavier components from a gas cap or retrograde pool is shown to be the greatest when the sand is cycled with a dry gas at a low pressure. This conclusion is in direct opposition to the belief that the most efficient production program is pressure maintenance and cycling at or near the dew point. The results are calculated from: (I) constant volume, variable composition pressure-volume-temperature tests on a mixture of trap gas and liquid from a producing well; (2) published equilibrium constant data and the measured composition of the dew-point material; and (3) the fact that in a sand section of homogeneous permeability, injected gas displaces reservoir gas nearly, quantitatively. The results are based on the simplifying assumption that variable permeability systems may be defined by the ratio of two statistical parameters, and that gas injected into an actual sand will behave as though the sand were composed of many layers, each of constant permeability. Introduction Pressure decline in gas-condensate type reservoirs is accompanied by the formation of a liquid phase throughout the reservoir. Over the past ten years the processing of the material from these types of reservoirs for the heavier hydrocarbon components and the return of the light fractions to the reservoir ("cycling") has become increasingly popular. It has often been stated that the purpose of such a program is to prevent the loss of the retrograde liquid phase formed in the reservoir. The purpose of this paper is to present the results of laboratory tests and computations concerned with several possible methods of producing a gas cap or condensate type of reservoir. The results show that the recovery of heavier hydrocarbons for this type of reservoir is not a maximum under conditions of cycling at or near the dew-point pressure. Instead, variations in permeability and the ability of the dry injected gas to revaporize condensate, point to cycling at a considerably reduced pressure as the optimum production-method. In addition the paper suggests a way of evaluating sands for their permeability variation. The calculations presented in the following sections of the paper are in terms of the production of the butanes and heavier fraction from the gas cap of a field which had an original pressure of approximately 3000 psi. Specifically, the calculations show: 1. To what extent the condensate formed in the reservoir after pressure decline can be recovered by the cycling of a dry absorber-plant gas through the sands. 2. Whether there would be greater recovery of hydrocarbons if cycling were instigated at the original reservoir pressure.

Jan 1, 1948

By M. B. Standing, R. I. Parsons, E. N. Lindblad

The recovery of the heavier components from a gas cap or retrograde pool is shown to be the greatest when the sand is cycled with a dry gas at a low pressure. This conclusion is in direct opposition to the belief that the most efficient production program is pressure maintenance and cycling at or near the dew point. The results are calculated from: (I) constant volume, variable composition pressure-volume-temperature tests on a mixture of trap gas and liquid from a producing well; (2) published equilibrium constant data and the measured composition of the dew-point material; and (3) the fact that in a sand section of homogeneous permeability, injected gas displaces reservoir gas nearly, quantitatively. The results are based on the simplifying assumption that variable permeability systems may be defined by the ratio of two statistical parameters, and that gas injected into an actual sand will behave as though the sand were composed of many layers, each of constant permeability. Introduction Pressure decline in gas-condensate type reservoirs is accompanied by the formation of a liquid phase throughout the reservoir. Over the past ten years the processing of the material from these types of reservoirs for the heavier hydrocarbon components and the return of the light fractions to the reservoir ("cycling") has become increasingly popular. It has often been stated that the purpose of such a program is to prevent the loss of the retrograde liquid phase formed in the reservoir. The purpose of this paper is to present the results of laboratory tests and computations concerned with several possible methods of producing a gas cap or condensate type of reservoir. The results show that the recovery of heavier hydrocarbons for this type of reservoir is not a maximum under conditions of cycling at or near the dew-point pressure. Instead, variations in permeability and the ability of the dry injected gas to revaporize condensate, point to cycling at a considerably reduced pressure as the optimum production-method. In addition the paper suggests a way of evaluating sands for their permeability variation. The calculations presented in the following sections of the paper are in terms of the production of the butanes and heavier fraction from the gas cap of a field which had an original pressure of approximately 3000 psi. Specifically, the calculations show: 1. To what extent the condensate formed in the reservoir after pressure decline can be recovered by the cycling of a dry absorber-plant gas through the sands. 2. Whether there would be greater recovery of hydrocarbons if cycling were instigated at the original reservoir pressure.

