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By D. Hanson

Fox most of their practical applications metals are required to with-stand stresses of appreciable magnitude: indeed, it is because they possess the quality of resisting stress without becoming permanently deformed that they find such extensive use in the service of man. Metals and alloys must, in service, usually behave as elastic substances-or nearly so. It is not difficult to satisfy this condition at ordinary temperatures. Iron and its alloys, especially the steels, are at normal temperatures excellent elastic bodies, capable of satisfying most of the mechanical requirements of the engineer: where electrical, chemical or other properties are impor-tant, which cannot be met by steels, it is usually possible to find a non-ferrous alloy such as nickel, copper or aluminum, which will prove satisfactory. When the metals or alloys are not inherently sufficiently elastic, cold-working or heat-treatment may develop elastic properties to a sufficient extent for practical needs. By means of relatively simple, rapid tests we can measure such properties as elastic modulus, limit of proportionality and proof stress, upon which design can be based with confidence. The case of the soft metals, such as lead and tin, is well known to be exceptional. They possess no definite limit of elasticity, and the value of proof stress or tensile strength depends to a great extent on the speed with which the test is carried out. Design here must be based on other considerations than a well-established theory of the proportionality of stress and strain. It is now generally recognized that steels and non-ferrous alloys possess at temperatures not greatly exceeding that of the atmosphere, characteristics quite different from those existing at ordinary temperatures, and that they assume qualities similar to those of the soft metals. Not only have they no limit of elasticity, but the proof stress and the ultimate stress depend on the time of application of the load. Flow under load may persist for long periods of time, possibly indefinitely, and the determination of a true maximum stress becomes a matter of great difficulty.

Jan 1, 1939

By Oliver Bradley

THE utilization of casing-head gas in the manufacture of casing-head gasoline by both the absorption and the compression method is a most important factor in the conservation of our natural resources.. Any industry connected with the oil business, in general, possesses particular attraction for a large number of people not conversant with its basic principles, for the reason that the large fortunes made in the production and utilization of petroleum and its products have been given undue prominence. The general impression of the public that enormous profits are to be realized in the casing-head gas industry with minimum expenditures of both capital and effort has, in a large measure, accounted for the phenomenal expansion of the industry in recent years and, likewise, has resulted in many mistakes and loss of investment funds. It is true that many installations have been very profitable, but such instances are always the result of careful planning, experienced judgment and conservative estimates. The inception and subsequent activity in the manufacture of casing-head gasoline, enabling the business to assume an important position in the petroleum industry, are of, comparatively recent origin, as its greatest growth, particularly in Oklahoma, occurred during the years 1917 and 1918. Much information must yet be secured and systematized concerning the methods of manufacture of gascline from high-yield casing-head gas, and a large field is still open for the application of accumulated experience and good engineering practice in devising better methods of extracting gasoline from casing-head gas of the poorer grades. The absorption process is coming into general use as a most efficient system of treating casing-head gas, and even so-called dry gas. In fact, there is a decided tendency toward the universal adoption of the absorption process as against compression methods. However, a general discussion of the relative merits of these two systems is not within the scope of this article.

Jan 9, 1920

By A. C. Fraker, H. H. Stadelmaier

WIENER and Bergerl reported the existence of the nitrides Fe3NiN and Fe3PtNwith a cubic L1'2 structure. The present note shows that a similar nitride Fe3PdN can be observed and that the composition range between the iron nitride Fe4N and the nitrides Fe3NiN, Fe3PdN, and Fe3PtN is occupied by single-phase cubic nitrides with structures intermediate between L1' and L1'2. The materials used in this investigation were electrolytic iron of 99.9 pct purity, carbonyl nickel of 99.7 pct purity, sponge platinum of 99.95 pct purity, and palladium sheet of 99.8 pct. purity. Binary alloys of the transition metals were induction-melted in a crucible of fused alumina, powdered, and screened to a particle size of - 200 mesh. The powders were nitrided at 600°C in a gas mixture of ammonia and hydrogen, and the crystal structure was determined with the aid of a Wilson powder camera. The results are compiled in Table I together with information from the paper of Wiener and Berger.1 The compound at the nominal composition Fe3PdN has a diffraction pattern with prominent reflections of a face-centered cubic lattice (h2 + k2+l2 = 3, 4, 8, 11, 12, 16) and weaker superstructure lines (h2 + k2 + 12 = 1, 2, 5, 6, 9, 10, 13, 14). With decreasing palladium content the superstructure lines become weaker and approach the intensity of those of Fe4N. No analysis was made of the intensities, but it can be assumed that the structure is that found by Wiener and Bergerl in Fe3NiN and Fe3PtN, namely L1'2 (perovskite structure) with both palladium and the interstitial nitrogen fully ordered. The dependence of the lattice constant upon the solute atom (Ni, Pd, Pt) content can be explained tolerably well by simple lattice expansion due to subsequent work confirms this suggestion, it will be of significance to order-disorder theory. The author is grateful to Lester Guttman for discussions on this topic.

