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By E. J. Bonet, P. B. Crawford

It is fairly common practice to reinject water into the aquifer near the oil-water interface in water-drive reservoirs. There have been many studies of aquifer behavior without reinjection,l-5 but apparently no analytical studies have been made to indicate performance when injection wells are present in the aquifer. The diffusivity equation may be used to describe the pressure behavior in an aquifer. When sources are present it can be written as A general solution of Eq. 1 may be obtained as the sum of two solutions. One is a general solution of the homogeneous equation, obtained by dropping the source term in Eq. 1 and still satisfying the required boundary conditions. Another is a general solution of Eq. 1 satisfying homogeneous boundary conditions.1° The first solution, which corresponds to the aquifer without reinjection, has been given quantitative and qualitative treatment in the literature.l-5,8,9 The latter solution will be treated here. Solutions with variable injection rates are obtained by superimposing solutions with constant rates, so we have considered only the latter. Five cases have been treated here: 1. A linear aquifer of finite width and extent. Water is injected into the aquifer at point xo, yo at constant rate. The pressure along the line x = 0 is maintained at zero pressure. (See Fig. 1.) Equations showing the pressure distribution, rates, velocity and cumulative influx have been developed. Certain numerical results are shown. 2. A linear aquifer of finite width and extent. Water is injected into the aquifer at point xo, yo at constant rate. The rate of production along the oil-water water contact is maintained constant. Equations showing the pressure distribution inside the aquifer are presented. 3. A linear aquifer of finite width and extent. Constant pressures are maintained at opposite ends of the aquifer. Water is injected at constant rates at point xo, yo. Equations showing the pressure distribution are shown. 4. A linear aquifer of finite width and infinite extent. The pressure is maintained constant at the oil-water contact. Water is injected at a constant rate at point xo, YO. 5. A linear aquifer of finite width and finite extent. The pressure at the oil-water contact is maintained constant. Water is injected at constant rate per unit length along a line x,. The Linear Aquifer The linear closed aquifer, performing at constant terminal pressure was selected as the first case to be analyzed. The development of the equations is based on uniform injection per unit of thickness, and gravity effects are neglected. In practical application this condition is probably most closely achieved when the

Jan 1, 1970

By K. D. Jacob

ALL types of commercial phosphate rock produced throughout the world contain fluorine in quantities ranging from approximately 0.4 to 1.3 per cent in the Curacao and Christmas Island phosphates to 3.1 to 4.2 per cent in the phosphates of the United States and North Africa1. For a given type of rock, the fluorine content is usually roughly propor-tional to the phosphorus content. SIGNIFICANCE OF FLUORINE IN PHOSPHATE ROCK On the basis of chemical and X-ray diffraction studies, Hendricks and co-workers2 concluded that fluorapatite, Ca10F2(P04)6, is the essential phosphatic constituent of the commercial types of domestic phosphate rock. On the other hand, Bredig and co-workers3 have recently advanced the opinion, also based on X-ray diffraction studies, that the mineral phosphates usually contain carbon dioxide in the apatite lattice, and that the phosphate rocks of. the United States are really fluorcarbonate apatites. However, the domestic types of phosphate rock do not seem to differ greatly from coarsely crystalline fluorapatite in their behavior toward chemical reagents in general, and for the purpose of this paper it will suffice to consider fluorapatite as being the essential phosphatic constituent of these types of rock.

Jan 1, 1936

By W. C. Schroeder

During the post-war period, and particularly during the past few years, coal production has been maintained at a reasonably constant level. This is in contrast to the greatly expanded demand for oil and natural gas. Certain markets for coal, such as the railroad and for home heating, have tended to decrease, but this decline has been offset by an increase in demand for other uses, particularly for electric power. Since the United States has very large reserves of coal and relatively limited reserves of natural gas and oil, from the conservation viewpoint, it would be better if the increased demand were to fall more heavily on coal. Where coal has lost certain markets, the decision has not always been made on the basis of price, and, in fact, in many instances, the markets have been lost where coal could show a price advantage. There are various reasons for this situation but it can be attributed in the main to the preference of certain consumers for the convenience offered by liquid and gaseous fuels. In the production of chemicals such as benzene, phenol, or ammonia, coal still plays an important role. As co-products from coke-oven operations, a wide variety of aromatic chemicals are available. In recent years, however, the production has not been sufficient to supply the demand, and it is not profitable to build coke ovens to make chemicals unless there is a market for the coke as well. As a result, the petroleum industry is beginning to take a stronger part in the production of aromatic chemicals. Natural gas has almost displaced the coke-oven water-gas machine for the production of hydrogen for the synthesis of ammonia, as well as for the synthesis of methyl alcohol and other oxygenated compounds. This information is not new and is given here only as a basis for the discussion of the broad significance of the development of the gasification process. It is clear that if coal is to regain some of its old fuel markets, as well as to maintain a position in the field of chemical synthesis, processes must be available for converting coal to the type of fuel the customer wants, and for a cheap method of furnishing gaseous raw material to the chemical industry. The operation of coke ovens and water-gas machines is not the answer to this problem for at least two important reasons: (1) the limited supply and relatively high price of good coking coals, and (2) the relatively high costs of the combined operations of coking and manufacture of water gas.

