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By Harold R. Bradford

EXPANSION initiated during and after the war has placed industrial plants in new areas and increased reduction and manufacturing facilities in communities already established. With added expansion interest has grown in possible area contamination from waste products. Evolved flue waste contains many chemical contaminants that may or may not cause concern; however, atmospheric pollution has always been a problem to industrial communities. For some time effects attributed to small quantities of compounds of fluorine in various waste gases have been studied by industrial, medical, agricultural, and associated interests.1'2 Aside from an article by Churchill, Rowley, and Martin in 1948," little has been published on the subject of fluorine in coal except by foreign investigators. The first indication of fluorine compounds in coal was noted in England in 1934 by R. Lessing,4,5 who found that the presence of fluorine in Midland and West County coals was definitely established by etching of glass and by severe corrosion of porcelain fillings in a gas works scrubber. Etching of glass in a direct contact annealing kiln initiated research, and in 1944 four papers were published by H. E. Crossley,6-9 giving results of investigations of fluorine in coal of England by the Fuel Research Board, Department of Scientific and Industrial Research. These investigations studied methods of determining fluorine, the quantities present in various coal deposits, the geographical distribution of fluorine in British coals, occurrence of fluorine in minerals associated with coal, amounts of fluorine compared to other constituents of coal, the nature of fluorine compounds, and industrial significance of fluorine in coal. It was shown that British coals contain from 5 to 200 ppm of fluorine, which is probably present as fluorapatite [Ca10F2(PO4)6], often written as [3Ca3P2O8.CaF2]. The fluorapatite is intimately associated with shale in some coals and can often be separated from these coals along with the shales. H. E. Crossley8 also reported no correlation between the amounts of chlorine, sulfur, or ash and the amount of fluorine in different coals. He found, however, a relationship between the content of fluorine and phosporus in many British coals. Thus it should be possible to anticipate likely fluorine-rich coals from existing data giving phosphorus content. Behavior of the fluorine compounds of coal was compared with that of 12 fluoride-phosphate minerals in sink-float separations and solvent ex-

Jan 1, 1958

By Edward Hart

Having occasion several years since to make ferrous sulphide, I attempted to do so by fusing a mixture of coal-brasses (FeS2) and dried ferrous sulphate. A very nice-looking sulphide was obtained; but on attempting to use it, I found that it was insoluble in dilute hydrochloric and sulphuric acids. The subject was laid aside at the time, but has since been taken up; and some curious results have been obtained, which I believe are new. I have made the material by all of the following methods and the product seems to be pretty much the same, however obtained : (a) FeS2 heated to fusion. (b) FeS2, and FeSO4 heated to fusion. (c) FeS2, and Fe2O3 heated to fusion. (d) FeS2, and FeCO3, heated to fusion. (e) FeSO4, and S heated to fusion. (f) Fe2O3 and S heated to fusion. Obtained in this way the mass after cooling breaks easily and is very nearly black in color. On the upper surface of the fused cake the color is generally reddish or brownish black. When this is treated with dilute sulphuric or hydrochloric acid, it refuses to dissolve; but if touched with the point of a file or any piece of wrought-iron, solution of the sulphide takes place with the evolution of sulphuretted hydrogen. If the iron is removed the evolution of gas ceases, and only begins again when the iron is again brought into contact with the fused sulphide. The same thing happens if the iron is connected with the sulphide by means of a platinum wire. But in all the samples of fused sulphide I have obtained, if the iron is allowed to remain in contact with the sulphide for a certain time (which varies with different samples of the fused sulphide) and is then removed, solution of the sulphide continues. Zinc, tin, and magnesium have the same effect as iron. In hydrochloric acid aluminium acts more rapidly even than iron. In sulphuric acid it has little if any effect. Copper in HCl, when brought in contact with the fused sulphide, dissolves quietly without evolution of gas. The solution of copper chloride formed becomes,as it flows down over the sulphide, converted into copper sulphide.

Jan 1, 1887

For the year ending February, 1916 PRESIDENT WILLIAM L. SAUNDERS,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES F. RAND,1. NEW YORK, N. Y. BENJAMIN B. THAYER,3 NEW YORK, N. Y. FIRST VICE-PRESIDENT PHILIP N. MOORE,1 ST. Louis, Mo. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW, YORK, N. Y. SECRETARY BRADLEY STOUGHTON; NEW YORK, N. Y.

