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By W. M. Robertson

The formation of grain boundary grooves on surfaces of poly crystalline samples of cobalt and iron immersed in liquid lead has been studied. The grooves form by volume diffusion of the solutes cobalt and iron in the liquid. The diffusion coefficients of the solutes in liquid lead are derived from the measured rate of grooving. The diffusion coefficients are described by the relation D = Do exp (-Q/RT), with, for cobalt, Do = 4.6 x 10-4 sq cm per sec and Q = 5300 ± 800 cal per mole, and for iron, DO = 4.9 x 10-3 sq cm per sec and Q = 10,500 ± 1500 cal per mole. LIQUID metal-solid metal interactions occur at solid-liquid interfaces. Interfacial energy provides a driving force to change the morphology of the interface. Mullins1,2 has derived expressions for the kinetics of interface morphology changes driven by capillarity. These expressions can be applied to an isothermal system of a solid in equilibrium with a liquid saturated with the solid. Surface profile changes can occur by volume diffusion of the solute in the liquid, by volume self-diffusion in the solid, and by interfacial diffusion at the liquid-solid interface. A groove will form at the intersection of a grain boundary with a solid-liquid interface, reducing the total interfacial free energy of the system. The solid-liquid interfacial energy ? must be greater than half the grain boundary energy of the solid ?6 for Mullins' calculations to apply. If ? is less than ?b/2, then the liquid penetrates the boundaries, separating the grains rather than forming grooves. Boundary penetration did not occur in the work described here. where CO is the equilibrium volume concentration of the solid in the liquid, Dv the volume diffusion coefficient of the solid in the liquid, ? the interfacial free energy of the solid-liquid interface, O the atomic volume of the solid crystal, k Boltzmann's constant and T the absolute temperature. Eqs. [1] and [2 ] also apply to grooving by volume self-diffusion in the solid,1 with CoODv = D Self, where DSelf is the volume self-diffusion coefficient of the solid. For a grooving mechanism of interfacial diffusion at the solid-liquid interface, the groove width is given by2 where CS is the interfacial concentration of the diffusing species, and DS is the interfacial diffusion coefficient. Eqs. [1] and [3] can be used to determine the mechanism of groove growth. A t1/3 dependence of the growth indicates volume diffusion and t1/4 indicates interfacial diffusion. In some cases, volume diffusion and interfacial diffusion both can contribute substantially to the grooving process, causing the time dependence to be intermediate between t 1/3 and t1/4.3 For these cases, the relative contributions of the two processes can be separated.4 However, in many cases, one process will be dominant, and the data can be analyzed on the basis of Eq. [1] or Eq. [3] alone. The time dependences for volume diffusion in a liquid and volume self-diffusion in a solid are the same. However, the self-diffusion contribution of the solid is usually negligible compared to volume diffusion in the liquid. After the grooving mechanism has been determined, Eq. [1] or Eq. [3 ] yields the kinetic parameter A or B. The kinetic parameter can be used to calculate values for the unknown quantities in the product CD?. Usually C is known or can be estimated. If ? is known, then D can be calculated. In a measurement of grain boundary grooving of copper in liquid lead,' the time dependence indicated volume diffusion in the liquid. The quantities Co, Dv, and ? were obtained from the literature, giving excellent agreement between the observed values of A and the values calculated from Eq. [2 ].5 In a study of the grooving of several refractory metals in liquid tin and liquid silver, A1len6 educed that grooves formed by volume diffusion in the liquid. In a study of nickel in a nickel sulfide melt, Steidel, Li, and spencer7 found volume diffusion grooving kinetics. Both Dv and ? were unknown, so they could not obtain either one separately, though they did obtain a reasonable value for the temperature dependence of the product Dv ?. Several methods have been used to obtain surface profiles. It can be done by sectioning through the interface7 or by chemically removing the liquid from the solid surface after solidification of the liquid.6 However, if the liquid dewets the solid on removing the solid from the melt, then the interface can be observed directly. This method was used previously' and was utilized also in the present study. EXPERIMENTAL PROCEDURE Lead of 99.999 pct purity was obtained from American Smelting and Refining Co. Cobalt sheet was obtained from Sherritt-Gordon Mines, Ltd., with a nominal purity of 99.9 pct, the principal impurities being nickel, iron, copper, carbon, and sulfur. The sheet was

Jan 1, 1969

By Charles A. Ashburner

A very limited development has been made of the coal-fields of this Territory. This is to be accounted for by the fact that a number of the coal-fields lack railroad transportation, by the distance of other fields from the consumers (due to restricted settlements), and finally by the poorer quality of a number of coals which have been mined as compared to others which can be economically imported into the Territory. The consumption of coal in Utah during 1886, outside of that used by the railway companies, was: Tons. Utah coal,..........110,000 Wyoming coal,. .....19,000 Colorado coal,........* 4,945 Total,........... 133,945 It is estimated that there are 1100 miles of railroads in the Territory which use coal for fuel. The consumption of these roads for the year is estimated at 100,000 tons, making an aggregate consumption in the Territory of 223,945 tons. The consumption of coal in Salt Lake City duriug the year was as follows: Tone. From Grass Creek mines,.......21,000 " Pleasant Valley Company's mines,.. 12,700 " Utah Central Company's mines,.9,000 " Bock Spring mines,.6,500 " Almy mines .. ., .. .. . 6,000 " Miscellaneous sources,..5,800 Total ,.........60,000

