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By Richard Downs, Stephen P. Burke

The oxidation of pyritic sulphur associated with coal is important for the following reasons: 1. It is the predominant cause for the formation of acid mine drainage issuing from bituminous coal seams. This drainage pollutes the streams in coal regions, making the water unfit for industrial purposes and causing the disappearance of fish and wild life. As a consequence the movement of industry and especially recreational industry, so important to the population of these areas as an alternative means of livelihood, is impeded. 2. It is instrumental in effecting a series of reactions, which bring about the degradation and ultimately result in the spontaneous combustion of bituminous coal in storage. 3. It contributes to the breaking and shattering of the coal structure and is one of the causes of roof falls and floor lifts in mines. 4. It is the primary cause of the many nuisances associated with gob piles and the refuse of cleaning plants. 5. Its proper control and application might possibly be employed in the preparation of coal to reduce the inorganic sulphur content. The research that has been conducted on the oxidation of the various forms of iron sulphides is extensive and the literature voluminous. Nevertheless, few efforts have been made to determine experimentally and with some precision the mechanism of the reaction under the conditions of its occurrence in bituminous coal mines. It has generally been accepted that the oxidation of pyritic sulphur proceeds according to the reaction 2FeS2 + 2H2O + 7O2 ? 2FeSO4 + 2H2SO4 [1] The ferrous sulphate in the drainage streams is further oxidized by air to produce ferric hydroxide and more acid. Yet the literature fails to disclose any pertinent investigation on the mechanism of this reaction. The present contribution is concerned primarily with this aspect of the problem and while the work to be reported is not yet complete, it has yielded results from which interesting and significant conclusions may be drawn.

Jan 1, 1938

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By G. W. P. Rengstorff, R. B. Fischer

A study was made of the effect of impurities on the bend ductility of cast molybdenum. High purity molybdenum was repared by re-melting under high vacuum. The ductility of "transverse-grain" specimens indicated that intergranular brittleness decreased with an increase in purity of the metal. THE production of as-cast molybdenum with high ductility at room temperature would make working of the metal easier and increase the usefulness of the as-cast metal. Furthermore, a .knowledge of the factors that influence the ductility of as-cast molybdenum might be applied to the problem of making fusion weldments having satisfactory room-temperature ductility. Individual grains of commercial as-cast molybdenum are slightly ductile at room temperature. However, the presence of carbides at the grain boundaries may cause the metal to fracture in a brittle manner. This behavior has been discussed.' The amount and distribution of the impurities in as-cast molybdenum would be expected, from previous research on the metal, to have considerable influence on its ductility. Some effects of oxygen and carbon on the mechanical behavior of the metal were discussed by Parke and Ham,2 Woodside,3 and Zappfe. Landgraf, and Worden.4 Parke and Ham2 found that, if a sufficient number of molybdenum oxide particles were present at the grain boundaries, the intergranular cohesion was reduced to the extent that arc-melted molybdenum would rupture intergranularly during hot forging. They also found that if the oxygen content was less than 0.003 pct, the cast molybdenum was hot forgeable. It is suspected, however, that forgeable molybdenum may contain a small amount of oxide that could reduce the ductility of the as-cast metal at room temperature. Also, there is the possibility of the unfavorable distribution of other impurities having a detrimental effect on the ductility of cast molybdenum. The results of a study of the influence of purity on the room-temperature ductility of cast molybdenum are presented here. Vacuum Arc-Melting to Produce High Purity Mo One way of determining the effect of impurities on the ductility of molybdenum is to prepare and test metal as free of all impurities as possible. Accordingly, the present investigation was undertaken with this in view. Arc melting in high vacuum (less than 0.1 micron of mercury) was chosen as the method for reducing the impurities below the concentrations occurring in commercial molybdenum. Commercial arc melting of molybdenum is carried out at about 50 microns pressure. During the arc melting, carbon and oxygen in the metal react to form carbon monoxide. By virtue of the vacuum process, the partial pressure of carbon monoxide is maintained at such a low value that the reaction greatly lowers oxygen and carbon contents. An excess of at least 0.03 pct C is used in commercial arc melting to insure that the oxygen content will be below 0.003 pct. The excess carbon remaining after the deoxidation step forms carbides on freezing. Some of the carbides precipitate at the grain boundaries and, as will be shown, have an unfavorable effect on the room-temperature ductility. In the present work, only the small amount of carbon (0.003 pct) contained in the commercial powder-metallurgy molybdenum used for melting stock was present. Partial removal of oxygen from the melt probably occurred as the result of the volatilization of molybdenum oxides, or by distillation of oxygen at the high melting tem-

