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By J. M. McDowell, Morris Muskat

In both production and refining operations of the oil industry many processes are controlled by the gas-liquid phase relationships of the hydrocarbon mixtures of interest. The quantitative behavior of fractionating or distillation columns and stills depends on the changes in the equilibrium distributions of the hydrocarbon components between the gas and liquid phases as the pressure or temperature conditions may vary along the length of the column or as the gross operating parameters and compositions are varied. In oil producing operations the nature and amount of gas phase developed within an underground reservoir as it is being depleted and its pressure declines also involve the basic equilibrium gas-liquid phase interactions. The influence of surface conditions of temperature and pressure and various separation procedures on the nature and amount of stock tank oil and natural gas recovered from a given well stream is likewise determined by the same basic phase equilibrium characteristics of the hydrocarbon systems. Such equilibrium separation of the gas and liquid phases in a well stream is of importance both in establishing optimum separator conditions for obtaining maximum stock tank oil yields and in the general problem of crude stabilization. The phenomena involved in these problems and their quantitative aspects can, of course, be established in each individual instance by appropriate laboratory experimentation. It has been found, however, that by associating with the individual hydrocarbon components functional characteristics de- scribing their individual gas - liquid phase equilibrium behavior, the phase properties of the composite mixtures can be predicted by mathematical computation. These characteristics have been termed "equilibrium constants", or "equilibrium ratios"," and are defined by the general equation: where K, is the equilibrium ratio for the jth component, y, is the rnol fraction of that component in the gas phase, and xj is the corresponding mol fraction in the coexisting liquid phase. Considering the Kj as representing available and measurable properties of the individual components of a mixture, and as defined by Eq. (l), it is readily shown that in a coexisting gas-liquid system the rnol fraction concentrations of the individual components in the gas phase, y,, and those in the liquid phase, x,, are given by the expressions: where the nj are the corresponding rnol fraction concentrations in the composite system, and ng is the mol fraction of the whole which is in the gas phase. The basic unknown in Eq. (2) is n,: which gives the gross separation between the gas and liquid phases. This may be determined in principle by imposing the requirement that the sums of the mol fractions in both the gas and liquid phases are unity, i.e. by the equations: The solution of the equivalent Eqs. (3) lying between 0 and 1, when inserted into Eqs. (2), provides a complete description of the compositions of the coexisting gas and liquid phases. While the Eqs. (3) are essentially equivalent to polynomial equations, such transformations are of little value when dealing with multicomponent sys-

Jan 1, 1949

By Thomas A. Read

THE internal friction of single crystals of metals is affected markedly by a variety of factors, which, according to the literature, are without influence on the internal friction of polycrystalline metals at strain amplitudes less than 10-5. For example, the internal friction of a suitably oriented zinc single crystal is multiplied by a factor of l00 when the vibration amplitude is slightly increased, and the internal friction of a copper crystal is markedly increased by the application of a stress of 30 lb. per sq. in. for one minute. In this paper it will be shown that these, together with the other phenomena associated with the damping of mechanical vibrations in metal single crystals, can be satisfactorily explained, at least qualitatively, in terms of an atomic mechanism that has been proposed for quite another purpose-that of accounting for slip in metals. The extraordinary agreement between the observed behavior of the metal single crystals and the behavior that could be predicted on the basis of this atomic mechanism leads to the belief that the latter is probably essentially correct. If this is so, it follows that valuable information about the slip process in metals may be gained from measurements of internal friction on single crystals. In this paper the results of the only study to date on the damping of mechanical vibrations in single crystals of metals will be presented. EXPERIMENTAL PROCEDURE The internal friction of a material is a measure of the rate at which the energy of mechanical vibrations is converted into heat. The measure of internal friction used in the present paper is the decrement A, which is defined as the fraction of the energy of vibration lost per half cycle. The measurements described here were .made for longitudinal oscillations at a frequency of 33.5 kc. for the copper crystals, and at a frequency of 39 kc. for the zinc crystals. The method used is that of the composite piezoelectric oscillator. The single-crystal specimens are in the form of circular cylinders ¼ in. in diameter and 1 ½ to 2 ½ in. long. The crystal rods are waxed in a V-block and sawed to the proper length with a fine jeweler's saw. The ends of the specimen are ground flat, and one end is cemented with a very thin film of beeswax and rosin to the end of an x-cut quartz rod which is ¼ in. in diameter and 3 in. long. The length of the specimen rod is determined by the condition that its natural frequency for longitudinal vibration be the same as that of the quartz rod, within 0.5 per cent. The lengths of the specimens are thus different for different orientations of the cylinder axis with respect to the crystallographic axes. When the specimen and quartz rods are thus matched in frequency the adhesive is at a node of stress, and it has been shown experimentally that under these circumstances