Jan 1, 1888

By D. J. Weintritt, J. C. Cowan

Methods of studying oilfield mineral .scale deposition in the laboratory do not work for barium sulfate because only small nonadhering crystals ore formed. On the other hand, barium sulfate scale found in down-hole or surface equipment is strongly adhering and may contain very large crystals. Results suggest that most of the difference derives from the extremely low .solubility of barium sulfate. Firm adherence of scale and the consistent development of oriented crystals 100 microns and larger suggest a relationship between scale adherence and crysta1 growth. Data from this study indicate some reasons for barium sulfate's occurring as a deposit in oilfield waters. The unique characteristics as well as the associative properties of barium sulfate scale as related to calcium carbonate and calcium sulfate ere shown. INTRODUCTION The first observed deposition of barium sulfate scale in oilfield production equipment is unknown but probably coincides closely with the beginnings of the oil industry itself. Moore' described barite oolites in some producing wells in the Saratoga field, Tex., in 1914. Currently, positive identification of barium sulfate deposition is recorded in most of the major oil-producing areas of the United States. As efforts continue to identify the composition and functions of the materials found in scale deposits, the geographic and economic importance of the part played by barium sulfate will become even more important. This belief is based on the following Facts. 1. Many oil fields in the U.S. are in or entering their mature phase and the volume of produced water is increasing; thus, the cumulative effects of low-solubility minerals become more significant. 2. Secondary recovery techniques and increased emphasis on waste disposal systems require controlling the behavior of all constituents of water to prevent formation plugging. 3. The more general use of instrumental analysis has reduced the time and improved the accuracy of complete scale and water analysis. 4. Once formed, barium sulfate scale is resistant to present methods of chemical removal; therefore, costly mechanical methods are necessary. Thus, new methods of prevention and control will require specialized chemical techniques and better knowledge of the causes of scaling. Consider the results of some simulated field deposition studies illustrating this need (Fig. 1). The studies utilized a Scale Deposition Test Cell* and each coupon was exposed to 8,000 ml of a 300 me/liter solution of the various types of mineral scale. All tests were conducted at 140F. Only the calcium sulfate and calcium carbonate deposited scale. The solution containing 300 me/liter of barium sulfate exhibited copious amounts of precipitate, but none of the precipitate adhered. The fluids from the effluents were also allowed to impinge on glass slides. Fig. 1 shows the relative adherence of the three types of scale on unetched glass. The barium sulfate failed to deposit in the same manner as the calcium carbonate and calcium sulfate solutions.

By Charles H. Jacoby

In 1774 a Swedish chemist, C. W. Schule, first recognized manganese as an element. That same year Schule's associate, J. G. Gahn, isolated the element manganese for the first time. In 1856 the Bessemer process of steelmaking gave birth to the economic importance of manganese. Later, in 1882, Robert Hadfield discovered high manganese steels. Although the primary use of manganese is in the ferroalloy industry, two additional important uses for manganese are making chemicals and dry cell batteries. Manganese is also vital to plant and animal life. Various chemical compounds of manganese are used in fertilizers, feeds, glass manufacture, paints, varnishes, and for numerous medicinal and chemical purposes. For the study of industrial minerals and rocks, only the chemical and battery grade material is of- concern, but for the sake of comparison, metallurgical aspects are included in this presentation. Although currently the world's largest consumer of manganese, the United States is producing only minor amounts of ore at the present time. This is due primarily to the fact that although huge deposits of manganese occur within our borders, all are of such low grade as to be economically unfeasible to mine. For many years various government agencies and segments of private industry have devoted sizable sums of money and time in an attempt to upgrade ores from the various deposits, and also in an attempt to recover manganese from blast furnace slags. In view of current world prices, and the quantity of high grade material available, there is little likelihood that any of these approaches will be found to be economically feasible in the near future. Geology and Mineralogy Mineralogy There are over one hundred minerals that contain manganese. These minerals vary from those with compositions that are predominantly manganese to those having only minor percentages. [Chemical Mineral Composition % Mn Hausmannite Mn304 72 Polianite MnO2, 63.1 Pyrolusite MnO24 60-63 Cryptomelane KR8O16R (R=Mn) Variable PsilomelaneBa Mn Mn8O16 (OH).45-60 CoronaditePb R8O16R (R=Mn) Variable Hollandite Ba R8O16R (R=Mn) Variable Manganite Mn2O3•H20 62 Braunite 3 Mn2O3•MnSiO3 62 Tephroite 2 MnO•SiO2 54.3 Rhodochrosite MnCO3 47 Rhodonite MnSiO3 42 Spessartite 3 MnO•AI2O3•3SIO2 33.3 WadHydrous Mn OxidesVariable Franklinite(Fe Mn Zn)O(Fe Mn)sO3 Variable Asbolan Cobaltiferous wad Variable AlabanditeMnS63.14] Geology From a geological standpoint most manganese deposits are complex. In general, it can be said that all primary deposits of manganese are carbonates or silicates. The most productive and profitable have been those of sedimentary origin and residual concentrations. Examples of these residual types of deposits are associated with the metamorphosed lodes of Madhya, Pradesh, India, and the lateritic deposits of Orissa and Bihar, India; nodules in the residual clays of the Philippine Islands, US southern Appalachians and Arkansas, Ghana, and Brazil. Sedimentary manganese deposits are best exemplified by the Nikopol district of Russia and the Tchiatouri area of Georgia, USSR. Hydrothermal replacements are characterized by the rhodochrosite deposits of Butte and Phillipsburg, MT. In general, the hydrothermal type deposit has not resulted in any large tonnages being produced, but may have given