Jan 1, 1961

By Robert H. Richards

Walter Renton Ingalls recently gave a very interesting talk before the student mining society of the Massachusetts Institute of Technology. In it he showed the present status of mining as he sees it. In the talk he explained that, while discoveries of great mining districts are still pssible, they are being made less and less often; that the great mining companies, although there are large numbers of mines offered for sale, are finding it less and less possible to find new mines that are up to the standard of richness that they wish for purchase. The natural conclusion is that better, cheaper, and more efficient methods of mining, concentrating, and smelting are needed if the lower-grade mines are to be worked at a profit. This is true also if the high-grade mines are to yield their greatest profit. This paper deals only with the concentrating or ore-dressing problem, and gives some thoughts which point towards greater profit. In a paper on The Development of Hindered-Settling Apparatus the writer showed that there were two main lines of work that would lead to greater saving, lower tailing assay, and, therefore, greater profit. The first is the recrushing of middling or tailing products for the saving of the contained values. This is well understood and largely carried out in existing mills. The second is the saving of fine free mineral at the first opportunity. This is a matter less well understood in the mills, and to dwell upon this the present paper is written. The writer is himself convinced and hopes to convince the reader that, for obtaining the above result, not only is better classification needed, but also more classification; that is, there should be more spigots or pockets to the classifier. His attention was recently called to a small mill which had a three-pocket cone classifier fed with from 2 to 0 mm. stuff, supplying feed to four Wilfley tables. The first spigot had about all the

Jan 1, 1914

By Ralph Hultgren

FEW phase diagrams of alloys composed of two transition metals have been adequately studied, probably because of the high melting points involved. Transition metals are the elements that have inner shells incompletely filled with electrons. They comprise groups IIIa to VIIIa of the periodic table, including more than half of all metals. We have chosen to study two systems whose comparatively low melting points allowed the alloys to be melted in a molybdenum resistance furnace. The nickel-palladium system proved to consist of a simple series of solid solutions, but iron-palladium manifested several remarkable features. The main characteristics of the latter diagram were decisively established, but lack of time prevented precise determination of phase boundaries. The gamma to alpha transformation in this system is unusual and warrants further study. Grigorjew1 determined the liquidus and solidus of the iron-palladium system by thermal methods. He found a minimum melting point, but no eutectic. He also found that palladium lowered the gamma to alpha and raised the gamma to delta transformation temperatures of iron, with a complete series of solid solutions existing between gamma iron and palladium. His measurements also indicated a compound or super-lattice near the composition FePd3. Jellinghaus2 found that annealing at 500° C. greatly increased the magnetic coercive force of an alloy of composition FePd. X-ray dif-fraction photographs showed that a tetragonal ordered phase had formed during the anneal.

Jan 1, 1939

By C. W. Davis, R. S. Dean

AMONG naturally occurring inorganic compounds, magnetite has many unusual and interesting properties, and it is the purpose of this paper to call attention to these properties and review possible uses of magnetite that might be based on them; in other words, to see what uses may be found for magnetite as a physical rather than as a chemical entity, as a mineral rather than as an iron ore. The Mineral Physics Studies initiated in the Metallurgical Division of the U. S. Bureau of Mines a few years ago gathered together much information on mineral properties, and they are therefore the principal source of material for this paper. Magnetic Properties Of Magnetite And Possible Uses As A Magnetic Material Magnetite is unique among minerals for its great magnetic susceptibility, approximately one-third that of soft iron, and some magnetites are permanent magnets, or lodestones. The literature contains many measurements of magnetic properties of individual magnetite crystals, but no systematic survey of the effect of mechanical preparation and heat-treatment was available until the recent investigations of the Bureau of which included not only susceptibility but coercive force and remanence as well. For the purpose of orientation, Table 1 gives the magnetic properties of several samples of magnetite and of a few other substances3. This table indicates that when ordinary magnetite is powdered it decreases in susceptibility and increases in coercive force and remanence, approaching the properties of lodestone. The properties of lodestone are in fact probably due to the development of very large internal surface on fine grain size4.

