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By Arthur Gates

INTRODUCTION RITTINGER'S law of the energy expended in crushing is, as roughly stated by Professor Richards,1 that the work of crushing is proportional to the reduction in diameter; or, as I have more fully expressed it: "The work done in crushing is proportional to the surface exposed by the operation; or, better expressed for this purpose, the work done on a given mass of rock is proportional to the reciprocal of the diameter of the final product-assuming that all the mass has been reduced to one exact size, which is only theoretically possible.?2 Kick's law is stated by H. Stadler as follows:3 "The energy required for producing analogous changes of configuration of geometrically similar bodies of equal -technological state varies as the volumes or weights, of these bodies." In other words, the energy expended is porportional to the volume reduction, instead of the diameter reduction. That these two laws would give widely different results may be shown by a simple imaginary case. A ton of 16-in. cubes is broken to 1 -in. cubes at the first operation, and these are broken to 1/16 -in, cubes at a second operation. Since the first operation produces only one-sixteenth as much new surface as the second, the ratio of energy expended in the two operations would be by Rittinger's law as 1 to 16. By Kick's law, since the volume-reduction ratio is the same in both cases, the ratio of energy would be 1 to 1. This discrepancy is great enough to challenge a test by actual experiment, of which there has been, hitherto, but little compared with the amount of argument. The present paper is the record

Jan 9, 1915

By Lewis A. Smith

Chromium is one of the new metals, but considerable research has been required to determine an approximate record of its production from 1827 until the present. Its use in the form of pure metal is not extensive; of the chromite mined, about one-half is required for making ferrochro-mium, about two-fifths goes directly into refractories and the remainder is absorbed chiefly by the chemical trades. The industries that demand chromite for such uses are mainly in countries that produce little chromite, while the important chromite-producing countries are not generally consumers. The international flow of chromite is therefore of interest, as well as the political and commercial control of resources of the metal. World Production The first mining of chromite is said to have occurred as early as 1820, at the Roros deposit in Norway, but the first well-established output came from the Reed mine, in Maryland, about 1827. Thereafter the United States led the world in chromite production until 1860, when Turkey took the lead. Russia in turn became the chief producer from 1897 to 1902, inclusive. From 1903 to 1909, New Caledonia held first place, but alternated with Southern Rhodesia from 1910 to 1917, inclusive. In 1918, 1919 and 1920-1921, the United States, India and New Caledonia led, respectively. In 1922 Southern Rhodesia assumed first place and has since continued to be the world's foremost producer by a large margin. Fig. 1 illustrates the production of the leading countries from 1890 to 1929, inclusive. Fig. 2 shows the world production of chromite from 1890 to 1929, inclusive, in long tons and Table 2 gives the production by countries for the same period. The total world production for the 103 years, 1827 to 1929, ipclusive, is estimated at about 7,100,000 long tons, distributed as shown in Table 1. World Trade in 1928 In reviewing the figures for the flow of chromite in 1928, it is evident that the six countries that produce most consume little chromite and

Jan 1, 1931

By G. A. Alers, J. H. Bechtold, R. W. Armstrong

The plastic flow of .molybdenum was studied in compression at temperatures below the ductile-to-brittle transition in tension. It was found that molybdenum is ductile in compression at all temperatures down to —196°C. The yield strength continues to increase with decreased test temperature below the tensile ductile-to-brittle transition temperature range. Difficulty was encountered in correlating the experimental data obtained with existing theories of plastic flow. THE body-centered-cubic metals as a group show a rapid and very large increase in yield strength with decreasing test temperature.' It is of fundamental importance to the understanding of the mechanism of plastic flow that this general characteristic be examined carefully. Unfortunately, brittle fracture in low-temperature tensile tests prohibits the measurement of flow properties at very low temperatures. By using compression tests, fracture can be suppressed and the plastic flow of the bcc metals can be studied far below their tensile ductile-to-brittle transition temperatures. Molybdenum was chosen for this experiment and plastic-flow data were obtained down to —196°C.