Jan 1, 1983

By Lauren A. Wright

General prosperity marked the industrial mineral industries of the U.S. and Canada in 1962. For most commodities, production and sales exceeded 1961 figures, and for several commodities, all-time production peaks were reached. Many millions of dollars were spent on exploration for and development of industrial mineral deposits, construction of new plant facilities, and expansion and modernization of existing plants. This generally satisfactory state is attributable mostly to a continuing high rate of building and heavy construction. However, for large segments of the industrial mineral field, 1962 was a year of increasingly severe competition and of problems, either existing or potential, of overproduction and overcapacity. Such problems are of particular concern to the asbestos, cement, potash and sulfur industries. As in years past, the trend continued toward larger-scale operations to permit lower production costs per unit of material mined, toward more stringent quality controls and toward marketing methods that provide greater efficiency and customer convenience.

Jan 2, 1963

By J. M. Hodge, H. M. Reichhold, R. D. Manning

The work reported in this paper represents the first of a series of investigations of the factors governing notch toughness in ferritic materials. This paper is concerned with two of these factors, namely, the effect of ferrite grain size, and the effect of an alloy content of 3.64 pct nickel. Every effort has been made to hold other variables constant in order to isolate the effects of these two. The compositions chosen for study were 0.02 pct carbon in order to eliminate the variable of carbide distribution, one steel being a plain carbon steel and the other alloyed with 3.64 pct nickel. Both steels were fully killed with silicon, without an aluminum addition, so that the variable of deoxidation practice was held constant. Finally, all samples were water quenched from 1200°F and tempered 24 hr at 300°F in order to hold the quench aging variable constant and to decrease the tendency for grain boundary carbide precipitation. The ferrite grain size was varied by heat treatment over the range of A.S.T.M. grain size numbers of about 2 to 6 in each steel so that the effect could be evaluated individually and the notch toughness of each steel could be compared at comparable ferrite grain sizes. Materials and Experimental Procedure MATERIALS The materials for this investigation were obtained from Battelle Memorial Institute as 250 Ib induction melts which were forged into 134 in. square bars and then rolled into 0.6 in. square bars. Both steels were deoxidized with silicon, the aluminum content being held to a minimum. Check analyses of these materials are shown in Table 1. HEAT TREATMENT FOR GRAIN SIZE The grain size was varied by varying both the cooling rate and the austeni- tizing temperatures. The heat treatments used and the corresponding grain size values are tabulated in Table 2. A semicontinuous network of grain boundary carbide was observed in the microstructure of both the plain carbon and nickel steels in the as rolled condition and an additional heat treatment was necessary to eliminate this variable. Therefore, all samples were water quenched from 1200°F and tempered 24 hr at 300°F as a final treatment before testing. This heat treatment served to eliminate to a great extent the grain boundary carbide network and to hold the quench aging effect constant. IMPACT TESTING Standard keyhole Charpy impact tests were machmed after heat treatment. A bath of acetone and dry ice was used for refrigeration of the samples down to temperatures of —94°F (—70°C) and a bath of either methyl-cyclohexane or isopentane, cooled by

Jan 1, 1950

By Eric Jette

THE unusual physical, electrical and magnetic properties of the iron-nickel alloys has given rise to a voluminous literature. This work will be reviewed critically in "The Alloys of Iron and Nickel," a monograph of the Alloys of Iron Research Series, soon to be published. In what follows we shall therefore confine ourselves to those of the earlier investi-gations that involved the use of X-ray crystal-structure methods. The earliest X-ray work on the iron-nickel system was by Miss Andrews1. Using the powder method of X-ray analysis purely as a means of identifying the phases present, she located a region between 20 and 30 weight per cent nickel in which body-centered and face-centered phases coexisted. No lattice constants nor details of heat-treat-ment were reported. Bain2 also reported some qualitative observations. McKeehan3 made a systematic investigation over the whole of the system, giving many of his alloys four and some five different heat-treatments. In alloys furnace-cooled from 900° to 950° C. he found two coexisting phases between 0.15 and 30 per cent nickel. The precision of the lattice-constant measurements was low in comparison with what can be obtained today.. Even for alloys of the same heat-treatment, differences in the constants were often between two and ten parts per thousand. In regions where no change of lattice constant with heat-treatment should occur, differences of the same order of magnitude were found. Since the maximum change in the lattice constant of nickel with change of composition is only about 2 per cent of the constant for pure nickel, these variations in the constants for a given alloy cause the points

Jan 1, 1936

The Library of the above-named Societies is open from 9 A.M to 10 P. M. except on holidays. It contains about 70,000 volumes and 90,000 pamphlets, including sets of technical periodicals and publications of scientific and technical societies. Members of the Institute, with few exceptions, are forced to spend a portion of their time in localities isolated from sources of information. To these the Library, through its Library Service Bureau, can render valuable service through correspondence; letters requesting information will receive especial attention. The Library is prepared to furnish references and photographic copies of articles on mining and metallurgical subjects; to determine the existence of mining maps, and to furnish general information on the geology and mineral resources of all countries. All communications should he made as definite as possible so that the information received may he what is desired and not include collateral matter which may not be of interest. The time spent in searching for such collateral matter will be saved, and the information will be sent more promptly and in more usable shape.

