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By Victor Phillips

Cyclone thickeners have emerged from the development stage and now can be accepted as useful tools for the recovery of fine coal from a preparation plant circulating water. As primary thickeners in a closed water circuit operation, their advantages over conventional thickening methods are twofold-the lower initial investment and reduced area requirements.

Jan 8, 1951

By Nicholas J. Grant, Joseph T. Blucher

High-purity aluminum and an Al-10 pet Zn alloy zvere tested in axial fatigue from 80" to 900oF, at struzn vales of 5 and 150 pct per min, at a strain amplitude of 1 pcl. Cycles to failure were recorded as well as the load per cycle during the entive test. Several grain sizes were examined in each material. Examination was made of modes of deformation, initiation and growlh of' cracks, and vecovery mechanisms such as srbgrain formation and boundary migration. Strain rate effects on cycles to failure are first observed ahoi'e 50O0F, the highev vate vesulting in longer lije. Crack initiclion at room temperature may be truns-or iutercrystalline but fructures are transcrystalline. Abore 600'F, crack iniliation and growth ave largely inlercvystalline. Boundary wzigratiotz to 45-deg positions is observed above 70Oo F, and fractrrves are a combination of grain bol~ndary voids and cvacks. It is only in recent years that studies of deformation and fracture which prevail in fatigue at elevated temperatures have attracted significant attention.' Of such studies considerably less attention was given to high strain-low strain rate fatigue. Moreover, the majority of high-temperature fatigue studies were performed at conventional machine speeds (1000 to 10,000 cpm). As it is well-demonstrated in uniaxial creep-rupture series, at high strain rates, even at high temperatures, metals undergo work hardening with little or no attendant recovery or recrystallization thus the nature of deformation and fracture which is observed is similar to that encountered at lower temperatures.'-" Thus, for example, fatigue testing of a stainless steel at 750°F does not involve high-temperature deformation processes,2 and might more correctly be termed "fatigue testing at an elevated temperature". It was the purpose of this work to study deformation and fracture in fatigue as a function of low strain rates and temperature, selecting conditions which would result in grain boundary sliding, migration, fold and subgrain formation, and intercrystalline cracking in high-purity aluminum and a high-purity A1- 10 pct Zn alloy. Grain size was an additional variable. Extensive studies of the deformation and fracture behavior of these aluminum materials in simple creep had been done in the authors' laboratory, and were to serve as a basis of comparison for the observed effects in fatigue:'-'' the range of the creep test temperatures was 80° to 1150oF. MATERIALS AND EXPERIMENTAL PROCEDURE The compositions of the 99.99 pct pure A1 and the A1-10 pct Zn alloy are shown in Table I. Button-head specimens, with a liberal fillet, of 0.20 in. diam and of gage length 0.40 in. were machined from wrought bar stock. The ratio of 2:l gage length to diameter was selected after preliminary tests showed that a shorter length gave a shorter life, probably due to end effects, and after evidence of buckling in longer gage length specimens. After machining, the specimens were chemically polished to remove the worked outer layer, and were subsequently heat-treated to stabilize the selected grain sizes. Both the high-purity aluminum and the A1-10 pct Zn alloy were heat-treated to produce grain diameters of approximately 0.5 and 2 mm in each case. These grain sizes are referred to in the text as fine and coarse grain, respectively. One lot of the high-purity aluminum was heat-treated to produce a still coarser grain size in which the cross section was occupied by 2 to 3 grains. This structure is referred to as very coarsegrained. After heat treatment, the specimens were again electropolished. To avoid complications of both stress and strain gradients in the cross section of the specimen, a hydraulic, axial fatigue machine was designed and built. A button-head specimen, 1/2 in. diam at the head, was firmly gripped in a split-type holder free of any play in the grips. The test temperatures varied from 80" to 900°F. The strain amplitude in all of the reported tests was 1 pct for a total strain amplitude of 2 pct. The strain range was set by precision micrometers and measured by a precision dial gage. Constant strain rates of 5 and 150 pct per min were selected so that high-temperature type deformation and fracture would occur in the higher-temperature tests5,6 The strains and strain rates must be regarded as nominal values because they are based on the original specimen dimensions, which changed significantly as a result of necking and crack propagation, as can be observed from Fig. 8. For the elevated-temperature tests, a thermocouple was inserted into a well in the head of the specimen; the selected temperatures could be maintained with less than ± 5oF fluctuation during the entire test. To avoid changes in grain size before the test, specimens were heated to the test temperature in less than 15 min; similarly, they were cooled to room temperature after fracture with an air blast to avoid or minimize recovery or recrystallization. During the fatigue tests, load vs strain curves were recorded by a strain gage load cell for each fatigue cycle. In addition, the maximum values of load amplitude were recorded for the entire test.