Jan 1, 1959

By W. Tovote

This paper is based upon 12 years' experience in the Southwest, including three years that were spent in constant traveling as examining engineer for the Phelps-Dodge Corporation. The material was gathered during rather extensive work in Bisbee, Clifton-Morenci, Globe, and Tombstone, and also on short and rapid trips into most of the mining camps and prospect fields of New Mexico, Arizona, the desert country of California, and as much of Sonora as was safe at the time. My methods of observation and my deductions are not put forward as new or scientific; they are simply rough field methods, based upon short notes, rough sketches, and largely upon memory, which I have found useful for coördinating geological data for the purpose of passing quick judgment on mining possibilities in certain districts exhibiting uniform characteristics. The opportunities for observation have been better these last few years than ever before, due to the unprecedented activity in mining, which has caused the reopening of hundreds of old mines and the starting of even more numerous prospects all over the mining states. Possible Systems of Classification By Geological Provinces There are a number of well defined geological provinces in the territory under discussion, and a study of their individual features is of interest. The following are a few of those that are most striking in their uniformity. 1. The "Desert province," extending roughly from Wickenburg, Ariz., to and beyond Barstow, Cal. In its north-south extent it reaches up to the Colorado River and down into Sonora, but overlaps other provinces. It is characterized by a worn-down basement of schistose and granitic rocks, on which rest remnants of Paleozoic and pre-Paleozoic sediments, including very old limestones. The sediments are disrupted and contorted. Alteration in the mineralized areas is very prominent, especially in the schists and limestones. Cenozoic volcanic rocks, principally of semi-basic composition, have been intruded into this complex and sometimes cover it as lava flows. 2. The "Yavapai schist" province, similar to the one first mentioned, consists of metamorphosed basic and semi-basic rocks. It lies in northern

Jan 1, 1920

By Henry D. Hibbard, Edward L. Ford

The process of making washed metal now followed is in principle that described by Holley before this Institute in 1879, as the Krupp washing process. Sir Lowthian Bell also experimented extensively in England during 1877 and 1878 on refining iron and joined his interest with Krupp, the process being often referred to as the Bell-Krupp process. The only plant in this country now operating this process is that of the Brier Hill Steel Co., Youngstown, Ohio. This process may be considered as the sole survivor of the numerous methods conceived for refining crude iron, when the removal of phosphorus from steel-making material was the great desideratum affecting large districts. The east coast of England and all northern Germany, the homes of Bell and Krupp, respectively, could at that time make steel only from imported ores. These processes were in use or in various stages of development 40 years ago and all except the Bell-Krupp received their quietus from the development of the basic steel processes, both pneumatic and open hearth. The aim of the early refining processes was, first, the removal of the silicon, which could be done on a sand bottom, and later, the removal of the phosphorus, requiring a bottom which would give or permit a basic slag. The incidental advantages of increased yield and small fuel consumption were not generally recognized or considered; the aim of the later operations was the saving of the difference in value between low and high phosphorus irons, as well as hastening the removal of the metalloids. The chemistry of the washing process follows in part that of the puddling process, and indeed washing might be considered as the first half of puddling, since all the non-ferrous elements of the crude iron, except the carbon, are eliminated and the iron is maintained molten until cast. In puddling, the iron loses its carbon as well, and because of that, its fusion point rises above the hearth temperature; it freezes into a pasty malleable form, and is worked at once by squeezer, hammer, or rolls. Since Holley's paper, important improvements have been made from time to time in both plants and methods for washing iron, and the

Jan 1, 1916

By H. J. Beach, W. C. Goins

The laboratory development and field use of oil well cement compositions* with high resistance to drilling mud contamination are described. Resistance is obtained by adding a I-lb mixture composed of three parts paraformaldehyde to two parts sodium chromate tetra-hydrate for each sack of cement. This mixture neutralizes the cement-retarding properties of quebracho and other tannins, starch, sodium carboxymethylcellu-lose, Ignite, and monovalent salts of lignosulfonic acid. The retarding properties of calcium lignosulfonate are unaffected. The decontaminating mixture may be used in common cement (designated Type I by ASTM specifica-tions,' Class A by API Std. 10A2) or in a slow set slurry prepared from common cement by addition of calcium lignosulfonate. No changes in slurry viscosities or thickening times are caused by the protecting reagents. The method has been used in 185 field jobs where an improved success ratio has been obtained in plug setting. INTRODUCTION Field experience and laboratory investigations have established contamination by drilling mud as a major factor in oil well cement failures. During 1955, 12 attempts were required to set six open-hole cement plugs in the Timbalier Bay field, La. Eighteen to 30 hours elapsed between placing and testing the plugs in preparation for sidetracking operations. Considerations of rig time expense required immediate resetting where soft cement was drilled after a reasonable waiting period. Sea water drilling mud was used in each well and daily additions of thinners, usually lignites, had been required. Sodium carboxymethylcellulose had been added regularly to control fluid loss. The 50 per cent plug failures were attributed primarily to contamination by the mud. Similar experiences can be found in other fields along the Texas and Louisiana coasts where drilling muds normally contain large quantities of organic treating materials. Cement contamination was the subject of a survey by the Mid-Continent District Study Committee on Cementing Practices and Testing of Oil-Well Cements of the API.3 Data collected from member laboratories and released in Sept., 1951, reported the effects of a number of drilling mud treating chemicals on cement. The study revealed that many of the additives, notably the organic materials in relatively small quantities, had marked effects on the properties of cements tested. Severe losses in strength and erratic thickening time resulted from small additions of mud treating chemicals such as quebracho, starch, sodium carboxymethylcellulose, and lignite. The report included no recommendations of methods for overcoming the problem. One investigation of the contamination problem reported the successful use of activated charcoal in setting cement plugs after conventional slurries had failed.4,5 The investigation indicated that an optimum concentration of 5 per cent activated charcoal was effective in combating contamination from 16.7 volume per cent of treated mud. Laboratory and field muds were included in tests and contained varied quantities of ode or more of the following: quebracho, caustic, starch, lime, and calcium lignosulfonate. The function of the charcoal appears to be physical, removing the organic materials by adsorption. The method may be employed in API Class A or Class D (unretarded slow set) cements. The chemical approach presented here is based on

