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By J. M. Uys, T. B. King

The solubility of water in silicate melts of various compositions was measured. The basicity of the silicate did not appreciably affect the water solu-bulity at low-base content (acid compositions). Near the orthosilicate composition the solubility increased with basicity for silicates in which the cation displayed a weak ion-oxygen attraction and apparently decreased for those in which the cation showed a strong ion-oxygen attraction; metasilicates of the former class dissolved more water than those of the latter. Temperature had little effect on water solubility. The experimental results are interpreted on the basis of two modes of solution, the contribution of one decreasing, and that of the other increas -ing, with increased melt basicity. In the former, solution occurs through interaction with doubly-bonded oxygen atoms and in the latter, through interaction with singly-bonded oxygen atoms, or, in very basic melts, through reaction with free oxygen ions. THE hydrogen content of a steel melt is in a large measure determined by water dissolved in the slag. In some glasses water may be a major cause of "seeds". Water vapor in the furnace atmosphere is the primary source in both instances. A knowledge of the mechanism of water solution in silicate melts should help in assessment of practical methods for its control in steelmaking and glass refining. Walsh et a1.l measured the water content, expressed as hydrogen, of 40 pct lime-20 pct alumina-40 pct silica and 62 pct manganese oxide-38 pct silica melts as a function of the steam partial pressure, in equilibrium with the melt. Tomlinson 2 and, also, Russell3 investigated this relationship for a molten 30 pct soda-70 pct silica glass. In all three investigations, the solubility of water was found to be proportional to the square root of the partial pressure of steam. Moulson and Roberts 4 confirmed this relationship for a silica glass. On the basis of the square root relationship, Tomlinson2 and Russell3 interpreted the solution reaction as "network-breaking", similar to that expected on the addition of metal oxides to silica. Walsh et al.' postulated two possible modes of solution, one the mechanism suggested by Tomlinson and Russell and the other the reaction of the water molecule with an oxygen ion to form hydroxyl ions. These two modes of solution suggest opposite effects of melt basicity on water solubility. However, little appears to be known about the effect of melt basicity on water solubility. Walsh et a1.l found, in the lime-silica system, that the water content increased slightly with increased basicity. As these authors pointed out, this does not appear to be in accord with their further observation that slags containing little or no silica dissolve very little water. Kurkjian and Russell5 measured the effect of basicity on water solubility in alkali silicates in the composition range 15 to 45 mole pct alkali oxide. They found a minimum in the water content at about 25 mole pct alkali. This was interpreted on the basis of two concurrent solution reacZions; one in which solubility was proportional to the activity of doubly-bonded oxygen and, in the other, proportional to the activity of singly-bonded oxygen. The present work was aimed at establishing the effect of basicity on water solubility in silicate melts over as wide a range of compositions as practical. APPARATUS AND EXPERIMENTAL PROCEDURE The silicate melt was equilibrated with a "carrier-gas" of accurately known water content, quenched, and analyzed for water by a vacuum fusion technique. Some pertinent details of the equilibration procedure, analysis technique, preparation, and handling of the silicates are given below. Gas-Silicate Equilibration. The apparatus used to equilibrate the melt with the gas mixture was similar to that used by Walsh et al.' but with some important modifications.6 Purification trains were provided for nitrogen and hydrogen; whenever air or oxygen was used as carrier gas the nitrogen purifiCation train was used with the copper furnace at room temperature. Gas flow rates were measured with capillary flow meters; bleeders filled with a mixture of dibromo and tribromo ethyl benzene (density about 2 g per cc) were used for convenience in controlling flow rates.

Jan 1, 1963

By F. P. Bobrowski, G. B. Spencer, Alton B. Cook

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By A. M. Rahm

PROBABLY the majority of red brass sand castings are judged merely on the basis of outside appearance and the quality of machined surfaces. Many castings, however, must individually withstand a hydraulic or air-pressure test before being accepted as parts of more complicated machin-ery. Finally, there remains a comparatively small group of castings intended for uses of considerable responsibility where only the highest possible characteristics of the metal are acceptable, and for these specially cast test bars are required. The shape of the cast piece from which the test bar must be detached varies greatly from one country to another. The test bar as specified in the American Society for Testing Materials Specification B62-36 is widely used by the American foundry industry. The actual test piece is at the bottom of the cast block and has a riser about six times its mass. It is obvious that this test bar has an advantage over the actual casting. The latter rarely possesses a riser of as much as 30 per cent of its own weight and that riser cannot generally be located in so convenient a manner. Therefore, the characteristics of the test bar cannot possibly correspond to those of the casting itself. It must be taken into consideration that red brass if melted and cast in the best possible manner may show a tensile strength of 40,000 lb. per sq. in. with 35 per cent elongation in 2 in. Such a test bar would indicate that the metal was nearly perfect from the viewpoint of its gas and inclusion content. Barring some accidental defect, a casting cor-responding to such a test bar could be accepted as being quite sound. However, actual specifications do not demand such high characteristics; indeed, few specifications require over 30,000 lb. per sq. in. and 20 per cent elongation, while one Federal specification demands merely 27,000 lb. per sq. in. strength and 15 per cent elongation. It is obvious that

Jan 1, 1939

By Will H. Coghill, P. H. Delano, G. D. Coe

DATA concerning the actual net energy required for pulverizing coal are lacking from the literature on coal pulverization. Power data given in the literature concern gross power and frequently include the power expended on the air blast or product-conveyor system, as well as power lost through friction in the pulverizer itself. Consequently, such data supply no information regarding the net energy consumed in pulverizing or the relative grinding resistance of various coals. In the study of coal pulverizing much work has been done on what is known as "grindability-index numbers," but grindability tests have seldom considered the energy input (that is, the "cause" part of the system "cause and effect"). There are many records of the effect, but even these have questionable value because the "grindability" tests did not make a pulverized product by a method comparable with commercial pulverizers. In many of the tests, only a selected part of the coal was ground, and the remainder continued to be an unknown factor. Furthermore, none of the grindability tests provide the balanced circulating load common to all modern commercial pulverizing. In order to obtain better understanding of the fundamental principles of coal pulverizing, the Bureau of Mines is investigating the "cause" phase; that is, the net energy input or net power excluding friction between the moving parts of the machine. As a first step in the investigation, it was necessary to design and construct a laboratory machine in which no friction-loss corrections are involved, which could grind and finish a minus-3/4 -inch feed, which could be emptied rapidly and completely, which could operate with a continuous feed and finish in an air separator; and, most essential of all, which would be equipped with a measuring device for recording only that portion of the total power consumed in actual pulverizing, hereafter referred to as "net energy input" or "net horse-powerhours." The channel-roller pulverizer here-inafter described is believed to meet these requirements. HISTORY OF THE MACHINE The work started when Ralph W. Smith, engineer, St. Genevieve Lime Co., St. Genevieve, Mo., was appointed one of the consultants of the Bureau of Mines, United States Department of the Interior, in cooperation with the University of Alabama, to develop a machine for testing the abrasiveness of coal. Smith had already developed a machine for testing the abrasiveness of dentifrices,1 and it was thought the same principles might be applied to coal. Smith's machine had a revolving disk with an annular channel in which the sample was placed. Riding in the channel was a small block or runner of selected soft metal held