Jan 1, 1937

By Armando M. Lago

Secular and cyclical patterns of postwar sources and uses of funds of the mineral sector are analyzed. A simultaneous equation behavior model of sources and uses of funds is developed for both mining firms and integrated producers, and these models were put through the task of predicting the financial and expenditure be-havior of mineral corporations in response to mergers and changes in investment tax credits and depletion allowances. Finally, the quantitative analysis methodology is applied to the analysis of optimum capital structure of mining corporations. The postwar changes that have occurred in the expenditure and financial behavior of mineral corporations are reviewed, particularly the relative importance of factors that affect the industry's supply and demand for funds. This quantitative statistical investigation of factors affecting sources and uses of funds of mineral corporations is achieved through the formulation of a simultaneous equation model of sources and uses of funds. After a description of the study sample, the postwar cyclical and secular financial behavior of mineral corporations is analyzed in detail. An econometric model of mineral corporate financial behavior is formulated. This model is then estimated and reviewed. Policy issues regarding depletion allowances, investment tax credits, and industrial organization of the mineral sector are discussed. Finally, the optimum financial structure of mining firms is discussed and the effect of corporate financial structure on the mining corporations' average cost of capital is analyzed.

Jan 1, 1971

By H. Y. Jennings

An extensive field and laboratory experimental program was carried out to compare the waterflood behavior of carefully preserved soft and unconsolidated cores with measurements on the same cores after extraction. Results obtained from using idealized consolidated and unconsolidated porous media in which wettability could be carefully controlled were contrasted with the preserved core data. The controlled tests on idealized porous media investigated the effect of wettability, flood rate, core length, core permeability and consolidation on the displacement of high viscosity oils. It was concluded from these studies that waterfloods are more favorable when carried out with crude oil in preserved soft and unconsolidated cores than with the same cores after they have been extracted and re-saturated. Waterfloods are usually more favorable when carried out with crude oil in extracted .soft and unconsolidated cores than with refined oil of the .same viscosity in the same cores. The less favorable behavior of extracted soft and unconsolidated cores compared to preserved cores is due to alteration of the core by extraction. Preserved cores saturated with native water and oil should be used for laboratory displacement experiments because they more accurately reflect true reservoir behavior INTRODUCTION The demand for low gravity crude oil created by refinery modernization has focused attention on increasing the production of this viscous crude oil. Billions of barrels are in place in fields that are depleted, or nearly depleted, by primary production mechanisms. Since low gravity reservoirs are relatively recent, geologically, the solid matrix material is usually soft and unconsolidated sand. Such formations are also characterized by a high clay content. Evaluation of sophisticated oil recovery processes with the associated high capital investments has increased the demand for special core analysis tests on material from these soft and unconsolidated sand reservoirs. Data in this paper have resulted from an extensive field and laboratory experimental program. The initial objective vras to provide soft and unconsolidated sand cores for laboratory measurements with as little alteration as possible from their reservoir condition. A secondary objective was to compare the waterflood behavior of these carefully preserved cores with measurements on the same cores after they had been extracted and resaturated. When the comparison showed markedly different behavior the final objective was to attempt to explain the difference by making measurements on idealized porous media free of clay in which initial wettability could be carefully controlled. EXPERIMENTS MATERIALS Core Material The preserved cores used in this study were obtained with as little alteration as possible from their reservoir conditions. Special techniques were developed to satisfy this objective. The cores were cut with native crude whenever the crude had the necessary properties to satisfy the minimum drilling fluid requirements. A pure hydrocarbon chromatographic tracer was added to the crude to provide a simple, safe and inexpensive method to distinguish between oil filtrate and formation oil. Details of the tracer technique used in this study and the procedures used to handle and process the soft, unconsolidated cores have been published.' The core samples were then preserved and packaged at the well site with a dip-applied strippable plastic, or by using a rubber sleeve from a rubber-sleeve core barrel. The final step was to insure that the carefully taken and preserved samples were not altered by processing in the laboratory. Some soft and poorly consolidated sands were carefully shaped in the lab and encased in a protective mounting without disturbing their three-dimensional integrity. Many samples were so poorly consolidated that they literally flowed from the package when the seal was broken. A technique was developed to obtain cylindrical plugs from these samples by using liquid nitrogen as the drilling fluid in a conventional core-drill, drill-press assembly. The idealized porous media consisted of sintered rods of Alundum RA 139, outcrop sandstone identified as Al-hambra sandstone and packs of No. 130 Nevada sand. This sand is 95 per cent 140-200 mesh. (Physical properties of these porous media with those representative of preserved cores are in Table 1.) The natural cores and most of the idealized porous media were 1 1/2-in. in diameter and 3-in. long. The samples used to study the effect of core length were 1 1/2-in. in diameter and 12-in. long. Liquids Water and oil produced from the formations being studied were protected from the atmosphere and collected in carefully cleaned glass or plastic-lined containers. The production was free of chemical additives such as emulsion breakers and corrosion inhibitors. The crude oil was

