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By E. W. Newman

During 1943 and 1944, there was an urgent need for certain grades of optical calcite (Iceland spar) for instruments for ' military uses. To find a supply of this material, prospecting was carried out in Montana, California and Colorado. Although some production was obtained by the work in California, the best results were from prospecting the large calcite veins of south central Montana. The bulk of the optical calcite mind during World War II has come from that area. The Bureau of Mines took an active part in the search for optical calcite in Montana. It examined most of the known calcite veins in the 70-mile distance between Wilsall, on the Shields River: and Absarokee, on the Still water River, and conducted exploration on several of the deposits. The Geological Survey also took an active part by mapping many of the veins. Actual mining of the calcite was performed at first by Calcite Operators, Inc., and later by the Metals Reserve Co., through an agent. A sorting plant was established at Clyde Park, where custom material could be sold. These activities stimulated mining by private operators. To be suitable for military uses, the calcite mined had to meet rigid specificstions as to both size and quality. Individual crystals had to be clear and transparent and if in the form of rhombs had to measure at least 7/8 in. on each edge. Some color and a few inclusions in the calcite were allowable, but material with incipient or developed cleavages, or showing twinning other than parallel to the base, was unacceptable. History of Deposits The existence of large veins of calcite in south central Montana has long been known, and for many years the farmers of this region have used the common vein calcite for producing grit for chicken feed. According to reports, the fist optical calcite produced from Montana came from the Cartwright deposit near Grey-cliff,' but until recently the mining of optical calcite in Montana has been limited to spasmodic searching for small crystals suitable for making nicol prisms for saccharimeters and microscopes, or for mineral specimens. The possible need of substantial amounts of optical calcite for military uses began to appear late in 1942 and early in 1943, therefore the Polaroid company began searching for a source of supply in Montana and California. Work on the Wade property near Clyde Park was started on a small scale in the fall of 1942, by .4. H. Hansen, of Clyde Park. During the winter and spring of 1943, a modest quantity of optical calcite was mined and shipped to the Polaroid Corporation, Cambridge, Mass. Most of this was produced from the "Hansen vug," which was found close to the surface. Early in the summer of 1943, mining on the Wade property was undertaken by Calcite Operators, Inc., a company organized for mining optical calcite from the

Jan 1, 1948

By E. W. Newman

During 1943 and 1944, there was an urgent need for certain grades of optical calcite (Iceland spar) for instruments for ' military uses. To find a supply of this material, prospecting was carried out in Montana, California and Colorado. Although some production was obtained by the work in California, the best results were from prospecting the large calcite veins of south central Montana. The bulk of the optical calcite mind during World War II has come from that area. The Bureau of Mines took an active part in the search for optical calcite in Montana. It examined most of the known calcite veins in the 70-mile distance between Wilsall, on the Shields River: and Absarokee, on the Still water River, and conducted exploration on several of the deposits. The Geological Survey also took an active part by mapping many of the veins. Actual mining of the calcite was performed at first by Calcite Operators, Inc., and later by the Metals Reserve Co., through an agent. A sorting plant was established at Clyde Park, where custom material could be sold. These activities stimulated mining by private operators. To be suitable for military uses, the calcite mined had to meet rigid specificstions as to both size and quality. Individual crystals had to be clear and transparent and if in the form of rhombs had to measure at least 7/8 in. on each edge. Some color and a few inclusions in the calcite were allowable, but material with incipient or developed cleavages, or showing twinning other than parallel to the base, was unacceptable. History of Deposits The existence of large veins of calcite in south central Montana has long been known, and for many years the farmers of this region have used the common vein calcite for producing grit for chicken feed. According to reports, the fist optical calcite produced from Montana came from the Cartwright deposit near Grey-cliff,' but until recently the mining of optical calcite in Montana has been limited to spasmodic searching for small crystals suitable for making nicol prisms for saccharimeters and microscopes, or for mineral specimens. The possible need of substantial amounts of optical calcite for military uses began to appear late in 1942 and early in 1943, therefore the Polaroid company began searching for a source of supply in Montana and California. Work on the Wade property near Clyde Park was started on a small scale in the fall of 1942, by .4. H. Hansen, of Clyde Park. During the winter and spring of 1943, a modest quantity of optical calcite was mined and shipped to the Polaroid Corporation, Cambridge, Mass. Most of this was produced from the "Hansen vug," which was found close to the surface. Early in the summer of 1943, mining on the Wade property was undertaken by Calcite Operators, Inc., a company organized for mining optical calcite from the