Jan 10, 1915

By W. A. Alexander, L. M. Pidgeon

Metallic magnesium and similar meta!s near the top of the electromotive series have been commercially produced by the electrolysis of a suitable molten salt. Despite the success of electrolysis, sufficient inherent objections exist to justify the search for a direct reduction method. Such a method would widen the choice of raw materials, relax the rigid electrolytic requirements of raw-material purity, and, by obviating direct current, over simplicity of plant equipment. This paper describes the pilot-plant development of one such method, which has subsequently formed the basis of operation of six commercial plants-—one in Canada and five in the United States. Unlike aluminum, magnesium is volatile at relatively low temperatures. This physical property, which produces its greater inflammability, also offers possibilities of direct reduction that are not available with aluminum. In the basic reaction MgO + X = XO + Mg if X is nonvolatile, the reaction may be forced to the right at high temperatures by the evolution of magnesium vapor, despite the large negative value of the heat of reaction which is almost bound to follow the use of any available commercial reducing agent. The cheapest X, of course, is carbon, but this notable advantage is modified by the production of a volatile oxide CO, so that both Mg and CO are evolved simultaneously. Elaborate devices are required to shock-cool the equilibrium mixture in order to prevent back reaction. At best, a pyrophoric powder is produced, requiring redistillation to provide marketable metal. The practical development of this process, is due to F. Hansgirg, and his methods have recently been given a trial on a grand scale in the plant at Permanente, California, and smaller plants were previously built in Austria, England and Japan. A second class of reducing agents is available, those which produce nonvolatile oxides. When XO and X are relatively nonvolatile, magnesium is the only volatile member of the system. It may be evolved in a simple distillation step and condensed without the formation of powder. Two basic requirements must bc fulfilled in order that such a reaction may proceed: I. The reducing agent when heated to a reasonable temperature in presence of MgO must cause the production of an appreciable equilibrium vapor pressure of magnesium. This magnesium must be removed continuously. z. A supply of heat must be maintained. In order to fulfill the first requirement, operations must be conducted in vacuo or in a stream of Hz. Owing to its greater efficacy and relative safety, vacuum has been employed in the work to be described. The choice of a suitable reducing agent formed the subject of an extensive series

Jan 1, 1944

Jan 1, 1967

Jan 1, 1967

By Frank A. Hill

After a long struggle with an underground mine-fire and its accompanying evils, having experienced the discouragement of many retreats, the uncertain hope of varying advances, and the gratification of final success, I am tempted to give the members of the Institute some of the details of the fight. I do not write with the thought of treating a novel subject, but with the hope that some one as unfortunate as ourselves may be led by our experience to avoid our mistakes and to profit by our successes. The fire occurred on June 16, 1890. It was a calamity awful in its results, ringing the death-knell of thirty-one stalwart miners, bringing sorrow and desolation to many homes, and destroying in a few hours the work of years. While there have been a number of disasters in the history of American mining in which there was a greater loss of life and property, I know of none in which so simple a cause led to results so serious. A description of the mine, with the details of the accident, is necessary for a full understanding of the conditions existing at the time. The Hill-Farm-Parrish mine is in Dunbar township, Fayette county, Pa., about one mile from Dunbar station, on the Pennsylvania and Baltimore & Ohio railroads, about four miles south of Connellsville, nine miles northeast of Uniontown, and in the heart of what is celebrated as the Connellsville coke region. The mine is owned and operated by the Dunbar Furnace Company ; and all the coal produced is made into coke and used in the company's furnaces, one mile to the east. The mine is opened by two slopes, the HillFarm and Parrish, the latter known also as the Ferguson. The Hill-Farm slope is 2600 feet northeast of the Parrish. There are 150 ovens at the former and 70 at the latter slope. The Hill-Farm slope is 4100 feet in length, and the length of the Parrish at the time of the accident was 3700 feet. The average dip of the coal is about 8 degrees S of W. The workings of the two slopes are con-

Jan 1, 1893

By K. Adam

Grinding in steel mills adversely affects the flotation of pyrrhotite. The electrochemical nature of inter action between pyrrhotite and active metals was investigated by contacting pyrrhotite with platinum at different applied potentials. Flotation tests, scanning electron microscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy were wed to examine the surface properties of pyrrhotite. The formation of hydroxide or oxide and sulfate species of iron through the oxygen reduction reaction at the cathodically polarized surface of pyrrhotite was shown to be the mechanism responsible for the reduced floatability of pyrrhotite.