Jan 1, 1958

By Charles C. Russell

Pressures developed by the coal during the coking process have been responsible for serious trouble to many companies that operate or build by-product coke ovens. The insidious nature of this trouble is indicated by the fact that oven operators, unless they have ascertained the characteristics of the coals they use, cannot determine the existence of dangerous pressures until after the damage has been done. A rather popular misconception is that ease of pushing of the charge at the completion of the coking period indicates that no dangerous pressure has been developed, but this is far from the truth; pressures developed during the coking period are often completely dissipated by the shrinkage of the charge in the completion of coking, and so any criterion based on the ease of pushing is futile. However, methods of testing coals are available that will definitely distinguish the dangerous coals from those that are safe, and such methods have been brought to a high degree of certainty. The operator should take no risk that involves either a lack of knowledge of the behavior of coals during coking or the failure to believe that certain of the coals or coal mixtures can cause damage to the oven structure. This merely tends to minimize the problem and leads to claims that coking coals of all kinds may be carbonized with no danger of damage to the oven structure provided some particular kind of byproduct oven is used. This lack of appreciation of the true situation is in itself one of the main factors leading to damage of coke-oven structures. Coals that develop more than a certain safe pressure cannot be used in by-product coke ovens without causing damage to the side flue walls. The following paper presents a highly certain method for the measurement of the pressures developed during the carbonization of coal—a method that is the culmination of many years of work on the problem in which a number of methods for the purpose were investigated and used. While actual pressures found may appear to be small when expressed in pounds per square inch, the number of square inches in each oven wall is so large that the total pressure on the oven wall becomes an enormous load.

Jan 1, 1940

By Eric J. Jette

In thermodynamic studies of gas mixtures and liquid solutions, the respective problems have been greatly simplified by the use of two general limiting laws; Dalton's law of partial pressures and Raoult's law. It is generally recognized that these two laws have a common physical and chemical basis which may be stated as follows: The law may be expected to be strictly valid only for systems in which the different molecular species are so nearly the same in their physical and chemical properties that a molecule is unable to recognize whether its neighbor is one of its own kind or not. Positive and negative deviations from both laws are frequently encountered. The occurrence of negative deviations in both gases and liquids is ascribed to attractive forces which, in the more extreme cases, may be so large in magnitude and so highly specific in character as to lead to the formation of definite chemical compounds. Positive deviations in gases develop only at higher pressures where the intermolecular distances are so decreased that factors such as molecular size and shape, which ultimately become concerned with the repulsive forces, come into play. In liquid mixtures, positive deviations are generally considered as due to differences in the symmetrical (nonpolar) fields of force which surround the various molecular species and which are supposed to give rise to a tendency for each species to associate with its own kind and thus to "squeeze out" the other variety. Fundamentally this also involves the existence of repulsive forces between unlike molecules. If the fields of force are unsymmetrical (polar) a tendency towards compound formation results. Stated in more exact terms, strict adherence to the law means that the "activity" (or any adequate measure of this quantity) of a component in a mixture is a linear function of the molecular (or atomic) fraction of that component between the mol fraction limits 0 and 1. A positive deviation means that the activity is greater than corresponds to the law; a negative deviation that the activity is less. The deviations from Raoult's law have been fully discussed by many writers1

Jan 1, 1934

By David Cole

At the time flotation appeared upon the metallurgical horizon in Arizona, the writer, under the direction of Dr. Ricketts, was engaged in remodeling and enlarging the No. 6 Concentration Plant of the Arizona Copper Co. at Morenci, and the work had been in progress nearly a year before the Inspiration experiments with flotation had disclosed the revolution in concentration that was at that time impending. The simplified flow sheet worked out for the remodeling of the Morenci plant had been based upon the removal of the freed metal in a minimum number of stages by treatment upon tables equipped with Butchart riffles, the latter being adapted to accomplish both classification of feed and removal of the metal at one operation, substantially as described in my previous paper.l The scheme of treatment for the slime was based upon the well-known fact that after copper sulphides, such as chalcocite and chalcopy-rite, etc., are reduced to a certain extremely fine state of comminution they are definitely beyond the reach of separation upon any of the concentrating devices then known. By using drag-belt classifiers (which served as conveyors as well as separators), the overflow ,would be of the usual "slimes" class. Experiment had shown that when these drag-belt overflows were properly diluted (that is, to about 5 to 7 per cent. solids in the feed under treatment) the very fine sand, and especially the very fine but still granular sulphide particles, would, if given a short distance to fall, quickly settle out in prime condition to yield an excellent recovery on vanners; a further valuable feature would be that the very fine non-separable final overflow tonnage might be discharged direct to tailing, thus conserving space requirements so as to permit within the old building, without embarrassment, the increase of capacity required. For reasons that are obvious, this kind of feed preparation for the slime could not be successfully accomplished in any form of pointed boxes or