Jan 1, 1953

By Charles S. Barrett

Metallurgists are making use of the stereographic projection to a steadily increasing extent. In the last five years no less than 20 papers in American metallurgical journals alone have employed the stereographic projection; recent books on physical metallurgy, plastic deformation, X-rays and their applications, and crystal structure use it. Mineralogists have used the stereographic projection for many years in the description of symmetry classes and crystal planes, for it presents an accurate, easily understood plot of any angular relations in crystals with all unessential features eliminated (such as the accidentally determined size and shape of crystal faces). In metallography and physical metallurgy the projection is much used for the analysis of markings appearing on polished grains: slip lines, twins, cracks, structures formed by precipitation, magnetic-powder patterns, etch pits, etc. Data from certain types of X-ray photograms are most conveniently analyzed by its use, particularly those for determining the orientation of single crystals or the preferred orientation of grains in an aggregate. Calculations of how to tilt or cut a crystal parallel to a certain crystallographic plane or to reflect X-rays from a certain plane are rapidly carried out. It has been adopted almost universally to the exclusion of other methods by those studying the deformation of metallic crystals, save where the accuracy required is greater than a few tenths of a degree. Any directional property in a crystal or polycrystalline material can be shown on a stereographic projection; for example, the modulus of elasticity, yield point, etc. It has been repeatedly called to our attention that there is need of an elementary explanation of the principles and methods of stereographic projection, covering all the common applications in the field of metallography and physical metallurgy. The following contribution is an attempt to fill this need. The description of each method is supplemented with references to publications in which the method has been used. For convenience to the reader, these illustrative references are chiefly in American journals, particularly the publications of the American Institute of Mining and