Jan 1, 1948

By B. B. Kunkle

The history of this refinery has been one of expansion. It now has the capacity to produce 240,000 tons of cathodes annually. A general flowsheet and descriptions of the plant layout, operations involved, and equipment used at one of the world's largest and most modern electrolytic copper refineries are presented. THE El Paso copper refinery of Phelps Dodge Refining Corp. was originally constructed by the Nichols Copper Co., in association with Phelps Dodge Corp. and the Calumet & Arizona Mining Co., in order to refine anode copper produced at the smelters of the two latter companies. Initial production was obtained from the plant in January 1930 and its annual refining capacity was 100,000 tons of anodes. In order to keep pace with Phelps Dodge Corp.'s increasing copper production in the Southwest, it became necessary in 1937 to increase the El Paso plant's refining capacity to 160,000 tons of cathodes annually. This was accomplished by adding two sections to the electrolytic tank house, increasing the number of anodes placed in each commercial electrolytic tank from 33 to 37, and making changes in the dc circuits which made it possible to put three generators on each of the two circuits instead of two, thus increasing the amperage on each circuit from 10,000 to 14,800 amp. The capacity of the two furnaces from which refined shapes were cast was increased by raising the sidedoor bays on the furnaces 6 in. An increase of 70 pct in the productive capacity of Phelps Dodge Corp.s Morenci Branch in 1942 again made it necessary to expand refining capacity. In order to accomplish this, Defense Plant Corp. set up a project to increase the capacity of the El Paso plant to 240,000 tons of cathodes annually. This project consisted of enlarging the tank house approximately 50 pct, the construction of another wire- bar furnace, and corresponding increases in other departments where necessary. The engineering work on this expansion was begun in March 1942. Actual construction was under way by August 1942, and the work was completed by March 1944. These additional facilities were purchased from Defense Plant Corp. by Phelps Dodge Refining Corp. in August 1949. The plant is in El Paso about eight miies east of the center of the city and near Highway 80 and the main lines of the Southern Pacific and Texas & New Orleans railroads. The plant site covers approximately 494 acres of company-owned land that is ideally adapted for its use, being well-drained sandy soil and having enough slope so that a minimum amount of excavation was required when the plant was constructed. There is still ample room on the plant site for any future plant expansion. The plant is constructed on four different ground levels and so arranged that the unrefined copper is unloaded on the highest level at the north side of the plant and the refined copper is shipped out from the lowest level on the south side of the plant. The receiving or unloading platform, weighing and sampling rooms, main floor of the tank house, acid and condensate storage tanks, and the slimes and copper sulphate plants are on the first or highest level. The tank house basement, yard scales, charging and furnace bays, balloon flue and stack, brick-storage building, substation and power house, boiler feedwater treating plant and pump house, water storage tanks, and change houses are on the second level. This second level also contains ample yard area for setting-up furnace charges, and for storage of custom scrap, cathodes, scrap anodes, blister, coke, and poles. The casting wheels, inspection conveyors, cathode shears, wire-bar scalping machine, slag

Jan 1, 1952

By Marlin J. Veesaert

Urban quarries offer one of the greatest opportunities for profit in nonmetallic mining with limited financial risk-if properly evaluated, planned and developed to meet market needs. Location, with respect to market, is the prime consideration. Geologic considerations and quality of rock are nearly as important. Cost factors and return on investment (ROI) are the principal financial considerations.

Jan 8, 1979

By C Gunther

Many definitions have been advanced and many limitations advocated in the use of the terms, veins, lodes and ledges. The following definitions appear to follow the best usage. A fissure vein, according to Lindgren, is a mineral mass tabular in form as a whole, though often irregular in detail, filling or accompanying a fracture or series of closely set and intimately related parallel fractures in the enclosing rock, the mineral mass having been formed later than both the country rock and the

Jan 1, 1932

By George Bell

THE mine and milling plant of Demonstration Gold Mines, Ltd., is near the city limits of Baguio, Mt. Province, P. I. The mine road connects with the main highway to Manila. The nearest railway point is near sea level, approximately 40 miles distant. The Baguio district is very mountainous and has one of the heaviest rainfalls in the world. It is therefore difficult to maintain roads or to impound tailings and mine dumps. All supplies are trucked into the district direct from Manila or the nearest railway point, which means uncertain deliveries and high freight rates. Installation of equipment is difficult and costly. The average elevation at the mine is 4000 ft. and the climatic condi-tions.are ideal except for a three months rainy season. The company generates its own power for mining and milling opera-tions with three 400-hp. Ruston Diesel engines direct connected to 250-kw. General Electric alternating current generators. Labor conditions have been excellent, although at present social security laws are causing some unrest. Labor receives a higher average wage rate in this district than other labor in the Islands. The com-pany also furnishes free living quarters, hospitalization and work-men's compensation. Taxation has been reasonable up to the present time, but some of the new mining legislation may make it difficult to operate and pay dividends. The future depends largely upon the continuation of $35 gold and the political outcome in the Islands.