Jan 1, 1985

By S. G. Cupschalk, F. A. Dahlman, J. J. Wert

Studies have been undertaken to determine the indicidual effects of particle size, degree of long-range ovder, antiphase domain size, and root mean square stran on the microhardness and yield strength of ordered alloys. Dnta have been analyzed for Cu3Pt initzally ordered to a value of 0.82 and after deformations of 1 and 6 pct. It was observed that deformation fleatly reduced the degree of long-range order. Furtherrnore, wztkin this range of relatively small deforntntlons, the average particle size changed very little while the antiphase domain size was greatly reduced. Smultaneosly, the mcrohardness changed by a factor of two durzng the deforrtation process. PREVIOUS studies have reported some of the effects of cold work on the broadening of X-ray diffraction peaks. These investigations were performed on powder and wire samples representing both ordered and disordered states; i.e., the specimens were initially studied in a severly cold-worked condition. By comparing the difference in line shape between the annealed and cold-worked peaks, fundamental information was obtained concerning particle size, strain distribution in different crystallographic directions, degree of long-range order, and change in antiphase domain size. Considerable theoretical work has been done concerning the analysis of diffraction data obtained from cold-worked metals. Stokes' expressed the change in diffraction profiles in terms of Fourier coefficients. Much of the work in this area has been summarized by warren2 in an extensive review article concerning the analysis of plastic deformation by X-ray diffraction. Cohen and Bever3 applied these techniques in studying the effects of cold work on alloy systems exhibiting long-range order. They utilized the Fourier coefficients of fundamental peaks in conjunction with those of the superlattice peaks to determine the change in antiphase domain size. Little work of this nature has been reported for ordered systems that have undergone small degrees of plastic deformation. The purpose of this investiga-tion was to determine the effects of small deformations in such a material with respect to particle size, strain distribution in various crystallographic directions, antiphase domain size, degree of long-range order, and hardness. EXPERIMENTAL PROCEDURE CusPt was used for the initial investigation since the order-disorder transformation takes place with- out a change in crystal structure. The transformation is readily detectable via X-ray diffraction techniques due to the large difference in the scattering factors of copper and platinum. Additionally, the alloy is relatively low melting (approximately 1300°C) and is easily deformable in both the ordered and disordered states. 1) Specimen Preparation and Cold Working. A 100-g, 12-in. diam., cylindrical specimen of Cu3Pt was prepared by melting and casting 99.99 pct pure Cu and Pt i.n vacuo. Prior to any mechanical working, the material was homogenized in a vacuum for 60 hr at 100O0C, and surface defects were removed by machining to a depth of approximately 116 of an in. The material was then cold-rolled, with an intermediate anneal, into a strip approximately 12 in. wide by 14 in. thick. Straightening and flattening removed another 0.025 in. from the thickness. After a recrystallization treatment at 750°C for 30 min, the specimen was slow-cooled from 55OoC, at the rate of 6°C per hr, down to 150°C to induce superlattice formation. This treatment yielded an ASTM grain size of 7 and a degree of long-range order equal to 0.83 0.06. After obtaining X-ray and Knoop hardness data, the sample was cold-rolled approximately 0.75 pct in one pass through a hand-operated jewelers' mill. X-ray and hardness data were again obtained and the specimen was reduced an additional 5.41 pct in a single pass through the mill. 2) X-Ray Measurements. The specimen was examined in the ordered condition and after the two degrees of cold working previously mentioned using a General Electric XRD-5 unit equipped with a spectrometer and scintillation counter. Using Mo-Ka radiation with a zirconium filter, six orders of the 100 reflection were obtained. It was anticipated that point counting would be necessary for an accurate determination of the low-intensity peaks and tails: however, it was demonstrated that, by using a scanning speed of 0.2 deg per min and the appropriate time constant, the recorded data were sufficiently accurate. Thus, for ease of experimental procedure, all peaks were recorded on chart paper. Specimen position in the holder was considered to be insignificant after making a series of measurements of the same peak area in different positions with respect to the beam. Since peak overlapping did occur at high values of 20, it was necessary to separate the peaks graphically prior to analyzing the data in order to minimize this source of error. The peak tails were also carefully drawn to obtain the best possible data. Fourier coefficients of the line profiles were calculated on an IBM 7072 computer, and graphical meth-ods2j3 were employed in analyzing the results. For this type of calculation, in which the line profile is represented by intensities taken at set intervals, the intervals selected must be sufficiently small to give an accurate representation of the line profile. It was decided that for 20 = 0.02 deg the line profiles were

Jan 1, 1967

By S. Chander, V. N. Sharma

Nickeliferous laterite ore from Sukinda, Orissa (India), consists of very fine particles agglomerated into larger aggregates. The ore is chemically and mineralogically complex and presents many characterization and beneficiation problems. In this study the results of a detailed investigation to characterize the ore by several techniques are discussed. Various techniques used for characterisation include elemental analysis, electron microscopy, electronspectroscopy for chemical analysis, x-ray and electron diffraction, differential thermal and thermogravimetric analyses, EDAX analysis, Mössbauer and infrared spectroscopy. Generally one method compliments the other and it is shown that a combination of several techniques is necessary to fully characterize the ore. The scope and limitations of the techniques are also discussed.