Jan 1, 1917

By J. B. Davis

This paper has been prepared at the suggestion of Mr. Dunbar D. Scott, to supplement his " Evolution of Mine-Surveying Instruments."† Before entering into a detailed history of solar instruments, a few remarks will be made touching upon land-surveys in general, and on what has led to the development of these instruments.The oxidation of metals melted in contact with air takes place with dissimilar results. Tin, lead or zinc are examples of a class, the oxides of which float on the surface of the melted metal. First a film is produced, which covers the surface; then, if agitation from any cause exposes new metal to the action of the air, additional oxidation takes place, and the film is increased in volume. This change goes on until a considerable quantity of oxide (or " dross," as it is technically called) is formed; depending, of course, upon the duration of the exposure of the metal to the atmosphere. When such metals are poured, the dross may be skimmed off; and clean metal will be left underneath. The removal of such oxides is, therefore, merely a mechanical process. In the case of copper, however, the result is quite different. The sub-oxide of copper (Cu2O) is readily soluble in molten copper; and therefore, instead of the formation of a film of oxide, to be finally removed as dross, the surface of the metal remains bright and clear, because the oxide has been dissolved as soon as it was produced. It is customary in the process of copper-refining to leave a small quantity of oxide in the metal, in order to oxidize any traces of bismuth, arsenic or antimony which have not been entirely removed. As a result, these metals exist in the commercial product as oxides, and not as metals, which would form an

Jan 1, 1901

By N. H. Harrison, J. K. Rodgers, S. Regier

This paper presents comparisons of data obtained from a laboratory reservoir study and from a calculated behavior prediction with the actual production history of a condensate reservoir. A small non-commercial discovery was depleted under closely controlled conditions and the well fluids were sampled at frequent intervals. Data on the reservoir and production variables were accumulated on a fixed schedule. A laboratory reservoir study war made using the initial well fluid samples as charging stock. The production procedures and operating conditions were held constant throughout the study wherever possible and in general paralleled the field work. The well fluid compositions and the cumulative recoveries ar a function of the reservoir pressure were also calculated using conventional flash vaporization procedures and equilibrium constants. Comparisons based on the composition of the well fluid show good agreement, the laboratory study agreeing within experimental accuracy with the field work and the calculated data comparing equally well. The gas-oil ratios are also in good agreement, but with somewhat greater deviations at the higher pressures. In the overall picture, it is believed that a model st,~tiy can predict within experimental accuracy the production history of a condensate reservoir. Better equilibrium constants for the heavier hydrocarbons are needed in order to attain improved composition accuracy by calculation. INTRODUCTION In Aug., 1955, a gas condensate well was completed in San Juan County, Utah, that was initially thought capable of good commercial production. These conclusions were derived principally from core data and electric logs, which indicated good permeability, porosity and gas content. However, after the usual series of potential tests it was found that the reservoir pressure had declined some 22 per cent, and it was obvious that the zone tapped was but a small pocket or trap. It became apparent that, with a controlled depletion of a small reservoir, a unique opportunity was available to compare laboratory and calculated studies with an actual field depletion and to further the present knowledge of condensate reservoirs. FIELD WORK The Coalbed Canyon Well No. 1 was conventionally completed in the Paradox limestone formation to a total depth of 5,912 ft. The producing zone from 5,762 to 5,806 ft was perforated with four jet shots per ft. The wellhead and field equipment were also conventional, the major items consisting of a two-pass indirect fired line heater, a high- and a low-pressure separator with the necessary controls and accessories, gas meters, back-pressure regulators, flare stacks and condensate stock tanks. The initial testing of this well con-sisted of a series of flow potential and pressure build-up tests during which some 30 MMcf of gas was produced. The reservoir pressure declined from an estimated 2,300 to 1,782 psig during this period, from which it was concluded that the reservoir was very small. In order to approach steady-state conditions in the reservoir and so provide optimum conditions for making comparisons, the field depletion was programmed to approach, if possible, constant production conditions. Bi-hourly readings were taken of the tubing pressure, the pressure and temperature of the separators, oil and gas rates, and other pertinent operating data. The gas rate, as indicated by the orifice meter, was held constant by the adjustment of the choke in the line heater. The temperature of the first stage separator was held constant by adjustment of the line heater jacket temperature. Practical considerations of production made the maintenance oi a constant gas rate impossible. The test started with a gas rate of 4 MMcf/D and a separator pressure of 250 psig. This rate was maintained until the choke was fully opened. The gas rate then declined with the falling tubing pressure and production was continued until the rate was about 2