Jan 1, 1937

By Henry P. Ehrlinger, James C. Bradbury

Tripoli is a naturally occurring, very finely divided form of silica found chiefly in some midwestern and southeastern states and used commercially as fillers and abrasives. Definitions Tripoli is a microcrystalline, finely particulate, more or less friable form of silica that appears to be the product of leaching of siliceous limestone or calcareous chert. The term was originally applied to a deposit near Seneca, MO, that resembled material of that name found near Tripoli In North Africa (Hovey, 1894). The two deposits were subsequently found to have different physical characteristics -the North African tripoli, now called tripolite, is a diatomite, composed of the siliceous skeletons of microscopic marine plants called diatoms; the Missouri tripoli contains no diatom remains. The term tripoli, however, continued to be used for the Missouri material and is now applied in a general way to most silica deposits similar to it in characteristics and geologic origin. In commercial trade tripoli is commonly understood to designate material from the Missouri-Oklahoma field; silica from southern Illinois, the other major producing area, is referred to commercially as amorphous silica. Each term, however, may be used commercially for material, regardless of place of origin, that has the characteristics or uses commonly ascribed to the material from one or the other major producing area. For example, in the commodity price listings, Engineering & Mining Journal routinely lists under Tripoli, prices "f.o.b. Elco, IL" and "f.o.b. Seneca, MO, and Rogers, AR," and under Silica, amorphous, prices "f.o.b. IL," and "f.o.b. bierks, AR." Amorphous silica, the commercial designation given to southern Illinois tripoli, is, like the term tripoli, a misnomer. Mineralogically, the southern Illinois deposits are composed of microcrystalline quartz, and no amorphous material has been detected during X-ray and scanning electron microscope investigations (Leamnson, Thomas, and Ehrlinger, 1969; Thomas et al., 1970; Keller, 1978). Soft silica is another term that has been applied to Illinois and Tennessee tripoli, presumably to distinguish it from the more compact Missouri material. It has also been used in the ceramic trade to distinguish tripoli from "hard" silica, or silica flour, produced by pulverizing silica sand (Heinz, 1937). Rottenstone, produced commercially in Pennsylvania, is similar to tripoli in that a major constituent is finely particulate silica, and its uses are much the same as those of Tripoli-as abrasives and fillers. The origin of rottenstone also is similar to that of tripoli-decomposition of a siliceous sedimentary rock. The parent rock is defined as a siliceous limestone (Gary, McAfee,, and Wolf, 1972; Thrush, 1968) or as shale. Heinz (1937) quotes a brief statement describing the Pennsylvania deposits -"a black impure shaly limestone grading into black shale"-but does not identify the source of the statement. For convenience, rottenstone is included with tripoli in the reporting of production statistics in US Bureau of Mines (USBM) Minerals Yearbooks. Other materials that have been called tripoli include siliceous deposits in San Bernardino County, California (USBM Minerals Yearbooks, 1934-1941) and in Nevada (Chandler, 1960). These, however, differ in composition and/or origin from tripoli and, therefore, should not be identified by the name tripoli.

Jan 1, 1983

By K. E. Brown, J. P. Brill, T. C. Doerr

A wide range of intermittent gas-lift tests way conducted in a 1,500-ft experimental well through 11/4- and 11/2-in, nominal size tubing. The well was equipped with two gas-lift valves, four Maihak electronic pressure transmitters and surface facilities to measure casing and tubing pressures, temperature, liquid production and the rate and volume of gas injected. For each tubing size, tests were conducted varying the slug length, gas volume injected and liquid viscosity and surface tension. From these tests, an empirical "fallback" or liquid loss correlation has been developed. No general fallback correlation could be obtained, and the correlation is presented in the form of one curve for each slug length of a given liquid and lubing size. A conceptual model has been developed which combines the fallback correlation with equarions which govern liquid slug pow. A mathematical simulation of the model in the form of a digital computer program is used to calculate total recovery, gas volume used and clearance time for a given test. Tubing pressures at the gas-lift valve and at the gm-slug interface are calculated as a function of time. Tubing pressures at the surface during slug clearance ore also calculated. The results compare favorably with the test data and verify the conceptual model. The extent to which the model can be used for other tubing sizes, depths, liquids and gas-lift valves can only be determined with additional experimental data. Data are also necessary so that a fallback curve can be constructed for the particular test conditions studied. INTRODUCTION The flow of liquid slugs in vertical conduits has long been an established production method in the petroleum industry. Under the name "intermittent gas lift", many advances have been made in engineering design. However, the unsteady-state nature of liquid slug flow has discouraged attempts to describe the problem analytically. The result has been that intermittent gas lift is dominated by rules-of-thumb engineering practices developed over many years. The advent of slim-hole completions has increased the demand for a more rigorous solution to the intermittent problem. Small-diameter conduits offer more frictional per intermittent cycle. Small-diameter conduits are defined to be 1%-in. nominal size tubing or smaller. When oil is produced from the reservoir in which it is found, and transported to surface tanks by intermittent gas lift, three separate flow stages are encountered: flow of the fluids to the wellbore through a porous medium, vertical flow of a liquid slug from the point of gas injection to the surface, and horizontal flow of the liquid slug through the surface flowlines from the wellhead to the surface tanks. The three stages are depicted schematically in Fig. 1. The present study deals with liquid slug flow in both the vertical and horizontal conduits, ending when the bottom of the liquid slug reaches the surface. Due to the large number of variables involved, the analytical study of intermittent gas lift is extremely complex. The possibility of flow regimes other than slug type, the nature of the force fields acting on the system, the interfacial instabilities involved, the varying operational principles of existing gas-lift valves and the complete unsteady-state nature of the physical phenomena occurring in an intermittent gas-lift cycle relate some of the difficulties encountered.