Jan 1, 1948

By John M. Campbell, W. E. Portman

A series of correlating charts have been prepared to enable the field engineer to predict the amount of stock tank fluid produced by stabilization of first stage separator fluid. The charts shown are particularly convenient for estimating the relative effect of temperature and pressure in economic studies. Further work is planned to investigate the factors affecting stage separation' yo supplement this preliminary work. The direct correlation of separation variables is dictated as a convenience to eliminate the trial and error calculation necessary when using the standard flash vaporization equations. These are obtained by a material balance using the equilibrium vaporization ratio K, and have appeared in the following, or similar. form many times in the literature. where La = mols of any component n in the separator liquid Ko — equilibrium vaporization ratio for any component at separator pressure and temperature Fa = mols of any component n in the feed Vn = mols of any component n in the vapor V = total mols of separator vapor These equations may of course be effectively and accurately solved by use of digital and analog computers. However, these are not usually readily available in field offices and the need often arises for fast results during routine operational problems. Consequently, many methods have been devised in an attempt to simplify the basic calculation.2-14 The methods proposed are generally satisfactory, but do not eliminate trial and error methods and the necessity of subsequent calculations to obtain the answer in volume terms. The purpose of this work. therefore, was to develop accurate charts that would give the result directly in gallons. When using stage separation the recoveries would be lower than those shown, for stabilization usually gives about 95 + per cent recovery on the potential stock tank components in the separator liquid. The recoveries are shown in terms of a 14 psi Reid Vapor Pressure product which has a true vapor pressure of 14.7 psia at 98°F. Consequently, this product represents a stable stock tank liquid under normal storage conditions. To estimate natural gasoline re- coveries by stabilization the volume shown may be multiplied by 1.20 for 18 Ib RVP natural gasoline and 1.36 for 26 lb RVP natural gasoline. PROCEDURE The five analyses shown in Table 1 were chosen since they were representative of wellstream compositions often found and had almost the same propanes plus liquid content, expressed in gallons per 1,000 std. cu ft of wellstream. The distribution of the components though is widely variant. A temperature range of 0-100°F. and a pressure range of 200 to 1,250 psia was chosen inasmuch as most separations fall within these limits The K values used were modified values of those originally published by Katz and Hachmuth.' In the range chosen these have generally given good results when predicting fluid recoveries. The choice was somewhat arbitrary, for the authors' personal experience has shown that

Jan 1, 1957

By C. M. Shigley

The record of the largest magnesium plant in the country utilizing sea water as a primary raw material stands as another victory in the struggle for large-scale production of pure chemical elements from the oceans. Bromine was the first element to be economically and commercially recovered when, in 1933, a six million pound per year unit was built on the Atlantic Coast near Wilmington, North Carolina, by the Ethyl-Dow Chemical Co.' The bromine was reacted with ethylene to produce ethylene dibromide, a necessary associate of tetraethyl lead in ethyl antiknock fluid. Within eight years that plant was doubled and redoubled, and another large unit was put into operation at Freeport, Texas, taking bromine from the Gulf of Mexico. In 1940, in fortunate anticipation of the impending demand for magnesium and the limitations of the production from natural brines, the Dow Chemical Co. turned again to the sea, and designed and erected a plant at Freeport to produce 18,000,000 lb. of magnesium per year from sea water.2 In March 1941, two months after the new plant had been put into successful operation, construction of an 18,000,000-lb. Government-financed addition was started. Late in 1941, as a part of the $400,000,000 defense program intended to produce 600,000,000 to 700,000,000 lb. of magnesium per year, Dow was asked to build and operate for the Government a 72,000- ooo-lb. plant near its original plant at Freeport. Within a few days after the Japanese made their attack at Pearl Harbor, preparation of a site was started at Velasco, Texas, for the construction of the Texas plant of the Dow Magnesium Corporation—the largest known magnesium plant utilizing sea water as its raw matcrial. Less than six months after the first piling was driven, urgently needed magnesium was in steady production. Five months later, the plant had exceeded its rated capacity. It remained above rated production until the general magnesium curtailment was applied to Government-owned plants in September 1944. Credit for the construction and operation record of the Dow magnesium plant must be divided among the efforts of a very determined group of men, an extremely favorable location, and a simple process. It is with the two latter aspects of the plant that this article will deal. The site for the new enterprise was chosen near Velasco, Texas, on property bordering the Brazos River at a point approximately 6 miles inland from the original magnesium plant and 7 miles inland from the Freeport Harbor on the Gulf of Mexico. This location was far enough away from the operating units to reduce both interference from construction and the vulnerability of closely bunched manufacturing operations to the then feared air attack. Yet the distance inland was not too great for the economical construction of a barge canal from the harbor to serve both the transportation of raw

Jan 1, 1949

By P. Rama Rao, D. H. Sastry, T. R. Anantharaman

Deformation (a) and twin (a') stacking-fault densities in cold - wor ked filings of fcc silver alloys containing 2, 4, and 6 wt pct Sb have been estimated from Debye-Scherrer peak shifts and asymmetries, respectively. Evidence has been obtained for a possible strain-induced transformation in a two-phase alloy containing 9.0 zut pct Sb. Using Fourier analysis of X-ray line profiles, the effective particle sizes and root mean square strains have been determined for the three fcc alloys in the cold-worked condition. The values of the compound fault probability 0.5a + a') evaluated from peak shifts and asymmetries are in reasonable apeement with those derived from peak broadening. COLD work of fcc metals may produce both deformation and twin (also called growth) stacking faults, which can be detected and quantitatively estimated by X-ray diffraction techniques.' In addition to peak broadening, deformation faults produce a shift in peak positions and twin faults an asymmetry of the Debye-Scherrer reflections. Besides stacking faults, a reduction in the size of coherently diffracting domains and distortion within these also broaden the powder reflections of deformed fcc metals and alloys. Fourier analysis' of peak shapes provides quantitative infor- mation about the effective domain sizes, lattice strains, and also the compound fault probability (1.5a + a'), where a and a' represent deformation-and growth-fault density, respectively. The Paterson method2 for determination of a from peak shifts, the warren3 or wagner4 method for evaluation of a' from peak asymmetries, and the Fourier analysis for quantitative estimates of all the contributory causes of peak broadening have, in the course of the last decade, been extensively applied to obtain data for a number of deformed fcc metals and alloys. One of the useful results of earlier measurements of a in several solid solutions is a correlation between a and the solute valence as well as electron concentration per atom (p) in alloy systems based on a particular solvent. The work of Smallman and westmacott5 on Cu-Zn, Cu-A1, and Cu-Sn, of Foley, Cahn, and ~aynor' on Cu-Si and Cu-Ge, and of Rama Rao and Anantharaman7 on Cu-Si and Cu-Sb has revealed a common trend in the increase of a with p and also a with valency of the solute. Cahn and Davies' and Ad-ler and wagnerg have observed similar trends for silver alloys containing cadmium, indium, and tin. Data on a for silver alloys with a pentavalent solute element are not, however, available. It is primarily to fill this need that the present investigation on Ag-Sb alloys was undertaken. Utilizing the Patersonand Warren methods, values of a and a', respectively, have been determined in three silver alloys containing 2, 4, and 6 wt pct Sb. By Fourier analysis of the broadening of Debye-Scherrer peaks, effective particle sizes, lattice strains, and the compound fault probability (1.5a +a') have also been evaluated.