Jan 1, 1953

By A. J. Miller, G. R. Brophy

THE Grossmann principle1 for the calculation of hardenability of steel from composition is attractive because of its simplicity. It postulates that the hardenability of a steel for any particular grain size may be expressed in terms of an ideal critical diameter, which is the product of an ideal critical diameter for a "pure" iron-carbon base multiplied by a succession of factors for each element of composition contained, including the incidentals. It infers that the multiplying factor for a given quantity of an element is constant for all combinations of composition. Grossmann has stated that in the great majority of cases the experimental values of hardenability are found to be well within 10 per cent of the calculated values. The validity of the scheme has been confirmed in principle by Crafts and Lamont2,3 and by Kramer et al .4 Their results differ from the original in the magnitude of the effect of some elements but, since they accepted the product concept and followed its direction, it is to be expected that similar results would be obtained. Crafts and Lamont, in their second paper, recognized that the factor relations for manganese and nickel were not continuously linear, but beyond certain critical amounts increase sharply. Austin, Van Note and Prater5 demonstrated nonlinear relations between hardenability and alloy contents. Their curves for chromium, silicon, manganese and nickel were all convex upward to show decreasing incremental effects. They concluded that Grossmann's factors underevaluate the hardening effect of low percentage additions of these elements, and overevaluate the larger additions. [ ] More recently W. Steven6 has found that the factor method fails when applied to complex steels containing two or three principal alloying elements other than carbon. Multiplying factors derived from his results bear a complex relation to composition and are not constant for a given amount of an element as the base composition varies. C. A. Liedholm7 found that, using either the Grossmann or the Crafts-Lamont multiplying factor values, not only were

Jan 1, 1945

By Richard D. Dick

The Los Alamos National Laboratory was involved in an oil shale fragmentation research program in cooperation with a Consortium of industrial companies to investigate the feasibility of using modified in-situ (MIS) recovery of oil from oil shale. Field tests were conducted at the Anvil Points Mine, Colorado, in the thick oil shale beds of the Green River formation. Part of the program included obtaining data about fragmentation by instrumenting the tests with accelerometers, velocity gauges, and the CORRTEX technique (Continuous Reflectometry for Radius versus Time Experiments). Some of the rock motion data from accelerometer and velocity gauges is presented, along with some conclusions. In addition, the signal recording system is briefly explained. The CORRTEX technique is discussed, and some results on explosive performance and stem behavior using the method are discussed.

Jan 1, 1984

By E. C. Houston

The presence in the Tennessee Valley of extensive deposits of olivine, a silicate of magnesium and iron that contains approximately 28 per cent magnesium, has been recognized since 1896 when Lewis8 published a survey of basic magnesium rocks of western North Carolina. A recent field survey by T.V.A.7 showed that more than two hundred million tons of high-grade olivine occurs above local drainage levels in western North Carolina and northern Georgia. Except for sporadic attempts to work the olivine for its nickel and chromium contents,10 the ore received little attention industrially until 1926 when Goldschmidt3 suggested its use in the manufacture of refractories. Only one instance is recorded of an attempt to utilize the ore commercially for its magnesium content;" in this case a process was used in which olivine was treated with sulphuric acid, the resultant mixture was leached with water, and the leach solution was purified and evaporated to form epsom salts, which was the end product. As a part of its program of contributing to the development of the natural resources of the region, the Tennessee Valley Authority became interested in the olivine deposits as a source of metallic magnesium because of their high magnesium content and proximity to hydroelectric power. Studies were undertaken to determine the feasibility of producing magnesium chloride by extraction of olivine. The experimental work was carried out successively at the T.V.A. Minerals Testing Laboratory, Norris, Tenn., at the Georgia State Engineering Station,* Atlanta, Ga., and at the T.V.A. laboratory at Wilson Dam, Ala. The present paper describes a process. developed through the pilot-plant stage, whereby magnesium chloride suitable for reduction to metallic magnesium can be prepared from olivine by extraction with hydrochloric acid and subsequent purification. Research on the magnesium-from-olivine process, originally intended for peacetime use, was given impetus by the shortage of magnesium that existed at the beginning of the current world war. By the time the process was sufficiently developed to justify a proposal for its inclusion in the war program, the shortage had been met by expansion and development of other processes. However, it is believed that the magnesium-from-olivine process may have advantages that will warrant consideration of its use after the war, when the economics of the various processes rather than production on a wartime scale will be the criterion for commercial production of magnesium. Description OF Process Metallic magnesium is produced electro-lytically by the Dow and the Elektron

Jan 1, 1949

By W. W. Odell

ONCE it was believed that anthracite or coke were the only fuels generally available and suitable for the generation of water gas, particularly so when this gas was made in the generators of standard carburetted water-gas sets such as are commonly used in the manufacture of city gas. During the past 8 years, practice has changed considerably and it is -now common to find gas plants operating without anthracite or coke and using bituminous coal in the generator. This change in fuel has appreciably increased the marketability and sales of certain coal producers' products; accordingly it is of interest to coal operators and others to know the reason for this change, the present trend in practice and the adaptability of various coals for generation of water gas. This paper briefly discusses these conditions and some of the factors relating thereto. BITUMINOUS COAL NOT IDEAL BUT CHEAPER THAN COKE In spite of many changes which have been made in both process and generating apparatus for using bituminous coal as generator fuel more efficiently, in general it is not an ideal fuel for this purpose. It is supplanting coke because it costs less; it is so much cheaper per ton delivered at the gas works that water gas made therefrom costs less per unit-volume than that made from coke, even though the quantity of generator fuel consumed per therm (100,000 B. t. u.) of gas made is greater with coal. This is the reason why so many city gas plants, as well as others, are using bituminous coal instead of coke.