By P. G. Shewman, T. L. Wilson

Using published surface-diffusion (D,) data and published sintering equations, it is shouln that surface difusion should dominate the neck-growth stage of intering for all materials in which D, has been measured (six metals and A1as). Also, grain boundary diffusion can be expected to contribute appreciably to shrinkage and possibly to neck growth below some critical temperature of the order of 70 pct 01- the absolute melting temperatuve. In view of the widespread conclusion in previous sintering work that volume diffusion dowzinates neck gvowth, experiments were conducted using spherical copper powders to test this conclusion. Scaling studies on neck growth at 950°and 1020°C clearly demonstrated that suyface diffusion dorninates. Kinetic studies on shrinkage gave more equivocal results that indicated an increasing role of' grain boundary transport at lower temperatures. Five diarszeters from 100 to 300 u were used in the scaling sludy and a temperature range of -650' 10 950 C was covered in the shrinkage studies. All experiments were conducted in dvy hydrogen. In 1949, Kuczynski published his now classic paper on the determination of the transport mechanism in sintering from the time laws of neck growth. In the interim, these laws have been applied to many systems and slightly modified by several authors. Essentially all these authors concluded that, for crystal- line materials, the dominant transport mechanism in neck growth is volume diffusion. This stems from the observation that the neck radius increases about as t"5 and that the activation energy approximates that for lattice diffusion. A related but independent series of studies stems from Mullins' rigorous analysis of the growth of the groove formed where a grain boundary meets a free surface." xperimental work stemming from this analysis has shown that for each crystalline material studied (Au, Ag, Cu, Ni, Fe, Pt, Al2O3) surface diffusion was clearly the dominant transport mechanism for groove widths up to the order 10 to 20 p. The ratio of the quantity of material being carried by lattice diffusion to that carried by surface diffusion increases linearly with the groove width, so surface diffusion is dominant for all widths under 10 to 20 u. The analysis of the relative contributions of surface and volume diffusion to grain boundary grooving, and to neck growth in sintering, shows that they are quite similar. Thus, using the available surface-diffusion data and the approximate equations of Kuczynski, or the more rigorous recent equations of Nichols and Mullins, 3 it can be shown that the small necks between particles must grow almost entirely by surface diffusion. The purpose of this study was to re-examine the basis for the conclusion that the neck-growth stage of sintering proceeds by volume diffusion. Using spherical copper powders, of several different diameters, precise experimental measurements were made of both neck growth and shrinkage. Application of Herring's scaling laws to the neck-growth data clearly indicated that neck growth occurred by surface transport, even though the neck radius increased as or Using the recent analysis of Mullins and Nichols as well as published data on surface diffusion, it is shown that the observed time law, as well as actual rate of neck growth, can be satisfactorily explained by a surface-diffusion mechanism.

Jan 1, 1967

By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös' law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963