Jan 1, 1939

By C. E. Lundin, D. T. Klodt

The binary alloy systems, Y-Ti, Y-Zr, and Y-Hf, have been investigated throughout their entire composition regions. There is no compound formation in any of the systems, and each system is characterized by a single eutectic reaction. The eutectic compositions and temperatures are as follows: A eutectoid reaction pct Y and 870°C occurs in the Y-Ti system, whereas a peritectoid reaction,: pct Y and 880°C occurs in the Y-Zr system. Peri-tectic-type reactions at temperatures above the eutectic levels are postulated for the yttrium and hafnium transfovmations. The development of the technology of yttrium has been given considerable attention during the past few years, and studies of binary phase equilibria have, of course, taken a prominent position in this development. In many respects yttrium, in the third group of metals of the periodic table, is similar to the adjacent group of metals, titanium, zirconium, and hafnium, and the knowledge of the phase relationships of yttrium with these metals is basic to their technology. MATERIALS AND EXPERIMENTAL PROCEDURES Materials. The metals for this investigation were supplied by the General Electric Co., Aircraft Nuclear Propulsion Department. The yttrium was in the form of an arc-melted ingot, and the other metals were in the form of high-purity, iodide-Process crystal bar. Table I lists the purities of these materials. Alloy Preparation. Melting was done by conventional techniques in a nonconsumable electrode arc furnace in an atmosphere of purified argon. Melting conditions for each binary system were the same. Each alloy button was inverted and remelted several times to assure homogeneity. Accurate weights of the charges and resultant alloy buttons were obtained to indicate deviations from intended compositions. No chemical analyses were obtained since melting weight losses were consistently in the range of 0.1 to 0.2 pct of the total weight. 10- or 20-g buttons for each 5.0 wt pct composition increment were melted to survey the three individual alloy systems. Additional alloys differing in composition by 1.0 or 0.1 wt pct increments were also melted to study selected regions of the systems. Metallograpllic Techniques. Standard metallo-graphic techniques were followed for mounting and rough grinding. Preliminary polishing was accomplished using 6-u diamond paste as an abrasive on a Metcloth Lap. Final polishing was done on a Microcloth-covered wheel using 1-u diamond abrasive paste. Purified kerosene was used as a lubricant for both polishing stages. • sothermal- Annealing. Alloys were sectioned for as-cast structlure examinations and then homogenized in preparation for isothermal-annealing treatments. Homo{:enization was accomplished by cold pressing the alloy buttons followed by 72-hr anneals at 1100c. The alloys were encapsulated in Vycor or quartz for the homogenization treatments or for isothermal anneals. Resistance-wound or resistance-element tube furnaces were used for the annealing treatments. The homogenized alloy buttons were cold rolled until cracking occurred or until a -in. specimen thickness was obtained. Small -in. square) specimens for the isothermal anneals were then sawed from the alloys. Each specimen was wrapped in tantalum foil before being sealed in the capsule. Temperatures during the anneals were controlled The time at temperature necessary to equilibrate the structures during the anneals was determined for each alloy system by holding triplicate specimens of alloys at a constant temperature for three different periotls. The specimens were quenched and examined microscopically to determine the number and amounts of phases present in the micro-structure as a function of time. Melting Studies. Eutectic temperatures of the three alloy systems were established from the results of incipient-melting studies conducted on as-cast alloys. Specimens to be melted were suspended on a tungsten wire inside a graphite cylinder placed in a glass vacuum chamber. An optical pyrometer was used to follow the temperature of the specimen as it was inductively heated in a high vacuum. The temperatures were corrected for emissivity losses by standardizing the pyrometer with known-melting-point metals. Accuracy of the temperature measurements is estimated to be + 10°C. The melting point of the yttrium was determined to be 1550°C by this technique. The invariant-temperature levels were also checked by an anneal-quench technique. This technique consists of annealing a series of