Jan 1, 1942

By L. B. Harris

Continuous cyclic unloading during tensile work hardening of polycrystalline zinc at room temperature enables specimens to sustain greatly increased extension. Such enhanced ductility is associated with creep-type extension, during which the cyclic component appears to promote relaxation of internal strains. It is possible to trace the transitions from tension, through enhanced cyclic extension, to fatigue and relate the observed behavior to simpler types of deformation. DISTINCTIVE deformation behavior has been shown to occur when loading includes both cyclic and unidirectional components. For aluminum and copper extended by a sequence of progressively biased strain reversals, coffin1 observed greater fracture ductility and lower flow stresses than during monotonic tension. This may be compared with the reduction in hardness obtained from conventional fatigue softening. But fatigue softening is accompanied by enhanced fatigue life,' whereas Benham3 found that fatigue life was reduced when copper continuously extended during axial load cycling. The corresponding specimen elongation, for large cyclic load amplitudes, was greater than during normal tension. Under different conditions, Bendler and wood4 found that torsional fatigue initiated extension in copper under low tensile loads previously in equilibrium with the specimen; fatigue life was again reduced. Thus there is a type of cyclic softening which is associated with reduced fatigue life and which occurs when the cyclic loading is accompanied by a unidirectional strain component. Further, the fracture ductility or extension obtained from the unidirectional component can exceed that obtained in the absence of cyclic load. Specimen extension was not initiated by axial fatigue at small load amplitudes;3 hence Benham's work distinguishes between fatigue at large and small amplitudes, the former often being linked with unidirectional deformation because of similarities in strain Structure. The initiation of tensile extension during torsional fatigue,4 however, occurred with small amplitudes. Comparable changes in behavior have been ob- served during creep. kennedy' found that combined cyclic and creep stresses on lead at 32°C increased the rate of elongation over that for simple creep, the consequence being a reduction in creep life. It was also demonstrated that small cyclic stresses applied after creep deformation initially increased recovery, but that prolonged application produced only normal fatigue hardening. It is clear that physical properties can be changed by interaction between the cyclic and unidirectional deformations, but owing to the number of different ways in which the deformations can be combined and the large number of possible variables for each combination, trends of behavior become easily obscured. One definite conclusion is that enhanced ductility or increased extension can be obtained by cyclic action, and it is this process that has been investigated for the tensile test by measurements of the extra tensile strain produced by the addition of a cyclic tensile component. EXPERIMENTAL PROCEDURE Material. Specimens were 99.99 pct Zn wire of 1.6 and 2.0 mm diam. Mean grain diameter was 0.02 mm, sufficiently small to give a ductile necked-down fracture under all loading conditions. All experiments were conducted at an average temperature of 20°C. Normal Tension. Unidirectional tensile curves at different strain rates were obtained from an In-stron testing machine, on which load-time curves were recorded autographically, using gage lengths of 5 and 10 cm. Straining was at constant cross-head velocity, and quoted strain rates are with reference to initial specimen length. Measurements of total elongation under simple tension were also made on the tensile machine that had been modified to incorporate an added fluctuating load. Combined Tension and Rapid Cyclic Load. An electromagnetic vibrator was coupled to the elastic beam of a Hounsfield ensometer- and driven sinus-oidally from a power amplifier at frequencies from 20 to 360 cps, the flexible connecting links on the tensometer being replaced by rigid fixtures to eliminate lateral vibration in the specimen. One end of the specimen was pulled by the normal extension drive of the tensometer while the other end, fixed to the elastic beam and vibrator, was subjected to rapid oscillations of load. It was thus possible to apply cyclic load to a tensile test without altering the rate of extension of the specimen

Jan 1, 1964

By J. J. Pfeiffer, A. A. Oming, J. W. Myers

The method used to process washery refuse for use as a building material aggregate is described. Results of studies made in investigating this process are summarized. The Bureau of Mines, in cooperation with two commercial coal producers, studied the feasibility of using coal washery refuse in manufacturing lightweight aggregate for building materials. Lightweight aggregate is used in making masonry products of lower bulk density than can be produced from conventional aggregate such as sand, gravel, and crushed rock. Among the advantages of lightweight masonry are reduced deadweight loads which reduce materials cost, lower cost of construction labor, and improved thermal and sound insulation. A process for making lightweight concrete aggregate from coal-washery refuse appeared attractive because of the availability of raw material which contained sufficient fuel to carry out the processing. Vast quantities of such refuse have accumulated throughout the coal-producing areas of the U.S. Generally it is stored in unsightly piles, creating a problem of air pollution and using space that could be devoted to other purposes. Conversion of the refuse to lightweight aggregate could remedy these conditions and effectively utilize a material normally considered waste. The first part of the program was conducted in cooperation with the Truax-Traer Coal Co. to determine the feasibility of utilizing refuse from the company's coal preparation plant at Ceredo, W. Va., in manufacturing lightweight aggregate. The aggregate was to be used in making cement blocks comparable to those known in the building trades as cinder blocks. This project was completed in 1954. Based on the results of this work, the cooperator began commercial development and formed the Trulite Corp. for this purpose. A plant capable of handling 120 tpd of refuse was constructed for approximately $120,000. It began operating on June 1, 1955.' In 1959 a similar study was made, under a cooperative agreement with the Carbon Fuel Co. of Charleston, W. Va., to rrscertain the suitability of refuse from its plant for conversion to lightweight aggregate. Under this program various modifications of equipment were made, and the investigation of process variables begun in the previous project was extended. PROCESSING METHOD The formation of lightweight aggregate from coal-washery refuse js governed, in part, by the fusion characteristics of the mineral constituents of the refuse when heated above their softening temperatures. The heat required for this purpose is supplied by the combustihle matter in the refuse. Some of this combustible matter is coal with high ash content, but most of it is carbonaceous shale. Whereas the density of aggregate prepared from clay or shale depends largely on expansion, the density of aggregate made from refuse is reduced by burning out the combustible matter and, to a lesser extent, by expansion of the residue in the fuel bed. A chain-grate stoker with an updraft air system was chosen for the conversion process in preference to a downdraft sintering machine or a rotary kiln. In down-draft sintering, which operates on the overfeed burning principle, the volatile matter from the refuse would distill off without burning, resulting in inefficient combustion and interfering with proper operation of the equipment. The rotary kiln is designed primarily for processing material that lacks, or is low in, combustihle matter with the heat of reaction supplied from external sources. Washery refuse, which is relatively high in carbonaceous material, could burn at the wall of the kiln causing clinker formation with resultant decrease in throughput and increase in production cost. With an up-draft air stream on a chain or traveling-grate stoker, the volatile matter would be carried into the ignition and burning zones where the heat could be utilized more efficiently. The combustion procedure in this type of unit may be considered as consisting of four periods: 1) initial ignition of the top of the bed by furnace radiation, 2) ignition travel through the bed until the whole bed is ignited, 3) burnout of the combustible material with high air rates to fuse and expand the residue, 4) a cooling period. Investigation of the process required a study of the variables that affect both