Jan 1, 1967

"The reduction works of the Boston & Montana Reduction department, near the north end of this dam is one of the reduction plants belonging to the Anaconda Copper Mining Company, the other being at Anaconda. These works employ about 1,100 men and have a capacity of about 3,800 tons of crude ore per day. This plant is now being remodeled to embody results of experiments and investigations which have been made with a view to more economic.al treatment of ores. A brief description of the plant as it will be after the remodelling is as follows:Concentrator Department: Consists of six units or sections, each section treating from 550 to 600 tons of crude ore per day. This department is not being. remodelled at the present time. A concentrating process, however, has been developed and partially installed in the old mill, and an experimental section embodying this concentration process has also been installed at the concentrator at Anaconda."

Jan 1, 1913

By John A. Ames

Webster's dictionary nearly equates portland cement with its current primary definition of cement. While such equation may be a triumph of common usage, the confusion between the terms cement and concrete unfortunately is very widespread. Full definition of cement properly would extend to many substances, but for purposes of this chapter cement is restricted to "varieties" of portland cement including "portland-pozzolan" cement. Among the usually recited historical notes concerning cement is that it was developed by the Romans. Their use of cement in the great structures of Rome, and even in the far corners of their Empire, such as Hadrian's Wall in the north of England, testifies to the antiquity of a major cement industry. From English sources we know of John Smeaton's carefully proportioned hydraulic cement mixed in 1756 and of Joseph Aspdin's patented cement to which, in 1824, he gave the name portland cement. (He claimed that his cement mortar looked like the famous dimension limestone quarried from the Isle of Portland on England's south coast.) The year 1971 marked the centennial of portland cement manufacture in the United States. A fair historical account of the many real contributors to the cement industry between 1756 and 1972 unfortunately would be too extensive for this chapter. Development of rotary kiln practice and burning at higher temperatures clearly was the major move into today's technology. As part of the 4th edition of Industrial Minerals and Rocks, this chapter on utilization focuses on inferred interests of the anticipated readers. The main period for which statistics are cited generally is that since the 3rd edition (1960) of this same volume. Cement manufacture is the processing of selected and prepared mineral raw materials to produce the synthetic mineral mixture (clinker) that can be ground to a powder having the specified chemical composition and physical properties of cement. Cement making incorporates a number of distinct steps, but it is characterized by the key pyroprocessing (or "burning") step, which brings about the necessary changes in the raw materials. This pyro processing is a chemical process. Conversion of large volumes of mineral raw materials into specification-controlled cement at relatively low cost is the objective. Statistics on the cement industry are of uneven quality. The U.S. Bureau of Mines (USBM) is the principal collector of available data. These statistics can be only as good as the quality of information supplied by the reporting companies. The data perhaps most often questioned relate to productive capacity of the industry. The questions submitted by USBM are valid, nevertheless, and the information gained from them, as good as is available, is what is generally used. The Portland Cement Association also is a source of much quality information. The year 1972 witnessed a test of the adaptability of cement industry statistics. This was the year of conversion from barrels and sacks of cement as the units of measure to tons and hundredweights. The barrels and sacks related to volumetric measures in that a sack was judged to be 1 cu ft (weighing a "standard" 94 lb). A barrel was 4 sacks. Volumes of concrete are stated in cubic yards, and the number of cubic feet of cement in a cubic yard of concrete was a sensible approach to the mensuration involved. However, cements do not weigh the same amount from plant to plant or from type to type, and the buyer was more interested in getting an assured weight for his money than in "buying air." Thus, a sack, in accepted practice, became 94 lb instead of 1 cu ft, and a "barrel" became 376 lb, regard- less of whether it would fit into 4 cu ft of space. With the de facto dealing in weight rather than in volumes, the awkward numbers made little