Jan 1, 1980

By G. Bruggeman, K. G. Kreider

Grain boundary dij]usion coefficienls were measured in tungsten between 1400° and 2200° C and can be expressed by the equation sq cm per sec This activation energy confirms some eavlier estimates made .from tungsten sintering experiments. Grain boundary diffusion was found to occur in sub-bozrndavies having -misorientations of less than 10 deg. The actiuation energy for this subboundavy diffusion is equal to that for dijjusion in incoherent grain boundaries with in the limits of error. This is shown to be consistent with the dislocation model of Low-angle boundaries wheve diffusion occlcvs along- the dislocation 'YPipes" comprising -tile boundary. RECENT investigations of the sintering of tungsten powders all report activation energies which are considerably less than the activation energy for tungsten volume diffusion. Kothari' reports a value of 100 * 5 kcal per mole, Hayden and Brophy' obtained 90 kcal per mole, and Vasilos and smith3 found 110.7 kcal per mole from their sintering studies. Since most determinations of the activation energy for volume diffu-sion4-' fall between 120 and 160 kcal per mole (the true value seems most likely to be nearer 150 kcal per mole), the conclusion is drawn that the mass transport leading to densification during sintering is accomplished by grain boundary diffusion. This interpretation is consistent with various diffusion models of the sintering process. 10-12 Vasilos and Smith calculate diffusion coefficients from their data which fit the equation D * 1.36 x 10* exp(-llO,700/HD However, no direct measurements of tungsten grain boundary diffusion have been made. Furthermore, considerable disagreement exists between the directly measured values of tungsten volume diffusion.'-' In order to corroborate the inferred results of the sintering experiments concerning grain boundary diffusion and to provide accurate diffusion data essential to the analysis of the kinetics of creep, oxidation, precipitation, and so forth, the present work was undertaken to measure self-diffusion in single-crystal and polycrystalline tungsten between 1400" and 2200°C. It is within this temperature range that tungsten sintering is done, the re crystallization of tungsten occurs, and the widest application of tungsten as a high-temperature material will probably be made. EXPERIMENTAL PROCEDURE Radioactive WlE5 was produced by irradiating tungstic acid in a neutron flux of 1.2 x 1012 neutrons per sq cm per sec for 36 hr. A 2-week waiting period was allowed for the decay of w"~ also produced by the irradiation. (w"~ has a half-life of 24 hr.) The half-life of the remaining isotope was determined to be 75 days confirming the presence of w lE5 and the absence of any undesired radionuclide. Specimens 4 in. in diam and $ in. thick were cut from polycrystalline swaged tungsten rods (recrystal-lized) and from Linde single-crystal rods. Chemical analyses of these materials appear in Table I. Actually upon closer examination, the single-crystal specimens were found to consist of several subgrains separated primarily by tilt boundaries in which the misor-ientation ranged from 3 to 10 deg. Thus, it was possible to measure boundary diffusion coefficients in these low-angle subboundaries as well as in the incoherent boundaries of the polycrystalline specimens. The two faces of each specimen were ground flat and parallel within 0.0001 in. The radioactive tungstic acid was dissolved in concentrated ammonium hydroxide, placed on the ground flat of the specimen, and evaporated to dryness. The oxide was then reduced in hydrogen at 1000°C resulting in a layer of wlE5 approximately 1 p thick. The diffusion anneals were performed in vacuum in a tantalum resistance furnace. Time at temperature ranged from 10 hr at 1400°C to 2 hr at 2200°C. The penetration profile was determined by measuring the residual activity after successive removal of surface layers by grinding on metallographic polishing paper. Extreme care was exercised to insure that sections were always taken normal to the diffusion direction; this was verified repeatedly by checking that front and back surfaces of the specimen remained parallel. The activity was measured with an end-window Geiger-Mueller counter. The sides and edges of the specimen were well-shielded to eliminate possible effects due to surface diffusion. The weight of the