Jan 1, 1927

By J. C. Uy, A. A. Burr

A quantitative relationship between the allotropic phase boundaries of zirconium-base binary systenzs and the solute metallic valence is shown through an intermediate thermodynamic parameter. A simplified equation relating this parameter to the phase boundaries is briefly reviewed, and data from the literature are used to show the relationship of this parameter to the solute metallic valence. It has been reported that the solute metallic valence can be used as an index of phase stabilization in zirconium-base binary alloys.' It was shown that the algebraic sign of the slopes of the hcp/bcc phase boundaries of zirconium alloys correspond to the algebraic sign of the metallic valence of zirconium minus the metallic valence of the solute, or, in other words, a solute whose metallic valence is higher than that of the solvent tends to stabilize the high-temperature phase while one whose metallic valence is lower than that of the solvent tends to stabilize the low-temperature phase. Further analysis of the zirconium binary systems has revealed a quantitative relationship between the solute metallic valence and the relative slopes of the two-phase allotropic boundaries. This relationship involves a thermodynamic quantity whose significance can be seen in the following section. PHASE-STABILIZATION PARAMETER Let Qb be the difference between the partial molar heats of mixing of a given solute in the two allotropic phases of the solvent which are in equilibrium with each other at a given temperature, thus A relationship between this term Qb and allotropic phase boundaries has been employed by several au-thors'-= in the evaluation of phase diagrams, and can be briefly derived as follows. Referring to Fig. 1, consider the general case of two allotropic phases, each having a small mole fraction (Xa,Xb) of the solute, in equilibrium at temperature T and atmospheric pressure as represented by the reaction. solute in ß phase =solute in a phase If now a reaction occurs such that an infinitesimal amount of the solute is removed from the ß phase and added to the a phase, there would be a partial molar

Jan 1, 1967

By T. Egleston

The direct process for the manufacture of iron which is principally used in the United States, in New York and New Jersey, is called the Jersey forge, the Champlain forge, the Catalan forge, the Bloomary forge or fire, and sometimes a Forge fire. Dr. T. Sterry Hunt, who has discussed the process as applied to the beach sands of Canada as well as to ores, in the Report of the Canadian Geological Survey for 1867-69, has shown that the name of Catalan forge is incorrect, as this process in no way resembles the Catalan, but is really the old German b1oomary modified by long use in this country. Dr. Hunt gives the probable history of the introduction of the process into the United States, and a series of historic citations of great interest relating to it. Notwithstanding the improvements which have been made in the constrnction of the furnace and its greater output, the process to-day, in all its essential features, is carried out as Karsten described it. It should now be known as the American Bloomary. The name of Jersey or Champlain forge or fire is not sufficiently distinctive. The name of Bloomary, by which the process is usually distinguished, is objectionable, not because it is incorrect but because it is indefinite, as the Knobbling fires, which are a very slight modification of the Walloon process, for making blooms either from pig iron or by sinking scrap, are also called Bloomaries, and although Knobbling fires are only used in a few localities where charcoal pig is made, and special grades of charcoal-refined blooms are required, one does not, without an explanation, know whether the blooms are being manufactured from ore or pig. The name Forge fire is equally indefinite, as it might just as well apply to any of the five direct methods of making blooms which have been in use in Europe, but which have now mostly gone out of date. The name of American Bloomary, however, is the one which most completely describes it, and is the one least open to objection. The names of' German, Jersey, and Champlain bloomary are too local, and these adjectives are thought unnecessary by those who use the process, and we shall not therefore describe it under any of these names, but as the American Bloomary process.

Jan 1, 1880

By A. M. Gaudin, C. S. Chang

Adsorption was measured for barium ion and laurate radical, using radioactively marked agents, over wide range of concentrations. Laurate adsorbed in absence of barium fails to float. With barium, flotation-effective laurate coating needs not exceed 5 pct of monolayer. Barium adsorption then is several fold larger. No barium laurate coating is obtained. IN general, fatty acids or their alkali salts do not cause clean quartz to float. However, the presence of multivalent ions, such as the alkaline-earth metal ions and heavy-metal ions, can activate quartz and thus make it respond to soap flotation. The mechanism of activation and soap flotation of quartz has been studied.'-' The problem was attacked by making flotation tests rather than by careful adsorption measurements on suspensions of ground quartz in solutions containing the activator and the collector. Attempts have been made to determine the adsorption of barium ion and calcium ion on quartz. The results have only qualitative value as the analytical methods were not adequately precise. Artificial radioactivity and progress in radioactivity detection have introduced a new analytical tool, which can have a sensitivity several orders of magnitude greater than that of other methods."-" In the experimental work described in this paper the radioactive tracers, barium 140 and carbon 14, were employed. Lauric acid was synthesized, having a radioactive carbon atom and was used with Ba" to study the adsorption of barium and laurate ions from aqueous solution on ground quartz. Flotation tests, using the vacuum flotation technique,' were run in conjunction with the adsorption experiments. The object of this investigation was to understand better the reaction mechanism of barium activation and soap flotation of quartz. Methods and Materials Quartz Sample Preparation: Lumps of hand-picked quartz, washed free of stains, were reduced in size to —20 mesh in laboratory crushers. The product was boiled in concentrated hydrochloric acid to remove the abraded iron. The cleaned product then was ground dry in a laboratory porcelain mill, using siliceous pebbles, to pass through a 200 mesh screen. The ground product was deslimed by sedimentation at 37 microns. This —200 mesh +400 mesh material was subjected again to boiling with concentrated hydrochloric acid, followed by washing with distilled water and further desliming. The cycle was repeated until no trace of iron could be detected in the wash liquor. During the final washing, the pH of the wash water was checked to insure the complete removal of the acid from the mineral. The quartz then was rinsed with conductivity water. The resulting product was dried in a drying oven and stored in mason jars. The impurities (spectrographic) were as follows: Al, 0.01 to 0.001 pct; Li, Mg, Mn, Na, each less than 0.001 pct; Fe and Cu not detected. The specific surface of the quartz sample was determined by the krypton gas adsorption method.' The average of two measurements was 881 sq cm per g. The calculated specific surface for 37/74-micron quartz particles, using a surface factor of 1.96; is 900 sq cm per g. This is in good agreement with the measured value of 881 sq cm per g. Beta-Counting Method: The radioactive isotope of barium used in the experimental work was barium 140. It has a sufficiently long half-life, 12.8 days, emits high-energy beta particles (up to 1.0