Jan 6, 1918

By K. Tangri, B. Swaroop

Simultaneous measurements of lattice (elastic) strain by X-ray line shift method and total strain with an electrical strain gage have been carried out on polycrystalli,ne nickel with the help of a specially designed tensometer attachment for the X-ray dif-fractometer. During the initial stages of deformation, the rate of increase in lattice strain closely follows the total strain until the plastic strain sets in. From then onwards, the two strains deviate from each other and with further increase in afiplied stress the rate of increase of lattice strain eventually decreases. Depending upon the mode of unloading, both compressive and tensile strains have been observed in nickel deformed up to 0.29 pct strain. These results have been explained on the basis of the effects of clustering of dislocations and also the production and behavior of point defects during loading and unloading, respectively. POLYCRYSTALS deformed plastically in a uniaxial tension test show residual lattice strains (hereafter referred to as RLS), which broaden the X-ray line profiles and shift their peak positions.''4 It is known that uniform straining of a crystal lattice (macrostrain) produced movement of ddfraction line peaks, whereas nonuniform straining (microstrain) causes line broadening.= Though the nature and origin of RLS in deformed metals is not yet clearly understood, these are believed to be due to the presence of some form of a locked-up stress system. Several possible detailed interpretations6'" of the stress system have been proposed by various workers and common to all these interpretations is the assumption that different parts of the aggregate have different tensile yield stresses; e.g., that a part A yields under a lower applied stress than a part B. Therefore, during the deformation process, the elastic strain in A will be less than that in B, and, after completion of deformation, B will tend to contract further than A but will be prevented from doing so by the restraining influence of A. Thus, when equilibrium is reached, A will be in compression while B is in tension. Although there is general agreement on the correctness of this argument, controversy still exists as to the exact nature of the parts A and B in a deformed metal. In an alternative approach to the creation of parts A and B, many other investigators have assumed that the RLS observed in unloaded specimens are in some way connected with the lack of proportionality between lattice strain and applied stress in the region above the yield stress." cullity13 has prepared a schematic summary of the results of previous workers, mainly Smith and Wood,2'11 which suggests that, above the elastic limit, the lattice strain may increase less rapidly with respect to strain, or may even decrease with increase in applied stress. If the applied stress is then decreased, the lattice strain would decrease along a line parallel to the loading line in the elastic region and thus produce a compressive residual lattice strain after unloading. At equilibrium, to balance these compressive stresses? there would have to be regions under tensile stress which may well be the grain boundaries or the substructure walls formed during deformation. The present investigation was undertaken to gain a better understanding of the nature and origin of RLS and also to experimentally verify the salient features of this hypothesis. EXPERIMENTAL Stress and strain determinations were made with a specially constructed tensometer attachment for the X-ray diffractometer, Fig. 1: which permits the following measurements simultaneously on a sheet specimen under uniaxial tension at various stress levels during loading and unloading: a) lattice strains, E=. in a direction perpendicular to the direction of pulling (x direction) from shifts in X-ray line peak positions; b) the total strain, ex, in the direction of pulling. with the help of an electrical strain gage affixed to the back of the specimen directly below the area irradiated by X-rays: and c) the applied stress, with the help of a load cell which consisted of a calibrated stainless-steel sample of dimensions identical to those of the specimen under investigation, and to which it was coupled. Because of its high stacking fault energy.I4 nickel

Jan 1, 1970

By J. S. Browning

The U.S. Bureau of Mines has been experimenting with flotation processes to separate the spodumene-beryl ores mined at Kings Mountain, N.C. The success to date as well as the present status of the process is discussed. Further experimentation is underway and studies will be made on the milling costs involved in the flotation process. The pegmatites of the Kings Mountain-Lincoln ton, N.C., area constitute the largest known domestic reserve of beryl and spodumene. The reserve is estimated to contain 90 million tons of pegmatic material with 1,280,000 tons of recoverable Li,O(lithia) as spodurnene.' The pegmatites also contain 0.4 to 0.5 pct beryl disseminated throughout the orebodies. The pegmatites may contain a potential reserve of 240,-000 tons beryl, equivalent to approximately 34,000 tons of BeO. Different flotation methods for separating beryl from feldspar or quartz, or both, have been developed by various investigators.2-7 On the other hand, published information is limited on concentration of spodumene-beryl ores. As the response of beryl and spodumene to flotation is essentially the same, a successful separation of the two minerals depends upon use of a selective depressant or a selective collector for one of the minerals. Several years ago, the U.S. Bureau of Mines, recognizing the need for developing a large domestic supply of strategic beryl, undertook studies to develop improved methods of recovering this mineral. Because of the low beryl content of the pegmatites, economic production of the beryl entails its recovery as a byproduct of spodumene flotation. Thus, the development of procedures that would provide for maximum recoveries of the spodumene, as well as the beryl, was a primary objective of the studies. Tests were made on run-of-mine ore and spodumene flotation tailing from the Foote Mineral Co.'s spodumene concentrator at Kings Mountain (Fig. 1). Pet-rographic analyses of the ore and flotation tailing are given in Table I. Detailed analyses and examinations of the ore and tailings revealed that the beryllium was present in the form of a low-alkali beryl. The crystals were small, rarely larger than 14-mesh diam, and were clear and colorless. About 10 pct of the Li20 content of the ore was present in the mica and feldspar components of the pegmatite. In some weathered ores the associated clays also contained small amounts of lithia. This is typical of pegmatites in the Kings Mountain area. LABORATORY TESTS In the past, a vigorous chemical treatment of the spodumene surfaces with acid or caustic soda has been considered essential for satisfactory selective flotation of the spodumene from the other minerals in pegmatites. Many tests were made during this investigation to determine if chemical treatment of the spodumene could be eliminated in favor of a reagent combination that would depress the other minerals while selectively floating the spodumene. A simple reagent combination and process was developed that gave better spodumene recovery and grade of concentrate than the more elaborate acid or caustic treatment methods previously used. The finely ground ore pulps were conditioned with either an ammonium, alkali, or alkaline earth lignin sulfonate and sodium fluoride, and the spodumene was floated and cleaned using oleic acid as the collector. The spodumene tailing was deslimed, conditioned with sulfuric acid and coco amine acetate, and floated to reject mica. The mica tailing was thickened and conditioned with hydrofluoric acid, then washed to remove the acid. The washed pulp was conditioned with sodium hydroxide for pH control, and the beryl was floated and cleaned with oleic acid as the collector. Table II summarizes the results of the laboratory test work. About 77 pct of the spodumene and 75 pct of the beryl were recovered from the pegmatitic material. The spodumene concentrate assayed 6.1 pct Li20 and 0.01 pct BeO, and the beryl product assayed 3.0 pct Li20 and 1.57 pct BeO. Similar results were ob-