Jan 1, 1962

By Henry J. Williams

The main difficulty in the determination of silicon in pig-irons containing very high percentages of that element, has been due to their almost complete insolubility in acids, or mixtures of acids. The object of the present paper, which presents no new principle, is to suggest a method of determination which has repeatedly given accurate results, and which obviates completely the tediousness and uncertainty of the usual slow solution in acids. This method has been tried with pig-irons containing from 7 to 14 per cent. of combined silicon, and properly called ferro-silicons. When reduced to an impalpable powder in the agate mortar, an 11 per cent. ferro-silicon was found to resist the action of all acids, or mixtures of acids, with the exception of sulphuric acid of about 1.25 specific gravity. But the action of this acid, even during long continued heating, was very slow, 72 hours being necessary to com pletely dissolve half a gramme of the metal. The complete decomposition of 1 gramme of the metal may, on the other hand, readily he effected in a few minutes by fusion with sodium carbonate in a covered platinum crucible over a blast-lamp —the idea being to dissolve the silicon, leaving the iron in condi tion to be readily attacked by acids. The silicon dissolves as soluble sodium silicate, and metallic iron remains in a very spongy and finely divided condition. The addition of a little hot water

Jan 1, 1889

By R. F. Mehl, R. W. Parcel

THE rate of the decomposition of austenite in eutectoid steels, forming only pearlite, may be expressed fundamentally in terms of the rate of nucleation and the rate of growth of pearlite nodules. This matter has received much attention in recent years. (The basic references are listed in ref. 1; references of particular import to the present work will be given separately.) Systematic data have been developed for plain carbon eutectoid steels.:! Although the physical factors affecting the rate of nucleation, N, in case of plain carbon steels have presumably been identified, they cannot as yet be evaluated quantitatively.' Several somewhat successful attempts, however, have been made to calculate the rate of growth, G. In the latter case the important factors determining the edgewise growth of pearlite have been assumed to be: 1—the interlamellar spacing; 2—the concentration extremes and concentration contours of carbon in austenite in front of the growing pearlite interface; and 3—the rate of diffusion of carbon in austenite.* The only systematic data on N and G for pearlite in alloy eutectoid steels are those for Co-steels;6 there are no data on alloy eutectoid steels in which the alloying element is known to decrease the rate of formation of pearlite, apart from a few scattering data reported earlier' for steels containing manganese. This paper reports a systematic study of N and G for eutectoid alloy steels containing molybdenum and nickel, respectively. In order to provide information of help in understanding the results, new data are presented on the effect of molybdenum on the interlamellar spacing of pearlite, So; data on the effect of nickel on So have already been published.' The alloys used were in five groups: 1—Pure Fe-C-Mo alloys (Table I) were supplied by the Climax Molybdenum Company of Michigan, Detroit. They were made from Armco ingot iron of standard analysis, Acheson graphite, and ferro-molybdenum, melted in silica-lined crucibles in a high frequency induction furnace. The ferromolyb-denum was added to the melted steel, followed in 5 min by 0.08 pct Al. The ingot as-cast measured 23/4x 31/4x10 in.; it was hot-forged at 1150°C to a bar 1 in. sq.