Jan 1, 1975

By C. H. Li, R. J. Stokes, T. L. Johnston

Dislocation half-loops, artificially introduced by sprinkling with carborundum, were subjected to stress using three-point loading. The different stages of loop expansion and multiplication were then correlated with the macroscopic stress-deflection curve. Loop expansion started at approximately one-third of the "yield stress," defined here as the motivation stress. Above one-half of the "yield stress" simple multiplication commenced while about two-thirds of the yield stress gross multiplication developed short slip-line segments. These values were not affected by the age of surfaces exposed to both dry and wet air. Slip was not detected on unsprinkled crystals below two-thirds of the "yield stress." Thus the stress to activate intrinsic sources, defined here as the activation stress, was approximately twice the motivation stress. This relationship was independent of the strain rate used. It is concluded that lattice resistance takes the form of a viscous drag rather than a static type of force. THE importance of surface condition and environment as one of the more significant factors controlling the mechanical properties of ionic solids has recently received renewed attention.1-4 In some materials, notably the alkali halides, exposing freshly cleaved specimens to the atmosphere results in a progressive hardening and embrittlement of the crystals. This has been attributed to the surface layer becoming "aged," thereby restricting the motion of dislocations in such a way that pileup and eventually fracture results. It is necessary therefore in studying the mechanical properties of ionic crystals to inquire first into the density and distribution of dislocations in the normal cleaved surface and to understand the role these dislocations play in the onset of plastic flow. Knowledge of the effect of environment on this behavior will then assist in understanding the mechanism of embrittlement on aging. In the work reported here a method is described for studying the initiation of plastic flow from dislocation sources in the surface of magnesium oxide crystals. Preliminary results are described of the influence of surface age on this behavior. EXPERIMENTAL TECHNIQUES The magnesium oxide used in this investigation was obtained from the Norton Co. and had a nominal purity of 99.5.pct. Single-crystal specimens, having dimensions typically 1/4 by 1/8 in. cross section and 1 in. in length, were prepared by cleavage over (100) planes from the parent crystal. They were deformed under three-point loading with 3/4 in. spacing between the two end supports and a constant rate of deflection at the center of 0.001 in. per min. The maximum strain rate therefore was 1.5 X 10-5 sec-1. Reasons for choosing this particular form of loading will become apparent in a later section. In addition, a number of confirmatory type tests have been performed at higher loading rates where the maximum strain rate was increased to 1 x 10-3 sec -1. Following deformation the crystals were etched to reveal the dislocation distribution. In a previous paper5 we described a satisfactory etching solution consisting of 5 parts of saturated ammonium chloride, one part of sulfuric acid, and one part distilled water. Immersion of the crystals for 1/4 hr at room temperature developed reproducible conical etch pits at the points where dislocations emerged through the surface. It should be mentioned that dislocations freshly introduced by room temperature deformation gave sharply pointed etch pits which generally distinguished them from the almost flat-bottomed pits obtained on "grown-in" dislocations. The distinction is obvious in the photomicrograph included in Fig. 5(b). Annealing crystals at 1000°C for 12 hr on the other hand gave sharper etch pits on the grown-in dislocations and the distinction was no lower -possible; a similar observation has been reported for lithium fluoride. We have succeeded furthermore in chemically polishing magnesium-oxide crystals. Boiling in fresh 85 pct ortho-phosphoric acid for only 1 min resulted in a microscopically smooth surface which could again be etched to reexamine the dislocation distribution. This boiling time was sufficient to remove the surface damage introduced by cleavage (see next section). SURFACE DISLOCATION SOURCES There are a number of ways by which dislocations may be introduced into cleaved surfaces to act later

Jan 1, 1960

By Fred C., Bond

DETERMINATIONS of circulating load in a classifier operating in closed circuit with a grinding mill are usually made from screen analyses of the mill feed and classifier products. The percentage remaining on someone selected screen size must be used in the calculation, and, because of the wide variation in average particle size between the mill feed and classifier overflow, an accurate and representative result at the selected mesh is often difficult to obtain. To overcome this difficulty and reduce the time required in making the determination, I have devised a method which uses the liquid-solid relationship in the circuit rather than screen analyses. The quantities required for the calculation include only the usual dilution and feed tonnage measurements, which should be made regularly in the course of ordinary mill operation and, in addition, the amount of new water added to the classifier, or to the head of the mill with the new feed. If measurements are obtained on both of these quantities it is possible to check the calculated circulating load, and to calculate the percentage of moisture in the new feed to the mill; or, if the latter is known, to check the feed tonnage.