Jan 1, 1961

By C. V. Millikan

When a flowing oil well is being drilled in with cable tools, it is difficult to determine when an additional streak of pay sand is drilled. By placing a gas meter on the gas-release line from the oil and gas separator, any increase in volume of gas that comes with oil production is recorded. In addition to the better knowledge of sand conditions, these data are a valuable aid in determining the size and depth of shots, plugging off water, and estimating ultimate production. The meter also gives a record of operation while the well is drilling in; and if allowed to remain on the well after completion will give information that may lead to a more efficient recovery of the oil from the sand. A VERTICAL cross section of any oil sand will show great variation in porosity and oil content. In some sands, the entire thickness contains oil, the variation being only the degree of porosity or oil content, but more often the pay streaks are distinctly separated by shells or barren streaks. These pay strata vary in number and may be thin or thick. The total thickness of the sand may be several tens of feet while the part containing oil may be only 1 or 2 ft. thick. The amount of production is not proportional to the thickness of the sand but rather the thickness of the pay streaks. If the total thickness of the sand or the amount that can be drilled is small, or if the initial production is small, the depth at which each stratum of pay is encountered can be determined sufficiently accurately for all present economic purposes. However, when drilling through sand of considerable thickness, giving large initial production, especially where conditions necessitate that the production go through the same gas trap with that from one or more wells already producing, it is difficult to determine the depth at which the pay strata are encountered even accurately enough to guide the placing of shots, and small pay streaks are apt not to be recognized at all.

Jan 9, 1925

By H. A. Lesser, H. L. Stone, G. H. Bruce

ESSO PRODUCTION RESEARCH CO., HOUSTON, TEX. A mathematical model that represents the conduction heating of a rock formation of limited permeability is formulated. Heat is introduced by the injection of a hot condensing gas into horizontal fractures through the formation. The fractures are assumed to be equally spaced; the flow of fluid is linear. The model consists of three coupled partial differential equations and two functional relationships. Temperature histories for both fractures and formation are obtained by numerical procedures. Application of the model in predicting in situ heating of oil shale is illustrated with four sample cases. Influences of shale thermal diffusivity, fluid pressure in the fracture and fracture spacing upon heating rate are demonstrated. In all cases considered, several years were required to heat all the formation to 700F with 1,000F steam. Less than 32 per cent of the injected heat was utilized for heating the shale. To facilitate extensive calculations of this type, a set of seven dimension-less quantities are derived. With this dimensionless system, the effect of controllable parameters on economics can be explored. INTRODUCTION Vast deposits of hydrocarbons are contained in oil shale formations in the western United States and in other countries. These hydrocarbons, known as kerogen, are difficult to recover because they are immobile solids and because the rock formations in which they are found have very limited permeability. The kerogen can be converted through pyrolysis to recoverable liquids and gases if the formation temperature is elevated to the range 600 to 800F. To accomplish this heating, the formation might be artificially fractured and a hot fluid injected into the fractures. If the injection and production wells are vertical and the fractures horizontal, interwell communication will be established and the hot fluid will flow from an injection well to a production well. In this process, some of the heat in the fluid will be given up and conducted into the formation. Products of pyrolysis will flow from the heated rock matrix into the fractures and be produced, commingled with the injected fluid. The practicality of such a process is strongly influenced by the rate at which heat can be transferred from the hot fluids to the formation. An analysis of this heat conduction problem is the subject of this paper. Linear flow of a condensing gas through a set of horizontal, equally spaced fractures is considered. Temperature histories for both fractures and formation are obtained from numerical procedures. The analysis also applies to formations containing streaks of natural permeability instead of fractures. Heat flow problems similar to the one treated here have been studied by other workers. Thomas1 has solved a radial problem in which he considers the injection of a noncondensing gas into a single, horizontal fracture and approximates the temperature profile in the fracture by a step function. The solutions to other problems, which are less similar to the present problem than the one treated by Thomas, have been reviewed by Spillette.2 In addition to these mathematical studies, a field test of an in situ shale oil recovery process using hot natural gas as the injected fluid has been reported.3 The first part of this paper is concerned with the mathematical development of the problem. The differential equations, boundary conditions and functional relationships which describe the physical model are formulated and the equations are cast into finite difference form. The method of solution of the difference equations is discussed (Appendix B). The second part of this paper presents results computed for a typical oil shale formation for which steam at 1,000F is the injected fluid. Fracture spacing, horizontal and vertical thermal diffusivities