Jan 1, 1962

Jan 1, 1923

By E. J. Fasiska, H. Wagenblast

The dilalion of a ivon by interslilial carbon was measured by two independent techniques —dilatometric mesurements at 719 c and X-ray measurments of the urlil cell parameters a1 room temperature after quenching. The relative expansion per increase in cavbon content by both methods is (2.9 + 0.3) x 10-3 pev at. pcl C nrzd is temperature- independent within experimental error. This corresponds to (6.3 5 0.6) cu cm per g-atom for the partial gram-atomic volume of carbon in a iron-only slightly smaller than the atomic volume for iron in the same temperature vange. THE only previous quantitative study of the dilational effect of carbon dissolved in a iron was performed in 1934 by Burns1 which, at the time, generated some discussion of possible sources of experimental error.2 For a system of such widespread importance, we felt that a new investigation was merited. Both X-ray diffraction and dilation measurements were used to determine the expansion of the a iron lattice by dissolved carbon, avoiding as much as possible any previous experimental problems and deficiencies. The dilation method at solution temperature offers not only measurements which are free of residual strain but also, in conjunction with the room-temperature X-ray measurements, a method to detect any large temperature dependence of the partial gram-atomic volume of carbon. To insure that quenching strains did not affect the room-temperature X-ray measurements, wire specimens of constant carbon content but different diameter were examined for such an effect. SPECIMEN PREPARATION The material used for both experimental techniques was "Ferrovac E" iron received in the form of 19-mm-diam rod and stated as having the following impurity contents: C, Cr, Cu, Mn, P, and V, each in the range of 10 to 50 ppm; Co, O, Mo, S, and Si, 60 to 100 ppm; W, 200 ppm; Ni, 230 ppm; N, 4 ppm. The stock material was cold-swaged to 0.71 mm diam for the Debye-Scherrer X-ray camera specimens and portions were cold-rolled from 6.3 mm diam to 0.79- and 0.25-mm sheet for X-ray diffractometer and dilation measurements. The wires were annealed in wet hydrogen for 6 hr at 840°C and 15 hr at 720°C, and then quenched into 0°C water. A chemical analysis for carbon after this treatment gave 0.0046 + 0.0014 at. pct C. Three portions of these wires were subsequently held at 719°C in three different hydrogen + methane mixtures and then quenched, resulting in carbon concentrations of 0.0283, 0.0598, and 0.1067 at. pct C by chemical analysis. After carburizing, the wires were swaged to 0.48 mm and electroplated with silver to prevent carbon loss during subsequent heat treatment. The final heat treatment consisted of holding the wires at 72 1°C for 5 min in a He-2 pct H mixture followed by quenching into 0°C brine. The wires were held at room temperature for a few minutes to remove the silver plating using a phosphoric acid-hydrogen peroxide solution, and then stored in liquid nitrogen until the measurements were made. EXPERIMENTAL TECHNIQUE A) Dilation Measurement. The dilatometer consisted of a gas-atmosphere vertical tube furnace modified so that length changes of a ribbon-shaped specimen could be measured externally. This was done by installing a gas-tight mercury seal at the top of the furnace as shown schematically in Fig. 1. The specimen (21.0 cm long, 1.27 cm wide, and 0.25 mm thick) was suspended in the center of the furnace by 3-mm-diam quartz rods with the upper one passing through the cap of the mercury seal. Above the cap, the upper quartz rod was coupled to a lever exerting a load of about 25 g (-12 lb per sq in.) on the specimen and having a 10 times mechanical magnification. The vertical position of a marker at the other end of the beam was read with a traveling microscope with a precision of 0.01 mm. The temperature gradient of the furnace was meas-

Jan 1, 1968

By J. L. Huitt, B. B. McGlothlin, J. J. Day

Laboratory tests were made with pure minerals and actual reservoir rock samples to study the effects of hydrothermal (steam m hot water) treatments on reservoir rock properties. These tests showed that hydro-thermal treatment of many reservoir rocks can result in significant rock softening. The softening was attributed primarily to the partial destruction of dolomite and kaolinite and the synthesis of montmorillonite in the presence of excess silica. In many cases, the softening was great enough to cause considerable healing of propped fractures; therefore, a serious reduction in welt productivity could result. In other tests it was found that the addition of ammonia to a hydrothermal treating fluid in a concentration as low as 0.013 Ib/lb of water not only could prevent rock softening but could cause rock hardening. The results of X-ray diflraction analyses of rock samples showed that when ammonia was added to the treating fluid, ammonium-mica and analcite were formed instead of montmorillonite. No significant permeability damage was observed in the sandstones that were subjected to the ammonia-hydro-thermal environment; in some sandstones, permeabifity improvements resulted. INTRODUCTION As the use of steam or hot water becomes more prevalent in well stimulation methods. the need for information on the effects of such treatments on reservoir rock properties becomes increasingly apparent. Several works have been published on high-temperature changes in rock properties,',' but these are more applicable to in situ combustion operations than to steam or hot water injection processes. The mineralogical literature contains many publications which report on the changes occurring with various pure minerals in hydrothermal systems. A review of this literature denotes the ease with which entirely new, crystalline mineral phases can be synthesized from other minerals in hydrothermal environments at temperatures, pressures and residence times typical of those encountered in oilfield thermal recovery or stimulation processes. Discussions of many of these experiments are given by Deer et al. Grim,' Roy et al., Zen\ and Hawkins.' One of the most significant of these pure mineral studies is the hydrothermal synthesis work of Levinson and Vian" in which montmorillonite was synthesized from naturally occurring minerals; i.e., kaolinite, quartz and carbonate minerals (particularly dolomite). These reactions occurred at 575F in only 2 days and at 300F in 5 days. These results may be applicable to petroleum reservoir rocks since the minerals studied were those which are commonly found in sandstones. Furthermore, the environmental conditions imposed in the studies were very similar to those involved in thermal stimulation of petroleum reservoirs, e.g., steam or hot water injection. Other studies have suggested that weak rocks could be hardened by "electrochemical induration", a process in which an electric current is applied to a clay-containing rock body. These tests can be regarded as hydrothermal treatments since they were conducted in some instances with aqueous solutions and since clay temperatures during the electrical treatment reached a maximum of about 100C. Although a number of studies of the reaction of pure minerals have been reported, very little has been published on the reactions of petroleum rock-hydrothermal systems. No work has been reported on preventing the more detrimental rock changes in rock softening which might occur during the injection of steam or hot water into reservoirs. The studies described in this paper were conducted to provide such information. EXPERIMENTAL APPROACH The laboratory tests included studies of the effect of hydrothermal treatment on core samples from several different reservoirs. The hydrothermal treatments (simulated steam treatments) were conducted with distilled water at 575F, for the most part, for periods of 2 to 6 days. This temperature level was selected because it represented that temperature which would probably prevail in several cases under consideration for steam injection projects. The core samples, as well as the pure mineral samples, were contained in high-pressure stainless steel, autoclave-type pressure vessels. The effects of the hydrothermal treatments were evaluated by measuring the penetrometer hardness, formation rock embedment strength and permeabilities of the core samples before and after the treatments (Fig. 1)'" In addition, the mineralogical changes in the specimens were studied by X-ray diffraction. Concomitant with the core sample studies, the mineralogical changes were studied in greater detail by conducting hydrothermal synthesis experiments with pure minerals at similar temperature levels and residence times. For the most part, samples of finely-crushed pure dolomite.