Jan 1, 1967

The production of bituminous coal in Pennsylvania started a few years after that in Virginia. For forty-five years all the production came from the Pittsburgh bed, and since that time its total output in value has exceeded that of any other single mineral deposit in the world. It has been impossible to separate the outputs of the four counties producing it at that time, as none of it came from Greene County until many years later, and the figures in the first column of Table 49 represent all the coal coming from Allegheny, Fayette, Washington and Westmoreland Counties. The years prior to 1790 are grouped on account of space limitations, they were made in the same manner as the later ones. All outputs have been rounded into hundreds, or thousands of tons because their accuracy does not warrant further subdivision. All figures are net tons, and all represent production and not shipments; this distinction in the early days when transportation facilities were scarce meant a great deal. In the period 1820-1835, more coal was used in salt-making in western Pennsylvania than for any other single purpose, but not a ton of such coal was handled by any transport agency. Later the iron industry used large quantities of local coal without shipment, and other instances can be cited. Prior to 1832, the only means of shipment of coal, excepting by wagons, was by the rivers, and this tonnage was larger than is generally believed. In Table 23, all of the available data about production from the Pittsburgh bed have been shown. After 1844 the river shipments above Pittsburgh are accurately reported by the Monongahela Navigation Company, but its figures do not include tonnage loaded on the river below Dam No. 1, nor that brought down Saw Mill Run. Prior to 1844 no tonnage records were kept although the amount moved was considerable. The information about local production, not shipped, whether used domestically or for manufacturing is necessarily incomplete. Column 7, shipments by railroad, river and canal, includes the figures in column 4, and until at least 1857 are quite evidently too low. The figures in column 9 are largely estimates based on the data shown and prior to 1870, and perhaps later, are much more likely to be lower, rather than higher, than the actual ones. This table was prepared over a period of years, and as additional data were found the revisions necessary were almost always upward. Clearfield County was the next producer in the state, shipments-in small amounts going down the Susquehanna River; some were made later via the West Branch Canal. Railroad facilities became available in 1862, and the growth in production increased rapidly and steadily. All available data and the estimated totals are in Table 24. Butler County began mining a few years after Clearfield, the early output

Jan 1, 1942

By D. H. Turner, F. A. Crossley

The titanium-rich corner of the system Ti-Al-Si has been studied to determine the phase relationships in the temperature interval 600° to 1200°C. Metallographic examination of long time isothermally annealed specimens was the means of investigation. PART of a program on phase relations and transformation processes of titanium alloy systems included the study of the titanium-rich corner of the Ti-Al-Si system. The investigation covered ternary compositions in the range 2 to 8 pet A1 and 0.1 to 2 pet Si and binary compositions in the range 0.2 to 2 pet Si. Temperatures were in the range of 600" to 1200°C. Alloys containing 6 pet A1-0.1 to 0.5 pet Si were investigated down to 400°C. Partial vertical sections are presented for 2, 4, 6, and 8 pet Al. The Ti-Si system has been reported by Hansen et al.' It is characterized by a eutectoid decomposition, ß = ± a + Ti3Si3, at 860°C. The maximum solubility of silicon in a is reported to be about 0.5 pet at the eutectoid temperature. The solubility of silicon in 0 increases from 0.9 pet at the eutectoid temperature to approximately 3 pet at the eutectic temperature, 1330°C. Several investigations in the composition range of interest have been reported for the Ti-A1 system."' These investigations are in agreement on the phase fields, but differ to small extents on boundary positions. However, very recent, and as yet unpublished, findings" " indicate that there are perhaps two phases which occur at lower aluminum contents than the ? (TiA1) phase, and that the solubility of aluminum in a titanium is less than 6 pet. In the present investigation phase relations found are in agreement with the published literature exemplified by the work of Bumps et al.3 Therefore, it is probable that the partial system reported herein is metastable and does not represent true equilibrium. Experimental Procedure High purity Bureau of Mines titanium sponge of 103 Bhn hardness, granulated aluminum shot of 99.7 pet purity, and silicon powder of 99.8 pet purity were used in making the alloys. For the work in the range from 600" to 1200°C, 100 g ingots were prepared by arc melting. Melting losses were negligible and spot checks by chemical analysis showed good agreement between nominal and analyzed results. Nominal compositions are used throughout this paper. Ingots were forged to 3/8 in. rounds and cut into specimens for heat treatment. Isothermal anneals in the range from 600" to 900°C were preceded by solution treatment at 1000°C for 1 hr, followed by furnace cooling to the annealing temperature. Samples were sealed in evacuated Vycor bulbs for heat treatments up to 1000°C. Higher temperature anneals were done with the samples sealed in quartz bulbs under a partial pressure of argon.