Jan 1, 1967

By K. L. Komarek

Based on theoretical and experimental evidence a discussion follows of the behavior of phosphorus -bearing iron ores in the R-N Direct Reduction Process and suggestions are made of methods of reducing the amount of phosphorus in the metallic end product. In ferrous metallurgy a direct reduction process is one in which iron ores are reduced to metallic iron with gaseous or solid reductants without the appearance of a liquid phase. A number of attractive features have induced several companies and government agencies to invest in the development of direct reduction processes. A summary of all direct reduction processes up to 1954 has been given by Barrett,' and Wiberg,2 and Willems3 have reviewed the most recent developments in this rapidly expanding field. Many difficulties have been encountered in direct reduction processes and the nature of these difficulties has varied from process to process. One problem common to almost all of them is the removal of phosphorus which is one of the reasons for the rather pessimistic outlook given by some government publications4'5 to direct reduction processes. In this paper an attempt is made to give a theoretical explanation of the variations in phosphorus removal observed in the R-NY Direct Reduction Process. However, many conclusions are general enough to be applicable to other processes. Most iron ores treated by the R-N process yield products lower in phosphorus than the original ore. A qualitative account of the factors has been given by Stewart, Reed, and Herasymenkoe but the erratic removal of phosphorus from some ores and the general importance of this problem make a more careful analysis of the theoretical aspects desirable. In the R-N process mixed ore or balled fines, ex-

Jan 1, 1963

By Patricia J. Rand, Kailish Narayan

Atlantic Richfield Co. began operating a commercial uranium solution mining project in April 1975, in Live Oak County, Tex., 10 miles southwest of the town of George West. The operation is designed to produce 250,00 lb of U308 per year and is jointly owned by Atlantic Richfield Co., Dalco, and U.S. Steel. The proprietary process employed in this operation consists of injecting an alkaline leaching solution into the ore-bearing formation through a pattern of injection wells. The uranium-bearing solution is then removed through producing wells using submersible pumps in central production wells. The produced solution is pumped through a pipeline to the plant area where the uranium is extracted. The barren solution is refurbished and returned to the pattern area for reinjection. The injection field and plant site are located in the drainage of Spring Creek, a small intermittent stream tributary to the Nueces River. Land use in the area is primarily agricultural cattle ranching and farming---but several producing gas fields are present in the areas as well. A nine month enviromental baseline study was conducted on the property beginning in Feb. 1975. Plants and animals of the Clay West area were identified and representative terrestrial and aquatic communities were analyzed. Physical and chemical parameters of the soils were described and analyzed. The surface and underground waters were analyzed chemically; radionuclides, heavy metals, nutrients, and pesticide concentrations were measured in the creek sediments; bacteriological measurements were made in creek water and sediments; radionuclide and chemical levels in plants and animals, both terrestial and aquatic, were measured. These studies, though not required by existing, state or federal laws, were considered necessary to assess the existing conditions before operations began on site. The in-place leaching technique for uranium mining eliminates the enviromental disturbances associated with open pit or underground mining. No grinding and crushing of ore is needed, nor are large tonnages of waste tailings produced. Surface subsidence is not expected since less than 5 lb of uranium is present per ton of rock and even complete removal of such small amounts should not cause subsidence. Solution mining has fewer environmental problems than conventional mining. Members of the Texas Water Quality Board recognized the differences which exist and have recently formulated new environmental control procedures which apply specifically to solution mining. Some of the solution mining activities which are of particular concern are discussed in the following pages. Process Description The produced uranium-bearing solution is pumped through a pipeline from the pattern area to the plant area. The first pattern area consists of a nest of 125 fluid injection, production, and monitor wells [(Fig. 1)]. Injection wells have 4-in. casings and are spaced 50 ft apart on a square grid. Production wells have a 6-in. casing and are located in the center of each square. A block flow sheet of the plant is given in [Fig. 2]. The produced solution goes through parallel trains, each consisting of a carbon column and an ion exchange column in series. The carbon column removes any sand present in the produced solution and the ion exchange column extracts the uranium. The depleted solution is treated with chemicals and returned to the field for reinjection. The uranium retained in the ion exchange column is removed periodically with a sodium chloride solution. Uranium-bearing solution from the ion exchange column is passed through a charcoal column for removal of impurities and then to a precipitation tank where the uranium is precipitated as yellowcake slurry. The yellowcake slurry is clarified, filtered and dried to produce a granular yellowcake product. Environmental Considerations Sources of waste solutions to storage reservoirs, the backwash reservoir and atmospheric discharges are shown in the block flow sheet [(Fig. 2)]. These waste solutions pose a relatively small problem and are adequately controlled by conventional means. There is one area, however,