Jan 1, 1968

By Ihor A. Kunasz

Introduction Lithium minerals occur predominantly in pegmatites which contain mineral assemblages derived from the crystallization of postmagmatic fluids or from the metasomatic action by residual pegmatitic fluids. They have been the traditional sources of raw materials for ceramic and chemical industries. With the discovery of Searles Lake, brines became new sources of lithium. Indeed, the 1960s may well be referred to as the "brine decade" because several brine bodies of significant economic importance were discovered. In the United States, the brines of Clayton Valley, Nevada, are presently exploited by Foote Mineral Co. The brines of the Great Salt Lake of Utah, the Smackover formation, and the Imperial Valley geothermal field, have been defined as important resources of lithium. In South America, new occurrences have been identified in Bolivia and Argentina. At the Salar de Atacama, Chile, new production capacity is scheduled for 1984. Following the termination of the AEC purchase program in 1959, several companies such as Maywood Chemical Co., American Lithium Chemicals, and Quebec Lithium Corp. were forced to close their operations. Nevertheless, with the development of new applications in glass ceramics, air conditioning systems, synthetic rubber, and metallurgy (aluminum potlines), the lithium industry grew steadily, and with the potential application of lithium metal in batteries and nuclear reactors, a healthy growth can be foreseen. New products and new applications are likely to stimulate exploration for expanded, reserves as well as the search for new sources from which lithium could be extracted economically. Geochemistry of Lithium Lithium is the third element in the periodic table. It is the lightest of all the metals, having an atomic weight of 6.938, an ionic radius of 0.68Å and a charge of +1. The geochemistry of lithium has been extensively studied and has been summarized by Rankama and Sahama (1950), Goldschmidt (1937), and Hortsman (1957). The distribution of lithium in igneous rocks is controlled by its size and its charge, and by the (MgO+FeO) / Li2O ratio. In the early stages of crystallization of a magma, that ratio is very large. Consequently, both magnesium and iron are removed by ferromagnesian minerals in preference to lithium which is then concentrated in the residual magma. This results in an enrichment of lithium in silicic rocks and pegmatites (Strock, 1936). Pegmatites are coarse-grained igneous rocks formed by the crystallization of postmagmatic fluids. Minerals within pegmatites may also form by metasomatism (Jahns, 1955). Genetically, the pegmatites are associated with neighboring intrusives. Mineralogically, granitic pegmatites contain feldspar, quartz, and mica as the main constituents and a variety of exotic elements such as lithium, beryllium, tantalum, tin, and cesium, which may or may not occur in economically significant concentrations. Detailed studies by numerous investigators (Cameron et al., 1949, 1954; Hanley et al., 1950; Jahns, 1953, 1955; Page et al., 1953) indicate that pegmatites often exhibit an internal zonal arrangement, with each zone containing a specific suite of minerals. The lithium minerals are usually found in the intermediate zones, and although as many as 13 zones have been recognized by Cameron, et al. (1949), a complete zonal arrangement is rarely found. Zoning of pegmatite bodies has also been observed on a regional basis. The regionally zoned pegmatite sequences exhibit mineral assemblages and complexity according to their re-

Jan 1, 1983

By Edmund M. Wise

NATURE has provided us with many metals, but with few really good ones, and frequently the better metals are the rarer. It is to this circumstance that many physical metallurgists, inventors, and just plain experimenters owe their employment, for much of their work is directed, consciously or otherwise, toward the alleviation of some of the more serious shortcomings of the cheaper, less noble, and weaker metals; by alloying, age-hardening, passivating, cladding, plating, and other useful dodges, which sometimes permit the substitution of one of the less gifted metals for one of the really good ones. As a matter of fact, the varied needs of our complex civilization could be quite well met with only five metals, if they were sufficiently abundant, and one of the five would certainly be platinum, the most noble and versatile that nature provides. Many metals are difficult to handle and seem to take pleasure in defying their investigators to find good uses for them, and finally when a use is found it is frequently quite a specific one; in other words, a hole has to be found--or perhaps made-to fit the peg. It is for this reason that a large amount of research must be con- ducted before the more recalcitrant metals become really useful. In platinum, however, we have a metal that inherently possesses so many valuable attributes that it became useful as soon as methods for producing it in massive ductile form were devised, and once its complicated chemical behavior was understood it became principally an aid to research rather than the subject thereof. In recent years, much research has been done to further improve