Jan 1, 1937

By Arne Bergholm

Australian rutile was chlorinated in the presence of CO or carbon. The chlorination velocity in CO was found to be strongly influenced by temperature and proportional to the CO concentration, but independent of the Cl, concentration. In the presence of carbon, the reaction velocity is much higher. The reactivity of the carbon and the distance between the carbon and the rutile surfaces are important variables. The reaction velocity is approximately proportional to the Cl, concentration and independent of the CO concentration of the surrounding atmosphere. Experiments with fluidized-bed chlorination of carbon-rutile mixtures indicate that the motion of the bed has little influence on the reaction velocity. At low temperatures, the chlorination velocity of dense tablets is much greater than that of TiO, coke mixtures suitable for fluidization. The reaction mechanism is discussed. In the industrial production of TiCl, rutile is chlorinated in the presence of carbon. Disregarding intermediate steps, the reaction may be expressed by the following equations: The ultimate object of this study was to find out whether the reaction velocity was higher in fluidized bed operation compared with chlorination of pelle-tized carbon-rutile mixtures. From a literature survey and preliminary experiments it was learned that some basic knowledge about the reaction mechanism was needed for a good experimental design. Therefore the following sets of experiments were carried out: 1) Studies on the reaction velocity in the chlorination of rutile with CO as the only reducing agent. 2) Chlorination of separate rutile-carbon tablets. 3) Chlorination of rutile-carbon tablets at different temperatures with various kinds of carbon, various grain sizes, and various tablet-making techniques. This series of experiments was carried out not only with pure chlorine but also with mixtures of chlorine with argon, CO and CO,. 4) Chlorination of rutile-carbon tablets made in a strictly standardized manner. 5) Chlorination of static-bed rutile-carbon mixtures. 6) Fluidized-bed chlorination of the same mixture. The experiments 4 to 6 formed the final and direct test of the main question: Static bed vs fluidized bedo. Although there are many patents and papers dealing with the general aspects of chlorination, only few experiments from which detailed information can be obtained have been reported in the literature. Pamfilov and coworkersl3 have studied chlorination of TiO, with CO or carbon as the reducing agent. They found that the weight decrease per hour at 600o to 800°C amounted to 11 to 14 pct with CO and 45 to 51 pct with carbon. They suggest that phosgene might be an intermediate in the chlorination of TiO,. Takimoto and Hattori have chlorinated reduced titanium oxide (TiO) and found a very high rate of TiC1, -production. They proved that the composition of the gas from the chlorination of rutile-carbon mixtures contained mainly CO. They reported for instance 74.7 pct CO, and 5.6 pct CO at 800°C at which temperature the Boudouard equilibrium composition is 12 pct CO and 88 pct CO. Seligman and Segerchano6 have studied the chlorination of TiO. They proved that Ti0 and chlorine react rather rapidly at temperatures as low as 300°C. Above 400°C, the reaction was complete. At 500°C the velocity of this reaction was much higher than was chlorination of TiO, + C. McTaggart,7 Nishimura, et al. and Wilskam have chlorinated mixtures of carbon and various kinds of rutile or beneficated ilmenite. Nishimura, et al. also report the results from reduction of TiO, with H2, CO, or carbon. At 900°C only 1 pct Ti O is formed in 2 hrs. At 1100°C 23.1 pct Ti, 0, was formed if elementary carbon was present. No carbide formation occurred below 1400°C. McIntosh and Cofferll have observed that the CO, content of the exit gases from chlorination of rutile and calcined petroleum coke is appreciably higher than found in the Boudouard equilibrium. At 900°C the ratio (CO, /CO + CO) is about 80 pct, whereas the equilibrium value is about 2 pct. W. E. Dunn12 has studied the chlorination rates of several TiO,-bearing minerals with CO + Cl, or COCl . Chlorinations were carried out either in a fluidized reactor or a fixed-bed reactor, both having a 30-mm diameter. The results obtained in both reactors were comparable. It was proved that benefi-ciated ilmenite (i.e., ilmenite from which the iron oxide had been removed by chlorination) was chlorinated 10 times faster thanrutile. Sore1 slag showed an intermediate rate. When phosgene is used, the