Jan 1, 1953

By A. M. Gaudin, C. S. Chang

Adsorption was measured for barium ion and laurate radical, using radioactively marked agents, over wide range of concentrations. Laurate adsorbed in absence of barium fails to float. With barium, flotation-effective laurate coating needs not exceed 5 pct of monolayer. Barium adsorption then is several fold larger. No barium laurate coating is obtained. IN general, fatty acids or their alkali salts do not cause clean quartz to float. However, the presence of multivalent ions, such as the alkaline-earth metal ions and heavy-metal ions, can activate quartz and thus make it respond to soap flotation. The mechanism of activation and soap flotation of quartz has been studied.'-' The problem was attacked by making flotation tests rather than by careful adsorption measurements on suspensions of ground quartz in solutions containing the activator and the collector. Attempts have been made to determine the adsorption of barium ion and calcium ion on quartz. The results have only qualitative value as the analytical methods were not adequately precise. Artificial radioactivity and progress in radioactivity detection have introduced a new analytical tool, which can have a sensitivity several orders of magnitude greater than that of other methods."-" In the experimental work described in this paper the radioactive tracers, barium 140 and carbon 14, were employed. Lauric acid was synthesized, having a radioactive carbon atom and was used with Ba" to study the adsorption of barium and laurate ions from aqueous solution on ground quartz. Flotation tests, using the vacuum flotation technique,' were run in conjunction with the adsorption experiments. The object of this investigation was to understand better the reaction mechanism of barium activation and soap flotation of quartz. Methods and Materials Quartz Sample Preparation: Lumps of hand-picked quartz, washed free of stains, were reduced in size to —20 mesh in laboratory crushers. The product was boiled in concentrated hydrochloric acid to remove the abraded iron. The cleaned product then was ground dry in a laboratory porcelain mill, using siliceous pebbles, to pass through a 200 mesh screen. The ground product was deslimed by sedimentation at 37 microns. This —200 mesh +400 mesh material was subjected again to boiling with concentrated hydrochloric acid, followed by washing with distilled water and further desliming. The cycle was repeated until no trace of iron could be detected in the wash liquor. During the final washing, the pH of the wash water was checked to insure the complete removal of the acid from the mineral. The quartz then was rinsed with conductivity water. The resulting product was dried in a drying oven and stored in mason jars. The impurities (spectrographic) were as follows: Al, 0.01 to 0.001 pct; Li, Mg, Mn, Na, each less than 0.001 pct; Fe and Cu not detected. The specific surface of the quartz sample was determined by the krypton gas adsorption method.' The average of two measurements was 881 sq cm per g. The calculated specific surface for 37/74-micron quartz particles, using a surface factor of 1.96; is 900 sq cm per g. This is in good agreement with the measured value of 881 sq cm per g. Beta-Counting Method: The radioactive isotope of barium used in the experimental work was barium 140. It has a sufficiently long half-life, 12.8 days, emits high-energy beta particles (up to 1.0