By Forrest V. Williams

The dislocatiorl and stacking-fault structuve of epitaxial GaAs1-,PX lms been examined by chemical etching. The layers were groun in the (100) direction and etch Pils were developed on (111} planes which nad been lapped and polished on the epiLaxia1 layevs. Tile effecL of the jollolcing cariables on the quality of the epilaxial layers has been examined: doping leuel, grouth rate, and composition. High stacking-faullL densilies weve found in the GuAsi_xpx layers. These are not observed in heavily dolled epitaxial layers tzar in layers with low phosphorus compositions. The dislocatiorz density in GuAsi-x px was highest at the sub-stvate- epilaxia1 layer interface. Composilion changes introduced dislocations in the epitaxial layers. ManY semiconductor p-n junction lasers of Group TIT-Group V compounds and their alloys have been reported in the past several years. Laser action at visible wavelengths in GaAsl-x,Px was first reported by Holonyak and Bevacqua. GaAs, a direct transition semiconductor which lases, and Gap, an indirect transition semiconductor which does not lase, form a continuous series of solid solutions.2 Laser junctions can be fabricated in GaAsl-xPx crystals with phosphorus compositions up to about 40 mol pct. In addition to the production of coherent radiation in these crystals, the efficient recombination radiation of p-n junctions in this material has equally important potential in the development of low-power semiconductor lamps. To achieve a high conversion efficiency of electrical to optical energy in p-n junctions in this material, the relation of physical properties of the crystal to luminescence efficiency must be better understood. Although the electrical, optical, and device properties of GaAsl -xPx junction lasers are understandably of considerable interest, the work to date indicates that the more serious problems are the chemical and metallurgical difficulties encountered in the growth of this material.3 In addition to the problems of chemical purity, crystal imperfections, such as dislocations and stacking faults, can be expected to affect both the efficiency of the radiative recombination process and the perfection of the p-n junction.3 The last requirement, i.c., that of the perfection of the p-n junction, is a particularly troublesome one in the fabrication of laser diodes. To obtain good laser diodes, the p-n junction must be flat, which permits the radiation to be reflected from the resonant cavity boundaries. Junction planarity is extremely sensitive to the crystal perfection of the semiconductor material. Also, it is known that at high dislocation densities (-105 per sq cm) it has not been possible to build laser junctions in GaAsl-xPx . Few studies have been reported on the crystal defect structure of GaAsl-,P,. The first serious study seems to be that of Wolfe, Nuese, and Holonyak,3 who examined the dislocation structure of monocrystalline bulk (nonepitaxial) material grown by halogen vapor transport. In this paper are reported some observations on the dislocation and stacking-fault structure of GaAsl_,P, crystals grown by a vapor transport process on substrates of GaAs. EXPERIMENTAL Crystal Growth. The GaAsl-xPx crystals were grown in an open-tube flow system, using two sets of reagents. GaAs, Pr(red), and HC1 were employed in one method. The transport reaction is =950JC GaAs+HC1 = GaCl +1/4As4 +1/2H2 and the deposition reaction is 2GaAs1-xPx +GaCl3 Composition control is obtained by the flow rate of the HC1 and the vapor pressure of the P4, which is maintained in a separately controlled furnace. The second method has been described by Ruehr-wein4 and utilizes gallium, AsH3, PH3, and HC1. The same transport and deposition reactions as above are involved. Composition control is obtained solely by the flow rates of the three gases involved. All of the crystals were grown on chemically polished GaAs substrates oriented on the (100) plane. The thicknesses of the epitaxial layers were typically 100 to 300p. Revealing of Dislocations. Dislocations were re-vealed on both the( 111 ) and { l l l }b faces by chemical etching. The specimen to be examined was mounted at 54.7 deg, lapped on glass with 3-p alumina, polished on cloth with 3-p diamond paste, and, to remove work damage, chemically polished at room temperature for