Jan 1, 1953

By David W. James, Howard Jones, George M. Leak

Conditions are described for producing, by primary recrystallization, a matrix suitable for the growth of large grains near (110)[001] orientation in silicon iron strip by secondary recrystallizaliun in a steep temperature gradient. The orientation distribution of these large grains is expressed in terms of rotational deviations about the cross-rolling direction, the rolling direction, and the normal to the sheet, the deviational spread increasing in that order. With the aid of cowplenientary published data on the orientation dependence of growth rate, it is shown that this observation is consistent with the oriented-growth theory of recrystallization lextures. It is conclutled that growth-rate and orientation-distribution data obtained in a steep thermal gradient should be used with caution to account for isothermally Produced recrystallization textures. SEVERAL authors have reported methods of growing large grains by re crystallization of a small-grained matrix in silicon iron 1- B and pure a cr The present study was a preliminary in the growth of single crystals and bicrystals for surface relaxation," grain boundary mobility, and grain boundary diffusion studies. The method was to control the growth of a seed crystal into a suitable primary re crystallized matrix by feeding through a steep temperature gradient. The driving energy for growth derived from the grain boundary energy released as the seed crystals grew into the matrix. Thus, stability of the matrix against normal grain growth was considered to be essential for success. It was known that the manganese sulfide dispersion present in commercial silicon iron performs this function during secondary recrystallization to the (110)[001.] texture.12 Hence commercial, rather than high-purity, material was used throughout. The paper describes the growth conditions for grains large enough to be used as seed crystals for further growth into single crystals. The orientation distribution of the seed crystals is analyzed and its significance for the theory of recrystallization textures is discussed. EXPERIMENTAL PROCEDURE Strip material was supplied by the Steel Co. of Wales, Ltd. The chemical analysis in weight percent was Si, 2.90; C, 0.015; Mn, 0.059; P, 0.011; S, 0.027; Ni, 0.032; 0, 0.009; Fe, balance. A gradient furnace of similar design to one described previously4 was loaned from B.I.S.R.A. It consisted essentially of a vertical water-cooled copper slot projecting downwards into the hot zone of a molybdenum furnace. Hydrogen was passed through the furnace to protect both heating element and specimen from oxidation. Strip specimens up to 8 cm wide and 0.2 cm thick were sealed into the furnace at the mouth of the copper slot. A coating of light oil on the strip surface maintained the seal during translation of a specimen. The maximum temperature gradient in the region just below the copper slot was 500°C per cm over 1 cm, with the hottest point controlled at 1175°C. Several large grains would usually grow by secondary recrystallization from the primary matrix when a specimen was immersed in the hot zone for about 30 min. A back-reflection X-ray camera was constructed to facilitate rapid and accurate orientation determinations of the large grains produced. It was possible to reproduce a standard geometry, with regard to strip and camera, without the tedium of careful alignment on each occasion. Specimens, typically 4 cm wide and 75 cm long, were cut with the longitudinal axis parallel to the rolling direction of the original strip. The surfaces were cleaned by immersion alternately in a hot aqueous solution containing 2 pct hydrofluoric acid plus 10 pct sulfuric acid and in cold 10 pct nitric acid. The nitric acid etch was just sufficient to reveal the grain structure. Rolling and annealing treatments to prepare the matrix (discussed below) were followed by growth of seed crystals in the gradient furnace. The matrix was transformed to a single crystal by growth of a selected seed crystal connected to the matrix by a thin neck. 4,5 Growth was promoted by controlled feeding into the gradient furnace. Several single crystals of controlled orientation were grown successfully from seed crystals by twisting the interconnecting neck in a reorien-tation jig.4 EXPERIMENTAL RESULTS AND DISCUSSION Growth Conditions. A suitable matrix for growth of large grains was prepared starting from primary re-crystallized strip 1.9 mm thick. This was cold-rolled in two stages each being followed by a recrystallization anneal at 800°C for a few minutes. Such treatment gave the required growth matrix only if the two cold-reduction stages were each performed in several passes and in the following ranges: the first, 30 to 70 pct; the second, 10 to 50 pct. Immersion in the temperature gradient otherwise resulted in an equiaxed

Jan 1, 1967

By W. F. Domis, F. von Gemmingen, R. W. Whitmore, F. Garofalo

Constant-load creep-rupture tests at 1100°, 1300° and 1500°F were made on a Type-316, 18 Cr-8 Ni-ZMo, austenitic stainless steel to determine the relationship between ruptzire life and other aspects of creep behavior, The test program was designed on a statistical basis to check the variability of various creep properties and to determine emprically the dependence of minimutn creep rate and ruptzire life on initial stress, The dependence of the rupture life, tn, on the initial stress, a,, is found to be related to the stress dependence of the wrinimum creep rate, i,, and secondary creep strain, The instabilities or breaks found in the conventionual log - logt, plots can be traced to either a change in the linear dependence of log i, on log a, or to a change in secondary creep strain. In the alloy tested, rupture is found to be predowmanantly of the inter crystalline type, For this material, the secondary creep strain is -found to depend on the nature of the grain boundary precipitate, which affects grain boundary migration. It has been shown for a variety of metals and al tested at elevated temperatures under creep conditions that the empirical relationship exists between rupture life, tr, and minimum creep rate, i,. This relationship, in which C and a are in some cases independent of stress or temperature, shows in a general way that creep rupture depends on creep behavior prior to tertiary creep stage. To determine more fully the factors which control creep rupture requires, therefore, more knowledge of the relationship between rupture and creep behavior. To obtain such information, constant-load creep-rupture tests have been made on a Type-316, 18 Cr-8 Ni-2 Mo, austenitic stainless steel at 11000, 1300°, and 1500°F. These tests were designed on a statistical basis to determine the variability of the various creep properties measured and to determine empirically the stress dependence of minimum creep rate and rupture life. As a result of this work, various empirical relations have been established defining more closely the factor, C, in the relation between rupture life and minimum creep rate. This factor is found to be proportional to the amount of strain during secondary creep. The variation of secondary creep strain with rupture life and temperature is determined and its effect on rupture behavior discussed. The variability in minimum creep rate and rupture life is also dis- cussed and the dependence of these quantities on initial stress is interpreted. TEST MATERIAL AND TEST PROCEDURES The material tested is an austenitic stainless steel, AISI Type 316, of the following composition: C, 0.07 pct; Mn, 1.94 pct; P, 0.01 pct; S, 0.021 pct; Si, 0.38 pct; Cr, 18 pct; Ni, 11.4 pct; Mo, 2.15 pct; All 0.003 pct and N, 0.043 pct. The material was received as a hot-rolled 0.5-in. diam bar which was sectioned into 3.25 in. long blanks. Each blank was heat treated by holding 1/2 hr at 2000° F followed by water quenching. A 3/8-in. coupon was removed from each heat-treated blank and the microstructure was examined, the grain size determined, and the hardness measured. The microstructure was found to be uniform from blank to blank and the grain size was found to range from 4 to 6 ASTM numbers. Hardness, measured using a 20-kg load, varied between 127 and 148 Vpn. Tensile creep-rupture specimens having a 0.25 in. diam within a 1.5-in. reduced section were machined from the heat-treated blanks. Constant-load tests were made on these specimens at 1100°, 1300°, and 1500 F. Six specimens were tested at each stress level. Three creep-rupture machines were employed for tests at each temperature, two specimens being tested in each machine for each stress level. To minimize any effect due to local inhomogeneities along the length of the as-received bar the specimens were randomized before test. Each specimen was tested to rupture and in most cases an autographic extension-time curve was obtained. For very low stress levels at 1500°F no auto-