By Castle. J. E., J. L. Gillson

In this chapter there is a wide difference in the meaning of some words used for rock and mineral names as defined by scientists and tabulated in the "Glossary of Geology and Related Sciences," published in 1957 by the American Geological Institute, and the meaning as used by the commercial producers of feldspar. It is necessary, therefore, to define these terms giving both the "scientific" and the "practical" definitions. There is no ambiguity about the name feldspar itself. This is a general term for a group of related minerals which are silicates of aluminum, combined with sodium, potassium and calcium. The feldspars are the most abundant minerals of the igneous rocks, and since these rocks make up the largest proportion of the earth's crust by volume (although not of the actual surface area of the continental land masses) the feldspars are the most abundant minerals of all. The igneous rocks themselves are classified on the basis of the variety of the feldspar present. The potash feldspars, which are called orthoclase and microcline, are the dominant minerals of the granites and syenites, and of their fine grained equivalents, the rhyolites and trachites. The plagioclase feldspars form an isomorphic series, of which the sodic endmember is called albite, and the lime endmember, anorthite. The members near the sodic end, albite, oligoclase and andesine are the characteristic feldspars of the granodiorites and diorites, and of their fine grained equivalents, the dacites, and andesites. These feldspars-orthoclase, microcline, albite oligoclase and andesine-are the feldspars used commercially. Labradorite, a member of the plagioclase group, in which the lime exceeds the soda in the chemical composition, is the common feldspar of the gabbros, anorthosites, norites, basalts and other so-called "basic" rocks. Although some attempts have been made to use labradorite as a commercial feldspar, none is now used except as an ornamental stone. The mineral anorthite is very rare. Since the feldspar in most of the common igneous rocks is relatively fine grained, and mixed intimately with other minerals, from which it can be separated cleanly only with difficulty, most masses of the common rocks cannot be used as sources for the feldspar contained in them. It is only the rarer types of rocks in which the feldspar is very coarse-grained, or ones containing very little of the iron-bearing minerals which are objectionable impurities in commercial feldspar, that are quarried to yield an acceptable product. The most widespread type of such a rock from which commercial feldspar can be produced, is that called "pegmatite." These rocks are dikes and bodies of irregular shape and of a size measured in feet or yards in most cases, rather than in miles. They are more commonly associated with granites, rather than with other coarse-grained igneous rocks. Many of them contain crystals of various minerals, including the feldspars, that are much larger than are found in the host rock, the granite, and in many there are large masses of feldspar that are sufficiently free from iron-bearing silicates so that products acceptable to the ceramic industry can be produced, in some cases simply by hand sorting. Most of this feldspar in pegmatites, however, does contain intergrown quartz up to 25 pct. Pegmatites are so important, not only as commercial sources of feldspar, but also of other minerals which are produced com-

Jan 1, 1960

By M. Schmellenkamp

By comparing two longwall operations, one begun in 1956 and the other in 1960, the author is able to demonstrate the increases in production and performance made possible by longwall mining. These achievements have been brought about by continuous development of longwall mining equipment and associated roof supports. Because of this progress, longwall mining is able to provide, under proper conditions, high production per man-shift, remarkable cost savings, dependable roof control, safe working conditions and truly continuous production. It may seem odd that the title of this paper is not simply "Longwall Mining" but instead "Progress in Longwall Mining." However, the word "Progress" definitely has its place in longwall mining. If it had not been for progress in the development of longwall mining equipment and roof supports, the longwall mining method would not be able to compete in production and performance with modem coal mining machines. The longwall mining method was practiced at the beginning of the century and there were several successful operations in coal fields in Illinois. In those early days of longwall mining, the coal was undercut by hand 2 to 2.5 ft at the bottom of the seam and packwalls were built in the gob to support the roof. The roof eventually subsided and the weight of the subsiding roof was used to ride the face and break the undercut coal. Utilizing natural weight to soften the coal face is still practiced in modern longwall mining; however, the packwalling method has been replaced by the caving method and the roof is now supported by yielding steel roof supports and forepoling steel headers. The purpose of these yielding-type roof supports is to provide a safe working area for the crew along the entire longwall face, to permit continuous mechanical mining across the prop free face, and to provide a strong resistance for the roof by forming an even breaking line at the gob for the roof to cave. Roof supports and associated forepoling headers should be kept as close as possible to the face in order to prevent a caving between face and supports, especially under friable roof. This means that the coal should be extracted in small slices, allowing only a narrow roof area to be exposed and unsupported. The coal planer with its relatively high cutting velocity of 75 ft per min provides such an extraction of coal and has proved its high performance under difficult mining conditions. Since 1951, several longwall faces in southem West Virginia and Pennsylvania which have been equipped with the coal planer and friction-type manual roof supports have been successfully operated. Compared to today's longwall mining, these longwall faces required such a large crew, primarily to handle the roof supports, that the actual high production per shift was charged with too high a labor cost, thereby decreasing the tons per man. Yet, even then the longwall faces outperformed the conventional mining system under the same conditions. In order to demonstrate the progress that has been made in the development of longwall mining, a comparison will be made between a longwall face in Arkansas which was installed in 1956 and a modemized longwall face started in 1960 in southern West Virginia. LONGWALL MINING IN 1956 The 320-ft longwall face was developed in a 32-in. thick coal seam near Greenwood, Ark. The method of mining the 320-ft coal block was the advancing system in which three entries on either side of the face were driven ahead of the advancing longwall face. The face was equipped with a coal planer and a Panzer conveyor; timbering was done with wooden timbers and cribs. The roof supports were set without any pattern. The crew to operate the planer and to handle the roof supports (timbers and cribs) consisted of 15 men per shift. During a period of approximately eight monthsof single shift operating time, the average tonnage produced in this relatively low seam amounted to about 263 tons of clean coal per shift. To show the development in the coal plow from then until now, it should be pointed out that the standard plow was used in this operation. The plow was equipped with rigid bottom bits which could not be adjusted if the plow started to climb, thereby leaving bottom coal to be recovered by pick hammers end causing delays in production. The height of the plow