Jan 1, 1962

By J. E. Strassner

Oilfield emulsions are stabilized primarily by film-forming asphaltenes and resins containing organic acids and bases. Adding inorganic acids and bases radically changes the physical properties of these films and their emulsion-stabilizing properties. Interfacial films show one of three different physical characteristics when retracted in pendent drop tests. These compressed films have rigid, soap-type or minimum film properties depending on the quantity of asphaltenes and resins in the crude oil and on the pH and composition of the brine. There exists for each crude oil-brine system an optimum pH range over which the adsorbed film exhibits minimum contracted filtn properties. In this range, intmfacial tension is high — frequently near its maximum value — indicating the absence of highly surface-active specier; crude oil-brine emulsions generally show minimum stability; and surfactant requirements for breaking these emulsions are significantly reduced — sometimes no surfactant is needed. About two-thirds of the world's crude oil is produced as emulsions that must be treated (demulsified) to be marketed.' Approximately three-fourths of all domestic crude oil produced must be treated. The percentage of crude requiring treatment increases as fields become older and more water is produced. Demulsification most frequently is attained through use of surfactants, heat and electric treaters. It is estimated that over 75 percent of all oilfield emulsions are broken by chemicals generally containing alkylene oxide condensates. Although acids and bases are known to affect emulsion stability:-' they rarely are used in the oil field except in batch treatment of the most severe emulsions. Nevertheless, pH adjustment by using acids or bases in demulsification has some advantages over other methods. Mainly, it is cheaper. Acids and bases frequently are cheaper to use than surfactants, or can appreciably reduce the amount of surfactant required for demulsification. Secondary advantages are that less oil is lost by emulsi-fication into the aqueous phase, and that less corrosion is encountered when the optimum pH is basic. Limitations to the use of pH include (1) use in brines containing high concentrations of reactive ions, (2) closer supervision for pH control than is required for surfactants and (3) need for corrosion protection when the optimum pH is sufficiently acidic. These factors indicate that the economics of pH con trol in demulsification will be maximized when relatively large treating facilities are needed, when relatively large surfactant concentrations are required to break an emulsion, when a relatively low concentration of the aqueous phase is emulsified in the oil and when the emulsified aqueous phase contains relatively low concentrations of reactive ions. Because there are no broad guide lines for using pH control in breaking oillield emulsions (and because the limited guides available are highly specific and frequently contradictory), this paper will attempt to clarify the principles involved in using acids and bases to break emulsions. These principles also should be useful in refinery separations and in other oilfield applications where stable or unstable petroleum emulsions are involved. Principles of Emulsion Stability Oilfield emulsions generally occur as water droplets dispersed in oil (w/o) and occasionally as oil droplets in water (o/w). These emulsion droplets are usually in the 0.1- to 10-micron range. However, more coarsely dispersed water droplets frequently are present in the emulsion. Pure hydrocarbons and water will not form stable emulsii except in extreme dilutions where the large distance brtween droplets inhibits coalescence. An emulsion breaks because interfacial tension acts to minimize the surface area of the dispersed drops by coalescence. However, emulsions can be stablized for long periods of time by the presence of a third phase that adsorbs at the oil-water interface and inhibits coalescence of the dispersed phase."' Emulsions generally are stabilized by (1) repulsive charges on the surfaces of the dispersed phase and (2) adsorbed films that, being preferentially wetted by the continuous phase, act as a physical barrier to inhibit contact between the dispersed droplets. Both these factors generally are important in stabilizing and in breaking o/w emulsions. However, repulsive charges are less effective in stabilizing w/o emulsions which generally are stabilized by adsorbed films.V or this reason the nature and importance of these films at oil-water interfaces were examined closely; as will be shown, pH changes were found to affect the films significantly, and this work led to laboratory tests of pH- adjustment in emulsion breaking. This paper will present evidence to show that emulsions are stabilized primarily by films that form around droplets