Jan 1, 1962

By N. Van Wingen

EFFective sand permeabilities can be ascertained from core analysis if the laboratory data are compensated to allow for the presence of connate or residual water. Such adjustments can be made by applying empirically derived correction factors. Effective sand permeabilities can be estimated also from analytical studies of field depth-pressure measurements. In one method the time rate of pressure build-up after a well is shut in from steady-state flow is required, and in the other the direct measurement of a steady-state rate of flow and the corresponding equilibrium pressure. The results of the investigation discussed in this paper demonstrate that these methods for determining mean effective sand permeabilities can be correlated. Introduction In recent years many investigators have demonstrated the practical value of an accurate knowledge of the physical and dynamical characteristics of reservoir sands containing oil and gas. Of these factors, which serve to completely define a porous medium as a container or carrier of fluids, the dynamical characteristics are of particular interest to the production engineer because they afford a direct measure of the rate at which the oil or gas content of a reservoir will become available. The constant that defines dynamically the porous medium as the carrier of a homogeneous fluid in viscous motion is the "permeability." Coke-analysis Method The generally accepted practice in com-piling permeability data has been to analyze in the laboratory core samples taken in the course of drilling through the productive horizon, and to obtain the mean measure of the productive ability or permeability for the interval open to production by graphical integration of the permeability profile. An average permeability ascertained in this manner, however, is useful to the production engineer only for comparisons of wells drilled in the same horizon, as permeabilities determined in the laboratory are measures of only the ability of a porous medium to transmit a single fluid. As a result of many investigations, it has been shown, however, that under actual reservoir conditions water is coexistent with the petroleum and that its presence greatly reduces the permeability of the sand to oil. Empirical relationships showing the effect of the presence of any immiscible fluid A (such as water) in a porous medium on the permeability of the medium to a fluid B (such as oil) have been established separately by Hassler,1 Dunlap,2 and the writer (Fig. I),3 so that the average specific or dry-core permeability as determined in the laboratory can be corrected to give the true measure of the ability of the horizon penetrated to transmit oil, provided the percentage of pore space occupied by connate water is known accurately.

Jan 1, 1942

By N. Van Wingen

EFFective sand permeabilities can be ascertained from core analysis if the laboratory data are compensated to allow for the presence of connate or residual water. Such adjustments can be made by applying empirically derived correction factors. Effective sand permeabilities can be estimated also from analytical studies of field depth-pressure measurements. In one method the time rate of pressure build-up after a well is shut in from steady-state flow is required, and in the other the direct measurement of a steady-state rate of flow and the corresponding equilibrium pressure. The results of the investigation discussed in this paper demonstrate that these methods for determining mean effective sand permeabilities can be correlated. Introduction In recent years many investigators have demonstrated the practical value of an accurate knowledge of the physical and dynamical characteristics of reservoir sands containing oil and gas. Of these factors, which serve to completely define a porous medium as a container or carrier of fluids, the dynamical characteristics are of particular interest to the production engineer because they afford a direct measure of the rate at which the oil or gas content of a reservoir will become available. The constant that defines dynamically the porous medium as the carrier of a homogeneous fluid in viscous motion is the "permeability." Coke-analysis Method The generally accepted practice in com-piling permeability data has been to analyze in the laboratory core samples taken in the course of drilling through the productive horizon, and to obtain the mean measure of the productive ability or permeability for the interval open to production by graphical integration of the permeability profile. An average permeability ascertained in this manner, however, is useful to the production engineer only for comparisons of wells drilled in the same horizon, as permeabilities determined in the laboratory are measures of only the ability of a porous medium to transmit a single fluid. As a result of many investigations, it has been shown, however, that under actual reservoir conditions water is coexistent with the petroleum and that its presence greatly reduces the permeability of the sand to oil. Empirical relationships showing the effect of the presence of any immiscible fluid A (such as water) in a porous medium on the permeability of the medium to a fluid B (such as oil) have been established separately by Hassler,1 Dunlap,2 and the writer (Fig. I),3 so that the average specific or dry-core permeability as determined in the laboratory can be corrected to give the true measure of the ability of the horizon penetrated to transmit oil, provided the percentage of pore space occupied by connate water is known accurately.

Jan 1, 1942

By Morris A. Dodd

The nodulizing process described converts finely divided zinc calcine into a dense purified nodule. These zinc nodules are suitable for direct use in zinc reduction furnaces, especially the horizontal retort type, for the production of metal or American process zinc oxide furnaces for producing lead free zinc oxide. The basic reactions are carried out in a rotary kiln fired with fuel oil or natural gas. The combustion gases travel countercurrent to the flow of the zinc bearing material. Volatile impurities are carried out of the kiln with the combustion gases and a small portion of the finely divided feed material. The gases are cooled and the larger solid particles are separated from the stream before the resultant fume is collected in a conventional cloth filter baghouse. The fume collected can be further processed by conventional wet processes for the recovery of metallic values such as lead and cadmium. In order to nodulize the calcine properly it is elevated to a point of incipient fusion. The agglomerated material falling from the kiln is cooled and then sized by passing through a screening and crushing system consisting of a jaw crusher and a roll crusher in closed circuit with a vibrating screen.