Jan 1, 1968

By J. D. Doherty

A. R. POWELL*—Mr. Doherty has outlined in a most thorough manner valid arguments for the development of an industry in this country making syn. thetic liquid fuels from coal. No thoughtful person will dispute the statement that it is essential to carry on fundamental and applied research and acquire engineering "know-how" by the erection and operation of two or three large plants in the near future. Considerations of national security indicate that this should be done, irrespective of any temporary present surplus of natural petroleum. It is the belief of the discusser and of many others interested in coal technology that our energy picture of the future will include an increasing utilization of coal directly, without any conversion to liquid fuel, as a source of energy. A fact that is sometimes forgotten is that petroleum fuels have often been cheaper than coal in many locations and over long periods of time, and this price factor has been of great importance in expanding the use of petroleum fuels at the expense of coal. Synthetic liquid fuel made from coal must necessarily be several times as costly as the coal from which it is made, and this fact alone will have a profound effect on the future energy pattern of our country. This complete change in the economic relationship between solid and liquid fuels will lead to the substitution of coal itself for many uses now supplied by the relatively cheap petroleum fuels. From the standpoint of conservation of our natural resources, the substitution of coal itself for liquid fuels wherever possible when the age of synthetic liquid fuel arrives is also logical. At least 50 pct of the energy of coal is lost during conversion to liquid fuel. Nor is this com-pensated for by a higher utilization effi-ciency of the liquid fuel in most cases. For example, modern steam-boiler plants can operate at equal fuel efficiencies with either coal or fuel oil.

Jan 1, 1950

By Hertha Freche

THE diffusion of magnesium and silicon from the core into the high-purity coating of Alclad sheet is important commercially, and led to the use of a duplex product for the study of diffusion by means of spectro-graphic analysis of successive layers. It has been found that in the duplex materials the diffusion of magne-sium from an undersaturated aluminum-magnesium alloy into its high-purity aluminum coating is approximately of the same order of magnitude as the diffusion of silicon from a saturated aluminum-silicon alloy into its high-purity aluminum coating. However, if magnesium and silicon are both present in the alloy in the ratio of Mg2Si they appear to diffuse in the approximate ratio of this compound. Finally, if the alloy contains silicon in excess of the amount required by magnesium silicide, the amount of diffused silicon in the high-purity aluminum coating will also be in excess. The interdiffusion of metals in the solid state is of both scientific and technical interest, because it is helpful in the study of the alloy structure and in the solution of problems pertaining to the strength and surface condition of the fabricated product. W. C. Roberts-Austen1 carried out the first quantitative determination of the coefficient of diffusion of gold into lead. This classical experiment was followed by a series of investigations on the diffusion of metals and nonmetals in iron and steel and in nonferrous metals and alloys. Recently the diffusion of copper in coated strong aluminum alloys was investigated by A. Burkhardt2. This appeared to be the first published investigation on the diffusion of metals into aluminum.

Jan 1, 1936

By W. Ivanick, Frank W. Glaser

ORDERING reactions of Fe-Si compositions in the a region have been mentioned in a number of review articles.7-8 However, little is known in regard to the critical temperature, T at which this transformation takes place. Greiner and Stoughton,' in a study of the constitution of iron-rich Fe-Si alloys below 800°C, placed the onset of order at a composition of about 4 to 5 wt pct (7.5 to 9.5 atomic pct) Si. They observed that at this composition the ductility and strength begin to decrease sharply and brittleness develops. During X-ray studies they observed only the appearance of superlattice lines for compositions containing 12.5 atomic pct Si. More recent X-ray diffraction studies- etected the appearance of superstructure lines (corresponding to the calculated positions of [Ill] and [ZOO] reflections) for alloys containing 9.5 atomic pct. This fact confirms Greiner and Stoughton's original hypothesis in regard to the onset of order at compositions containing about 7.5 to 9.5 atomic pct Si. The physical properties.of Fe-Si alloys containing more than 10 atomic pct Si have been studied only to a limited extent. Their extreme brittleness and difficulties of sample preparation render them of little industrial use in comparison with alloys in the 0 to 10 atomic pct Si range. The properties of Fe-Si alloys reported to date are mostly properties measured at room temperature on ordered compositions It appears that because of experimental difficulties fully disordered alloys could not be produced in the critical composition ranges and their properties could therefore not be reported. In Figs. la, lb, and lc, a summary of physical properties of Fe-Si alloys, measured during recent investigations of the influence of silicon additions to iron, is presented. No mention of determination of the critical temperature, T for disorder could be found in the literature. The following is an account of work done in an attempt to: 1) produce the disordered state of various Fe-Si alloys and establish the critical temperature, T for disordering, and 2) compare the electrical and thermal conductivity characteristics of the ordered and disordered phases as functions of composition. Materials, Preparation of Test Samples, and Testing Methods Fe-Si alloys with high silicon contents (about 10 atomic pct) are usually prepared using powder metallurgy techniques. This method insures accurate compositions and high purity through the use of protective atmospheres during solid state diffusion alloying of the mixed powders."" Iron and silicon powders were mixed in the desired proportions, cold or hot pressed, and then homogenized at 1150°C for periods ranging from 6 to 12 hr under a protective getter and in a hydrogen atmosphere. Fully homogenized samples were quenched in water from various and successively higher temperatures to establish the critical temperature for disorder. Temperatures were determined using Pt—Pt-Rh thermocouples in contact with the test samples. Test bars were approximately 0.6x1.25x7.5 cm. Electrical measurements were made at room temperature by determining the potential drop over a 1.5 cm span for a current of 10 amp. Densities of the samples were determined by immersion. High temperature electrical resistivities were measured using previously described techniques.'" Specific heat conductivity up to 200°C was measured by heating one end of the test bar and water-cooling the other; heat conductivity was then obtained by subtracting the rate at which heat entered the water from the