By H. G. Schneider

The Smackover oil and gas field lies in Ouachita and Union Counties, Ark., in the south-central part of the state, in T.15 and 16S., R.15, 16, and 17W. It is 10 miles north of El Dorado, the principal business and railroad center in the south-central part of the state, and extends from the town of Smackover in all directions. Productive territory having an aggregate area of nearly 55 sq. mi. has been developed. It extends 6 miles from north to south and 12 miles from east to west. The field may be divided into two parts: the east district, which includes the area east of the town of Smackover, and the west district, which includes the area west of the town of Smackover. In relation to the neighboring productive fields of Arkansas, the Smackover field is 9 miles north of the El Dorado oil and gas field, 8 miles slightly west of north of the East El Dorado oil and gas field, and 16 miles east of the Stephens oil field. Smackover was discovered in May, 1922, when the Oil Operators Tnist drilled well No. 1 on the J. T. Murphy farm, in the southeast quarter of sec. 8, T.16S., R.15W. This well is located almost on the top of the Norphlet dome and was drilled to the Nacatoch sand. It had an initial open flow volume of 30,000,000 cu. ft. of dry gas per day, and a rock pressure of 950 lb. per sq. in. In July, 1922, the V. K. F. Co. completed the first oil well in sec. 29, T.l5S., R.l5W., on the north side of the Norphlet dome, and 3 miles north of the first gas well. This well started the active development of the north and northwest sides of the dome.] The field was extended westwards, when oil was discovered in the Nacatoch sand, during October, 1922, in sec. 4, T.l6S., R.l6W., 51/2 miles west of the original gas well. This opened up the so-called "light oil district," which is located on a structural terrace, for which the name

Jan 1, 1924

By Harold Roast

THE object of this investigation was to compare the arsenical antimony-lead alloy with some of the regular bearing-metal alloys. With this end in view, the following tests were made: 1. Chemical analyses to show the composition. 2. Thermal analyses. 3. Macroscopic examination of fractures. 4. Microscopic examination. 5. Tensile tests. 6. Crushing tests. 7. Scleroscope tests. 8. Brinell tests, at temperatures from 80° to 400° F. Tests 3 to 8 were conducted on both sand-cast and chill-cast specimens. For the purposes of this paper the alloys have been numbered from 1 to 6; their composition is as follows: LEAD, ANTIMONY, TIN, COPPER, ARSENIC, NUMBER PER CENT. PER CENT. PER CENT. PER CENT. PER CENT. 1 82.64 12.95 4.40 0.01 none 2 27.54 9.94 59.87 2.65 none 3 77.65 20.75 none 0.13 1.47 4 82.95 16.85 none 0.20 none 5 83.78 15.35 none 0.05 0.82 6 0.15 7.87 84.13 7.85 none The analysis, in the case of the antimony, was made by solution in sulfuric acid and titrated with permanganate. For tin, the ferric-chloride method was used; for copper, the alkaline separations, and the thiocyanate methods; for arsenic, volatilization of arsenic and titration with iodine. The lead, with the exception of alloy 6, was taken by difference.