Jan 1, 1941

By Thomas A. Read

The internal friction of single crystals of metals is affected markedly by a variety of factors, which, according to the literature, are without influence on the internal friction of polycrystalline metals at strain amplitudes less than 10-5. For example, the internal friction of a suitably oriented zinc single crystal is multiplied by a factor of ioo when the vibration amplitude is slightly increased, and the internal friction of a copper crystal is markedly increased by the application of a stress of 30 lb. per sq. in. for one minute. In this paper it will be shown that these, together with the other phenomena associated with the damping of mechanical vibrations in metal single crystals, can be satisfactorily explained, at least qualitatively, in terms of an atomic mechanism that has been proposed for quite another purpose—that of accounting for slip in metals. The extraordinary agreement between the observed behavior of the metal single crystals and the behavior that could be predicted on the basis of this atomic mechanism leads to the belief that the latter is probably essentially correct. If this is so, it follows that valuable information about the slip process in metals may be gained from measurements of internal friction on single crystals. In this paper the results of the only study to date on the damping of mechanical vibrations in single crystals of metals mill be presented. Experimental Procedure The internal friction of a material is a measure of the rate at which the energy of mechanical vibrations is converted into heat. The measure of internal friction used in the present paper is the decrcment A, which is defined as the fraction of the energy of vibration lost per half cycle. The measurements described here were made for longitudinal oscillations at a frequency of 33.5 kc. for the copper crystals, and at a frequency of 39 kc. for the zinc crystals. The method used is that of the composite piezoelectric oscillator. The single-crystal specimens are in the form of circular cylinders M in. in diameter and I 1/2 to 21/2 in. long. The crystal rods are waxed in a V-block and sawed to the proper length with a fine jeweler's saw. The ends of the specimen are ground flat, and one end is cemented with a very thin film of beeswax and rosin to the end of an x-cut quartz rod which is 1/4 in. in diameter and 3 in. long. The length of the specimen rod is determined by the condition that its natural frequency for longitudinal vibration be the same as that of the quartz rod, within 0.5 per cent. The lengths of the specimens are thus different for different orientations of the cylinder axis with respect to the crystallographic axes. When the specimen and quartz rods are thus matched in frequency the adhesive is at a node of stress, and it has been shown experimentally that under these circumstances

Jan 1, 1941

By Ramesh Malhotra, Hubert E. (Deceased) Risser

THE WORLD Coal, as a source of energy and as a source of coke for the smelting of iron ore, has contributed significantly to the development of every major industrial nation of the world A number of other materials-oil, natural gas, wood, waste materials, water, and, in some applications, nuclear materials -can be used satisfactorily for the generation of heat and energy, but no generally acceptable and economic substitute has been found to supplant coke in iron ore smelting in conventional blast furnaces. In the development of many nations, coal provided the initial source of energy for industrialization Although coal provided more than 60% of the world's energy each year between 1902 and 1929, oil and natural gas have surpassed it as a source of energy in more recent years (Ref. 38, pp. 439, 441). Despite the rapid rise in importance of other fuels, a considerable amount of the total energy consumed is still supplied by coal. In 1972, coal supplied 32.1 % of the total world energy (Ref. 49, pp. 2-3). To produce this energy, 2.4 billion metric tons of coal were consumed-a 16.0% increase over the amount consumed in 1962. A further worldwide increase in the amount of coal used to supply energy is projected. According to Dr. Karlheinz Bund (Ref. 37, p 145), by the year 2000 world coal consumption could amount to 5 billion mt. Coal Resources and Production The world's coal resources are estimated to be about 10,872 billion mt. Of this amount, 1,297 billion mt are classified as measured reserves (Ref. 50, p. 57). In Table 13.A.1 the estimates of measured reserves and total resources, recent production, and the ratio of measured reserves to production of major coal-producing countries are shown. About 90% of the world's total coal resources are estimated to be in the USSR, the United States, and China. The United States ranks second in the world in coal resources, but in measured reserves, it ranks first. Because of the difference in rate at which available coal resources are being exploited, the ratio of measured reserves to actual production varies widely among areas and countries. France and East Germany have the lowest reserve to production ratios, 49.5 and 60.1, respectively. In Mexico, where currently less than 5 million mtpy of coal are produced, the ratio is 1257 For all countries producing more than 200 million mtpy of coal (except East Germany), the ratio ranges from 350 to 670. For the United States, the ratio is 669.7. In Table 13.A.2, distribution of the world's coal resources by area is shown. More than 97% of the total resources lie in the northern hemisphere, with Asia, including European USSR, having 63.4%. Only 1.9% of the total coal resources are estimat-

Jan 1, 1976

By N. A. Zeigler

GRaphitization phenomena occurring in solid cast iron have principally been studied from the angle of the reactions taking place during annealing of white castings in the manufacturing of malleable iron. The selected bibliography at the end of this paper presents the high spots of the published information in this field. Graph-itization of gray iron upon reheating has received much less attention, primarily because only on rare occasions is this material subjected to any kind of industrial heat-treating. Moreovcr, articles made from gray iron are seldom used commercially at temperatures when any graphitization can take place. When used in such conditions, it is assumed that the articles can be replaced at frequent intervals, which can be afforded because of the low cost of gray iron. However, there is at least one commercial process in which articles made from gray iron, during their manufacturing processing, are subjectcd to rather high temperatures; that is, manufacturing of cast-iron enamelware, which is glazed at about 1600° to 1700°F. (870' to 930°C.) From practical experience, it has been found that one of the convenient and economical compositions of gray iron suitable for enameling is, in round figures, as follows: Si, 2.50 per cent; Mn, 0.35; S, 0.07; P, 0.80; T.C., 3.35; C.C., 0.70. Since this iron usually is cast into thin-walled sections, the percentage of com- bined carbon in it is relatively high. Upon heating in the enameling furnaces, this combined carbon graphitizes, which causes permanent dimensional changes of the articles. Obviously, from practical considerations, it is desirable to maintain these dimensional changes as constant as possible. In the course of experimentation with this iron, two series of experimental heats were prepared in which the manganese to sulphur ratio of the standard cupola metal was offset by ladle additions of: (I) progressively larger amounts of sulphur, and (2) progressively larger amounts of manganese. Each one of these ladle charges was cast into experimental plates 8 by 4 in. and about 5/16 in. thick. All told, 13 ladle charges were thus treated. All of them are listed in Table I, together with their chemical analyses. It may be noted that the manganese to sulphur ratio in these samples ranges between 1.2 and 30.2. Every one of these compositions was subjected to thermal allalysis, using an automatic, self-recording differential dila-tometer. The specimens used in this instrument are 50 mm. long and 4 mm. in diameter. During the dilatometer cycle they are kept under a vacuum of about 3 microns. Each one of them was subjected to a thermal cycle by heating it to I830°F. (1000°C.) in 3 hr. and cooling to room temperaturc in 5 hr. Figs. I, 2 and 3 present three automatically recorded dilatometer curves for irons: Serial No. I (normal composition), Serial No. 6 (high sulphur), and Serial No. 13 (high manganese). All three of these figures are