Jan 1, 1963

By T. S. Lovering

The use of geothermal energy is expanding very rapidly. This type of energy has proven commercially profitable for generation of electricity, for space heating, process heating, auxiliary heating of water in conventional steam power plants and for recovery of chemicals contained in natural hot water and steam. Two types of geothermal energy sources are recognized: 1) hot springs in regions of nearly normal heat flow that tap a deep reservoir through which water moves slowly to a hot springs conduit and then rapidly to the surface; 2) hyperthermal areas in which the water is heated by a relatively concentrated heat source related to volcanicity. If there is a geologic trap that provides a geologic analog to a steam boiler, as at Larderello, Italy, the hyperthermal area will have a convecting system that develops superheated water at relatively shallow depth and may provide natural steam in large quantities. If a hyperthermal area is to be productive for a long time, the underflow into the reservoir should be slow enough to allow the heat source and convective system to heat the underflow to the working temperature, and the production rate must not exceed this rate of underflow. A model based on a typical aquifer suggests that the rate of movement of water through the reservoir be such that a few years are spent in transit between isotherms that are spaced about 2°F apart. The possibility of finding blind geothermal areas is illustrated by discussion of the techniques developed in evaluating the subsurface temperatures in the East Tintic district of Utah where a map of isotherms at water level (2000 to 2000 ft below the surface) shows that a hyperthermal area may exist a short distance southeast of the mining district. Very nearly all of the energy that man currently uses comes ultimately from the sun's radiation. This includes water power, fuels such as wood, peat, coal and petroleum, the wind and all our animal power. In the paper summarizing a conference on solar energyl6 the average amount of solar energy received daily on the earth is taken at about 1 cal per m2 per min or slightly less than 2 pcal per cm2 per sec; this is almost exactly the amount of energy on the average that the earth liberates in regions of normal geothermal gradient due to its own internal heating. In many places, however, the energy released is many times the average and in some of these hyperthermal areas, geothermal steam is used for generation of electricity, and hot springs are used for heating buildings and private dwellings, process heating, auxiliary heating of water in conventional steam power plants, and chemicals may be recoverable from both hot water and steam. The use of hot springs waters for heating houses goes back hundreds of years but until recently was confined to a few dwellings close to the hot springs. In Korea, some houses had hot spring water channeled through conduits in the floor centuries ago and thus the Koreans can be credited with pioneer development of radiant heating. In Iceland at present nearly a third of the population uses natural thermal water for domestic heating." The Reykjavik system pipes hot spring water at about 94°C throughout the city and has devised insulated double pipes that allow the water to be piped for some 25 km with a drop of only 1°C for every 5 km. The actual cost to the Icelandic consumer is only one-third the cost of heating by imported coal and yet the industry is one of the most profitable in Iceland. The most profitable use of geothermal energy has been its conversion into electricity which can be transmitted economically much greater distances than hot water. The largest installation at the present time is that at Larderello, Italy, where the Count of Larderello began to experiment in the production of electricity from geothermal steam 60 years ago — in 1904. He installed his first steam turbine, with a capacity of only 250 kw, in 1912 as the result of a local quarrel with the power company which furnished the current required in the Larderello chemical industry - an industry that then dated back nearly a century. As experience was gained in drilling deep holes to tap geothermal steam and in converting it to electric power, the capacity of the installation of Larderello gradually increased, but was all destroyed by the Germans during their retreat from Italy in the closing

Jan 1, 1965

By E. A. Gulbransen, K. F. Andrew

THIS paper. will present the results of our studies on the kinetics of the gas phase reactions of co-lumbium and tantalum with O2, N2 and H2. Studies on zirconium and titanium have been previously reported.9,11 Due to their high melting points and their many excellent physical and chemical properties, colurn-bium and tantalum have been finding their places as useful metals in science and industry. Chemically the metals are very inert to gas and liquid phase corrosion at room temperature. However, at moderate temperatures of 250°C and higher the metals react readily with oxygen and hydrogen. It is of interest to study the gas phase reactions of these metals for the following reasons: (1) to compare the rates of the several reactions with those of other metals and to correlate the rate data with theory and structure predictions, (2) to add basic information on the practical difficulties of the reduction, refining and working of columbium and tantalum, (3) to anticipate new uses for the metals and (4) to understand the role that the metals play as components in high temperature alloys. Literature Survey A number of papers exist in the literature on the gas phase reactions of columbium and tantalum with O2, N2 and H2; however, only fragmentary data have been reported on the kinetics of these reactions. Although the free energy of formation of the oxide Ta2O520at 25°C has been determined and some thermodynamic work has been reported on columbium and its oxides, the data are not sufficient to make equilibria calculations at elevated temperatures. Oxidation: 1. Kinetics: The rate of oxidation of columbium and tantalum has been studied by McAdam and Geil23 using the interference color method. Tantalum is reported to oxidize more slowly than columbium, zirconium and iron. The amounts of oxidation of columbium after 20 hr in air for several temperatures are reported by the Fansteel Metallurgical Corporation.36 Columbium starts to oxidize in air at about 200°C. The oxide is said to be adherent and prevents further oxidation until the temperature is raised. Columbium is reported not to become brittle on heating in air for short periods like tantalum because the oxide film prevents further reaction. The columbium oxides dissolve into the metal when heated in a vacuum at temperatures between red heat and 1200°C. Above 1200°C the oxides are reported to evaporate. Columbium, in the oxide free state, is an active getter in vacuum tubes. 2. Preparation and Structure: G. Grube, O. Kuba-schewski and K. Zwiauer15 have studied the decomposition of Cb2O5 in argon. They find that CbO2 is formed slowly at 1150° and rapidly at 1300°C. Cb2O5 can be reduced to CbO2 by moist H2. The reduction of this dioxide to the lower oxides is rapid. By varying conditions CbO2, Cb2O3, CbO and Cb2O can be formed. CbO2, CbO and Cb2O have independent lattices while Cb2O3 is a stoichiometric mixture of CbO and CbO2. In a later paper O. Kuba-schewski" has shown that CbO is cubic and that CbO2 has a rutile type of lattice. The most exhaustive work on the oxides of columbium is that of G. Brauer.8 The number and constitution of the solid phases in the binary system Cb-O were investigated by the preparative, analytical and X ray methods. He indicates that only the oxides Cb2O5, CbO2 and CbO exist with limited regions of homogeneity. The solid oxide Cb,O, exists