Jan 2, 1922

By F. O. Shuck, F. E. Butler

A diaphragm diffusion cell suitable for use with liquid metals was designed and tested by measuring the diffusion coefficients for a Hg-10 pct In alloy at 25°C. The binary diffusion coefficient and the coefficients for In and Hg tracers were measured at this composition. The measured coefficients for both tracers were less than the binary diffusion coefficient. When these coefficients were combined with the activity correction term of Darken, the predicted binary coefficient was somewhat higher than the experimental value. In recent years a number of investigators have been studying diffusion of liquid metals in order to gain a better understanding of the liquid state and to examine possible applications to liquid metal processing. The bulk of this work has involved either self-diffusion or diffusion of low concentrations of solute metals in an essentially pure solvent metal. The most common experimental technique employed has been the capillary-reservoir method of Anderson and saddington1 since it is well-suited to measurements involving low concentrations of solutes. As an expansion of previous studies, an investigation of the variation of diffusion coefficient over large composition ranges has been undertaken in this laboratory. Although it is possible to modify the capillary-reservoir method for such measurements, the technique loses its principal advantage of requiring only small quantities of solutes. Therefore, it was felt desirable to investigate other possible experimental techniques applicable to measurements over large composition ranges. A technique which has been used widely in measurements of other liquid systems and seemed potentially applicable to studies of liquid metals was the diaphragm cell. This method has been found to combine relative simplicity of operation with accurate and reproducible results. In use with normal liquids, the tyiical diaphragm cell utilizes a porous glass disk. However, because of the high surface tension, it is not possible to use a diaphragm of such fine pore structure with liquid metals. Furthermore. projected use at high temperatures makes the use of glass undesirable. Consequently, the first problem was the search for an appropriate cell design. EXPERLMENTAL Diaphragm Cell. A number of possible cell designs were examined. Prototypes of several were constructed and tested. The final design is shown in an exploded view in Fig. 1. The cell consists of two identical chambers, one on either side of a 0.20-in.-thick partition. The chambers are 0.15 in. deep and have a volume of 3.45 cu cm. Each chamber is provided with two small threaded holes for filling and emptying. The filling holes may be sealed with stainless-steel screws. Drilled lengthwise through the center partition is a 0.250-in.-diam hole. Inserted into this hole is a rod having seven 0.059-in.-diam holes drilled radially through it. The total "hole" volume is 0.078 cu cm. When the rod is properly aligned, the holes in it constitute the "diaphragm" through which diffusion occurs. The center section was of Teflon and the rod and face plates were of Plexiglas. Four such cells were constructed and used in this study. Subsequent to this investigation, a similar cell constructed entirely of iron was fabricated and tested at higher temperatures. Several considerations led to this final design. It is desirable to minimize the volume of the cell chambers to decrease the time required for a measurement. However, the total volume of metal in the diaphragm must be small in comparison with that in the chambers. To facilitate filling and emptying it is desirable to have a diaphragm which may be closed.

Jan 1, 1970

By C. Dirksen

This study investigates whether oxygen consumption during segregated forward combustion may be affected by natural convection. Linear theory indicates that thermal instability occurs in a horizontal porous medium when the modified Rayleigh number N 'Ra exceeds a critical value of about 40. Most experimental results, including those described here, indicate this value to be about an order of magnitude smaller. N ', is derived from "differential similarity" and the proper time scale factor is also obtained. The critical value of N'ra for a horizontal, water-saturated porous medium at atmospheric pressure subjected to a uertical temperature gradient was found to be about 3.0. The ambiguity in the value of N'R, arising when fluid properties cannot be assumed constant is indicated. Natural convection was observed for oblique systems below N 'Ra , while simultaneous horizontal flow did not affect N Racrit. The expected range of values for the various parameters pertaining to segregated forward combustion is indicated and the corresponding values of N 'Ra calculated. Only under very favorable conditions, such as high permeability, high pressure and low top temperature, can the critical value of N 'R, be exceeded. Thickness of the convection layer should not become too large, since the time required to obtain significant mixing is proportional to the square of the thickness. For an oblique combustion frant the conditions for significant mixing may be less strenuous. LNTRODUCTION Laboratory1,2 and field314 experiments have shown that a markedly upgraded oil can be produced by in situ forward combustion. Under certain conditions injected air may move through a high permeability, gas-saturated channel over the oil-saturated layer, while combustion takes place, exclusively, at the horizontal interface (Fig. 1). Such a channel may be a natural gas cap, or it may result from a forward combustion process in which injected air and combustion gases fingered through the top of the formation, causing a premature breakthrough at the production well. In this particular case of segregated forward combustion, the air stream moves parallel to the combustion front. Molecular diffusion and transverse mechanical dispersion will be insufficient to cause all the oxygen in the air stream to reach the combustion front. When the oxygen in the air stream is not completely consumed in the combustion process, it will reach the production well and create a serious fire hazard. In addition, the reduced efficiency may make the process economically unprofitable while also serious corrosion problems may be experienced in the production we11.3 This undesirable situation should, therefore, be prevented. However, in a situation as depicted in Fig. 1, an unstable temperature gradient exists in the gas phase. The combustion is taking place at the lower boundary at a nearly constant temperature that may be anywhere from 600 to 1,200F, depending on the conditions. The upper boundary of the gas phase is overlying, impermeable rock; its temperature might be around 100F, but may increase to 300F or higher due to conduction and convection as the combustion process continues. This represents a steep temperature gradient and it is conceivable that under those conditions free or natural convection will take place in the gas