Jan 1, 1968

By H. H. Rachford, D. S. Howard

In the withdrawal of fluids from tilted aquifers it is of value to be able to predict pressure patterns during the course of the pressure decline. As an example of this, in the displacement of fluids from oil reservoirs being produced by water-drive, prediction of the reservoir pressure is an important factor in fixing production rate. The prediction of pressure patterns in the depletion of an inclined aquifer has conventionally been made by solving the well known flow equations for the pressure Patterns in a horizontal aquifer, and correcting these patterm for the pressure difference due to the hydrostatic head associated with the vertical distance between a point in the horizontal aquifer and the corresponding point in the tilted aquifer. Inasmuch as the equation describing flow in tilted strata is different from that for horizontal flow. there was question as to the validity of the simple corrective procedure current1y in use. To examine the magnitude of error made using this procedure, an inclined aquifer was chosen for which the error was expected to he large, and the equation for flow in this tilted stratum was solved numerically. The results of the conventional procedure of correcting the solution of the equation for horizontal flow was compared with the solution of the correct equation by studying the difference between predicted pressures by the two methods. Three forms of the hydrostatic head correction were studied. The results for all three forms of the head correction are similar. The error in the approximate solution is quite dependent on the position of the horizontal aquifer with respect to the inclined one. The error is greatest at the producing end ad increases with amount of fluid withdrawn. The magnitude of the errors is not large if a good choice is made for the position of the horizontal datum. The most satisfactory position for the datum in all cases is near or slightly about the mid-point of the inclined stratum. Use of the best approximate method studied with the best datum tested yielded predicted pressures in error no greater than 7 psi. INTRODUCTION The movement of water by expansion from an aquifer to displace fluids from a contiguous oil reservoir was first recognized over 20 years ago.9 Since that time much work has been done to relate this mechanism to reservoir behavior mathematically. The result of this effort on the part of many workers has led to an understanding of underground fluid movement which has enabled us to follow and predict the behavior of the water-drive reservoir. One reason that good progress has been made in the application of mathematics to the study of pressure patterns and water movements in aquifers has been that the differential equation which describes this process is of a relatively simple form. The equation for the isothermal, horizontal, viscous flow of water through homogeneous sandstone is identical with that for the diffusion of heat through homogeneous solids, and this equation and means of obtaining solutions for it with many types of boundary conditions have been studied extensively. That this work has been highly successful is clearly emphasized by the large number of solutions developed for problems of interest both by methods of formal mathemat-

Jan 1, 1957

By R. W. Smith, T. J. Smolik

Recent work indicates that fluosilicate ions and or fluosilicate amine complex ions play important roles in fluoride activation of bery and feldspars in cationic flotation systems. In an attempt to further confirm conclusions reached in this earlier work, an infrared and X-ray diffraction study of the action of fluorides in cationic flotation of silicates was undertaken. It should be noted that in recent years considerable use has been made of infrared spectroscopy in studies of surface phenomena,2-4 and these studies have established the excellence of the technique. In the present study infrared spectra were obtained for various products of the reaction of HF and dode-cyclamine hydrochloride with quartz, microcline and beryl. These spectra were compared with one another and spectra of several inorganic and organic substances. In addition to infrared spectra, X-ray diffraction patterns were run on many of the reaction products obtained. A model 137 B Perkin Elmer Infracord double beam spectrophotometer containing sodium chloride optics was used to obtain the spectra. Infrared samples, except for the dodecylamine sample, were prepared by thoroughly mixing the substance to be analyzed with purified KBr in steel vessels on a Wig-L-Bug amalgamator. One-half in. pellets weighing 100 mg were than pressed under vacuum. Details concerning percentage of the substance to be analyzed in the pellets are indicated on the spectra. In all cases except for dodecylamine a KBr pellet was placed in the reference beam of the spectrophotometer to cancel bands due to possible impurities in the KBr. The dodecylamine sample on which an infrared spectrum was obtained was prepared by placing pure dodecylamine between two salt plates. X-ray diffraction patterns were obtained with a Norelco instrument, using a copper target tube, nickel filter and Geiger tube detector. The samples were ground into powders and either placed on glass slides with glue or placed into regular powder sample holders for diffraction studies. Goniometer scanning speed varied from 1°/min to 1/8°/min. EXPERIMENTAL RESULTS AND DISCUSSION Infrared spectra of microcline, beryl and quartz were obtained first and are shown in Fig. 1. These spectra agree reasonably well with previously reported spectra.5,6 The microcline (Fig. 1 a) and beryl (Fig. 1 b) were from good Black Hills crystals. The quartz (Fig. 1 c) was from a large, clear Brazilian crystal. It is not clear whether absorption bands of minerals are due to molecular vibrations, lattice vibrations or both. Fig. 2 shows infrared spectra of dodecylamine (Fig. 2 a) and dodecylamine hydrochloride (Fig. 2 b). The dodecylamine spectrum checks quite closely with that reported in Sadtler.8 Little is known of the spectra of hydrochloride salts of amines,9 and a spectrum of dodecylamine hydrochloride could not be