Jan 1, 1951

By R. Schuhmann, G. W. Powell

The concept of local equilibrium is examined and, in particular, the applicability of the concept to two-phase binary diffusion couples is discussed. It is concluded that, if binary solid solutions are treated thermodynamically as ternary solutions, vacancies being the third component, then recent experimental observations of nonequilibrium interface compositions (i.e., compositions different from the phase diagram values) are consistent with a state of complete dynamic equilibrium at the interface. CLASSICAL approaches to diffusion and to other irreversible processes often utilize a postulate of "local equilibrium". That is, one assumes even in the presence of gradients, fluxes, and time changes of properties, a) that the Second Law can be formulated locally, and b) that thermodynamic equations of state among intensive properties are identical with those for equilibrium phases. A direct consequence of this assumption, for example, is that one would calculate the total entropy of a nonequilibrium phase simply by integrating the entropy density (eu per unit volume) over the volume of the phase, assuming that entropy density is the same function of energy and particle density as for equilibrium phases. In the study of diffusion and of diffusion-controlled phase transformations, metallurgists take this concept of local equilibrium for granted and utilize it automatically. In fact, experimental evidence of all kinds is overwhelming that "local equilibrium" is a valid limiting law, approached more and more closely as gradients and rates of change approach zero. On the other hand, we have neither experimental nor statistical thermodynamic proof that this principle of "local equilibrium" should remain rigorously valid at high gradients and for rapid processes. Theoretically, in fact, one would expect deviations because interactions between adjacent volume increments of material affect the evaluation of entropy. Also one observes experimentally structural and small energetic differences between equilibrium and nonequilibrium phases. The purpose of this paper is to present a thermodynamic framework for the study and correlation of deviations from strict local equilibrium in isothermal diffusion and related processes. This procedure, in effect, preserves the principle of local equilibrium by thermodynamically assigning the deviations from static equilibrium properties to a defect component. Although this theory is entirely phenomenological, the possibility does exist of correlating the theory with experimental observations of defects under favorable circumstances. The most immediate application appears to be to the equilibria at the interfaces in two-phase binary diffusion couples. A recent pertinent work by Eifert et al.1 has shown that the concentrations of aluminum in the a(fcc) and B(bcc) phases at the 0-8 interface in Cu:Cu-12.5 wt pct A1 diffusion couples are greater than those given by the phase diagram. It is postulated by these authors that the supersaturation of the o phase at the interface provides the driving force for the a-to-B lattice transformation; the excess free energy of the a phase, ?Gaxs, arising from the greater-than-equilibrium aluminum concentration is about 3 cal per g-atom. On the basis of the schematic free energy-composition diagram shown in Fig. 1, Eifert et al. concluded that the thermodynamic situation at the interface is one of the partial equilibrium; that is, = for the more mobile aluminum whereas will be reexamined in the latter part of this paper. THERMODYNAMIC PROPERTIES OF DEFECTS A rigorous analysis of the thermodynamics of defects requires an added degree of freedom in the Phase Rule sense, because the standard formulations of solution thermodynamics (partial molal properties of components, free energy minimization, equality of chemical potentials, and so forth) involve the implicit

Jan 1, 1970

By Aureal T. Cross

THIS paper is a review of the published literature on research in coal geology, principally exclusive of resource studies, which appeared or became available during 1950 and the latter part of 1949. This report is not to be construed as being complete. The papers referred to in the bibliography are those among many more, which were read either in full or in abstract. Undoubtedly other papers were published' which either escaped the author's notice or were not available to him. Those which were seen in abstract only (about one fourth of those listed) were not available in time for the inclusion of more than a notice. An outline of all papers listed in the bibliography has been arranged by subjects and reasonable subdivisions with some papers cited under more than one subject. Most papers are indexed according to the principal subject of discussion or research only as to an unusual or noteworthy section of the entire report. There will likely be some disagreement as to the quality or merit of some of the papers selected and the specialist may be supercritical of the outline or organization of papers in his field. It may be that attention has occasionally been drawn to papers reporting old information or conclusions of questionable value. Conferences and Meetings One of the best indications of the growing interest in coal geology problems in the United States is the increasing number of times this- field has been the focus of attention at conferences and meetings. Notable among these are the joint meeting of the Society of Economic Geologists and the Geological Society of America at El Paso, November 1949, at which the principal thesis was concerned with low rank carbonaceous fuel deposits, especially of western United States. Among the papers given which are already available were those presented by Barghoorn,16 Parry,180 Roe,153 and Parks.162 At the annual meeting of the Botanical Society of America in New York, December 1949, a joint meeting of the Paleobotanical and Microbiological Sections was held for which a symposium on Microbiology in Relation to the Geologic Accumulation of Organic Complexes was 'organized. Publication of the six papers presented by Ralph G. H. Siu, Elso S. Barghoorn, Irving Breger, Claude E. ZoBell, James M. Schopf, and A. C. Thayson is anticipated. At the regular meetings of the Paleobotanical Section at the same time, several other papers of interest reported on coal ball studies, partial coalification of petrified wood, and floras. In Chicago, April 1950, a symposium on Applied Paleobotany was held by the Society of Economic Paleontologists and Mineralogists in conjunction with the American Association of Petroleum Geologists. The five papers presented at this meeting dealt with the use of Paleozoic plant microfossils for stratigraphic work, J: M. Schopf, Devonian-Mississippian fossils of the black shales, Aureal T. Cross, Mesozoic plants of stratigraphic value, Th. Just, plant microfossils of the Tertiary, L. R. Wilson, and studies of the Brandon lignite, Elso S. Barghoorn. Early publication of these in the Journal of Paleontology is expected. The Nova Scotia Research Foundation and the Nova Scotia Dept. of Mines sponsored an excellent 3-day conference in June 1950, which, dealt with several aspects of coal geology. Papers on coal classification, P. A. Hacquenbard, structure and sedimentation problems in Nova Scotia, T. B. Haites, new techniques of thermal analysis, W. L. Whitehead, geochemical investigations of Nova Scotia coals, Irving Breger, the role of fossil plant spores in coal correlation and the stratigraphy of the coal-bearing strata of the Appalachian Region, Aureal T. Cross, were given. Some discussions of these papers by those in attendance were recorded, and the entire proceedings is being prepared for publication. In September 1950, an unusual 3-day field conference was held by the Ohio and West Virginia Geological Surveys under the sponsorship of the Coal Geology Committee. This study of the stratigraphy sedimentation, and nomenclature of the Upper Pennsylvanian and Permian coal-bearing strata of southeastern Ohio, southwestern Pennsylvania, and northern West Virginia .was augmented by two discussions on associated rocks (clays and shales) and stratigraphic nomenclature at Wheeling, and Morgantown, West Va. An extensive guidebook was prepared, and transcriptions of the Morgantown meeting were made. As a follow-up of the September field conference, a round-table discussion 'was held on this general topic at a special open meeting of the Coal Research Committee in conjunction with the November meeting of the Geological Society in Washington. Short prepared statements to invite discussion were given on each of several topics by L. M. Cline, Carl O.