Jan 1, 1967

By J. M. Woodall

GuAs crystals which have been grown in quartz boats by the horizontal Bridgman method in the pvesence of Ga20 vapov have beetz found to have carrier and donor distributions which do not correspound to those expected from simple dopant seg-vegation during directional freezing; Instead, the carrier distribution is determined by the heat-trentnzent history of the crystal, while the donor distribution, zohiclz is principally due to silicon, is fixed by the pozuth rate, the geo)tlet.ry of the crystal growth vessel, and tlze initial Ga20 pressure. WHEN semiconducting materials are made into doped crystals by the normal freezing method,&apos; they usually exhibit doping variations along the growth axis. If a) there is no dopant diffusion in the solid, b) the dopant is distributed uniformly in the melt, and c) the distribution coefficient, k, does not vary with composition, then the doping variation along the growth axis is represented by the equation: where C is the doping level in the solid at a point where a fraction g of the original liquid has frozen, and Co is the mean concentration. When the dopant is either a singly ionized shallow donor or shallow acceptor, C also represents the carrier concentration. Even though this equation accurately describes the dcping profiles of a large number of normal freeze systems, there are several special systems for which Eq. [I] does not apply. One such system is the horizontal Bridgman method for preparing oxygen-grown GaAs crystals using quartz vessels. Several workers2"* have shown that GaAs crystals grown by the horizontal Bridglnan method using quartz vessels are generally contaminated with silicon in concentrations in excess of 5 < 10lG atoms per cu cm. This contamination is ascribed to a reaction: occurring at the walls of the crystal-growth vessel which liberates silicon into the melt and Ga2O vapor. It has been shown4 that this reaction, and, hence, the silicon contamination, can be suppressed by the addition of oxygen to the crystal-growth apparatus. It is the purpose of this paper to describe a special apparatus capable of yielding single crystals of GaAs grown in the presence of oxygen and to describe both the kinetics of silicon suppression in this system and the relationship between the carrier concentration profile and the silicon concentration profile. EXPERIMENTAL-CRYSTAL GROWTH A schematic diagram of the apparatus used in the oxygen addition experiments is shown in Fig. 1. The most important features of this apparatus are: a) the use of a sand blasted quartz boat, h) a quartz rod of length 1, with a hole of cross section A, that is placed near the boat to limit the free space volume V, over the melt during the growth, and c) the temperature gradient at and near the solid-liquid interface. Sand blasting the boat is necessary to prevent wetting of the melt. The quartz rod retards the diffusion of the GazO vapor away from the melt to the colder portions of the ampoule. A crystal is prepared by first loading a 5.5-in. boat, which has been cleaned in aqua regia, with 40 g of 99.9999 pct Ga along with 1 to 8 mg of Ga203 powder. GazO3 is a convenient source of oxygen since it reacts with gallium at the melt temperature to form Ga20 vapor, the species which apparently controls the suppression of silicon contamination. The loaded boat, the quartz rod, and the 99.9999 pct As are placed in the ampoule as shown in Fig. 1. Generally, GaAs seeds were not used since most of the unseeded growths resulted in monocrys-tals. The ampoule is evacuated to 10-5 Torr and sealed off. The GaAs melt is synthesized by placing the ampoule into a two-zone horizontal Bridgman furnace. The two zones are separated by several sandwiched layers of -in. Fibre-Fax board drilled with holes slightly larger than the OD of the ampoule. This causes a very large temperature gradient between the two zones, which is necessary for single-crystal growth. The two-zone furnace is mounted on a stand fitted with a roller bearing which allows uniform motion of the furnace in a horizontal direction. A uniform velocity of the stand is achieved by the use of a windlass device which winds up a wire attached to the stand. Movement of the solid-liquid interface is accomplished by fixing the position of the ampoule and moving the stand. Growth rates investigated in this experiment were between 0.4 and 1.2 in. per hr. The composition of the melt is fixed by maintaining an arsenic reservoir at 618°C. The stand is moved away