Jan 1, 1957

By W. F. Carew, F. A. Crossley

The stress for rupture in 500 hr at 1000° F has been reported to be about 13,000 psi higher for Widmanstitten than for equiaxed microstructures for the Ti-7A1-3Mo alloy.1,2 Also, limited data indicated Widmanstatten and equiaxed micro-structures to have approximately the same creep resistance at 1000°F.' Recently, data have been obtained which show Widmanstatten structures to be significantly more creep resistant than equiaxed structures at 1000°F, see Fig. 1. These data represent several ingots and several heat treatments of the solution treat and age type. The thermal history and tensile properties corresponding to the creep data are given in Table I. The creep data were taken from creep-rupture tests. The associ- ated rupture data are given in Table 11. It may be noted that total creep deformations are considerably greater for equiaxed structures. Previous evaluations of stability indicated that all of the structures tested are stable with respect to exposure to stress at elevated temperature.1,2 For a minimum creep rate of 10-4 in. per in. per hr the difference in stress levels is indicated to be about 17,000 psi. Holden,et found an irreversible contraction upon heating three a-ß titanium alloys in the equiaxed condition above their ß-transus temperatures. The alloys were: Ti-6Al-4V, Ti-155 A (5Al-1.3Cr-1.5Fe-1.2Mo), and C-130 AM (44-4Mn). The net contractions in length between the original equiaxed and the final Widmanstatten structures measured at room temperature were: 0.4, 0.4, and 0.7 pct, respectively. The greater creep and rupture resistance of the WidmanstStten structure of the Ti-7Al-3Mo alloy may be associated with the phenomenon

Jan 1, 1959

By Paul L. Russell

Of the potential applications of nuclear explosives to mining, excavation is perhaps the most obvious and the best understood, and probably the most practical for use in the near future. Large quantities of rock and earth can be moved by proper emplacement of nuclear explosives, but economic and practical relationship must be determined between the known capabilities of nuclear explosives and the required excavating to remove overburden. On an energy yield basis, even the cheapest of the present commercial explosives cost more than the most expensive nuclear explosive. Comparing the energy yield of a megaton thermonuclear device with the yield of TNT shows that one energy yield per dollar is 400 times greater for the thermonuclear device. However, small-yield nuclear devices (a few 10's of kilotons yield) are less efficient blasting materials than chemical explosives, with the result that the heat of explosion is utilized less effectively. While only 1 lb of conventional explosive is required to excavate 1 cu yd of rock, or about 2 million cu yd per kiloton, nuclear devices excavate from 100,000 to 300,000 cu yd per kiloton. This changes the economic situation, and it is thus apparent that nuclear explosives are cheaper only for the large explosions.