Jan 1, 1978

By Michael Perch, Charles C. Russell

Nearly 75 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69.9, and in 1938 it was 61.3. To produce a net ton of pig iron 1757 lb. of coke was required in 1940 and 1760 lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank' standardized by the American Society for Testing Materials. Although this method of classification has been an American stand¬ard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1944

By F. W. Glaser, Benjamin Post

A LTHOUGH most transition metals form a wide variety of boride compounds, the existence of only one zirconium boride, ZrB2, had been established prior to this investigation.' The crystal structure and some properties of a hitherto unreported zirconium boride, ZrB12, are described in this paper. Only one other dodecaboride of a transition metal, UB12, has been reported up to the present.' Chemical analysis of the new compound showed 44 pct Zr and 56 pct B, compared with 41 pct Zr and 59 pct B computed for ZrB12. The difference is within the range of error of the analytical method employed. ZrB12 shows marked metallic properties. It is obtained as a fine black powder. Measurements of electrical resistivity were made at —79°C, + 22°C and +64°C. At 22°C the electrical resistivity is approximately 60 microhm-cm. Over this range the temperature coefficient of resistivity is +0.00162. The thermal conductivity at room temperature is 0.122 watts per cm per "C. The product of the electrical resistivity and thermal conductivity is therefore 8.05, which is not far from the normal Wiedemann-Franz ratio (approximately 7.5 at room temperature). These measurements were made on hot pressed samples which were not always high density specimens. The hardness of ZrB12 on the Rockwell A scale varies between 92 and 92.5. Crystal Structure Determination Single crystals of ZrB12 of a size suitable for X-ray diffraction analysis could not be obtained and powder samples had to be used. Filtered Cu radiation was used throughout. Powder diagrams were indexed on the basis of a face-centered cubic unit cell. After correction for film shrinkage, a Bradley and Jay extrapolation³ to ? = 90" indicated that a, = 7.408 ±0.002A. The volume of the unit cell is 406.5A.V he assumption that there are four "molecules" of ZrB12 per unit cell leads to an X-ray density of 3.63 g per cc. The measured density is 3.7 g per cc (as measured by the immersion method). Relative intensities of reflections were determined by integrating the intensities of diffraction peaks using the count register of a North American Philips wide range spectrometer. Intensities measured in this way showed good agreement with photographic intensities estimated visually using multiple film techniques. The usual Lorentz, polarization, and multiplicity corrections were applied to the observed intensity measurements. There are striking similarities between ZrB12, and UB12. The unit cell of the latter is also face-centered cubic and contains four molecules. a, = 7.473, compared with 7.408 for ZrB12. The radius ratio rB/rU is 0.57; rB/rZr is 0.54. In both ZrB12, and UB12 the four metal atoms in each unit cell are in special positions; only the boron positions need be determined. The latter may be inferred from the extent to which diffraction of X-rays by the 48 boron atoms reinforces or weakens the diffraction by the metal atoms. This effect is relatively much greater in the case of the zirconium compound. In their determination of the crystal structure of UB12, Berthaut and Blum' assumed holohedral symmetry (space group Oh5 , Fm3m) and reported that the U atoms are in positions 4(a): 000; 01/2 1/2; ½ 0 ½ ; ½ ½; the boron atoms were reported to be in positions 48(i) with x = 1/6: ½xx; ½xx; x½x; x½x; xx½; xx½; ½xx; ½xx; x½x; x½x; xx½; xx½

Jan 1, 1953

By Fred D. Rosi

Introduction There is probably no field in which materials research has played a greater role than that of electronics. However, to trace present and future patterns of materials research in electronics is not an easy assignment, since this industry has a high degree of dynamism in its growth, and is busily engaged today in the scientific improbabilities of only recent yesterdays. On the other hand, this task seems especially appropriate since electronics is a truly frontier industry - one whose place in American industries has advanced from 50th prior to World War II to 6th in 1967, with sales of more than $22 billion. And this growth has been associated with the equally rapid progress of science and technology over the period - in particular with the emergence of materials science as a vital force in underscoring this progress. For several reasons this parallel growth is not too surprising. First, by its very definition electronics is a science that essentially deals with the nature, behavior, detection, generation, control and utilization of electrons in solids or at their surfaces. Second, in the electronics industry, systems are made of an integration of components, and these components with their interconnections are made of materials. Thus, the basic building blocks of systems are materials; and it has been largely the advances in materials research and technology that have led to new and improved devices and systems. It follows, therefore, that the broadening of the frontiers in electronics through the exploration of new territories is tantamount to scientific discovery and materials innovation to a degree found in no other major industrial activity. But to put this in the proper perspective of present and future materials trends, it would be appropriate first to survey historically the progress in electronics by pointing out major scientific discoveries and associated materials research patterns that have led directly to its tremendous growth. Then from this base we can consider recent trends in materials research that could form the basis for future progress in the electronics industry. In my review I shall examine the areas most familiar to me, so I must acknowledge at the outset that this survey is not all-inclusive.