Jan 1, 1953

By C. G. Dunn, F. W. Daniels

IN recent publications1-5 the existence and behavior of subgrain boundaries in high-purity metals has been clearly brought to light. Lacombe and Beaujardl by means of special etching methods disclosed in polycrystalline sheets of aluminum the existence of substructures differing in orientation by small amounts (about 1/4"). Boundaries of these structures at relatively high temperatures had the remarkable property' of moving about while the ordinary boundaries remained stationary. Cahn2 also observed substructures in bent and annealed single crystals of aluminum, zinc, magnesium, and rock salt. The position of subboundaries could be explained in terms of a dislocation mechanism of polygonization in which dislocations move into lines at right angles to the bent glide planes thereby relieving elastic stresses in these planes. Guinier and Tennevin8,6 disclosed the further interesting feature that polygonized structures coarsened significantly upon prolonged annealing. Somewhat similar subgrain phenomena have been observed in silicon iron of commercial purity. Although some evidence for the development of macro-mosaic structures in silicon iron already has been reported by one of the authors6,7 under the phenom-enological term "crystal recovery," much better evidence recently has been obtained due to improved etching techniques. In addition, phenomena regarding structural changes have been uncovered. The present investigation is divided into three parts: (1) The phenomenon of Laue spot sharpening on annealing cold-rolled crystals, (2) the phenomena of polygonization and subgrain coarsening The material used in the present investigation was high-grade commercial silicon iron sheet of nominal composition, 3.3 pct Si, 0.004 C, 0.011 P, 0.010 S, 0.04 Mn, 0.01 Al, 0.04 Cu, 0.01 Sn. Large single crystals of this material Were prepared for cold-rolling or bending as scheduled. Cold-rolling of 12 pct was carried out on a laboratory 8-in, diam rolling mill. The bending deformations were performed by pressing the crystals between a solid Fig. 2—lllustrative foue patterns to show Laue spot sharpening. a (Left)—Specimen as cold rolled, b (right)—After 48 hr at 1400°C. round bar and a mating half cylinder, both heavily greased. Individual specimens were cut from the deformed crystals, and the cut edges were deeply etched prior to annealing. Laue photographs were made using 40-kv tungsten radiation. The technique used to disclose the various subboundaries was an electropolish and electroetch in a bath of chrome-acetic acid.' The anodic polishing done at 22 v was immediately followed by etching at a reduced voltage, which was dependent upon the nature of the subboundaries. Phenomenon of Laue Spot Sharpening on Annealing Cold-Rolled Crystals Fig. 1 gives the initial and final orientations of the specimens cold-rolled 12 pct. Each specimen was annealed at a temperature and for a time which caused significant structural changes as evidenced by alterations in Laue patterns. Representative Laue patterns and micrographs showing the essential changes are given in Figs. 2, 3, and 4. The essential points to be derived from these illustrations follow: 1. Annealing at 950°C clearly develops a substructure with the orientation of the cold-rolled specimen. 2. The subboundaries formed obviously separate regions of nearly the same orientation. Some of the subboundaries appear as a sequence of dots similar to those observed in aluminum by Lacombe and Beaujard,' but whether this is due to extremely small differences in orientation is not known at present. 3. The substructure coarsens upon prolonged annealing. 4. Prolonged annealing also causes a decrease in orientation spread according to Laue spot sharpening'

Jan 1, 1952

By J. A. Herbst, D. W. Fuerstenau

An analysis of the kinetics of dolomite grinding in a dry ball mill reveals that the following approximations apply for the parameters of the batch grinding model: (1) the size discretized selection functions are proportional to the specific power input to the mill, and (2) the breakage functions can be taken as invariant. These approximations are shown to provide the basis for accurate predictions of product size distributions obtained for several mill speed, ball load, and particle load combinations within the normal ball mill operating range. The engineering implications of these findings are discussed.

Jan 1, 1974

By I. R. Kramer

Single crystals of aluminum were pulled in tension in a solution of paraffin oil and stearic acid. The critical resolved shear stress did not change with the concentration of the stearic acid solution; however, the extents and slopes of Stages I and II were affected greatly. The observations lend evidence that the weakening effect of surface-active agents is controlled by the rate of desorption of the metal soap formed by the reaction of the surface-active agent and the metal surface. IT has been shown by various investigators1-" that surface-active agents markedly affect the mechanical properties of single crystals. (A surface-active agent, for the purpose of this report, is defined as a long-chain organic molecule which contains one or more polar groups. Usually, however, investigations have considered only molecules having one polar group.) In general, when single crystals are deformed in some solutions containing surface-active agents, the creep rate, Fig. 1, is increased and the yield strength is decreased. The fatigue strength has been reported to be affected also.ll Rehbinder and his asociatesl' explained the "weakening" effect of surface-active agents in terms of physical adsorption. They assumed that a large pressure was created in microcracks which existed on the surface of the crystal." Harper and Cottrell,' from their study of the effects of surface conditions, found that the deformation characteristics of zinc single crystals were not altered by a solution containing a surface-active agent unless the surface of the specimen had an oxidized surface. They concluded that the role of the polar molecule was to remove the strengthening effect of the oxide coating. Later, And-radeetBpresented additional evidence which appeared to agree with this conclusion. In contrast, Klinken-berg et al.7 reported data which confirmed the results of Rehbinder. Using zinc and cadmium crystals which had been cleaned by electrolytic polishing, a large increase in the creep rate was observed when Lle specimens were tested in a 1 pct oleic acid-paraffin oil solution. They also reported that the creep rate