Jan 1, 1953

By R. L. Rickett, W. C. Leslie

The influence of deoxidation practice, prior thermal history, and aging time and temperature on the strain-aging behavior of low-carbon open-hearth steels was investigated. The criterion of aging employed was the increase in yield strength in the tensile test, after straining and aging. Composition, prior heat treatment, and aging conditions were all found to be important in governing the strain-aging characteristics of these steels. THAT deoxidation changes the strain-aging propensities of low-carbon steels has been known for a long time, but there has been little agreement, and even contradiction, between results obtained by different investigators and between results obtained in the laboratory and in the mill. This investigation was begun in the hope that some of the uncertainties connected with the strain aging of commercial steels could be eliminated. In considering this problem, it was necessary to define strain aging and to examine the methods used to measure this property. Strain aging can be defined as the changes in properties of a metal or alloy with time, after cold working. The rate at which these changes occur increases as the temperature is raised above atmospheric. The requisite plastic strain is the principal distinction between strain aging and quench aging, the latter being due to precipitation from supersaturated solid solution. Strain aging is also characterized by rapid attainment of maximum hardness at high aging temperatures and lack of softening (overaging) at low aging temperatures. Several possible criteria of strain aging have been listed by Sachsl and by Davenport and Bain.' Because changes in mechanical properties are the most easily measured and the most commonly used, consideration of methods to be used in this investigation was confined to three tests: tensile, notch-impact, and hardness. Hardness tests are the most economical and easiest to perform, but produce only one measure of strain aging. Also, as pointed out by Felmly, Hartbower, and Pellini,³ hardness changes due to aging are not pronounced for steels containing more than 0.15 pct C. Notch-impact tests require careful preparation of large numbers of specimens. Above and below the transition temperature the test lacks sensitivity; furthermore, it is extremely difficult to impart a uniform strain to the specimens, followed quickly by aging and final testing; machining must generally take place after straining. For these reasons, the tensile test was selected for use. Although this test requires a considerable expenditure of time, labor, and money in preparation of the specimens and performance of the test, more information can be gained than from any other single mechanical test, information which includes upper and lower yield points, yield-point elongation, tensile strength, strain-hardening exponent, reduction of area, and elongation. Low and Gensamer' and Schwartzbart and Low5 lso used the tensile test, taking the increase in flow stress after straining in tension and aging as a measure of strain aging. In our work, as in theirs, each specimen was strained an arbitrary amount, sufficient to pass through the

Jan 1, 1954

By H. C. Theuerer

EVEN the highest purity silicon available for semiconductor use contains significant amounts of donors and acceptors, usually aluminum, phosphorus, and boron. Aluminum and phosphorus can be removed from silicon by adaptations of the zone refining techniques' widely used with germanium. Removal of boron, however, has been a difficult problem. The approximate distribution coefficient for boron in silicon is 0.8, so that while zone refining is possible, it is not very effective in any reasonable number of passes. It has been found, however, that boron can be effectively removed from silicon by treatment of a liquid zone with hydrogen and water vapor. Starting with 40 ohm-cm, n-type silicon, use of zone refining coupled with hydrogen

Jan 1, 1957

By E. Lifshin, R. E. Hanneman

QUANTITATIVE applications of the electron micro-beam probe frequently involve the evaluation of complex mathematical expressions and/or the analysis of large amounts of experimental data. The purpose of this communication is to describe briefly a versatile and useful computer program system that is applicable to analyze rapidly a wide variety of practical microprobe problems. This system consists of a group of ten FORTRAN programs that can be stored on tape, cards, or in the memory disc of the computer. These programs, or links, can be run individually or in any prespecified sequence without interrupting the operation of the computer or without destroying information which is being transfered from one link to another. For the program system described here a GE-235 computer with disc storage was used, so that the DCHAIN method of program linking was employed. Included in the library are programs to: 1) initiate analysis of a new set of data and transfer control between all other programs in any predetermined manner; 2) generate theoretical calibration curves of composition vs relative intensity; 3) generate empirical deviation parameters from least-square fits of experimental calibration data from standards of known composition; 4) convert raw X-ray data to corrected composition; 5) determine inter diffusion coefficients by Matano analysis of con centrat ion -distance data on a uniaxial diffusion couple; 6) determine activation energies and frequency factors of temperature-activated processes such as diffusion; and 7) generate calibration curves for determination of the thickness of thin films using microanalysis. A detailed description of these computer programs and their underlying principles is available on request from the authors."' The first program to generate theoretical calibration curves of corrected relative intensities vs composition uses the Poole and Thomas atomic number correction' and the Philibert absorption factor' with a voltage-dependent mass absorption coefficient for electrons in the alloy. A modified Castaing fluores- cence correction is also used which includes the effects of both Ka and KO radiation and over voltage.' Once the theoretical curves have been calculated in 1 wt pct intervals, these results are least-squares fit to obtain Ziebold deviation parameters' which are stored in COMMON in the computer memory. The net discrepancies between the original theoretical calibration curve and the regenerated curve using the Ziebold parameter are computed. Although this link is explicitly written for K-K fluorescent interactions, it can be applied to K-L, L-K, and L-L interactions as previously disc~ssed."~ Similar programs have also been written to utilize the Wittry fluorescence correction, Birks combined corrections, and various other corrections.' These modified programs have proved to be quite useful for quantitative comparisons of the results of the various theories. The program for conversion of raw X-ray data to corrected composition includes corrections for drift, backround, and instrumental dead time. The corrected intensities are converted to composition by use of the Ziebold equation"2 and parameter obtained from the program system. The results can be obtained for either atom or weight fractions. In addition to accurately computing interdiffusion coefficients the Matano analysis program calculates least-square smoothed values of concentration, concentration gradient, and curvature for each point on the raw input concentration profile. In order to obtain high accuracies a unique method of performing a least-square polynomial fit to incrementally advancing profile segments which overlap is used.' This program has been successfully modified for use in ternary diffusion problems3 and can readily be modified to handle analysis of diffusion profiles which include phase boundary discontinuities. This link is generally applicable to analysis of interdiffusion data obtained by other techniques as well as by the microprobe. The primary function of the next program is to least-squares fit experimental diffusion data to the normal Arrhenius function: D = Doexp(-Q/RT), to obtain values of Do and Q. In addition the probable error and one, two, and three u statistical confidence limits of DO, Q, and log D are evaluated. This program is also directly useful for analysis of any other simple temperature-activated processes including conductivity, and certain deformation and chemical processes. The program to generate calibration curves for film-thickness determination using the microprobe is based on a numerical integration of the equation derived by Cockett and ~avis.' Values of film thickness obtained by this program for copper on various substrates are in good agreement with measurements made by other techniques. Versions of the above program system have been prepared for use with or without a remote teletype connection to the computer for processing on either a real-time or time-share basis. The instrumentation coupling a microprobe to a teletype for automatic data collection and analysis by the presently described program system has been reported elsewhere by the authors.' If teletype equipment is not used to communicate with the computer, standard methods of card reading and tape reading can be used. In either