Jan 6, 1964

By A. G. Preban, R. J. De Angelis, J. B. Cohen, P. Gordon, D. C. Brillhart

Changes in stored energy, resistivity, density, X-ray line broadening, and dislocation arrangements (from transmission electron microscopy) have been mensured on copper specimens shock-loaded at 75 to 435 kbars. The stored energy in shock-loaded copper and changes in density and resistivity are larger than those after conventional deformation. A high density of twins makes an appreciable contribution to all the measured quantities. Dislocation densities rise to values of 1011 lines per sq cm at the highest pressure. The resistivity, density, and X-ray In a study of the effects of shock loading on copper, changes in stored energy, resistivity, density, hardness, lattice parameter, line broadening, and dislocation structure have been examined after subsequent annealing of specimens shocked to various pressures. This paper presents certain aspects of the data, taken by two groups, one at the Illinois Institute of Technology, and the other at Northwestern University, and compares the changes in these properties, and what they indicate about the effects of shock deformation. measurements yield dislocation densities in substantial agreement at all pressures, after correcting for the effects due to the twins. At the higher pressures, electron microscopy yields dislocation densities that are lower by a factor of about 5 to 10. Dislocation densities from stored -energy measurements are high; this finding can be rationalized by the consideration that the deformation twin boundaries present are largely incoherent. There is no evidence for homogeneous dislocation nucleation during shock loading. Shock loading any metal or alloy, such as copper, causes a large increase in yield strength, with dimensional changes of the order of only a few percent."' Other properties have not been extensively studied, but this result clearly indicates the importance of examining the substructure. Previous studies of the substructure of conventionally deformed specimens have been made using electron microscopy,3-6 X-ray diffraction,7,8 and etch pitting.9,10 The dislocation density can reach values of about 10" per sq cm; and the dislocations are arranged in cells approximately 0.15 in size. The substructure varies widely, however, from point to point in the specimen. The substructure of explosively loaded copper consists of cells of about the same dimensions6,11 but their size is more uniform.6 Profuse twinning occurs12,13 and the twins are often too small to be detected optically.6,13 The boundaries outlining these twins appear to be incoherent.14 There is now ample evidence 13-15 that twinning is a strengthening mechanism in fcc metals but this is only part of the strengthening effect in shock-loaded copper.* From the twinning systems which operate in shock-loaded single crystals,13 and from changes in texture on shock loading,17 it has been shown that both the

Jan 1, 1968

By A. L. Benham, W. E. Dowden, W. J. Kunzman

The mechanism involved in creating a miscible fluid displacement of typical reservoir fluids through porous media by light hydrocarbon mixtures usually involves a number of mixing and separation stages in the contact area. This mechanism has been illustrated on ternary diagrams for miscible displacement of reservoir fluid by rich hydrocarbon gases. A relatively simple method has been devised for calculating the approximate conditions for a miscible displacement of reservoir fluid by rich, light hydrocarbon gases or by LPG mixtures. Miscibility is favored by increased pressures, decreased temperatures, light reservoir fluids and light hydrocarbon-displacing fluids rich in the heavier components. The conditions for miscible displacements of five typical reservoir fluids by various light hydrocarbon mixtures were determined for a range of temperatures from 70" to 260°F and pressures from 1,000 to 3,000 psia. A correlation of these conditions was obtained using the variables of temperature, pressure, C,+ molecular weight of the reservoir fluid, C,+ molecular weight of the displacing fluid, and mol per cent methane in the displacing fluid. This correlation has been applied to data appearing in the literature with very good success. A partial check of the correlation has been made using a step-wise procedure with a windowed PVT cell. INTRODUCTION The term, "miscible fluid displacement", may be defined as any oil-recovery displacement process where there is an absence of a phase boundary or interface between the displaced and displacing fluids. A water flood would not be a miscible fluid displacement, although cycling in a condensate reservoir would be. Another example is displacement of oil by gasoline. Not so obvious, however, are the conditions under which fluids (such as propane, mixtures of propane and methane, or other similar systems) will give a miscible fluid displacement of oil. There are four standard miscible-fluid-displacement processes being used for the recovery of oil from an "nderground reservoir—(1) high-pressure dry-gas miscible displacement, (2) rich-gas miscible displacement, (3) miscible slug using a slug of LPG followed by a lean dry gas under miscible conditions, and (4) gas driven-slug process using a slug of LPG followed by a lean dry gas under immiscible conditions. The first problem faced by the engineer designing a miscible displacement process is to determine the conditions for miscibility. A number of papers have included discussions of the process of obtaining miscibility in these processes.1-8 However, methods for calculating the conditions for miscibility have not been published. This paper includes a method for calculating the conditions for a miscible displacement of reservoir fluid by a rich gas (LPG diluted with methane or natural gas). In this paper, a rich-gas miscible displacement process is defined as an oil-recovery process in the reservoir. The cost of a rich-gas miscible displacement will be decreased by diluting the LPG with methane or natural gas as much as possible. Therefore, it is important to be able to predict the maximum dilution for miscibility. MECHANISMS The mechanisms for obtaining miscibility between a displacing mixture of light hydrocarbons and displaced reservoir fluid often involve a number of displacing and mixing stages. As stated previously, the cost of a rich-gas miscible displacement is decreased by diluting available LPG with natural gas. The problem is to predict the maximum dilution allowed while maintaining miscibility. To get a picture of the displacing and mixing stages, it is helpful to consider these complex hydrocarbon mixtures as pseu do-ternary systems. Graphical representation of a complex system as a pseu do-ternary system can be thermodynamically rigorous if enough variables are used to describe the character of each pseudo-component in one of the phases. However, even if the characterization of each pseudo-component is not complete, pseudo-ternary representation does serve to illustrate the mechanism for obtaining miscibility and can be used to make some general conclusions concerning the conditions for obtaining miscibility. A phase diagram for the ternary system, methane-