Jan 1, 1945

By AIME AIME

WAR undoubtedly accelerates metallurgical progress, although its most obvious effect is a tremendous waste of materials. The necessity for restrictions in normal uses of metals results in a search for substitutes or for enhanced properties that will make a limited supply last longer. An insatiable demand for more metal to be produced more quickly favors trial of new processes, new metallurgical tools, and new methods of fabrication. Greatest advance is made, of course, in practical physical and process metallurgy. Theoretical or fundamental research necessarily must take a secondary position, and is so regarded in this review. It is not that developments in theoretical physical metallurgy are lacking entirely, but, following the same trend noted in other countries as they entered war activities, attention in the U.S.A. has been shifted strongly to those developments having an immediate practical application.

Jan 1, 1943

By D. J. Brown

Froth flotation is now used to recover millions of tons of fine coal,(-1/2 mm), every year. For example, in Great Britain, 4-million tons of flotation concentrate was produced in 1960, about 3% of the mechanically cleaned out- put and 2% of the total salable output. Coal flotation is not so widely practiced in the U. S. as it is in Europe since much American coal occurs in thick seams of high grade and does not require cleaning. However, in the U. S., as elsewhere, the increasing mechanization of coal mining machinery has lead to a lowering in size and grade of product from the mine and to an increasing need for cleaning of coal to improve the grade before sale. With an increasing proportion of fines in the product, froth flotation has assumed a greater importance as a cleaning process for coal. In the last three years, over 40 flotation plants have been put into operation in the Appalachian area of the U. S.80 Fine coal recovered by means of froth flotation may be used as a powdered fuel alone or mixed with coarser grades. The removal of this fine coal from washery water makes possible the recirculation and re-use of the water and also leads to improved and more consistent operation of jigs and other separating machines which function less effectively when there is a build-up of fine solids in the washery water. Finally, froth flotation is of assistance in the production of a clarified effluent which may be discharged from the washery without polluting local rivers, streams, or wells. The 1961 cost of installing a new coal flotation plant in Great Britain would be about $19,000 per ton of dry solids input per hour, including the cost of new buildings and coal and shale filtration and water clarification equipment. The figure for the gravity concentration of the large coal, the main plant, would be about $4,800 per tph. The operating cost for the new coal flotation plant would be about $1.10 per ton. Even at this level of cost the cleaning operation is economic in Great Britain for coking coals. In the U. S., a froth flotation cost of 14$per ton of cleanfilter cake was quoted early in 1958 for one operation,l though admittedly this was a special case. Assuming a cake moisture con- tent of 30%, it is estimated that this cost is equivalent to a figure of 256 per ton of dry solids input, for the incorporation of coal flotation in an existing washery. A cost oh 416 per ton of concentrate was quoted76 in a recent analysis of flotation economics, this cost being brought up to $1.11 per ton after payment of royalty, welfare and association dues and taxes. Capital cost was $120,000 for a plant producing 133 tpd of concentrate. Before considering the treatment of coal by flotation it is appropriate to survey some of the properties of coal which are of importance in the process.

Jan 1, 1962

By Walter B. Lenhart

Introduction and Importance of the Industry Sand, as described in this chapter, is a crude product used for ballast on railroads and highways, and as the fine aggregate in concrete, mortar, plaster and in asphalt paving materials. The sand used in glass, as a molding sand, and as a source of silica is described in Chapter 43. Sand and gravel together constitute the mineral raw materials of largest volume produced from the earth. In 1958, as reported by the U.S. Bureau of Mines,21 680,080,000 tons of sand and gravel (including industrial sand) were produced in the United States. The nearest competitor was crushed rock of which 532,818,000 tons were produced. Coal, both bituminous and anthracite accounted for only 431,616,689 tons in the same year. In dollar value, sand and gravel were exceeded only by cement, crushed rock and fuels. Hence it is a major unit of the mineral-producing industry. As an example, one plant in California operates around the clock at an average rate of 1,500 tons per hour, and at peak intervals has shipped over 4,000 tons per hour, all by trucks. Nevertheless, it is controlled by one man through a panel of push buttons that control the crushing, screening, washing, grading, stock piling, and reclaiming of the products. Because sand and gravel are low-valued commodities, but are used in every construction undertaking in every city, village, farm, dam and highway, they are produced in almost every county in the United States and southern Canada, by thousands of individual operators, very few of whom operate in more than one community. Many operations, particularly those established to supply the needs of major dams that are under construction, or of major segments of new highways, are temporary in nature, and the equipment installed is more or less portable. Because of the bulky nature of sand and gravel, there is very little interstate movement, and almost no exports or imports, except a little movement back and forth across the border of the United States and Canada. First, the material needs definition. Definitions Sand and gravel have been defined as continuously graded unconsolidated materials that appear in the earth's surface as a result of the natural disintegration of rocks. Both normally appear together, but in a wide variety of sizes, types and range of size classification. The American Society for Testing Materials has tentatively revised its definition of "sand" as: granular material passing the 3/8-in. sieve and almost entirely passing the No. 4 (4760-micron) sieve and predominantly retained on the No. 200 (74-micron) sieve, and resulting from natural disintegration and abrasion of rock or processing of completely friable sandstone (ASTM Designation C 58-55T). The Society's tentative revision of its definition of "gravel" is: granular material predominantly retained on the No. 4 (4760-micron) sieve and resulting from natural disintegration and abrasion of rock or processing of weakly bound conglomerate (ASTM 125-55T). Sand and gravel deposits contain materials from the finest silt to the largest boulders. Chemical definition of the two materials is nearly impossible. Sand and gravel always are