Jan 1, 1952

By H. S. Thomsen, W. C. Duesterhoeft, R. E. Hartline

The attenuation and phase shift which formations produce in the electromagnetic field of an induction-type electrical well-logging instrument are great enough to substantially affect the response of the tool to formation conductivity under normal logging conditions. The application of the general equations for the propagation of an electromagnetic field in a conductive medium to the transmitter-receiver coil pair of an induction-logging-tool coil system gives an expression for the response which properly takes the propagation effects into account. A comparison of a calculation of this type with the response computed from the commonly used geometric factor concept, which does not include the propagation effect, leads to a factor Go representing the ratio of the responses computed by the two methods. The value of Go decreases not only with increasing formation conductivity, but also with increasing transmitter-to-detector coil spacing. For a single coil pair with a 40-in. spacing, the value of Go is 0.972 in a 20-millimho/m formation. The value is reduced to 0.915 and 0.812 for conductivities of 200 and 1,000 millimhos/m. As a result, the basic signal generated by the induction-logging coil system is not linearly related to formation conductivity as expected from the geometric factor concept. A uniform conductivity scale can be obtained only by adding a suitable nonlinear element to the recording system. The addition of auxiliary coils, having spacings less than the main-coil span, to achieve focusing results in an even greater departure of the basic signal from linearity with conductivity. The solution of the field equations near the interface between two formations of different conductivity gives the curve shape on an induction logging tool in crossing the interface. The addition of auxiliary coils to achieve focusing can add anomalous character to the curve shape in crossing the interface, which might be mistaken for lithological detail. Preliminary calculations which include the propagation effects in the determination of the conductivity correction for thin beds lead to correction factors which are substantially smaller than those obtained from geometric factor considerations. It is apparent that thin-bed corrections derived from geometric factor calculations are of doubtful validity. INTRODUCTION Although the electromagnetic induction type of electrical well log has been used for a number of years and has gained general acceptance in quantitative well-log interpretation, no technically complete investigation of the mechanism and of its operation has been published. The studies which have been presented are based upon the premise that neither the shape nor the intensity of the induction field of the logging tool is in any way affected by the electrical characteristics of the formation. From the inception of induction logging it has been recognized that under some formation conditions the performance of the instrument could be expected to be substantially different from that predicted by the simplified analysis. This anomalous performance has been called "skin effect" since it is the result of the same phenomenon which causes high-frequency alternating currents to flow only near the surface of metallic conductors. In the range of conductivities encountered in the sediments, the formation actually does not exhibit the sharply defined conducting "skin" shown by metals. The gradual modification of the distribution of the currents in the formation, produced by the induction field of the logging tool, is the direct result of phenomena associated with the propagation of the electromagnetic field through the formation. Therefore, it can be much more appropriately described as the "propagation effect". One purpose of this paper is to review the results of a solution of the equations for the performance of a single transmitter-receiver coil pair induction-logging system which takes into account the propagation effect, showing the manner in which the tool performance established by this analysis differs from that derived from the less comprehensive analyses currently in use. PRINCIPLE OF OPERATION OF THE INDUCTION LOGGING INSTRUMENT The high-frequency alternating current which is maintained at a constant value in the transmitter coil

By W. B. Dancy, A. Adams

Laboratory test work on heavy liquid separation of sylvite from halite is reported. Numerous tests were run on sylvite ore sized in the ranges of 4x20 mesh, 10x65 mesh, 8x100 mesh, -8 mesh and -10 mesh with heavy liquids in the range of 2.05 to 2.15 sp gr. From the test results, it was concluded that, with the type of ore under study and a size in the range of -8 mesh, a recovery as high as 90% could be achieved with a product grade of 70% KCl. However, a final product at an acceptable recovery cannot be made with one pass, and the float must either be further processed with heavy liquids or dried and sent to a conventional froth flotation circuit. Potash ores occurring in this country consist essentially of sylvite and halite plus minor amounts of magnesium sulfate salts and montmoril-lonite-type clays. Recovery of potash minerals from evaporite ores in the North American potash fields is accomplished almost exclusively by use of amine flotation. European practice involves froth flotation as well as solution-crystallization processes. Laboratory and pilot plant test work has been reported in Europe and the U. S. on the application of heavy media separation to potash ore beneficiation. Work was probably discontinued because of lack of ore with the required very coarse liberation characteristics (1/8 to 1/2 in. liberation size). Sylvite, with a gravity of 1.99, and halite, with a gravity of 2.17, appear to be ideal for separation by heavy liquids, which are now available in gravities from 1.59 to 2.95. This paper reviews preliminary results obtained from laboratory test work on heavy liquid separation of sylvite from halite. TEST WORK The heavy liquids used in the tests under discussion were chlorobromethane, with a specific gravity of 1.923, and dibromethane, with a gravity of 2.490. These liquids, completely miscible, were combined in the proportions needed to give a mixture having the desired specific gravity. Feed for the laboratory tests was mine-run ore screened to the desired mesh sizes. In conducting the tests, the sample was fed at a constant rate into a stream of heavy liquid and the mixture directed into a small separatory vessel. The float overflowed into a collecting pan while the sink collected in the bottom of the separatory vessel and was removed at the end of the test. Approximately 500 g of feed constituted a charge. Pulp density of the feed was kept low to prevent particle to particle interference in separation. With feed in the range of 8x100 mesh, a pulp density of under 10% solids by weight was found advisable. With coarser feed the pulp density could be carried as high as 15% solids. Time of separation was very rapid. In the case of 4x20-mesh material, separation was effected in 15 to 30 sec; with -10-mesh feed, separation required about 1 to 2 min. SPECIAL EQUIPMENT Since heavy liquids are toxic to varying degrees, all separatory work was carried out in a standard laboratory fume hood. It was noted that complete removal of fumes was not being effected; therefore the hood construction was modified, resulting in a completely satisfactory arrangement for heavy liquid test work. In the interest of safety, details of this fume hood are reported here. Unlike most fumes, heavy liquid fumes tend to settle and flow like water, rather than to rise like a gas. Working on this assumption, a standard water drain was installed in the hood. Across the front of the hood a 1-in. barrier was constructed. In the rear of the hood a false back was installed, with an adjustable sliding door on both the bottom and top of this panel. As shown in Fig. 1, the exhaust fan pulled a vacuum behind the barrier, sucking the heavy fumes from the bottom of the hood. Another addition was the drying box, shown to the right of the hood. This is simply a box covered on top with hardware cloth and connected by a 6-in. inlet to the hood. Sample trays made of fine mesh wire filter screens were found ideal for drying samples. With this arrangement, air flowed completely through the sample and all fumes were drawn into the hood. In use, it was found effective to cover with a

Jan 1, 1963

By E. A. Gulbransen, J. W. Hickman

ONE of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film A comprehensive program has been undertaken to study these phenomena This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C Before the introduction of the electron diffraction technique, it «as necessary to use either direct chemical analyses or X-ray diffraction analyses to determine the nature of the oxide film formed on the metal or alloy Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry In special cases the information obtained may be identical, but in general both view-points are necessary Much of, the early work was carried out on the oxidation of bulk samples where thick films were obtained The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses Although much useful information has been obtained in this manner, little could be learned about the character of the protective oxides during the period when the films were actually protective Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective LITERATURE The oxidation of iron has been extensively investigated by X-ray and electron diffraction Jackson and Quarrell1 found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe304, between 515° and 900°C the stable film was FeO Above the upper change point of iron the oxide was found to be Fe304 prom 400° to 515°C , FeO, Fe304 or a mixture of the two oxides was found Recrystallization of the air-formed film below 400° and above 900°C led to the formation of Fe304 In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described