Jan 1, 1965

By W. R. Seyfried

THE -problem of extracting alumina from clay and low-grade bauxites has been the subject of considerable interest for some time. The basic reason, of course, lies in the fact that known reserves of high-grade bauxite are not inexhaustible and that the present commercial process cannot successfully cope with low-grade bauxites or clay. Ultimately it may be necessary to use these poorer raw materials for all commercial operations, An unprecedented demand for aluminum during the war emergency and the constantly threatened shortage of imported bauxite caused the United States Government to take an active role in this problem. Through the National Academy of Sciences, the War Production Board and the Defense Plant Corporation, it investigated processes and finally selected four to be used in the construction and operation of four experimental plants. Each plant was to be designed in such a way as to facilitate its incorporation into a larger commercial plant should the need arise. The Chemical Construction Corporation process, or "Chemico" ammonium sulphate process as it is better known, was one of the four selected. The extensive literature and patents on record before the war generally follow one of two process-types depending upon the extracting reagent used. One group uses an acid reagent, the other an alkali. The Chemico process uses an acid reagent. For those interested in other processes described in literature, there is a short bibliography at the end of this paper, The basic steps of all acid extraction processes are: (I) to make the aluminum silicates acid soluble, (2) to separate the released alumina from impurities and insoluble gangue, and (3) to recover the reaent for re-use. THE PROCESS AS PLANNED In April 1941, a group of chemists and engineers of the Chemical Construction Corp, became interested in the problem of extracting alumina from clays and low-grade bauxites and, under the leadership of Mr. Blakeslee Barnes, Vice President and General Manager of the Company, first drafted a process in July of that year-five months prior to Pearl Harbor. The work continued in our research laboratories and with a small pilot plant, By June 1943, the work had progressed to a point where it was possible to apply for a patent on the process which was U.S. patent 2,405,426, granted August 6, 1946. Immediately prior to the development of the Salem plant, the process was envisaged to be as follows: I. The first step was to make the aluminum silicates acid soluble. It was planned: (a) Clay or low-grade bauxite would be roasted at 700 to 800°C (1292° to 1492°F). (b) The roasted ore would then be leached .with hot aqueous ammonium bisulphate to form a slurry. In this way the

Jan 1, 1948

By James W. Shaffer

Aluminum is the most abundant metallic element of the earth's crust and is a constituent of nearly every type of rock (Clark, 1924, p. 13). The sources of aluminum and aluminous material most commonly used by modern industry are the bauxitic raw materials consisting of bauxite, bauxitic clay, and aluminous laterites. These are mixtures of hydrated aluminum oxide minerals and mineral impurities. End Uses Bauxite is used as an aluminum ore and in the manufacture of refractory products, aluminous chemicals, and abrasives. Other raw materials are used for aluminum ores, but their use is minor compared to bauxite. Refractory products made from bauxite are synthetic mullite, high-alumina fire bricks, castables, monoliths, cements, and ramming mixes used by the iron, steel, and cement industries. Chemicals made from bauxite are aluminum sulfate and sodium aluminate for water treatment and aluminum chloride used in refining crude petroleum. Among the abrasive products made from bauxite are coated abrasives, sharpening stones, and grinding wheels. Special grades of bauxite are used in the decolorization and clarification of raw sugar and lubricating oils. Bauxite has been used for road surfacing but mainly because other material was not more readily available. Perhaps the oldest use of bauxite and aluminous laterite is for a building stone. Ancient temples and more recent structures in India have been made from these and some varieties are suitable for decorative stone. Geology Mineralogy and Properties – Bauxite is a mineral raw material composed principally of one or more hydrated aluminum oxide minerals and impurities of silica, iron oxide, titania and elements in minor or trace amounts. The hydrated aluminum oxide minerals are gibbsite, boehmite and diaspore. Corundum is not included as a bauxite mineral although it does occur in some bauxite deposits. Boehmite and diaspore are both alumina mono-hydrates and have essentially the same composition, but diaspore has a greater hardness and a higher specific gravity because of a more tightly bonded and compacted atomic structure. Gibbsite is an alumina trihydrate mineral. Properties of bauxite minerals are shown in [Table 1].