Jan 1, 1959

By Nelson Severinghaus

Mineral fillers have been defined as inert materials that are included in a composition for some useful purpose. Because this definition and the scope of this review are not specific-indeed, exceptions abound-accurate total statistics are unavailable. One source estimates the total production in the United States in 1979 at 11.3 Mt (12.5 million st) valued at $534 million, averaging $49.19 per ton. Included are a broad group of minerals-asbestos, barite, bentonite, ground limestone and dolomite, clays, diatomite, feldspar, micas, silica, talc. Additional references will be made to synthetic mineral-derived fillers such as aluminum hydrate, precipitated calcium carbonate, and pyrogenic and precipitated silicas and silicates. A section on related uses at the end of this chapter covers absorbents and filters. Mineral fillers can be included in compounds to accomplish a variety of final results. Hardness, brittleness, impact strength, compressive strength, softening point, fire resistance, surface texture, electrical conductivity, and a host of other physical characteristics may be modified by the inclusion of fillers. These effects are the result of properties of the fillers, including chemical activity, hardness, particle size, shape and distribution, surface structure, color, density, and refractive index. To facilitate an overview of the mineral filler industry, this chapter will review the general usage of fillers, the inherent characteristics that intensify their utilization, and similarly their manufactured characteristics. Major using industries will then be examined in detail. Specific information on deposits and processing for industrial minerals will be found in the appropriate commodity chapter. All of these same minerals have additional significant uses based on their chemical composition or other characteristics. References will be found in other use chapters and summarized in commodity chapters. The chart in Table 1, updated from the 4th edition of Industrial Minerals and Rocks, illustrates the major mineral fillers (both natural and manufactured) and their more important end uses. Use of Mineral Fillers Archaeologists have found that more than 5000 years ago, bitumen used for mortar and waterproofing contained mineral contaminants that acted as fillers. Since that time man has added mineral products to compounds to improve certain characteristics. Perhaps the most common objective of filler usage is reduction of cost of the end product. Certainly the inclusion of a filler that costs 2¢ per 0.45 kg (lb) will reduce the cost of a plastic product whose resin costs 50¢ per 0.45 kg (lb). But the decision to use a specific filler is not that simple. It may "soak up" binder, making a compound more viscous and perhaps preventing its flow into a mold as an injection molding compound, but similarly will give good anti-sag characteristics to putty, caulking compound, or undercoating. Fillers may be incorporated to modify: 1) Cost 2) Physical characteristics 3) Flow characteristics 4) Fire resistance 5) Density 6) Heat conductivity 7) Color or brightness and opacity 8) Hardness, brittleness, impact strength 9) Deformity, viscosity, softening point 10) Processing problems 11) Electrical conductivity 12) Surface texture 13) Thermal expansion characteristics 14) Abrasion resistance

Jan 1, 1983

By N. A. D. Parlee, N. M. El Tayeb

Fe-V alloys with small percentages of vanadium show no deviations from Sieverts' Law up to P~, = 1 atm in the 1600º to 1750ºC region. At somewhat under 8 pct V and up to at least 20pct V, at 1604" and 1661 °C, nitrogen absorption follows Sieverts' Law at low Pn2 values, but deviates from this law beyond critical values of pn2, due to formation of a nitrzde phase of approximately VN composition. The behavior below these solubility limits can be described at all temperatures by the equations: RAO and parlee1 suggested that the nitrogen absorption curve for liquid iron alloys takes the general form shown in Fig. 1 when an alloy nitride precipitate is formed. They showed that the precipitation of 6 titanium nitride from liquid Fe-Ti alloys follows this general scheme and dealt with the general theory involved. Recently, Evans and Pehlke2 reported their research on the precipitation of aluminum nitride from liquid Fe-A1 alloys. Fountain and Chipman's recent paper3 on the precipitation of boron nitride from solid solution contains a fine example of the analogous behavior which they have been studying in the solid state. Researches on the absorption of nitrogen by liquid Fe-V alloys have been described by various authors.1,4-7 Most of this work has been confined to fairly low vanadium concentrations and rather high temperatures because of difficulties variously described as, formation of surface scums, bridging, and so forth. This behavior and the rough thermo- dynamic calculations made by chipman,8 over eleven years ago, indicated that excessively high vanadium concentrations should not be required for vanadium nitride precipitation. It seemed desirable to look for and study this precipitation in order to fill out the thermodynamically interesting nitrogen absorption data on these alloys. EXPERIMENTAL METHOD The general method used was essentially the same as employed by Rao and parlee,1 in which a Sieverts type of apparatus was used and the precipitation of the nitride detected by the "break-point" in the Sieverts' Law line, and by the visual observation of the formation of the new phase on the surface of the melt. There were, however, a few differences in apparatus and technique as described below. The oil manometer used by Rao and parlee' to measure low partial pressures of nitrogen was not employed. The present authors sought to avoid as much as possible the exposure of the liquid alloy to low total pressures of gas during the 6 to 10 hr long runs because of the heavy iron evaporation-loss errors involved. This was achieved, partly by keeping evacuation times to a minimum with fast pumping but largely by the use of two burettes, one for argon and one for nitrogen, and using them to equilibrate the alloy with mixtures of argon and nitrogen rather than nitrogen alone. Each run involved a careful sequence of operations. After melting, de-