Jan 1, 1967

By M. R. Geer Olds, H. F. Yancey

THE increase in the number of coal-cleaning plants employing dense-medium processes occurring since 1946 is especially interesting when viewed historically. Both sand and magnetite were introduced as material for heavy mediums at about the same time, sand in the Chance process in 1921 and magnetite in the Conklin process in 1922, but from that point on their records diverge. The Chance process enjoyed a steady growth from its inception, whereas no additional magnetite plants were built in the United States for over 20 years. Then, following the close of the World War 11, magnetite was again introduced, this time with marked success. During the following years some 47 plants employing magnetite medium were built. This rapid growth of dense-medium cleaning has been concurrent with widespread adoption of full-seam mining on one hand and a return to a more competitive market on the other. At a time when changing mining practice has provided cleaning plants with dirtier coal and changing market conditions have simultaneously demanded a cleaner product, the industry has through necessity turned to improved preparation. The inherently greater sharpness with which dense-medium processes can separate coal from impurity is thus helping to hold the line against ever-increasing mining costs and at the same time assisting materially in retaining badly needed markets. Although dense-medium cleaning unquestionably offers a distinct advantage when the washing problem is difficult, other methods can provide almost equally high efficiency when the coal is easy to wash. Moreover, fine coal cannot yet be treated by heavy medium in a proved process, although the Driessen cyclone is in the pilot-plant stage. Most of the present types of dense-medium equipment have been in use only a few years, and the dearth of information in the literature concerning their performance characteristics is entirely understandable, Nevertheless this information is necessary if the process is to be intelligently applied to individual cleaning problems. Without data on the efficiency of a process in a particular type of separation, it is difficult to assess the advantage to be expected from it. Similarly, the role of particle size in heavy-medium separation is important in some cases, yet there is little published information on this aspect. To mention only one more of the numerous points on which essential information is lacking, the bearing of medium characteristics on performance has been discussed only in qualitative terms. It was with the hope of providing information on some of these points that the Bureau of Mines built a dense-medium pilot plant for cleaning coal at its Northwest Experiment Station in Seattle in 1950. The plant has been operated continuously since that time, and over 50 runs have been made on 7 coals exhibiting a wide range of washability characteristics. An idea of the magnitude of this work will be gained from the fact that examination of the plant products has involved some 600 float-and-sink separations and about 2500 ash determinations. A laboratory pilot plant is especially well adapted to investigate many aspects of performance because close control over test conditions can be exercised and because a large number of tests can be made rapidly. On the other hand, factors such as consumption of medium and other cost items can be investigated satisfactorily only in a commercial plant. Actually, the two forms of investigation should be complementary, with the laboratory work pointing the way for confirming tests in commercial units. Pilot Plant The dense-medium pilot plant employed for this work comprises a 24x30-in. drum-type separating vessel, a 12-in. densifier, a 12-in. magnetic separator, a 26-in. x 9-ft vibrating screen, and the necessary pumps and conveyors for handling materials. Arrangement of these units corresponds with the flowsheet used in most commercial plants, except that a thickener is not provided for the feed to the magnetic separator. Coal and refuse discharge from the separating drum to the vibrator, which is divided longitudinally down the center. Medium draining through the first 3 ft of the screen is recirculated directly to the drum. Sprays on the middle 3 ft of the screen rinse medium from the products, and the last 3-ft section is for dewatering. Dilute medium from the rinsing and dewatering sections is pumped to the magnetic separator, where magnetic solids are recovered. These are pumped to the densifier, from which they return to the medium-drainage sump by gravity through a demagnetizing coil. The drum-type separating vessel is a scale model of a commercial unit. Feed enters axially at one end of the drum just below the surface of the bath, and float material overflows through a circular opening at the other end. Particles sinking to the bottom of the bath are picked up by lifting flights bolted to the inner wall of the drum, elevated out of the bath, and sluiced to the vibrating screen. Baffles suspended in the bath prevent float material from entering the sink-lifting flights. About 8 gpm of medium is used to sluice the feed into the drum. An additional 15 to 24 gpm, depending upon operating conditions, is added through two pipes dipping into the bath behind the baffle on the side where the sink-lifting flights enter the bath. The bath available for separation is 2 ft long and 13 in. wide, giving an area of 2.08 sq ft. Depth of bath from the surface to the top of the sink-lifting flights, measured vertically below the axis, is 6 in.