Jan 1, 1971

By W. J. Carlson, I. lwasaki

Manganese and silica in nonmagnetic tailings from the direct reduction-magnetic separation step were so closely associated that no physical concentration methods were effective. Dilute sulfuric acid dissolved manganese and iron rapidly; manganese in the form of silicates was virtually insoluble in sulfuric acid solutions, thereby governing the maximum extraction attained by leaching. Autoclave leaching at elevated temperatures and at high oxygen pressures reduced the iron extraction to less than one tenth without affecting the manganese extraction. There was an indication that autoclaving solubilized the manganese silicates appreciably. Elimination of iron from leach solutions was carried out by aerating the solution in the pH range of 6.5-7; a platinum-calomel electrode pair provided a reliable indicator for the end point of iron removal. The purified leach solutions were free of interfering impurities for the recovery of manganese as metal, dioxide, or carbonate. Manganiferous iron ores of the Cuyuna Range, Minn., are too low in iron content to be directly useful as iron ores, and too low in manganese content to be termed manganese ores. Common methods of physical beneficiation such as gravity concentration and flotation have not been successful in upgrading this material. The R-N process, when applied to manganiferous iron ores,1'2 produces sponge iron by direct reduction of iron oxides, while leaving manganese as manganous oxide. From fine grinding and magnetic separation of the reduced ore, a tailing is produced which is relatively rich in manganese and low in iron content. The nonmagnetic tailing can readily be leached with acids and then further processed to recover manganese in various forms. In this way, two processes, neither of which would be an economic solution to the Cuyuna ore problem by itself, may be combined to produce two marketable products, thereby rendering the over-all process economically more attractive. This article reports on the results of a leaching study on the nonmagnetic tailings, both in a batch agitation vessel and in an autoclave; on the problems involved in the purification of leach liquors by aeration; and on the recovery techniques used to produce manganese metal by electrolysis, manganese dioxide either by electrolysis or by autoclaving, and

Jan 1, 1968

By D. A. Thomas, E. S. Meieran

Tungsten wires were examined by transmission electron microscopy after drawing and after high-temperature annealing. Drawn wire consists of highly elongated grains called fibers, whose long axis is parallel to [110]. Each fiber is ribbon-shaped, with the wide dimension of the ribbon parallel to (001) and the narrow dimension parallel to (110). Furthermore, most fibers are bent about [I10] and twisted along their length. The fibers are divided into cells, which in some cases contain a platelet substructure lying on (110) planes. The misorien-tations of these platelets accumulate to allow the macroscopic twist of the fibers. During annealing, several competing reactions occur, starting at different temperatures and progressing at different rates. Among these processes are fiber-boz~ndary migration, polygonization, dislocation rearrangement, and possibly impurity segregation. The fiber-boundary migration accompanied by the formation of transverse boundaries during polygonization leads to an equiaxed grain structure although recrystal-lization does not occur. There is a relationship between the flow stress of the wires and their average subgrain width in the form sy = s0 + kyd-1/2 . Also, there appears to be a relatio'nship between wire ductility and the formation of transverse boundaries during annealing at about 800°C. THERE have been many investigations of the structures and properties of tungsten wires1-4 due to their commercial importance for use as lamp filaments. The structural studies have so far been limited to optical microscope and replica electron-microscope studies. due to the difficulty of .-me- paring from wires thin foils which can be examined by transmission electron microscopy. However, this difficulty has been recently overcome,5 and it is now possible to examine tungsten wires by transmission electron microscopy as well as by other techniques. In this paper, the structure of drawn tungsten wire is described, as are the changes in the structure during high-temperature annealing. Some discussion of the relationship between structures and properties is also given. EXPERIMENTAL MATERIALS AND PROCEDURES Commercial 0.030-in.-diam doped tungsten wires drawn at progressively decreasing temperatures between about 1400° and about 800°C were examined. The composition, mechanical properties, and optical microstructures are described in detail elsewhere.' All experimental materials were vacuum-annealed for 10 ot 30 min at temperatures at 100°C intervals between 700° and 2000°C. Specimens were thinned for examination in the Siemens Elmiskop I electron microscope by the method of Meieran and Thomas.5 STRUCTURE OF AS-DRAWN WIRE The optical microstructure of as-drawn tungsten wire has been described by Peck and Thomas.7 They observed that wire in longitudinal section consists of highly elongated grains called fibers whose width varies between 1 and 10 µ, while in transverse section the fibers appear to be elliptical in cross section and bent about their common [110] wire axis. They explained this unusual appearance as being due to the drawing of a bcc material with a [110] texture, and predicted that the wide and narrow planes of the fiber cross section would be parallel to (001) and (110), respectively. The fibers apparently bend about the [110] axis during drawing to maintain grain boundary continuity during drawing. Transmission electron microscopy offers a way of checking these predictions as well as providing a more detailed picture of the wire structure. Figs. 1, 2, and 3 are typical electron micrographs of

Jan 1, 1965

By K. R. Waugh, Barbara S. Brown, D. W. James

AN electronic data-processing system is described which permits rapid, accurate, low-cost processing of strain-dependent damping data utilizing equipment normally available within the service facilities of most large laboratories. On analyzing the record of a stress-dependent damping test, the operator usually measures the double amplitudes at several points on the decay curve. The logarithmic decrement is then calculated for decay between consecutive amplitudes. These values of 6 are plotted against the corresponding maximum surface shear stress, T, which is proportional to the average of the two amplitudes between which is calculated: where d is the specimen diameter. The period of the vibration is not necessarily constant during decay; thus, each cycle must be counted. A decay curve may extend to, perhaps, 1000 cycles, and at least two curves are always obtained for each specimen or set of conditions. It can, therefore, be seen that manual analysis of decay curves is both tedious and costly in terms of man-hours. Furthermore, the resolution of the record is often such that accurate measurement of amplitude is extremely dif-

Jan 1, 1969