Jan 1, 1963

By John P. Dolan, Charles A. Einarsen, GiIman A. Hill

his paper discusses how the following formation characteristics can be determined mathematically from drill-stem test pressure charts: true formation pressures, effective permeability of the entire section tested, well productivities, wellbore damage, and possible detection of barriers (faults, pinchouts, etc.). This paper also presents a practical method for im-mediate determination of eflective permeability and well-bore damage from successful double shut-in pressure tests. A list of recommendations for improving the reliability of drill-stem rest pressures is also presented. INTRODUCTION A drill-stem test is a temporary completion designed to sample the formation fluid and to establish the possibility of commercial production. Early pressure recording devices were used merely to verify proper operation of the testing tool. Until recently the accuracy of the pressure gauges has been insufficient for any reliable quantitative use of the recorded pressures. In view of the need for more reliable formation evaluation and as a result of the recent interest in exploration work employing the concept of hydrodynamic en-trapment,1,2,3,4 better pressure recording gauges are now in use. These devices can record pressure within 1 per cent above 1,000 psig and can detect differential pressures as low as 1/2 psig. In addition to formation pressure, several other reservoir characteristics can be determined from DST charts; namely, well productivity, formation permeability, wellbore damage, and the possible existence of bar- riers (faults, pinchouts, changes in permeability, etc.). This paper presents a practical method to interpret DST pressure charts for formation pressures and many other reservoir properties, a method that has been developed in analyzing approximately 4,000 DST charts during the last five years. The techniques used are a composite of published articles on drill-stem testing5,6, together with well-known pressure build-up analysis methods. THEORY It has been shown7,8 that the following equation may be used for analysis of pressure build-up curves: Po - Pw = 162.6 qu/kh log ( to + ?/?) .....(1) When this equation is applied to the curves obtained in drill-stem testing, the assumptions and boundary con-ditions are more nearly realized than in conventional flow and build-up tests on producing wells. Zak and Griffen9 have recently discussed in detail the use of this equation in analyzing DST charts. One of the problems with DST curves is the lack of reservoir data for precise analysis. Therefore, it is necessary to develop empirical rules and field methods for analyzing DST charts in quantity. For this reason, the empirical methods presented in this paper have been developed, and their derivation is found in Appendices A and B. METHOD USED FOR ACCURATE READING OF DRILL-STEM TEST CHARTS In order to apply the pressure build-up theory to DST charts, it is necessary to obtain a digitized expression for the pressure and time data recorded by the pressure gauge. These data may be either provided by the service company or interpolated by projecting a

Jan 1, 1958

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

It is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investi-: gators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by - experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from IIoo° to 17oo°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxida- tion of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned ' to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,= the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery0 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

It is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investi-: gators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by - experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from IIoo° to 17oo°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxida- tion of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned ' to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,= the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery0 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By L. Burris, G. A. Bennett, P. A. Nelson

Staznless steels ave rrzuch less seuel-ely attacketl by zinc lapov than by molten zinc systems. To determine the applicubility of stainless steels fov equipment items which would be exposed only to zinc vapor, the corvosion resistance of several stainless steels to zinc vapor was investigated in 500-hr- exposuves at 900° C. Two austenilic stainless steels, Types 304 and 3-17, suffered severe intergranular attack. Loss of nickel from these steels and micro-probe crnalyses indicated the probable formation of low-melting zinc-rich phases. Good vesistance to attack by zinc vapor, as determined by metallo-9-rpaphic excr)rtination and physical testing, Loas exhibited by Type 405 stainless steel, a jevvitic steel. Type 440C stainless steel, a tnartensitic steel, although suffering considevable loss in weight, was not structurally weakened. At Argonne National Laboratory liquid zinc and zinc-rich alloys are being employed as solvent media in pyrometallurgical processes under development for recovering and purifying discharged reactor-fuel materials.' Because of the high solubility of most metals in liquid zinc,' there are few metals which can serve as container materials for liquid zinc at temperatures much above the melting point. The poor corrosion resistance of the common metals and alloys to molten zinc has been discussed by Eldred.3 DeKany, Lavendel, and Burris4 tested some of the less-common alloys of the nonrefractory metals and found that they also have poor resistance to attack by liquid zinc and Zn-Mg solutions. Of the metallic materials, only some of the refractory metals such as tantalum, tungsten, and molybdenum and their alloys have shown resistance to attack by liquid zinc.4-7 In the process-development work at Argonne National Laboratory, tantalum and tungsten vessels have been used to hold liquid-zinc alloys. These vessels are housed in stainless-steel equipment, principally to permit maintenance of an inert atmosphere and operation at various pressures. In this experimental work, it has often been observed that Type 304 stainless steel suffers little attack by zinc vapor at temperatures up to about 800 °C. In contrast, severe attack occurs in areas where zinc condenses as a liquid. The extent of attack by zinc vapor on several stainless steels was investigated because there are possible useful applications of stainless steel for equipment items which would be exposed only to attack by zinc vapor. These applications include, for example, housings around processing equipment as indicated above and vapor lines leading from zinc stillpots or retorts to condensers. EXPERIMENTAL EQUIPMENT AND PROCEDURE The experimental procedure consisted in exposing stainless-steel test coupons to static zinc vapor for 500 hr at a temperature of about 900°C. The apparatus, shown in Fig. 1, consisted of a 12-in.-long closed tantalum tube jacketed in Type 304 stainless steel to prevent oxidation of the tantalum. A Zn-10 wtpct Mg* alloy charge of 293 g in the bottom of the