By J. J. Stokes

Literature on the electrolysis of aluminum from cryolite melts and on the structure of these melts is surveyed critically. Data on density, freezing point, and other properties are reviewed. Theories of the electrolysis are examined in the light of these data. Two theories are presented which account equally well for the observations. ALTHOUGH the production of aluminum is a large-scale industrial process, consuming approximately 3 pet of all of the electric current generated in this country, the mechanism of the Hall Process remains a 70-year-old mystery. It is a remarkable fact that the aluminum industry, which was established largely through research and owes much of its growth to research, still employs as its basic process the one developed by Charles Martin Hall while he was still a young man working in a woodshed. There are, of course, modifications in detail and a tremendous expansion of the size of the units used, but basically the process employs carbon anodes and a carbon-lined iron vessel as a cathode for the electrolysis of alumina dissolved in molten salt. Of the almost infinite variety of salts available, the relatively minor Greenland mineral, cryolite, 3NaF.A1F3, is still the only one which gives good performance in the electrolysis. In the early days, the process was thought of as a simple one. The dissolved alumina dissociated and, during the electrolysis, the aluminum was carried to the cathode where it was discharged and collected in a pool of metal. The oxygen was carried to the carbon anode where it reacted to form primarily carbon dioxide together with some carbon monoxide. About the only virtue that can be claimed for this hypothesis is that of simplicity. The actual mechanisms must be tremendously more complex. This paper is devoted to a rather narrow part of the whole subject, namely, what ions are present in the bath, and by what mechanism the current is carried. The complexity of the literature on this system is demonstrated in Table I, which shows the ions postulated as being present during the process. This system is not easy to investigate. Cryolite melts at about 1000°C, so that all the investigations are at relatively high temperatures. Molten cryolite fumes in air, particularly if excess aluminum fluoride is present. The cryolite changes composition on heating at 1000°C, principally by reaction with moisture in the air, but apparently also by reaction with oxygen. Cryolite reacts with most of the customary materials of construction, and those that are not attacked by cryolite seem inevitably to react with molten aluminum. Graphite is the only common material that is inert to the electrolytic bath. Pure cryolite can be held in platinum. There is hope that some of the newer refractories will stand up in bath, and their development for this purpose would be a major advance in the field. The techniques to be discussed, then, are not the most advanced ones. Rather, they are examples of old standardized methods applied under difficult conditions. The principal methods that shed real light on the mechanism are density, electrical conductivity, freezing-point lowering, transport number, viscosity measurements, and reactivity of bath with carbon dioxide. The first measurement to be discussed is density. This procedure is relatively straightforward. A hollow platinum bob is suspended by fine platinum wire from an analytical balance into the melt being investigated. Density1-4 of the system sodium fluoride-aluminum fluoride is shown in Fig. 1. There is a maximum in the density near the cryolite composition, but actually the maximum is on the NaF-rich side of cryolite, close to the composition NaF - Na3AlF8. Density measurements are also useful in giving a clue to the nature of cryolite-alumina melts.1, 4 On the first addition of alumina, density decreases, Fig. 2, although the density of alumina, either solid or liquid, is higher than that of cryolite. These density results indicate that the systems are not simple. A great deal of effort has been spent in measuring the electrical conductivity of molten cryolite and of cryolite with various additives. Conductivity measurements are quite easy for fused salts that can be measured in a dip cell, but no successful dip cell has been made available yet for cryolite. Recourse is had

Jan 1, 1959

By N. F. Neumann, A. W. Schlechten

Metal chlorides were formed by reacting metal oxides and calcium chloride; the effect of additions to the reaction mixture was studied. It was found that by use of proper additions, metal chlorides could be prepared from mixtures that were not reactive under ordinary conditions. ManY recent metallurgical developments involve the use of chlorine or chlorides as primary reagents; good examples are found in the production of ductile zirconium and titanium by reduction of their chlorides with magnesium. Various methods of preparing metal chlorides are used and many others have been proposed. Some chlorides are formed by the direct combination of a metal or alloy with chlorine. Other processes react chlorine and metallic oxides; carbon or other reducing agents are usually employed to reduce the metal oxides and so promote chlorination. Metallic chlorides have also been produced by the exchange of chlorine between metal oxides and a chloride, such as sodium chloride. This type of reaction was the basis for the old process of chloride roasting in which metal ores were roasted in the presence of salt. Soluble chlorides thus formed

Jan 1, 1959