Jan 1, 1970

By W. C. Lilliendahl, G. Meister

Uranium metal with a purity of about 99.9 pct was produced on a large scale by fused salt electrolysis with a material efficiency of about 90 pct. The material efficiency depends mainly on bath composition, electrolysis temperature, electrode smothering, and elutriation during washing of the powder. RESEARCH and development work on fused salt electrolysis carried on by the Westinghouse Lamp Div. Bloomfield, N. J., was done under the Manhattan District Corps of Engineers and later under the Atomic Energy Commission for the commercialization of uranium production for the first atomic pile at the University of Chicago in 1942. From the conception of the atomic bomb project it was recognized that metals with impurity levels having little metallurgical significance would be required. Permissible impurity levels were based on neutron absorption. Of particular significance was boron, which could not be present in amounts exceeding 1 ppm. The electrolytic method as developed in 1930 by Driggs and Lilliendahl,1,2 and later improved, yielded uranium of very low boron and other deleterious impurity content. No other method was capable at that time of producing uranium metal of the required purity.' The low boron content of uranium produced by the electrolytic process resulted from the availability of the reactants which were low in boron content, and from the inherent elimination of boron in the fused salt bath. Since the heart of any electrolytic process is the electrolysis cell, this paper will deal with the development of the original bath composition for the efficient production of uranium from a batch process to one of continuous operation. Emphasis also will be placed on other factors which will affect the material efficiency of the process. With the laboratory cell the material efficiency of uranium powder recovery in the early electrolysis was relatively low, about 35 pct based on the ratio of uranium recovered to uranium added. This early process also had other defects. The electro- lytic bath could not be used continuously. After three runs from a freshly charged crucible, the deposit showed a tendency to slip off the electrode as it was raised from the bath. This condition necessitated pouring the charge every fourth run and preparing a new bath. It was assumed at that time that this condition was caused by the increasing fluoride concentration with each addition of uranium salt, which adected the mobility of the uranium ions. Experimental The electrolysis cells differed in size only. They were of the floating cathode type. The laboratory cells were 21/2 in. ID and 6 in. deep and operated at 30 amp and 5 volts. Production was about 150 g metal powder per 8 hr. The plant cells (5 units) were 9 in. ID x 21 in. deep and operated at 1800 amp at 12 volts. The total production unit was designed to produce 250 lb of uranium powder per 8 hr day. Because of the tendency of uranium fines toward spontaneous combustion, material efficiencies were based only on the recovery of useful coarser metal which could be safely handled. The reported efficiencies are of particular significance only as related to the same group of experimental procedures. At the start of the project no changes were contemplated until previous data could be definitely confirmed. Therefore, the first experiments were with the 50 pct CaCl2-50 pct NaCl mixture. The material efficiency of uranium deposition as a function of the number of electrolyses is shown in Table I. In Table I, the decrease in efficiency at 800°C with number of runs is apparent and confirmed the earlier data. Operating at 900°C enabled the number of runs to be doubled, but before pouring the charge the efficiency of recovery became poor. This test indicated that the improved efficiency might have been caused by an increase in the fluidity of the bath.

Jan 1, 1958

By R. G. Knickerbocker, R. R. Lloyd, W. T. Rawles

In July 1041, the Experiment Station of the Bureau of Mines at Boulder City, Nevada, began a study of methods of producing magnesium metal from magnesium oxide, with particular emphasis upon the direct use of magnesium oxide in a molten chloride electrolyte. The program was extended to include pilot-plant study of chemical methods for the preparation of pure magnesia from dolomites and magnesites. Preliminary work on the production of magnesia from dolomite was done with the cooperation of Kobert D. Pike and the Harbison-Walker Refractories Co. These investigatipns included a cooperative arrangement whereby the Bureau tested certain steps of the Harbison-Walker-Pike process. The process finally developed by the Bureau includes the precarbonation mixing step of the H.W.P. flowsheet prepared by Mr. Pike. Two magnesium-reduction plants using MgO as a source of magnesium were being constructed in the West, and they enormously stimulated interest in various dolomite deposits as possible sources of the magnesia needed by them. This paper describes one phase of this program—the operation of a pilot plant for producing cell-grade magnesia from dolomite from Sloan, Nevada. The process developed for this purpose is an adaptation of a well-known process first proposed by Clossonl and modified by others,2"1 involving the use of calcium chloride and carbon dioxide. It is based on the following chemical reactions: MgCl2 + Ca(OH)2 = CaCl2 + Mg(OH)2 [1] Mg(OH)4 + CaCU + CO2 = MgCl2 + CaCO, + H2O [2] The first reaction proceeds almost completely to the right because of the much greater solubility of calcium hydroxide as compared with magnesium hydroxide. Under equilibrium conditions, when only the four components shown in reaction I are involved, the ratio of magnesium to calcium in solution, according to solubility-product relationship, will be: This reaction is the basis of present commercial processes for recovering magnesium from sea water and dolomite. The second reaction is, in effect, a reversal of the first reaction produced by adding COz. This reaction also proceeds nearly to completion, the solubility relationship being: Ca where P indicates partial pressure of COz, in atmospheres.