Jan 1, 1965

By Howard A. Meyerhoff

IN western Argentina, in the Province of Mendoza and the Territory of Neuquén, there is a series of solid bitumen deposits which are claimed to be the most extensive in the world. In a linear belt 500 km (311 miles) long, roughly paralleling the axis of the Andes but occupying a variety of positions with respect to the orogenic structures, more than 100 outcrops have been reported. Approximately 70 of these have been prospected, and some mining has been planned or attempted for about half this number. Limited tonnage, high sulphur content, inaccessibility, labor shortages, and disastrous fires have taken a heavy toll among these operations, and in 1947, only 4 deposits were being actively mined, but 8 more were being explored and developed with a view to placing them in production. Inasmuch as these deposits are currently yielding a substantial fraction of Argentina's limited domestic supply of solid fuels, a brief account of the deposits and of the small industry based upon them will provide a commentary on Argentina's fuel problem. CHARACTER OF SOLID BITUMENS The solid bitumens of Mendoza and Neuquén are petroleum derivatives, as is indicated by the following ultimate analysis: [CONSTITUENTS PER CENT Hydrogen6.8 Carbon82.4 Nit.rogenI.6 Oxygen2.7 Sulphur2.2 Ash4.3 100.0] In physical appearance they bear a close resemblance to coal and are commonly called carbón. Their specific gravity has an extreme range of 1.10 to 1.777 in 36 samples weighed, but the average is between 1.14 and 1.24. The material is black, lustrous to dull, with blocky to sub-conchoidal fracture. Though brittle, the purest material is softer than anthracite and exhibits slightly more cohesion. This bituminous material is generally known as asfaltita or asphaltite, but definitive chemical studies indicate that the term asphaltite or grahamite can be applied correctly only to the exceptionally pure material of the Auca Mahuida district in Neuquén. Some other name should be used for the chemically variable bitumens found in all other districts, and the designation "asphaltitic pyrobitumen" has been proposed by Carlos A. S. Piscione.1 At the present time these bitumens, are finding favor as solid fuel and as a gas-producing medium. They yield heat values of 8650 to 9750 cal,2 or 14,500 to 16,750 Btu per pound, and in consequence of their excellent heating qualities and the scarcity of imported coal, they are marketed as far away as Buenos Aires at a price of go to 95 pesos, or approximately $22 to 23, per metric ton. In burning, the material swells and decomposes into solid, fluid, and gaseous fractions which burn violently though nonexplosively. Its combustibility has been responsible for disasters and virtually complete destruction at Mina La Esperanza and Mina Santa Marta, and for minor mishaps elsewhere, as at Mina Escondida in August 1947.

Jan 1, 1947

By H. A. Doerner, F. D. DeVaney, J.B. Clemmer

Production of magnesium metal in the United States during the past decade has increased from less than 600,000 lb. in 1928 to more than 4,800,000 lb. in 1938.1 The growing industry has stimulated interest in methods of production and in sources of raw material. All of the present domestic production is from brines. However, the availability of large tonnages of magnesite in the state of Washington, together with the possibility of cheap power, have created interest in the utilization of magnesite for the production of magnesium metal as well as for other purposes. Magnesite, the carbonate of magnesium (MgCO3), usually is associated with limestone (CaC03) and dolomite (MgCO3. CaC03). It occurs in crystalline and microcrystalline (sometimes termed amorphous) forms.2 The more common crystalline mineral is found in various shades of white, gray, yellow and brown, the colors being due to impurities, chiefly iron. Magnesite has a hardness of 3.5 to 4.5 and a specific gravity of 3.0 to 3.1. It forms rhombohedra1 crystals in the hexagonal system, having a vitreous, pearly luster. The quarries and mines of the Northwest Magnesite Co. near Chewelah, Wash., are large producers of magnesite for refractories. The deposits are extensive, some veins being hundreds of feet wide. The boundaries of the veins are indefinite, and the magnesite is interfingered with dolomite. Calcite, talc, serpentine, quartz and shale are disseminated through the deposits. The quality of the ore cannot be determined by appearance or by simple tests; chemical analysis is required. These features make it difficult to determine the boundaries or total quantity of workable ore.3 Only the higher-grade ores are mined, and a considerable proportion of the magnesite content is discarded by hand-sorting and log-washing methods. After calcining, the sorted product meets the specifications for usual refractory material, as it contains approximately 81 per cent MgO, 7 per cent SiO2, 6 per cent CaO and 6 per cent Fe203 + A1203. A sample of the reject material had the following analysis after calcining: 65.4 per cent MgO, 6.3 CaO, 21.1 SiO2 and 6.5 R2O3. The percentage reported as R2O3 includes compounds whose chlorides are acid-soluble but give precipitates in ammoniacal solution that are ignited and weighed. The more common constituents are Fe2O3, A1203 and TiO2. The sorted magnesite product is not the best grade. even for refractory purposes, and leaves much to be desired for a reduction process. The rejected material contains a large proportion of magnesite. It is apparent that an effective concentration method would yield a higher recovery and a better product. In general, the refractory grade is not suitably pure for other uses. Recent developments in the production of