Jan 1, 1968

By Howard N. Eavenson

FROM the Pittsburgh coal bed in the four states of Pennsylvania, Ohio, Maryland and West Virginia has been produced an output that, at mine prices, represents a greater value than any other single mineral deposit in the world has yielded.12 While this distinction may in a few years pass to the gold reef of the Witwatersrand, it is possible that eventually, owing to the tremendous reserves still remaining, the ultimate yield of the Pittsburgh bed will be greater than that of any other known single deposit. Considering its importance, not a great deal has been written of its early history and development as a whole; most of the accounts have been of limited localities, or, at the most, of the area within a single state. In "Coal through the Ages" the writer mentioned some references to its early history, but this study will deal not only with its history but with the character of the bed, where and why it was first developed, and its effect upon the states in which it is found. It has not been the intention to write a detailed history of the development of the seam in each locality, as neither time nor inclination were available for doing such work, but only to show the influences that tended to hasten or retard such development. In general the historical matter ends about 1830, when geological surveys began to be made. Some of the maps show data available only since that time, and the sections about coal preparation and coking have been extended to the present time to show the changing conditions. It is believed that the early history includes all published records, and many more sources than those shown in the bibliography were consulted. It is quite likely that some references to coal in this area may be found in the unpublished papers of some of our early soldiers and colonizers, which exist in several libraries, and it is hoped that some future

Jan 1, 1938

Jan 1, 1943

By G. V. Raymor, James T. Waber, I. Rex Harris

The lattice parameters of a series of fcc alloys of cerium and thorium were measured at 93 " and 298OK. Lattice parameters were also estimated for 171OK. Substantial deviations, y, from Vegard&apos;s law were observed. Although y was negative at the two higher temperatures, it was positive and large at the lowest temperature. A variety of models, which have been proposed in the past, were considered, and the calculated values of y were compared with the observed values. The best agreement was achieved with values computed with Friedel&apos;s equation. THE purpose of this investigation was to determine the effect of temperature on the lattice parameter and on deviations from Vegard&apos;s law of Ce-Th alloys. A large negative deviation from Vegard&apos;s law was first observed independently by Weiner, Freeth, and Raynor&apos; and Van vucht2 in the room-temperature lattice parameters of Ce-Th alloys that form a continuous series of solid solutions. This observation was confirmed by Evans and Raynor. The allotropy of unalloyed cerium was reviewed recently by Gschneidner, Elliott, and McDonald. In two subsequent papers,5" these authors reported the influence of various alloying additions on the y= transformation, which occurs below room temperature. Although other rare earths tend to stabilize the double-hexagonal phase, thorium, plutonium, and scandium as solutes tend to stabilize the normal fcc phase. With addition of sufficient thorium as a solute, there is evidence that the formation of is suppressed and it becomes possible to pass continuously with decreasing temperature from the room-temperature phase to the fcc a phase. Thus there is a closed loop which is similar in many ways to the y loop well-known in ferrous alloys. A closed field also occurs in the pressure-temperature "equilibrium" diagram of unalloyed cerium. Because of interest in the effect of thorium additions and their influence on the a and phases, lattice-parameter measurements were made at low temperatures on the fcc phase for a series of alloys ranging from 10 to 90 at. pct Th. The results obtained at three temperatures are shown in Fig. 1. Evans and Raynors analyzed the deviations from Vegard&apos;s law in Ce-Th alloys in terms of changes in the occupancy of the 4f electron level in cerium,

Jan 1, 1964

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