Jan 1, 1954

By C. Richard Tinsley, Norman Miskelly, S. James Hodge

Construction of the Ranger uranium project, located 230 kms east of Darwin in the Northern Territory, Australia, commenced in January 1979. Energy Resources of Australia Ltd (ERA) was incorporated in February 1980 to acquire all the rights in the project. The total cost to ERA of these rights was A$407 million, made up of A$125 million in cash to the Federal Government and the issue of 125 million A$1.00 shares at par, plus a payment of A$16 million in cash to each of Peko-Wallsend Ltd. (Peko) and EZ Industries Ltd. (EZ). ERA's cash requirements to complete the project were estimated in October 1980 to be A$553 million. Project loans, secured by first ranking debenture stock, were arranged for a total of US$390 million, while second-ranking debenture loans totalling A$60 million were [ ] obtained from the vendors, Peko and EZ. Overseas participants (power utilities who had agreed to purchase uranium yellowcake under contract) arranged to take up 25% of the equity capital for A$102.5 million; Peko and EZ were allotted 30.5% each as satisfaction of vendors' consideration; and 14% representing A$57.5 million was issued to Australian residents in an underwritten public flotation in November, 1980. The loan and equity financing arrangements required the successful resolution of many complex and interlocking factors, including technical and economic feasibility, agreement with Aboriginal interests, compliance with Government policies, and securing of sales contracts.

Jan 1, 1985

By S. W. Zehr, G. S. Murty, W. A. Backofen

AN observation by Squires, Weiner, and phillipsl has stimulated interest in a mechanism of deformation at high temperature (above -0.5 of the absolute melting point) that is not usually thought to be involved in the creep of metals. They found precipitate-free or "denuded" zones along grain boundaries normal to the stress axis in tensile specimens of a hydrided Mg-1/2 wt pct Zr alloy after slow straining at 450° and 500°C. Their suggestion that the zones were a result of directional diffusion of magnesium atoms was supported with calculations from Harris and Jones2 which also tended to identify the process as Nabarro-Herring (N-H) creep3,4—a process that is characterized by Newtonian viscosity, with stress (o) directly proportional to strain rate (C), and one that proceeds by lattice diffusion. Material transport by diffusion along grain boundaries is an alternative basis for Newtonian viscosity, as demonstrated by Coble,5 and is favored over N-H creep for fine grain size and lower temperature.6 In either case, the strain rate sensitivity of flow stress, defined as m = d log o/d log E (which commonly appears in the empirical a = KEW), is unity. The experiments to be described here gave metallo-graphic indications of diffusional creep which were no less clear than those just cited, but the associated m (as measured by the method of Ref. 7) was much more like that of a Bingham material. For true Bingham behavior, (a — ao) E, where oo is an initial yield stress. Therefore, even if flow after yielding should occur by diffusional transport, m must increase from 0 as < is raised to reach unity only in the limit as One result is that the resistance to tensile necking conferred by Newtonian viscosity is lost, which would become increasingly apparent through the formation of more sharply defined necks as 6 is lowered. That trend appeared in these experiments. Most of the work was done on an extremely finegrained alloy of magnesium with -6 wt pct Zn and ½ wt pct Zr (Mg ZK60); the initial mean-intercept grain diameter, L, was 0.55 µ. Shown in Fig. l(a) is a germanium-shadowed carbon replica of the surface of a specimen that was coated with silicone oil,* heated to 270°C under a helium atmosphere, and then stretched locally -200 pct at an initial E = 3.3 x 10-5 sec-1. Under

Jan 1, 1969

THAT the march of civilization has synchronized with progress in the art of utilizing minerals is a proposition that needs no proof. It is a truism. Historians conveniently divide the time that the earth has been inhabited into the Stone Age, the Bronze (more accurately the Copper) Age, and the Iron Age. As archeologists are not entirely in accord as to dates, and as a few centuries make no difference whatever to this particular story, it may be approximated that the Age of Copper began about 8000 years B.C. and that it gave place to the Age of Iron about 1000 years B.C. The logic of this succession-stone, copper, iron-lies in the fact that copper first displaced stone, then iron displaced copper as the standard material out of which the utensils, implements, and weapons, the utilitarian articles of antiquity, were made. After the advent of iron, the mining and smelting of copper continued. Copper and bronze found use particularly in objects of artistic and ornamental nature; but the superior qualities of iron for many purposes were recognized. Useful manufactures of those days consisted principally of knives, hammers, chisels, spear-heads, arrow-heads, and battle-axes. First these were made of stone, then of copper and bronze, then of iron-particularly as there was plenty of iron ore, and the metallurgy was comparatively easy of accomplishment. Of course, the periods of transition dragged slowly. Definite as were the three Ages dominated by the mineral substance from which they get their names, ten or fifteen centuries probably elapsed from the time the first iron was smelted in a small charcoal furnace until it became the accepted material from which to shape a battle-axe. Contrast this with the pace of modern progress. In a brief span, half a dozen more or less deserving candidates for the distinction of having their name