Jan 1, 1946

By T. D. Tiemann

The chemical and mineralogical composition of Caribbean bauxite ores are described. Extraction of alumina by several processes from both Haiti and Jamaica bauxites is discussed and data presented. IMMENSE deposits of bauxite occur in the Caribbean islands of Hispaniola and Jamaica in the high plateau lands and have been excellently described by 0. C. Schmedeman.' The bauxite occurs as deposits in catchments or etched depressions in Tertiary limestone believed to have been deposited in the Eocene and Oligocene periods.' In appearance both the Haiti and Jamaica bauxites resemble a relatively high iron clay and have indeed been mistaken for such.' They are very soft and friable and disperse readily on vigorous agitation in water. The color range in general is light brown to red. Chemically, the outstanding characteristic of the bauxites is the low silica and high ferric oxide content. The extremely low silica makes them particularly valuable for the production of alumina in the Bayer plant since silica is responsible for the loss of both alumina and soda chemically combined as XNa,OYSiO2,ZAl2O2. The ferric oxide, only traces of ferrous iron are present, offers no interference in the production of high grade alumina. Typical oxide analyses of three types of ore are given in Table I2 and a list of the elements occurring in spectrographic quantities in Table 11." The size of the individual particles in the ore makes successful petrographic examination extremely difficult. The ores contain some relatively coarse grains of heavy minerals such as ilmenite, magnetite, and rutile, but other than occasional crystals of a few microns, the greater portion of the minerals are submicroscopic in size and approach colloidal dimensions. The mineralogic composition of the ores has been investigated by X-ray and differential thermal analysis.' These investigations indicate that the predominant mineral phases present are gibbsite (A1203.3H2O), boehmite (Al2O3.H2O), hematite (Fe2O3), and goethite (Fe2O3-H2O). There is no evidence of the occurrence of diaspore (Al2O3.H2O) in either the Haiti or Jamaica ores, but some type of "amorphous" alumina may be present in some of the bauxites of Jamaica." The temperature stability regions in the alumina-water system have been investigated and are given in recent literature. In the temperature range where the hydrated forms are stable, as determined by hydrothermal bomb methods," ibbsite is the stable phase to 155°C (311°F), boehmite from 155°C (311°F) to 280°C (536oF), and diaspore from 280°C (536°F) to 450°C (842°F). Although quite similar in many characteristics, the Haiti and Jamaica ore show a divergence in mineralogic composition that is reflected in the extractability of the alumina described in later paragraphs. Two principal differences occur in mineralogic composition. The iron-bearing mineral in the Haiti ores is predominantly hematite, while in the Jamaica ores goethite is predominant.4 Directly related to the extraction of alumina are the two minerals, gibbsite and boehmite. Boehmite is relatively high in the Haiti ores and in some of the less soluble Jamaica ores, while gibbsite predominates in the ores in Jamaica amenable to the American Bayer process of extraction. Pedersen and Related Processes In general, all processes for the extraction of alumina involving sintering or fusion of bauxite ores with limestone, soda ash, or a combination of limestone and soda ash followed by leaching, are based on the formation of alumina compounds that. yield alumina soluble in the subsequent leach. The principal idealized reactions in respect to alumina and silica for the three types of processes are as follows: Soda Ash Sinter: A12O3 + Na2CO3 = Na2O-Al2O, + CO2 SiO2 + Na2CO3 = Na2O . SiO2 + CO2 A12O2 + SiO2 + Na2CO3 = Na2O.Al2O8. SiO2 + CO2 Leach (with excess water): H2O + Na2O-A12O3 = 2 NaOH + A12O3 (insolution) H2O + Na2O-SiO2 = 2 NaOH + SiO2 (in solution) Soda Ash— Limestone Sinter: Na2CO2 + A12O3 = Na2O.A1203 + CO2 2CaCO3 + SiO2 = 2CaO . SiO2 + 2CO2 Leach (with excess water): Na2O' A1208 + H2O = 2NaOH + A13O3 (in solution) These latter reactions are the basis of the sinter process currently used for the recovery of soda and

Jan 1, 1952

By D. W. White

The kinetics of isothermal transformation of ß-to-u uranium have been studied over a broad temperature range in alloys containing from 0.3 to 4.0 atomic pct Cr. Two modes of transformation are indicated by the existence of two C-curves in the TTT diagram. The upper temperature mode is regarded as a nucleation and growth mechanism, whose rate is controlled by diffusion of chromium in the ß phase matrix. The lower temperature mode is martensitic in nature. The M, temperature increases with decreasing chromium content, suggesting that the two transformation processes become synonymous in unalloyed uranium. URANIUM metal undergoes two allotropic transformations in the solid state. The a phase, orthorhombic in crystal structure,' is stable from room temperature up to about 665°C. The ß phase, characterized by a complex tetragonal structure,' prevails from 665" to about 770°C. The y phase is body-centered-cubic3 and is the stable modification from 770°C up to the melting point (about 1130"). In uranium of reasonable purity, neither of the two high temperature phases can be retained by quenching. However, the addition of certain alloying elements to uranium makes it possible to retain either the y-uranium phase or the ß-uranium phase at room temperature. Chromium alloyed in small amounts with uranium will permit retention of the ß-uranium phase in a metastable state at room temperature upon quenching from a ß-phase temperature.' From available information' on the equilibrium phase diagram for the U-Cr alloy system (Fig. I), it is to be expected that, however sluggish in its rate, the ß phase in such alloys should decompose eutectoidally to a phase and elemental chromium. It was the aim of this investigation to measure the rate and study the nature of this decomposition as a function of temperature and of chromium content. The investigation was reported in classified literature about five years ago and has recently been declassified for publication. In the meantime, there have appeared the papers of Holden,5 Mott and Haines,".' and Butcher and Rowe8 ealing with the metallography and the crystallography of the ß-to-a transformation in U-Cr alloys. These investigators have confirmed several of the phenomenological observations that will be described in the present paper and have examined in considerable detail certain aspects of the transformation and its mechanism. Although all of these investigations have concerned themselves experimentally with U-Cr alloys for the most part, an important consequence has been a clearer understanding of the nature of the ß-to-a transformation in uranium metal itself. Experimental Procedure This investigation dealt with a series of uranium alloys varying in chromium content from 0.3 to 4.0 atomic pct (0.066 to 0.90 weight pct). On five of the alloys, rates of isothermal transformation from the ß to the a phase were measured over a wide temperature range, leading to the development of TTT (time-temperature-transformation) diagrams. Transformation rates were measured over certain narrow temperature ranges on additional alloys. The alloys were prepared by vacuum melting and casting, using zircon or magnesia crucibles and graphite molds. Electrolytic chromium was used as the alloying addition, and the uranium was Mallin-ckrodt biscuit metal that had been vacuum remelted and cropped to remove many of the nonmetallic impurities that had floated to the top of the ingot. The ingots, 3/4 or 1 in. diam, were reduced in size by swaging. Alloys containing less than about 2 atomic pct Cr were swaged at 250° to 275°C, with initial and intermediate anneals at 550°C after every 75 pct reduction in area. Alloys with higher amounts of chromium were swaged at 550" to 600°C, although at the smaller sizes some of them were reduced by the procedure used on the more dilute alloys. Before use as test specimens, the swaged rods were annealed at 700" to 720°C for several hours, followed by slow furnace-cooling. The purpose of the anneal was to achieve the maximum amount of solution of the available chromium into the ß phase, as well as to remove extensive preferred orientation. The isothermal transformation rates were measured dilatometrically, using a quenching dilatometer and an experimental technique similar to those employed by Davenport and Bain in their original work on the transformation kinetics of austenite in

Jan 1, 1956