Jan 1, 1962

By R. V. Norris

THE wage rates and working conditions in the anthracite. region of Pennsylvania have been governed for nearly 20 years by the award of the Anthracite Coal Strike Commission, appointed Oct. 16, 1902, by President Roosevelt. The report of this com-mission, made in March, 1903, was accepted and, with eight modifications made at various dates, has had .almost the force of law, and has kept this great indus-trial region free from strikes for almost a generation. In 1920, President Wilson appointed an Anthracite Coal Commission, and its report, accepted Aug. 30, 1920, governed wage conditions to April 1, 1922. Actually, the agreements have been for terms of two to four years, and lately, in 1916 and 1920, the employ-ees have continued at work pending the negotiation of new agreements which were made retroactive, and which have all been modifications of the original 1903 award. With the expiration, April 1, 1922, of the 1920 award approaching, Mr. Lewis, president, of the United Mine Workers of America, addressed a letter, on Feb. 20, to the operators, suggesting a meeting on March 15; this date was accepted by the latter, with the notation that the time was short. At the meeting, the Mine Workers presented 19 demands, and advised that if a satisfactory agreement was not reached by April 1.a suspension of mining would occur, contrary to the practice since 1916 of continuing work with a retro-active adjustment.

Jan 6, 1922

By J. H. Carpenter

LMENITE, rutile, zircon, and other heavy minerals are found in small amounts in the sand that covers most of Florida. Small enriched deposits occur on the beaches and coastal dunes. One beach deposit east of Jacksonville was worked during World War I and another near Vero Beach during World War 11. Both ceased operation when the resumption of imports reduced prices. Early in World War II reduction of rutile imports made a domestic source of the mineral necessary to maintain the expansion of armaments. Explorations made near Jacksonville discovered a relatively large body of low-grade ore about 10 miles inland from the beaches. A plant installed by Rutile Mining Co. of Florida using both flotation and tables encountered difficulties because of low plant capacity and organic slimes in the ore. In 1944 Humphreys Gold Corp. solved the problem of concentrating the low-grade ore by using the newly developed Humphreys spiral concentrator and by mining with a hydraulic dredge. This combination of low cost mining and concentration permitted the plant to continue operation in competition with foreign ores when imports were resumed following the war. The success of the Jacksonville operation renewed interest in Florida as a source of titanium. An extensive survey of the state was made by E. I. du Pont de Nemours and Co., Inc., under the direction of J. L. Gillson in 1945 to 1946. Sampling was carried on by drive pipe drilling to depths of 20 to 25 ft. Encouraging values were discovered near the location of the present Trail Ridge mine, 50 miles southwest of Jacksonville, near the town of Starke. The United States Bureau of Mines was interested in exploring for heavy minerals in Florida, and on the recommendation of both the state geologist of Florida and of Du Pont geologists, drilled deeper where marginal indications were found on Trail Ridge. In 1947 it was discovered that sufficiently higher values occurred at depth to make the deposit commercial. The orebody at Trail Ridge is a long sand deposit averaging about 1 mile in width and 35 ft in depth. It is approximately 1 1/2 miles wide at the north end of the portion now being worked, tapering to a blunt point 3 miles to the south. The ore reaches a maximum depth of 65 ft near the center and feathers out into barren sand at the edges. The ground surface is relatively flat and is covered with vegetation including pine, scrub oak, palmetto, and occasionally in swampy areas, cypress. The remain of a dense woody growth underlies and marks the bottom of the Ore 'One. It is difficult to drill through this layer, but in some cases where it is less than 5 ft thick it has been possible to drive through the wood. Sand lying below is coarser than that in the ore zone and contains no values. The wood layer consists of unconsolidated carbonized fragments of branches and other forest trash associated with a considerable amount of ar-

Jan 1, 1954

By J. Poijärvi, J. Rastas

Recently, when increasing attention has been paid to mercury for environmental reasons, the interest of several plants is directed to the removal of mercury from roaster and smelter gases. When Outokumpu Oy built its zinc plant at Kokkola in 1969, intensive development work was started to find an efficient and economic method for mercury removal from roaster gases. A process was developed, after laboratory research and pilot plant tests, to eliminate and completely recover mercury from the roaster gases. The process was commissioned in 1970. The behaviour of mercury in the roasting process and several possible methods of removing it from gases are discussed in this paper. Theoretical investigations and empirical tests show that the removal of elemental mercury from gases by sulphatization is very efficient. Further, it is stated how the technical process was built on this idea. The zinc sulphide concentrates contain small quantities of selenium, chlorine and fluorine. The role of selenium in the process is described. Similarly, the behaviour of chlorine and fluorine in the roasting, sulphatizing and scrubbing units has been discussed. Finally, the recovery of purified mercury and selenium from the precipitates is described.

Jan 1, 1973