Jan 1, 1933

By M. M. Rao, P. G. Winchell

The growth rates of bainitic plates were measured at 400°C in Fe-Ni-C alloys containing 0.10 atom-fract~on nickel and 0.0012 to 0.0075 atonz-fraction carbon. The growth rates are adequately represented by where xc is nearly the atom fraction carbon of the bulk austenite and PXCy is nearly the carbon atom fractlon in the ferrlte of radiids p In equilibrium with austetzite. The form of the equation is that predicted by a model in which carbon diffusion in austernite controls the gvowth, but the numerical constatnt is two orders of magnitude below that suggested by the model. THE growth of bainitic plates in steel is often assumed to be controlled by the diffusion of carbon away from the advancing plate tip. This hypothesis predicts that the growth rate will increase as the carbon content of the austenite, xCz, is reduced toward the carbon content of the saturated ferrite comprising the plate tip, PxCY The growth rate should vary approximately as (xCg- pxCy)-1. Experimental observation of the growth behavior at low carbon levels should provide a significant test of this model. An alloying element in addition to carbon is required so that low-carbon austenite can be experimentally observed while undergoing bainitic transformation. Nickel was selected. The presence of nickel complicates the interpretation of the data in two ways: First, diffusion of nickel during the transformation would make analysis very difficult. Nickel is assumed immobile during the transformation. Second, nickel affects the solubility of carbon in ferrite and austenite in equilibrium. This effect has been evaluated.&apos; At the completion of our experimental work Goode-now et al.2 published data in essential agreement with the observations to be reported here. Since their discussion is abbreviated and their data are scanty in the region of interest, we believe the present work is of significance. I) THE MODEL OF BAINITIC PLATE GROWTH The rate of lengthening of a plate is assumed to be controlled by the diffusion of carbon from the advancing ferrite-austenite interface into the surrounding austenite. The precipitation of carbides is assumed to be a secondary process. For ease of analysis the carbon-atom ratio,* pxCy, of austenite in equilibrium with ferrite which is convex with minimum curvature radius p, and the carbon-atom ratio, PxCY, of that ferrite in equilibrium with austenite are assumed independent of location on the ferrite-austenite interface. Since these carbon contents vary with the radius of curvature of the ferrite, p, their assumed positional independence must be held as an approximation. The consequences of these assumptions have been developed approximately by zener3 and Hillert,4 and the resulting equation for a platelet has been applied to bainite by Speich and cohen5 and Kaufman, Radcliffe, and Cohen.8 The Zener-Hillert equation* for plates is: The analysis of Hillert is supported by that of Hor-vay and cahn7 which involves no mathematical approximations but does include the assumption that the a/y interface coincides with an isoconcentration line. The solutions of Horvay and Cahn for elliptic paraboloids are replotted in Fig. 1. The shape of the paraboloid is expressed in terms of the ratio of the principal radii of curvature at its tip, A =p1/p2, which is also the ratio of the minor to the major axis of the elliptic cross section. The Zener-Hillert equation for plates is also plotted. The agreement is within a factor of two for (pxyaCr - xyC )/(xyC - PxCaY) between 0.5 and 100. This is the range of interest here and in most other work on bainite. The original form of the Zener-Hillert equation was the form given above with the right-hand side replaced by (pxCya -xCy)/(PxCya). This replacement is not appropriate here. 11) THE EXPERIMENTAL PROCEDURE Alloys were prepared and three kinds of experiments carried out. Continuous-cooling-transformation experiments were carried out on wires by measuring temperature and resistance during continuous cooling. Isothermal-transformation experiments were carried out on wires by measuring electrical resistance as a

Jan 1, 1968

By S. Feuerstein, J. M. Galligan

SURFACE effects in the deformation of metal single crystals have been noted by a variety of workers.&apos; A large majority of these experiments have used surface roughening or a second chemical constituent at the surface. We performed the following experiment to see how the presence of a fine polycrystalline layer influenced the stress-strain behavior of single crystals of zinc. Spherical single crystals oriented for single slip were acid-machined into cylindrical dumbbell-shape shear specimens having a gage length of 3.2 mm and a cross section of 20 sq mm. The crystals were then deformed varying amounts at the surface of the gage section with emery paper. Following this treatment, the crystals were heated for approximately 8 hr at 200°C. This resulted in a polycrystalline surface layer, with an observed grain size of approximately 1/10 mm in diameter. Deformation of these crystals was undertaken at 78°K in pure shear, the shear direction <1120> lying in the basal plane. The deformation apparatus has been described elsewhere.2 The presence of a polycrystalline layer markedly raises the first observed plastic deformation, as can be seen from Fig. 1. This yield stress is then followed by a region of low work hardening comparable to that observed in shear tests on similar untreated zinc single crystals. However, the extent of easy glide is quite seriously curtailed, and is followed by a more rapid increase in work hardening, reminiscent of Stage II observed in the deformation of fcc crystals. The higher yield can probably be attributed to the difficulty of penetrating the grain boundaries by dis locations from sources interior to the boundaries. If we associate this yield stress with this breakthrough, then we might expect that more dislocations would be trapped in the crystal than is normally the case. If there is an increased density of trapped dislocations, this could lead to an increase in the amount of trapping with increasing strain, giving a larger strain hardening in the crystal. Although other explanations can be given, it is quite tempting to characterize the region of increased work hardening as a manifestation of Stage II-type deformation. This seems reasonable if the polycrystalline layer is quite efficient in holding up a large number of dislocations. In zinc crystals, since it is well-known that the slip distance can be as large as the specimen dimensions, one would only expect to entrap a large number of dislocation with very large crystals or by applying surface layers. If this interpretation of increased strain hardening is correct, it might present a method of studying Stage II in single crystals of zinc. This research was supported, in part, by the Office of Naval Research (1959). The encouragement and stimulation given by Professor E. R. Parker is gratefully acknowledged.

Jan 1, 1965