Jan 1, 1969

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By M. C. LYNN

RECENT completion of a $40,000 lubricating oil plant will make it possible for students in the School of Petroleum Engineering at the University of Oklahoma to carry out on a large scale the entire process of refining crude oil, from the time it is received in tank cars and pumped through the 1/4-mile University pipe line to storage tanks on the campus until the various products appear in finished form. This plant is part of a $100,000 expansion program which this school has been carrying out during the past year. Two years ago the Oklahoma State Legislature appropriated $50,000 for the School to use in improving its laboratory facilities. A few months later a $30,000 PWA grant was ob-

Jan 1, 1937

By E. W. Pehrson, J. W. Furness

THE five charts presented here- with are part of an original group prepared by the U. S. Bureau of Mines showing the international trade in the principal metals and metallic ores. Charts 011 anti- mony, chromite, copper, lead, manganese, mercury, nickel, tin, tungsten, and zinc were published in the February, 1936, issue of the Engineering and Mining Journal. Those shown here include bauxite, aluminum, iron ore, pig iron, and the platinum-group metals.

Jan 1, 1936

Jan 1, 1891

By H. W. Hardinge

DISREGARDING for the present the economic side of a new device, let us turn to that feature of the conical pebble-mill which is of interest from a scientific point of view, and consider the device as a puzzle in which the theories of the cylindrical type of mill have been increased. Many articles have been written on the theory of the tube-mill, and explanations have been made which do not explain.; but these have evolved suggestions of practice which have resulted in changes in the tube as to length, diameter, feed, discharge, speed of rotation, rotation on hollow trunnions, rotation on rings, and changes in the operation as to quantity and size of pebbles, charge of load above or below the axis, crushing by causing the larger pieces of the material of the charge to act as grinders, etc. The practical worker in crushing is first interested in the endeavor to reach an economic means of accomplishing a desired end; but the improvements in crushing-practice have been largely left to the manufacturer of machinery, who, as a rule, has little, if any, knowledge of the specific requirements-such as sizing for concentration without pulverizing the metals, instead of pulverizing the rock or gangue; the metals being the more friable, while the rock is tough and not so easily disintegrated. A reversal of this practice is the aim of sliming direct for cyanidation. In the ordinary cylindrical mill, having a diameter of 4 or 5 ft. and a length of from 15 to 27 ft., it has been found that the maximum size of the particles of the charge must not exceed 1 mm. (about 25 mesh), some of which, upon entering the mill, is immediately reduced to a slime. The work upon the individual particle having been finished, it should be passed out of the mill; but, instead of this, the finely comminuted material

Jan 7, 1908

By Leonard Greenburg, William B. Harris, Gustäv Werner

HAULAGE in tunneling operations generally has been done with electric locomotives. As a rule, on short hauls the source of electricity is a storage battery mounted on the locomotive, which, of course, must be removed and recharged periodically. Where the distance from the recharging point to the tunnel face is very long, and where loads are heavy, trolley-driven locomotives are used. Diesel engines have been used in mining and tunneling operations in Europe for a number of years. The recent reports of studies in Belgium1 and by the Bureau of Mines in this country2-4 have indicated the potentialities of this form of power for haulage, mucking, bulldozing and many other underground operations. The hazards attending the use of Diesel engines in more or less closed spaces have long been known. The exhaust constituents that may create a harmful or objectionable environment are carbon monoxide, oxides of nitrogen and sulphur, carbon dioxide, aldehydes and smoke. Lack of precise information regarding the concentration of these gases and the ventilation requirements to reduce them to safe levels has to some extent suppressed their general acceptance in tunneling and mining work. Not until the work of the Bureau of Mines referred to above, and certain experience gained in the construction of the Delaware Aqueduct,‡ has there been available the requisite information regarding the conditions under which their use may be permitted. This paper concerns itself with the successful operation of Diesel engines underground in the construction of certain parts of the Delaware Aqueduct, and describes the conditions under which Diesel engines have been found to operate with a minimum production of noxious gases. The test data reported were obtained during the operation of Diesel engines over a period of two years.* STUDIES BY THE NEW YORK STATE DEPARTMENT OF LABOR Exhaustive tests were made by the Division of Industrial Hygiene, of the composition of the exhaust gases given off by a Diesel engine mounted on. a test block. These tests showed that certain quantities of the gases are discharged from the exhaust. On the basis of these figures, preliminary requirements of design and control

Jan 1, 1942