Jan 1, 1944

By Clarence Thom

This chapter presents, in summarized form, standard procedures for making separations of minerals from their ores by the froth flotation process to produce marketable concentrates. These are typical mineral separations which are being made commercially with the reagents and conditions generally used in the mining industry. Typical separations are presented for 17 metallic and 11 nonmetallic ores. The review of each includes a brief description of the mineral and the particular problem presented, general market specifications for its concentrates, an outline of treatment method, and kinds and quantities of reagents usually employed. This chapter does not include de- tails about ore preparation (crushing, grinding, and classification), elements of ore and pulp transportation (conveying and pumping), or concentrate preparation for market (thickening, filtering, and drying). In each presentation it is assumed, if not detailed further, that the ore is ground to the economical point of liberation of the minerals to be separated. Specific information, such as ratio of concentration and recovery, that depends upon the grade of ore being treated is considered beyond the scope of this chapter. Effective flotation separations that produce marketable concentrates may produce widely varying results in terms of percent recovery and still be economically profitable operations. Details of plant practice on specific ores are presented in Chapters 16 and 17. In this chapter the chemical names of the reagents are given. The extent to which different reagents are used in flotation plants in the U. S. is presented in Chapter 4. A compilation of the various flotation reagents, their trade names, manufacturers, and use has been prepared by H. T. Spedden. ANTIMONY The principal ore mineral of antimony, stibnite (Sb2 S3), is generally found in the U. S. in ore bodies in association with other valuable minerals such as galena (Pbs), sphalerite (ZnS), chalcopyrite (CuFeS2), or tetrahedrite (3Cu2 S – Sb2 S3), The sulfo-salt minerals of antimony, such as tetrahedrite or pyrargyrite, are often associated with high silver values, so that the presence of antimony may indicate economic importance even though the actual antimony content is low. Antimony is also significant to the mineral economy because of its occurrence in some ores where lead, gold, and silver are the

Jan 1, 1962

By Donald B. Evans, Robert D. Pehlke

The solubility of nilrogen in liquid binary alloys of iron with Litanium. zivconium, columbium, vanndiurn, and tantalum was measured for alloy composiLions up to the solalbility limils of lhe alloy nitrides. All five alloying agents were found to decrease markedly the activity coefficient of nitrogen in liquid ivon. The metal/nitvogen mole ralios in the alloy nitrides formed were generally .found to be slighlly greater than 1.0, but in no case greater than 1.5. From the experimental data, the standard free energies of fortmation of titanium and zir-conium nitrides have been calculated for the Lemperaluve range 1550° to 1750 C. The solublily Products for columbium, tantalum, and vanadium nitrides are also reported. A number of research investigations have examined the effect of refractory metals on the solubility of nitrogen in liquid iron. Although data on zirconium are not available, investigators are in agreement that titanium, vanadium, columbium, and tantalum markedly increase the solubility of nitrogen in liquid iron. This fact alone makes desirable the acquisition of thermodynamic data for these elements in liquid iron. Since refractory metals are known to be stable nitride formers, they have been suggested as steel denitrifying agents, and some of their nitrides have recently been considered as containment materials for liquid iron and iron alloys. Most available thermodynamic data for these metals relate to their dilute concentrations, but effective thermodynamic treatment of these applications requires data at concentrations near the solubility limit of the alloy nitride. Although some work has been done at relatively high alloy concentrations in liquid iron (particularly for vanadium 2,3 and titanium 2,4), the results have been somewhat contradictory. Disagreement may be partly attributed to the fact that the compositions of most refractory metal nitrides have been shown to be nonstoichiometric, and to vary 2,5-8 depending on the temperature and nitrogen gas pressure with which the solid nitride phase is in equilibrium. One purpose of this study consequently has been to determine the compositions of the refractory metal nitrides precipitated from a liquid iron solution. EXPERIMENTAL PROCEDURE Rao and Parlee2 and Evans and Pehlke 9 have discussed the technique for measuring the solubility product of an alloy nitride phase in liquid iron by finding the point of departure of the nitrogen solubility from Sieverts' law. The method consists of measuring the solubility of nitrogen in a melt of iron containing a known concentration of a second metal as a function of the nitrogen gas pressure over the melt. In this study the second metal was one of the refractory metals titanium, zirconium, columbium, vanadium, or tantalum. When the nitrogen pressure at which the refractory nitride forms is reached, a deviation of the measured solubility of nitrogen in the melt from Sieverts' law is observed in the form of a "pressure halt." The concentration of nitrogen in the melt associated with this breakpoint in the nitrogen-absorption curve is then used to calculate the nitride solubility. The Sieverts method was used to measure nitrogen solubility as a function of nitrogen pressure and temperature. The experimental equipment for this technique has been previously described in detail. 1,9 Charge materials used were vacuum-melted high-purity iron (Ferrovac-E) and the best commercial grades of the refractory metals obtainable (in all cases at least 99.8+ pct pure). Recrystallized alumina crucibles were used to hold all melts except those containing zirconium, for which zirconia crucibles were necessary. Temperatures were measured by a disappearing-filament type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diameter sight hole in the crucible lid. By means of a technique previously described, 9 in which the refractory-metal nitride was precipitated at one temperature then redis-solved by raising the temperature 50°C and precipitated again at a higher temperature, it was possible to obtain data over a temperature range of up to 200°C on a single melt. It was found that this technique could not be used with melts containing zir-