Jan 1, 1943

By J. M. Smith, D. Kunii, P. Adivarahan

Effective thermal conductivities were measured for seven samples of porous rocks through which gases or aqueous salt solution were flowing, parallel and countercurrent to the flow of heat. The results are analyzed in terms of the contributions of the solid and fluid phases to the total energy transfer. The solid contribution for the sandstone samples studied was found to be a Junction of the porosity and an effective thermal conductivity for the solid phase. The fluid contribution was a function of the Peclet number. Based upon the equations presented, the effective conductivity of the system can be estimated from the properties of the fluid, the flow conditions, and the porosity and pore-size distribution of the rock. INTRODUCTION Heat-transfer characteristics of porous media containing fluids are needed for the design and evaluation of thermal methods of petroleum production. The study reported here considers the problem of countercurrent flow of fluid and heat in sandstone rocks, and is a continuation of previous studies concerned with parallel and radial flow of energy and fluid in both rocks517 and beds of fine particles.6,10 In addition to these earlier works, Asaad,1 Kimura,4 Preston,8 Zierfuss and vlietll and waddams9 have reported effective conductivities for systems filled with stagnant fluids. There appears to be no published data on rocks through which fluids are flowing. The purpose of this study was to present such information and, particularly, to investigate the effects of properties of the rock and the flow rate on the results. The rock samples were naturally occurring sandstones from different locations and were similar to petroleum-bearing formations. The properties of the seven samples showing the range in porosities and permeabilities are given in Table 1. The mean pore sizes were calculated from mercury penetration data by averaging the radius with respect to pore volume. The details of this method and comparison with other procedures for estimating 7 are given elsewhere. Four fluids, nitrogen, carbon dioxide, helium and 10 weight per cent sodium-chloride solution were used with each sample. For Bartlesville sandstone, BA-5, runs were made at mean pressures from 15 to 250 psig using nitrogen. The other measurements were carried out at a mean pressure of 100 psig. The maximum temperature range eacountered was 70° to 300°F. The flow rate of fluid ranged from about 1.0 to 130 Ib/(hr)(sq ft), and this corresponded to a modified Reynolds-number range of 5 x 10-4 to 1.0. The variation in Prandtl number was 0.70 to 4.1. EXPERIMENTAL WORK The equipment consisted of apparatus to supply a constant flow of gas, or salt solution, at constant pressure to the bottom of a vertical test section, and metering and flow-regulation apparatus after the test section. The flow of salt solution was

By J. B. Clemmer, F. D. DeVaney, H. A. Doerner

Production of magnesium metal in the United States during the past decade has increased from less than 600,000 lb. in 1928 to more than 4,800,000 lb. in 1938.1 The growing industry has stimulated interest in methods of production and in sources of raw material. All of the present domestic production is from brines. However, the availability of large tonnages of magnesite in the state of Washington, together with the possibility of cheap power, have created interest in the utilization of magnesite for the production of magnesium metal as well as for other purposes. Magnesite, the carbonate of magnesium (MgCO3), usually is associated with limestone (CaC03) and dolomite (MgCO3. CaC03). It occurs in crystalline and microcrystalline (sometimes termed amorphous) forms.2 The more common crystalline mineral is found in various shades of white, gray, yellow and brown, the colors being due to impurities, chiefly iron. Magnesite has a hardness of 3.5 to 4.5 and a specific gravity of 3.0 to 3.1. It forms rhombohedra1 crystals in the hexagonal system, having a vitreous, pearly luster. The quarries and mines of the Northwest Magnesite Co. near Chewelah, Wash., are large producers of magnesite for refractories. The deposits are extensive, some veins being hundreds of feet wide. The boundaries of the veins are indefinite, and the magnesite is interfingered with dolomite. Calcite, talc, serpentine, quartz and shale are disseminated through the deposits. The quality of the ore cannot be determined by appearance or by simple tests; chemical analysis is required. These features make it difficult to determine the boundaries or total quantity of workable ore.3 Only the higher-grade ores are mined, and a considerable proportion of the magnesite content is discarded by hand-sorting and log-washing methods. After calcining, the sorted product meets the specifications for usual refractory material, as it contains approximately 81 per cent MgO, 7 per cent SiO2, 6 per cent CaO and 6 per cent Fe203 + A1203. A sample of the reject material had the following analysis after calcining: 65.4 per cent MgO, 6.3 CaO, 21.1 SiO2 and 6.5 R2O3. The percentage reported as R2O3 includes compounds whose chlorides are acid-soluble but give precipitates in ammoniacal solution that are ignited and weighed. The more common constituents are Fe2O3, A1203 and TiO2. The sorted magnesite product is not the best grade. even for refractory purposes, and leaves much to be desired for a reduction process. The rejected material contains a large proportion of magnesite. It is apparent that an effective concentration method would yield a higher recovery and a better product. In general, the refractory grade is not suitably pure for other uses. Recent developments in the production of

Jan 1, 1943

By P. B. Crawford, W. L. Huskey

A study has been made to determine the effects of random vertical fractures existing in a reservoir matrix on the effective matrix properties and producing characteristics of a well. The study indicated that short vertical fractures may distort the isopotentials by 1 percent in the vicinity of the fracture. A correlation was developed which showed the effect of fracture density on the producing capacity of a well. The correlation indicated that fracture shape had little effect on producing capacity, but that total fracture length was closely correlated with the producing capacity. Effective values of reservoir permeability were found to correlate closely with fracture density when measured parallel to the direction of flow. INTRODUCTION In reviewing the petroleum literature, it is found that in most analytical solutions of hydrocarbon reservoir behavior the assumption is made that the rock is uniform throughout although core analysis and well logging surveys indicate that substantially all reservoirs are heterogeneous and some are fractured. Only in recent years have investigators studied the effects of reservoir hetrogeneity. Russell1 discussed the effect of fractures in reservoirs. The literature indicates that fractures greatly affect the exploitation of man reservoirs. This is described by Elkins and Skov2 and Little-field et al. 3 Several types of reservoir heterogeneity have been studied by unsteady-state methods. In 1959, Landrum et al. 4 showed that transient phenomena in hydrocarbon reservoirs could be studied by thermal models. pickering5 studied the flow of heat in stratified linear reservoirs consisting of plates of different metals separated by sheets of rubber which were suddenly exposed to a low-temperature source at one end. Cotman6 studied both laterally and vertically heterogeneous thermal model reservoirs with special reference to cross flow. Another type of reservoir heterogeneity involves the presence of highly permeable, circular lenses around or near the wellbore which was studied by Miesch7 using a thermal and a steady-state model. Many studies have been made of the effects of induced hydraulic fractures on well performance. 8-10 Work regarding vertical fractures that exist initially in the reservoir was reported by Givens, et al.11 Since there appears to be little published work on the importance and influence on reservoir performance of fractures that exist out in the rock matrix, this study was conducted to determine the effects of vertical fractures on pressure distribution, producing capacity and the effective permeability of the reservoir rock. The analogy between the flow of electrical current through a conducting body and the flow of fluid in a porous medium provides a convenient method of studying various aspects of petroleum reservoirs. For electrical radial steady-state flow,12 For steady-state fluid flow, With the above analogy, it is only necessary to establish the ratio of the values of the electrical units in terms of the corresponding flow units to make the analogy quantitative. The ratios are shown below.