Jan 1, 1960

By W. M. Fox, D. P. Detwiler

IN the course of research on semiconducting inter-metallic compounds, it became necessary to obtain gallium metal of greater purity that that available commercially. Several methods were considered for further purification, including acid leaching,' fractional crystallization,' and zone-refining.3-5 The method of fractional crystallization was discarded as being equivalent to zone-refining in purification but inefficient in material and time. Both acid leaching and zone-refining were tried, and the method finally adopted is a combination of the two. The acid leaching technique has been reported' to produce gallium in which no impurities are detectable spectroscopically. Although this method is very effective in removing oxides and surface contaminants, semiconducting material made of gallium subjected only to leaching indicated little reduction in the concentration of metallic impurities. Zone-refining, however, appears very effective in removing trace metallic impurities, but comparatively ineffective in removing the surface oxide film. Consequently, the method evolved consists of acid leaching to thoroughly clean the surface, followed by zone-refining to remove metallic impurities. The low melting point and relatively high thermal conductivity of gallium introduce some difficulty in maintaining frozen and molten zones in zone-refining. To accomplish this, it is found necessary to reduce the effective ambient temperature by circulating ice water in coils about the regions that are to be kept frozen, while heat is supplied to the molten regions by resistance coils. The power supplied to the heating coils is regulated by a constant-voltage transformer and a variable autotransformer. Both heating and cooling coils are mounted on a transite base. The gallium ingot is held in a closed pyrex tube sliding inside the heating and cooling coils, the reciprocating method of Tanenbaum et al. being employed to move the molten zones through the ingot at a rate of 2 in. per hr. This apparatus is shown in Fig. 1. The results of a spectroscopic analysis f a zone-refined ingot, as well as of the material as-received and after acid leaching, are shown in Table I. The ingot was 32 cm in length, and received 37 molten-zone passes, the molten zone being about 4 cm long. The only impurity found was lead, the following elements being reported also as checked but not found in the pure material: Al, Sb, As, Ba, Be, Bi, B, Cd, Ca, Cr, Co, Cb, Cu, Ge, Au, Fe, Mg, Mn, Mo, Ni, Pt, Si, Ag, Na, Sr, Sn, Te, Ti, W, V, Zn, and Zr. There thus appears no indication of pickup of Al, Mg, or Si from the pyrex boat as reported by Zimmerman' in his fractional crystallization. Thus it appears that definite removal of lead from gallium occurs during the zone-refining process. It also may be concluded that a more sensitive analytical procedure than spectroscopy is required to evaluate quantitatively the purity of zone-refined metals. One such procedure which is proposed for use in the near future is the measurement of very low temperature resistivity. Although this will not identify the impurities present, it offers a very sensitive check of total impurity. Acknowledgment This work was supported by the Air Research and Development Command, United States Air Force.

Jan 1, 1956

By P. Beardmore, A. H. Holtzman, M. B. Bever

Specimens of the alloy CU3AU in the ordered and disordered states were subjected to explosive loading at shock pressures in the range from 160 to 475 kbars. The resulting changes in the resistivity, stored energy, microhardness, and microstructure were determined. By comparing the effects of explosive loading on ordered and disordered specimens a separation of structura1 and configurational changes has been made. In the pressure range from 290 to 370 kbars, representing a small increment of strain, the degree of long-range order in the ordered alloy decreased sharply. This change is attributed to the generation of shear stresses in excess of the theoretical shear strength of the alloy. Disordered CU3AU under explosive loading behaves in a manner considered to be characteristic of fee solid-solution alloys generally. The response of metals to high-velocity deformation and, in particular, to explosive loading has attracted much interest in recent years.' In general, metals are substantially strengthened by the passage of shock waves although the permanent strains are small. Explosive loading induces this strengthening by causing the metal to undergo rapidly a transient strain in a narrow region, first in the shock front and then in the rarefaction wave, which releases the pressure. The transient strain is given by e = 4/3 In V/Vo, where Vo and v are the specific volumes in the uncompressed and compressed states.2 The process produces many defects, which account for the strengthening. For the investigation reported here, an ordered alloy was chosen because it was expected to give sensitive indications of the near-neighbor effects produced by shock waves. The ordered alloy CU3AU was of special interest because of past work on the effects of conventional deformation on this alloy.314 The disordered alloy was included as a standard for comparison and as an alloy typical of a solid solution containing short-range order. The effects of explosive loading were followed by measurements of the resistivity, stored energy, and microhardness, and by metallographic examination. EXPERIMENTAL PROCEDURES Preparation of Specimens. Part of an ingot of the alloy Cu3Au prepared previously4 was cold-rolled with several intermediate anneals in vacuum to a final thickness of 0.042 in. Specimens of dimensions 2.0 by 1.0 by 0.042 in. were machined from this strip. After a recrystallization treatment of 1 hr at 565oC, half of the specimens were disordered by heating in evacuated Pyrex capsules for 1 hr at 460°C and quenching into water. Although they contained short-range order, they will be referred to as 'disordered" to indicate the absence of long-range order. The rest of the specimens were cooled slowly from 380°C to induce long-range order. The grain size of the ordered and disordered specimens was 0.012 mm. Explosive Loading. This was carried out at the Eastern Laboratory, Explosives Department, E. I. du Pont de Nemours & Co., by a driver-plate procedure described elsewhere.2 Two ordered specimens were stacked alongside two disordered speci-