Jan 1, 1965

By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By D. E. Wolfson, H. J. Gluskoter, M. R. Geer, John A. Harrison, H. F. Yancey, I. S. Latimer

When this chapter was prepared for the kst edition in 1942, continuous mining machines virtually were unknown, and hand loading in underground mines, which gave an opportunity to discard impurities, accounted for 55 percent of the production of bituminous coal and lignite as compared with the 1965 figure of 11 percent. Only 24 percent of the total production was cleaned mechanically, compared with the present (1965) figure of 65 percent. The amount of refuse discarded during preparation for the same period increased from 13 to 21 percent. Changes in the equipment used in the cleaning process were as follows: [ ] Unclassified nearly 8 percent. Data on the amount cleaned by flotation was not collected until 1960 when 1.8 million net tons was so treated. In 1965 this figure increased to 6.9 million tons. Although the great increase in mechanization and full seam mining has resulted in substantial increases in the impurity content of the raw coal as well as in a finer size consist, some phases of face preparation are still important, particularly the variability of the distribution and thickness of the interbedded impurities and the changes in the character of the roof and floor from place to place in the mine. Knowledge of these factors in relation to all phases of the mining operation, particularly selective mining, are still of importance to the treatment of raw coal in the preparation plant. The major characteristics of coal and impurities from the standpoint of mechanical cleaning are particle size composition, generally called size consist, density differences, the relative friability of the coal and of its associated impurities, hardness, and strength. Some of the other factors related to preparation are petrographic composition and rank. COAL PROPERTIES Rank Perhaps 95 percent or more of the coal cleaned mechanically is of bituminous rank. Only a very small tonnage is subbituminous and prac-

Jan 1, 1968

By Chas. F. Jackson

IN these days the headlines and spotlight have been focused largely upon the new processes developed and new plants erected to meet the multiplied demands for mineral products required for prosecution of the war. By comparison, the less spectacular achievements of the miner, who is meeting the demand for raw material without which these processes and plants would be useless, have received little attention. Attendance at the mining meetings here reported was small, averaging about 35 to 40, but interest was as keen as ever, and evidenced to your reporter that the miner is no less on the job than is the metallurgist. It is evident that the mine operators are not neglecting any improved methods and practices in their struggle to produce more in the face of diminishing labor supply.

Jan 1, 1943

By J. D. Verhoeven

The effectiue distriblltion coefficient has been Measured in a series of vertical, normal freezing experirtzents with large current densities passing through the solid-liquid interface. The results indicate that the effect of the current on solute redistribution is due to electvotransport in the liquid. The high currents produced extensive mixing in the liquid which was considerably reduced by solidifying in small lubing. Analysis of the convection indicates that it probably vesulls from a horizontal temperature gradient produced by the Joule heating- of the electvic crirver~t. Due to the strong dependence of this convection upon the specimen radius, it is conclnded that only for specit~ens with radii of less than somewhere between 1 and 2 mm wilt electric field freezing be getlerally effec-tire at enhancing the purification of zone-melting experittierats in loe-melting alloys. Experiments on 0.8-mm lubes illustrate some interesting potential applications of this techniqne as a means of solute control on smcrll specimens. In a number of papers published within the last few years'-4 it has been found that passage of large dc currents through the solid-liquid interface of a freezing alloy produces a change in the solute redistribution accompanying the solidification. It had been predicted theoretically by Hucke et al.s and by Pfann and Wagner that such an effect would occur as the result of electrotransport within the liquid boundary layer at the solid-liquid interface. These authors independently derived the following relation between the effective distribution coefficient and the variables of the process: Where k0 is the equilibrium distribution coefficient, V is the mobility of the solute relative to the solvent, E is the electric field intensity, D is the solute diffusion coefficient, R is the rate of interface motion, and 6 is the boundary layer thickness. Both groups of authors show that this equation predicts the possibility of extending the purification ability of zone-melting experiments by the addition of an electric current. However, there are other effects in addition to electro-transport which could be produced by the high dc current and might, perhaps, invalidate the applicability of Eq. [I]. For example, high electric current might affect the interface reaction or perhaps the equilibrium distribution which was assumed to exist at the interface. It was the purpose of this work to determine the applicability of Eq. [I] by systematically investigating a simple system for which all of the necessary parameters were known. It was of particular interest for speculating on the potential usefulness of this technique to determine the maximum practical field intensities obtainable, and the effect of these high fields upon convective mixing in the liquid. The initial work in this study was published in a previous paper3 which will be referred to as I. In that work, a current density of 2000 amps per sq cm was used with specimen diameters of 5 mm. The results gave a qualitative confirmation of Eq. [I.], and also showed that a large amount of convective mixing was produced in the liquid by the current. The present study is an extension of that work to smaller specimen diameters and higher current densities. Two points were overlooked in I and will be emphasized here: a) the value of ko has not been well-established in the Sn-Bi system and b) the observed convection could be due to thermal convection produced from the Joule heating. EVALUATION OF k0 To evaluate Eq. [ I.] it is necessary to know the value of the equilibrium distribution coefficient, k,. Tn I the value of k, was taken as 0.3 from a published phase diagram.7 According to ansen' the best data on the phase boundaries of the Sn-Bi system are those of Davidson.5 The data of Davidson give a k, value ranging from 0.21 to 0.25 for the compositions studied in this work, or an average value of around 0.23. In a recent publication, Rigaud and Tougas'10 determined ko by means of a solidification technique. For an alloy of approximately the same composition as that used in this work they obtained a ko value of 0.39. Hence, there is considerable uncertainty in the value of ko and, consequently, a series of experiments were made to determine k, more accurately.