By David J. Mack, A. H. Kasberg

The transformation characteristics are found to resemble a similar binary alloy. The differences are due to the alpha iron particles. While strength properties of the isothermally transformed alloys are high, ductility is low, resulting in high notch sensitivity. The elastic modulus can be varied widely and correlates with strength. Abnormal grain growth sometimes occurs. A CONSIDERABLE amount of work has been done on the isothermal transformation of high purity aluminum bronzes using the methods pioneered by Davenport and Bain.' The first isothermal study of these alloys was made by Smith and Lind-lief,' but more recently Mack", " and Klier and Grymko5 have continued the work. In commercial aluminum bronzes, one or more elements are always added to refine the ß grain size and to improve the mechanical properties. The effect of these elements on the isothermal transformation has not been reported in the literature. No systematic study of the properties of isother-mally transformed aluminum bronzes has apparently been reported, although adequate information is available on their properties after more conventional heat treatments. The fact that a eutectoid alloy will reject face-centered cubic a during isothermal transformation at appropriate temperatures2'" warrants investigation of the properties of such structures. Another cogent reason for determination of properties is the fact that the modulus of elasticity of the eutectoid alloy varies widely with the nature of the heat treatment." Preliminary experiments7 indicated that a high purity eutectoid alloy would not give reproducible results in property determinations because of ex- cessive ß grain growth during heat treatment, a single ß grain frequently occupying the entire cross-section of a standard test bar. For this reason a commercial aluminum bronze containing iron as a grain growth inhibitor was used. The isothermal transformation diagram of the alloy was first determined. On this basis, the heat treatments necessary to produce representative structures were selected and the properties determined. Material A commercial alloy (Ampco Grade 20) of the following composition was used: Cu, 83.68 pct; Al, 12.31 pct; Fe, 3.68 pct; Ni, 0.28 pct; and Mn, 0.03 pct. This alloy proved to be very close to the eutectoid composition and may be compared with the accepted value of 11.8 pct A1 in the binary Cu-A1 system. Comparison is valid only because of the "negative replacement effect" of the iron? Since traces of excess y² are present, the alloy is slightly hyper-eutectoid. The material was received in the form of 3/4 in. round, hot extruded bars. Specimens of approximately ? in. thickness were cut from this stock and drilled to allow suspension in the salt bath. The structure of the as-received material varied from 5 to 40 pct a + y2* in a matrix of ß. The amount of a + y² present was dependent upon the ß grain size of the extruded material. The coarse grained portions did not form as much a + Y, as did

Jan 1, 1952

By E. W. Newman

DURING 1943 and 1944, there was an urgent need for certain grades of optical calcite (Iceland spar) for instruments for military uses. To find a supply of this material, prospecting was carried out in Montana, California and Colorado. Although some production was obtained by the work in California, the best results were from prospecting the large calcite veins of south central Montana. The bulk of the optical calcite mined during World War II has come from that area. The Bureau of Mines took an active part in the search for optical calcite in Montana. It examined most of the known calcite veins in the 70-mile distance between Wilsall, on the Shields River, and Absarokee, on the Stillwater River, and conducted exploration on several of the deposits. The Geological Survey also took an active part by mapping many of the veins. Actual mining of the calcite was performed at first by Calcite Operators, Inc., and later by the Metals Reserve Co., through an agent. A sorting plant was established at Clyde Park, where custom material could be sold. These activities stimulated mining by private operators. To be suitable for military uses, the calcite mined had to meet rigid specifications as to both size and quality. Individual crystals had to be clear and transparent and if in the form of rhombs had to measure at least 7/8 in. on each edge. Some color and a few inclusions in the calcite were allowable, but material with incipient or developed cleavages, or showing twinning other than parallel to the base, was unacceptable. HISTORY OF DEPOSITS The existence of large veins of calcite in south central Montana has long been known, and for many years the farmers of this region have used the common vein calcite for producing grit for chicken feed. According to reports, the first optical calcite produced from Montana came from the Cartwright deposit near Greycliff,1 but until recently the mining of optical calcite in Montana has been limited to spasmodic searching for small crystals suitable for making nicol prisms for saccharimeters and microscopes, or for mineral specimens. The possible need of substantial amounts of optical calcite for military uses began to appear late in 1942 and early in 1943, therefore the Polaroid company began searching for a source of supply in Montana and California. Work on the Wade property near Clyde Park was started on a small scale in the fall of 1942, by A. H. Hansen, of Clyde Park. During the winter and spring of 1943, a modest quantity of optical calcite was mined and shipped to the Polaroid Corporation, Cambridge, Mass. Most of this was produced from the "Hansen vug," which was found close to the surface. Early in the summer of 1943, mining on the Wade property was undertaken by Calcite Operators, Inc., a company organized for mining optical calcite from the Montana and California deposits. This com-

Jan 1, 1945