Jan 1, 1964

By Joseph L. Gillson

Bentonite, designating a distinct type of clay, is a young name in mineral nomenclature in the light of the age-old names of most other useful nonmetallics. The earliest references in literature are to "soap clay" (1873) "taylorite" (1888) and finally "bentonite" in 1897, from its occurrence in the Fort Benton series of rocks near Rock Creek, Albany County, Wyoming. Bentonite is a rock term and consists largely of montmorillonite clay. The latter name was proposed in 1847 for a plastic clay found at Montmorillon, France. A clay of apparently identical properties was described by Cronstedt of Sweden in 1788 and a number of other similar clays found in France were given other names in publications from 1853 to 1856. The mineral name montmorillonite was recognized by Dana in 1892. The recognition of "clay mineral" distinctions which led to the present-day classifications of clays by their chief mineral content, dawned in the early part of the twentieth century. Grim6 has aptly said: About 1924, Ross10 and some colleagues of the U. S. Geological Survey began a study of the mineral composition of clays that led to a series of monumental papers on the subject. By the early 1930's what has come to be known as the clay-mineral concept became firmly established in the minds of a great many people actively studying clay materials. The clay mineral concept designates the major clays as kaolins, montmorillonites and illites and by this concept bentonites are now defined as "fine-grained clays containing not less than 85 pct montmorillonite" and a wide variety of clays found all over the world are included in that classification. They could all properly be called "montmorillonite clays" but the common commercial name is bentonite. For a period of over forty years from the time of the earlier discoveries, bentonite was thought to be only the sodium type highswelling clay produced principally in Wyoming. By the clay mineral concept, non-swelling montmorillonite clays also became known as bentonite. In the trade there are two broad divisions-sodium bentonite, often called Wyoming or "western," which expands in water and carries sodium as its predominant exchangeable ion, and calcium bentonite often called "southern," which has negligible swelling and carries calcium as its principal exchangeable ion. There are many intermediate gradations. Properties The mineralogy and chemistry of the clays are so complex that the subject cannot be summarized briefly. The reader is referred to Chapter 12 of this volume in which the subject is treated at some length. Grim6 gave the formula for montmorillonite as (OH)4Si8AL4020.nH2O. He wrote: Montmorillonite is composed of units made up of two silica tetrahedral sheets with a central alumina octahedral sheet. . . . Exchangeable rations occur between the silicate layers. . . . The words "tetrahedral" and "octahedral" refer to the coordination number of the cations in the unit cell in the crystallographic lattice. Carroll5a stated: That the montmorillonite structure is the same as that of mica, but the layers are not held together by K+ ions; and water and other polar molecules, such as organic molecules, can enter between the unit layers and cause expansion. Ex-

Jan 1, 1960

By W. R. Davis

This paper presents a sunimary of the results of a study of the Dornick Hills-Springer sand reservoir of the Velma Pool. Stephens County, Oklahoma. The data are of interest because this type of reservoir is unusual in the mid-continent area. The reservoir is characterized by very steep dips and a relatively thick producing section. Its up-dip productive limit is defined by truncation of the productive sands, and the down-dip limit is defined by deterioration of sand quality rather than by the presence of an oil-water contact. The crude oil is of 29" API gravity, is relatively viscous and was saturated with dissolved gas at the original reservoir pressure. Consideratiqn of the physical characteristics of the reservoir indicates that natural water encroachment will be negligible, and that the producing mechanism will be a dissolved gas drive augmented by gravity drainage. Performance to date tends to confirm this. INTRODUCTION It is the purpose of this paper to present some of the features of the Dor-nick Hills - Springer sand reservoir which are unusual in mid-continent operations. The study was undertaken in an attempt to define the producing mechanism or mechanisms that will control reservoir performance, as an aid in determining well completion and production practices. GEOLOGY The reservoir under consideration is a series of sand bodies of Pennsylva-nian age found in the Lower Dornick Hills and/or Springer formations. For the purpose of this paper, the sand series is referred to as the Dornick Hills-Springer sand. This sand series lies on the northeast flank of the Velma anticline, and dips very sharply to the northeast in TWP 1S-5W, the average dip being about 45º. However, as shown in Fig. 1. the trend of the pool swings eastward in TWP 1S-4W with a coincident de- crease in dip angle. In this portion of the pool the average dip is about 25". Faults in Sections 30-1S-4W and 32-1S-4W are shown in Fig. 1. These faults show only minor displacements for the horizon contoured in Fig. 1, but they do show a pronounced displacement of the immediately overlying beds. Similar faults are thought to exist in TWP 1S-5W; however, since the detailed geological studies necessary to properly define these faults were not available to the author, no attempt to show them in Fig. 1 has been made. The up-dip productive limit throughout the pool is determined by the truncation of the Lower Dornick Hills-Springer sand. The down-dip productive limit does not appear to be defined by edge water, but by a gradual reduction in permeability of the sands. No dry hole has produced a significant volume of water from this sand section. There was a small gas cap in TWP 1S-5W. Most of the wells in TWP 1S-SW encountered an oil sand 70 ft to 150 ft thick, a shale 20 ft to 80 ft thick, and another oil sand 50 ft to 130 ft thick. A few scattered wells in this area encountered other and bodies below these