Jan 1, 1968

By Hsun Hu

Direct observations were made on the recrystalli-zntion of a cold-rolled (110) [001] crystal of 3 pct Si-Fe by annealing thin sections of the specimen inside the electron microscope during examination. Subgrain formation, presumably by polygonization, occurs rapidly, followed by a slow increase in the subgrain size before recrystallization can be detected. No migration of the subgrain boundaries was observed, and the formation of recrystallization nuclei by coalescence of subgrains is suggested. Re-c~ystallization characteristics of various texture components were individually examined. AS reported in a previous paper: orientations of the various deformation texture components in a 70 pct cold-rolled (110) [0011 crystal of 3 pct Si-Fe were completely confirmed by transmission electron diffraction patterns taken at various areas of the specimen. These orientations can be summarized as follows: Over most areas of the deformed crystal (111) planes are parallel to the surface. These areas correspond to either $- the two main defor: mation textures, the (111) [112] or the (111) [112].2-5 Within a few areas, (100) planes parallel to the surface are frequently found. These areas represent the minor deformation texture component, the (100) [Oll] type, which is derived from rotated Neumann bands.2'4'5 Only in very rare instances are (110) planes found parallel to the surface. This orientation corresponds to the very weak texture component of the (110) [001] type. In a pole figure, this (110) [0011 orientation is located within the orientation spread between the two main (111) [1121 type textures. Usually the electron diffraction patterns taken at various areas of the specimen are very simple ones, i.e., for any one area the pattern consists only of sharply defined spots of a single orientation. In some areas, however, more or less continuous rings of weaker intensities are superimposed on a simple pattern, indicating the presence of a wide range of additional orientations. In order to understand in detail the recrystallization of this cold-worked crystal, the recrywtallization characteristics of each of the various deformation texture components must be examined. This can best be done by using a high-temperature stage and transmission electron microscopy techniques, whereby small areas corresponding to the various texture components can be selected individually for examination. The present paper presents results obtained by this method. MATERIAL AND METHOD Specimens were prepared from a previously studied1 single crystal of a commercial grade 3 pct Si-Fe alloy with an initial orientation (110) [00l], cold-rolled 70 pct from 0.014 in. to 0.004 in. in thickness. Thin foils were prepared by electrolytic polishing as described in the earlier paper.' Specimens of this thin foil were then mounted in a high temperature stage similar to the one designed by Whelan.6 A direct current was used as the heating source. The temperature of the heating grid was calibrated by means of a Pt vs Pt-10 pct Rh thermocouple in a vacuum chamber (0.01 to 0.02µHg). Maximum variation within the temperature range of 250o to 000°C was about ± 25°C. After the desired areas were selected for examination, the specimen was heated to a low temperature for some time while the selected area was constantly watched. When no further change in structure and orientation could be observed, a higher temperature was applied. Photomicrographs and diffraction patterns were taken from time to time during examination, with the heater temporarily turned off* while the photographs were

Jan 1, 1962

By David B. Reger

The discovery of prolific oil wells in old territory hitherto regarded as doubtful, if not worthless, and the rapid extension of a gas pool opened late in 1938 were the most interesting petroleum features in West Virginia during 1939. Oil activity in general was slow because of crude prices that were still fairly low at the end of the year, although substantially increased above those in January. Fewer oil wells were completed, but the average results were better than in 1938. Fewer gas wells, also, were completed, with greatly lessened average initial production. Many old oil and gas wells were abandoned, so that the total number of active wells has not changed appreciably. The account of operations, as gathered from trade journals and other sources, shows that 561 new wells were drilled, resulting in 101 new oil wells with 2261 bbl. of daily initial production; 366 new gas wells with 602,400,000 cu. ft. of daily open flow; and 94 dry holes. Besides these new wells, 61 old wells were drilled to deeper sands, with 12 bbl. and 13,328,000 cn. ft. of added production. On the new wells the oil average was 22.38 bbl. per well per day; and the gas average was 1,645,900 cu. ft. per well per day; the ratio of dry holes to completions was 16.76 per cent. From an exploratory standpoint one partly discredited oil area was revived by good new production, and another small oil pool may have been opened. Some of the results in gas exploration will require more drilling for true appraisal. It is certain, though, that one very considerable gas field in the sands of Mississippian age has been proved; and there is a probability of six new pools in the Middle Devonian shale. In the Oriskany sand (L. Dev.) the Elk-Poca pool has been extended considerably farther northwest into Jackson County; and farther north in Jackson County two widely separated wells, which may be pool openers, have been successfully completed. On the other hand, several important wildcats in various counties have been dry. Stratigraphically lower, some additional wells have been completed in the Newburg sand (Sil.) and one small producer has been completed in the Clinton sand (Sil.), the importance of which can scarcely be overestimated, because no Clinton production has previously been found in the state, although at least seven wells have been drilled through the sand.

Jan 1, 1940