Jan 1, 1975

By L. D. Fetterolf, G. T. Mahler, W. M. Peirce, R. K. Waring

Until recently, the only commercial method of producing magnesium has been fused salt electrolysis, despite a considerable amount of experimental work on the direct reduction of magnesium oxide. In this early work, a number of investigators demonstrated that magnesium oxide would react with any one of several reducing agents to produce magnesium vapor, but that the mixture of magnesium oxide and reducing agent must be heated to a high temperature even in a vacuum. In particular, it was demonstrated that silicon and aluminum are effective reducing agents and that when either of these is used the magnesium vapor can be condensed to massive metal. In spite of this knowledge, no successful commercial reduction process was developed, at least in this country, because of the operational difficulties imposed by the requirement of high temperature and vacuum and because of the high cost of the reducing agent. The outstanding experimental work done by Pidgeon, who carefully reviewed all of the known methods of making magnesium and then selected ferrosilicon reduction, overcame some of the operational difficulties. The process developed by Pidgeon comprises briquetting a mixture of calcined dolomite and reducing agent, preheating the briquets to about 600°C. in an externally heated alloy retort, reducing the MgO with silicon in an evacuated horizontal alloy retort heated externally to about II50 C., and condensing the magnesium vapor to a solid in a cold extension of the retort projecting beyond the front of the furnace. A major advantage of Pidgeon's process is that the retort is not cooled down between charges. Earlier investigators had used apparatus that necessitated cooling and reheating of the retort between charges. Early in January 1942, when the War Production Board was considering the Pidgeon process for quickly increasing the production of magnesium, The New Jersey Zinc Co. offered to have a research investigation of the process carried on, with the hope of assisting in its further development. This offer was accepted, and a two-retort pilot plant was built at Palmerton and put in operation on Jan. 29,1942. An intensive investigation of certain phases of the process was carried out in the ensuing four months. This investigation was completed in the last part of May 1942) and the pilot plant was then shut down. Subsequently, The New Jersey Zinc Co. was requested to have further development work done on the process, and a more extensive investigation was undertaken in August 1942 under contract with the War Production Board and under the supervision of the War Metallurgy Committee. This paper describes the ,phases of the investigation that are thought to be of sufficient general interest to merit publication.

Jan 1, 1944

By Ralph A. Sherman, J. M. Pilcher

BY surface treatment of coal is meant the application of a material, either solid or liquid, to the surface of pieces of coal. The purposes of surface treatment are varied. They may be to identify or "trade-mark" the coal, to modify the burning characteristics, the coking tendencies, or the behavior of the ash, to prevent the freezing of wet coal, or to control the dust. The control of dust is the usual purpose of surface treatment. TRADE-MARKING COAL The application of color to the surface of coal for the purpose of identification and registration of the trade-mark has been practiced to some extent. In 1928, the Glen Alden Coal Co. began to color its coal and adopted the trade-mark, "Blue Coal." The Old Ben Coal Co. later followed a similar practice with "Green Coal." A commoner means of identification of coal has been the stenciling of designs or pasting labels on large lumps or in the distribution of small cardboard tags through the smaller sizes. The details of the method used to color coal have not been revealed. Usually all of the coal is not treated, because of the expense. Only enough pieces are colored to show clearly when distributed through the coal. The patent literature gives information on some of the methods proposed. Esselen and Weiss 1 have patented the deposition of a coloring material in the valleys of the surface of the coal. Sperr2 covers the quenching of coke with water containing a pigment or dye that will deposit on the coke. He also suggests electroplating with copper or nickel. Glinsmann 3 subjects the freshly fractured coal surface to the action of an alkali or alkali earth ferricyanide and a ferric salt. Barsky and Hanson4 specify a method for the application of the same chemicals covered by Glinsmann.

Jan 1, 1943

By Thomas C. Wilder

The concentration and activity of oxygen in liquid copper has been measured by the reversible galvanic cell: at 1100°and 1200°C for the concentration range of oxygen of 3 to 5600 ppm Measurements for approximately thirly alloys at each temperature indicate that the activity of oxygen roughly follows Henry's law, the activity coefficients of oxygen being 0.12 and 0.205 at 1100° and 1200°C, respectively. These results compare javorably with the results of seven other electrochemical and gaseous equilibrium studies on this system, the free energy of the solution reaction 1/2 O2 = O (7 at. pct in Cu, liq) being -18.10 * 0.30 kcal per gfw at 1200°C. Estimates of the standard molar free energy of formation of CupO(S) are also made. Praclicul consideration of this cell as an oxygen sensor for liquid metals is discussed briefly. SOLID mixed-oxide electrolytes which have a defect structure in the anion sublattice have recently become a very popular means by which the chemical potential of oxygen is measured at high temperatures. Since the pioneering work of Kiukkola and Wagner1 such electrolytes have been used in numerous cell studies for determining the thermodynamic properties of metallic oxides and oxy compounds, the partial pressure of oxygen in vacuum systems and other atmospheres, and the properties of oxygen dissolved in metals and alloys. The use of a solid electrolyte in a cell for a fast reliable method of oxygen determination in liquid metals would be a very important tool to the process metallurgist. In copper, for example, the oxygen content of the molten metal in the cathode furnace is a prime factor in determining the "set" or solidification profile of cast wire bars. In this investigation the activity of oxygen in liquid copper was measured by an electrochemical cell employing the electrolyte ZrO2 + 7 1/2 wt pct CaO. The cell used at 1100° and 1200°C was

Jan 1, 1967

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