Jan 1, 1951

By Edward Martinez

The reactions occurring in the copper segregation process were studied by heating mixtures of chryso-colla, salt, and a reducing agent. The techniques used in this investigation were differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). The initial chloridizing of the oxide copper occurs below 500°C and cupric chloride may be the compound formed. Volatilization and reduction of the copper chloride take place above 550°C, although these reactions do occur to some extent below 550°C. A difference in the distribution of the metallic copper in the reducing agent was found when sodium chloride was used compared to magnesium or calcium chloride. Segregation was obtained with mixtures of cupric oxide, salt, and charcoal with no quartz or silicate present. Preliminary tests indicate that segregation may occur even in the absence of water vapor. The DTA and TGA techniques were found to be of great value in studying these reactions. The copper segregation process is a method for treating oxide copper ores. The ore is heated, most commonly in a kiln, with a reducing agent and a halide salt, generally sodium chloride, to approximately 700°-750°C and held for 30 to 60 min. The addition of the salt results in the migration and reduction of the oxide copper to metallic copper on the surface of the reducing agent rather than in the original mineral structure. The metallic copper can then be recovered by a subsequent leaching or flotation step.1-4 Experimental work in 1923 on oxide copper ores from the Sagasca mines in Chile led to the discovery of the reduction process. It was found that during the reduction of the copper mineral with coal, at about 700°C, the copper migrated to the surface of the coal instead of remaining disseminated in the ore. The unusual behavior of the copper, which caused it to migrate from the ore particles to the coal, was traced to the presence of a small quantity of sodium chloride occurring in the ore. Further experiments with oxide copper ores proved that the presence of a halide, either occurring naturally or admixed with the ore, caused the copper to migrate from the ore particles and to segregate in the charge. The ratio of salt to reducing agent may vary somewhat, but in general 0.5% to 1.5% sodium chloride and 0.5% to 1.0% coal or coke have been mixed with the ore. Less than stoichiometric amounts of salt are required to convert all the oxide copper to a chloride, so that a cycle of reactions appears to be occurring. Several investigations reported in the literature have proposed reactions to explain the mechanism of the process.5-10 There appears to be general agreement that water is necessary for the reactions to occur; that once the sodium chloride reacts with silica or silicates in the ore, the hydrochloric acid formed will convert the cupric oxide in the mineral structure to cuprous chloride. However, there appears to be a conflict of opinion on the reactions involved in the reduction of the cuprous chloride to metallic copper on the surface of the carbon. Rey has indicated that salt, water vapor, and

Jan 1, 1968

By S. F. Reiter, W. R. Hibbard

A survey of the effect of heat treatment on the room temperature hardness of Fe-Mo alloys has been made. Constant strain rate tensile tests were performed between room temperature and 1800°F. These data were analyzed to determine the effect of temperature and composition on the strain hardening coefficient and strain rate sensitivity. Constant load creep-rupture tests were made on these alloys and the results related to composition and structure. A relation between the high temperature strength of the precipitation hardened alloys and the volume of precipitate has been observed. IN view of the extensive use of ferritic materials at elevated temperatures, it is surprising to note the limited amount of information relating the variables of plastic deformation, i.e., composition, structure, temperature, stress, strain, and strain rate. Hollomon and Lubahn' showed how the several variables of plastic flow might be treated analytically. No data were available on carbon-free iron and its alloys in a form suitable for this analysis. Several German investigations2-" constitute most of the experimental work relating high temperature properties to the constitution of these types of materials. In order to obtain new data, the iron-rich alloys of the Fe-Mo system were selected for detailed investigation for the following reasons: 1—Some of the important effects of molybdenum on the mechanical properties of iron have already been studied.' , 821 2—By suitable heat treatment of selected alloys, it is possible to study strengthening effects of four types: AT -a transformation, B—substitutional, C—precipitation, and D—dispersion of hard inter-metallic compound. Materials and Treatment Four-pound ingots were vacuum cast, employing the same melting schedule previously used.? The raw materials were electrolytic iron and lamp-grade molybdenum. The ingots were forged to l/z in. sq. rod and one portion swaged to 0.350 in. diam rod for the production of 1 15/16 in. long button-head specimens. The button-head specimen blanks were solution treated for 16 hr at 2100°F in hydrogen of —70°C dewpoint and then water quenched. They were subsequently plunge ground to the standard 0.160 in. diam test bar. Micrographs of the solution treated alloys are given in Figs. la through Id. The higher molybdenum alloys contained large equiaxed ferrite crystals similar to those in Fig. Id. A portion of the % in. rod was hot rolled to 0.100 in., sandblasted, and cold rolled to 0.020 in. Strip tensile specimens having a 0.020x0.200 in. cross-section and a 2.25 in. gage length were machined from the sheet. The alloys containing molybdenum were subsequently annealed 1 hr at 1560°F. The iron strip was annealed 4 hr at 1300°F in wet hydrogen. The resultant structures are shown in Fig. 2a through h. The ASTM grain sizes were 1 to 3 as solution heat treated or 3 to 4 as annealed. The chemical analyses of the alloys are given in Table I. Carbon contents were obtained after the heat treatments in hydrogen. Alloy 15.9 pct Mo was tested as a cast alloy.'

Jan 1, 1956

By W. R. Davis

This paper presents a sunimary of the results of a study of the Dornick Hills-Springer sand reservoir of the Velma Pool. Stephens County, Oklahoma. The data are of interest because this type of reservoir is unusual in the mid-continent area. The reservoir is characterized by very steep dips and a relatively thick producing section. Its up-dip productive limit is defined by truncation of the productive sands, and the down-dip limit is defined by deterioration of sand quality rather than by the presence of an oil-water contact. The crude oil is of 29" API gravity, is relatively viscous and was saturated with dissolved gas at the original reservoir pressure. Consideratiqn of the physical characteristics of the reservoir indicates that natural water encroachment will be negligible, and that the producing mechanism will be a dissolved gas drive augmented by gravity drainage. Performance to date tends to confirm this. INTRODUCTION It is the purpose of this paper to present some of the features of the Dor-nick Hills - Springer sand reservoir which are unusual in mid-continent operations. The study was undertaken in an attempt to define the producing mechanism or mechanisms that will control reservoir performance, as an aid in determining well completion and production practices. GEOLOGY The reservoir under consideration is a series of sand bodies of Pennsylva-nian age found in the Lower Dornick Hills and/or Springer formations. For the purpose of this paper, the sand series is referred to as the Dornick Hills-Springer sand. This sand series lies on the northeast flank of the Velma anticline, and dips very sharply to the northeast in TWP 1S-5W, the average dip being about 45º. However, as shown in Fig. 1. the trend of the pool swings eastward in TWP 1S-4W with a coincident de- crease in dip angle. In this portion of the pool the average dip is about 25". Faults in Sections 30-1S-4W and 32-1S-4W are shown in Fig. 1. These faults show only minor displacements for the horizon contoured in Fig. 1, but they do show a pronounced displacement of the immediately overlying beds. Similar faults are thought to exist in TWP 1S-5W; however, since the detailed geological studies necessary to properly define these faults were not available to the author, no attempt to show them in Fig. 1 has been made. The up-dip productive limit throughout the pool is determined by the truncation of the Lower Dornick Hills-Springer sand. The down-dip productive limit does not appear to be defined by edge water, but by a gradual reduction in permeability of the sands. No dry hole has produced a significant volume of water from this sand section. There was a small gas cap in TWP 1S-5W. Most of the wells in TWP 1S-SW encountered an oil sand 70 ft to 150 ft thick, a shale 20 ft to 80 ft thick, and another oil sand 50 ft to 130 ft thick. A few scattered wells in this area encountered other and bodies below these

Jan 1, 1951

By J. E. Hilliard

Isobaric sections of the eutectoid region of the iron-carbon phase diagram have been exgerimentally determined at 35, 50, and 65 kb. The phase boundaries were located by metallographic analysis of specimens quenched after equilibriatwn at known temperatures and pressures. With increasing pres -sure a pronounced decrease in the solubility of FesC in austenite was observed together with a depression of the eutectoid temperature. These two effects resulted in a shift of the eutectoid composition toward a lower carbon content; at 65 kb the eutectoid was at less than 0.2 wt pct C. These results are in qualitative agreement with thermodynamic calculations. It has also been shown by calculations that Fe3C in contact with saturated austenite will be stable with respect to both graphite and diamond formation at all pressures above -3.5 kb. 1 HE investigation described in this article was part of a more general study of the effect of high pressure on transformations in Fe-C alloys. Thermodynamic calculations and exploratory runs made in 1959 at the start of the program indicated an appreciable change with pressure in the phase equilibria of Fe-C alloys. However, the calculations were not considered reliable enought to provide the quantitative information required for the interpretation of the effect of pressure on the kinetics of transformations. An experimental investigation was therefore made to determine a series of isobaric sections of the eutectoid region of the phase diagram at pressures up to 65 kb. EXPERIMENTAL PROCEDURE Materials. Seven alloys with analyzed carbon contents of 0.10, 0.20, 0.38, 0.60, 0.77, 0.93, and 1.20 wt pct C were prepared from Ferrovac" iron and high-purity graphite induction melted in magnesia crucibles under argon. The ingots were hot worked and swaged down to 0.19-in.-diam rod which was then centerless ground to a final diameter of 0.125 in. Samples for chemical and spectrographic analyses were taken from each end of the rods. The prin- cipal impurities were found to be Ni, Al, Co, and Si which were present in amounts up to 0.03, 0.02, 0.01, and 0.01 wt pct, respectively. Specimens were prepared by slicing the ground rods into pills 0.06-in. thick which were silver plated to reduce decarburization during the equilibration. Silver was chosen for this purpose because of its very low solubility for carbon and its mutual immisicibility with iron. High-Pressure Apparatus. The high-pressure runs were carried out in the "Belt" apparatus.' As shown in Fig. 1, this consisted of a cylindrical cell compressed between two Carboloy punches loaded by a uniaxle press. Radial support to the cell was given by the "belt" which was a Carboloy die heavily prestressed by a series of steel binding rings. Laminated gaskets of lava and metal separated the punches from the inner surface of the "belt". A cross-section of the high-pressure cell is shown in Fig. 2. Two specimen pills were located inside a resistance heater of 0.20-in.-diam Nichrome tubing. The ends of the tube were sealed with alumina and lava pills tamped in place after the

Jan 1, 1963

By R. M. Hudson

The removal of nitrogen from a nitrogenized low-carbon sheet steel that contained 0.011 wt pct N was determined during heat treatment in Hz-N, mixtures. TIze process followed a first-order rate law; that is, plots of the logarithm of nitrogen content in steel were linear with the time of treatment at a given temperature. The rate of removal increased with an increase in temperature from 900" to 1300°F. By 1400°F the rate in dry hydrogen had decreased to a value intermediate between the rates at 1200" and at 1300°F; in wet (2.47 vol pct water vapor) hydrogen the rate at 1400°F was less than the rate at 1300°F and nearly the same as the rate at 1200OF. The rate at a given temperature increased as the 3/2 power of hydrogen concentration in the atmosphere. While wet atmosplzeres were generally more effective than the corresponding dry atmosplzeres, the effect of water vapor was much less pronounced than the influence of hydrogen content. NITROGEN is the principal agent in the strain aging of ferrite, the effect of carbon being secondary.' To eliminate the return of the yield point after straining and aging, it is claimed2 that the amount of nitrogen in solution in steel must be reduced to 0.0002 wt pct. Strong nitride-forming elements (titanium, vanadium, zirconium, and aluminum) can act to eliminate strain aging by combining with nitrogen. It is extremely difficult to decrease the nitrogen content in commercial steels to the low level required by conventional coil annealing because of the poor contact between the strip surface and the reactive atmosphere. However, a variety of gas-metal reactions can be effected by use of the open-coil annealing method,3 in which the metal surface is fully exposed to the atmosphere. With this possibility in mind, the Applied Research Laboratory has studied the influence of time, temperature, and atmosphere composition on the removal of nitrogen from low-carbon sheet steel. MATERIALS AND EXPERIMENTAL WORK Samples from a commercial nitrogenized low-carbon steel (0.010 in. thick) in the cold-reduced condition were used. The chemical composition of this steel is given in Table I. The gas mixtures used are listed in Table 11. The moisture content in the "wet" annealing atmospheres was controlled at a +70°F dew point (2.47 vol pct water vapor) by passing the gas mixture through a glass tube packed with a solid mixture of 10 pct anhydrous oxalic acid and 90 pct oxalic acid dihydrate held at 127°F; this technique has been described previously.4 For "dry" atmospheres, the gas mixtures were passed through a cold trap immersed in liquid nitrogen. A hinged-top Hevi-Duty electric furnace was used with a Vycor-glass furnace tube. When the furnace was at the desired temperature, the gas mixture was passed through the furnace at a flow rate between 1.1 and 1.2 cfh; coupons (size 3 by 3/4 in.) of the steel were pulled into the center of the Vycor-glass

Jan 1, 1964

By Leo F. Reinartz

Part III of a four-part series on the history of steelmaking in the US, describes furnace developments, improvements during the last few decades, and the contribution of the AIME. THE invention of the dolomite machine was a great boon to the open-hearth furnaceman. By speeding up bottom making, it helped to increase tons per hour and decrease cost. The first homemade unit was built and operated before 1925 at the South Side works of Jones & Laughlin Steel Corp., Pittsburgh The first commercial machine, similar to those known today, was built for the Donner Steel Co., Buffalo, N. Y., in 1925. Heavy slab buckstays, 6 in. by 15 in., supplanted lighter I-beam buckstays as furnace framework in the middle 1920's. They greatly improved the rigidity of the furnace binding. Although the first sloping back wall had been in- stalled prior to 1920 on a small basic open-hearth foundry furnace at Columbus, Ohio, the impetus to install such back walls universally in ingots shops came after S. Naismith installed the first one on an open-hearth furnace at Illinois Steel Company's South works in June 1924. Before that event, back- wall life had already been improved somewhat by the use of chrome rock or metal-encased basic brick. Here again, these changes heralded major for- ward steps in furnace design, decreased costs, in- creased production, and improved safety and working conditions on the back standing of the furnace. Fuels Up to 1930, a number of different kinds of fuel were used to melt and refine steel in American open hearth furnaces. During World War I, powdered coal was used in a few plants as an open-hearth fuel, but because of the high sulfur and ash content in the coals, many operational difficulties arose. There were also dust, explosion, and accident hazards, so that after the War its use was discontinued. In some steel-manufacturing centers, natural gas was available as a fuel and gave good performance. In most steel-manufacturing centers, operators had to rely on producer gas made from bituminous coals in producer gas houses. Low-sulfur low-ash, high-fusion coals required for the manufacture of such gas were not readily available. The quality of producer gas was uncertain. The gas had to be pre-heated. Maintenance problems connected with the use of this fuel were serious. Tons per hour per month was unsatisfactory. Although petroleum had been first discovered by Edwin L. Drake at Titusville, Pa., in 1859, it was not until the early 1930's that heavy fuel oil residues for open-hearth use began to appear on the market. They were cheap; the calorific value was high, and it was not necessary to pass this fuel through the checkers to preheat it. Various plants began to use such oil as an open-hearth fuel. Others used it in combinations with tar, coke-oven, and/or blast-furnace gases. Because of its low calorific value, blast-furnace gas had to be preheated in the checkers. These fuels were cleaner and more dependable than producer gas. The dirty gas house adjacent to the open-hearth shop was no longer needed, and

Jan 1, 1961

By E. Buehler, J. E. Kunzler

High-pu.1-ity molybdenum has been heat treated, melted, and zone refined and the physical and chemical changes that are produced by these processes have been studied by making resistance ratio measurements. Pronounced effects are observed that are associated with recrystalliza-tion at about 1200°C and with melting. Melting alone is found to result in a substantial purification by the evaporation of impurities such as iron. Zone refining is found to be reasonably effective with four passes producing a three-fold decrease in resistance ratio and a minimum ratio of 0.0003. With the aid of low temperature measurenzents, it has been shown that the build-up of a deposit of the material being zone refined on the radio frequency coil used for heating can lead to contamination of the sample. CONSIDERABLE interest in high-purity refractory metals for the study of mechanical properties has developed during recent years. Also the need for highly pure metals in certain fundamental studies, such as electronic band structure, has become quite widely appreciated. Molybdenum can now be produced with sufficiently high purity to make it attractive for such investigations. The most suitable measure of chemical purity of metals used for many of these studies is its resistance ratio, R,.,o,/Ro, During the purification of molybdenum by zone refining and its subsequent evaluation by this technique, a number of informative observations were made. These observations concern the effectiveness of zone refining, the volatilization of impurities at the melting point, and the recrystallization of molybdenum and appear to be pertinent to other refractory metals. Also, the usefulness of low-temperature resistance measurements as an analytical tool for evaluating the presence of chemical impurities and physical defects in metals is again illustrated. Samples of high-purity molybdenum of known mechanical history were heated to various temperatures between 800°c and their melting point. Resistance ratios of the samples were measured after they had been given a specified treatment. The data were used, along with mass spectrographic analysis, as an aid in interpreting the nature of the processes that occurred in conjunction with each treatment. Changes in the concentrations of chemical impurities and physical defects are typical of things that effect the low-temperature resistivity. SAMPLES The starting material was obtained from Westing-house Corp., Bloomfield, N.J. It was in the form of molybdenum rods, usually 1/8 or 3/16 in. in diameter. These had been previously processed from bars, 5/8 in, in diameter, originally reduced from 4 in. diam arc-cast ingots, by hot swaging at about 1300°c. In the final step, the temperature was lowered to about l lOO°C which resulted in the production of elongated grains. Typical grains were about 0.03 mm thick and 0.6 mm long. The molybdenum was quite pure as is indicated by the results of mass spectro-scopic analysis1 given in Column 2 of Table I. Other nongaseous elements not listed in the table were not detected. ZONE REFINING AND THERMAL TREATMENT OF SAMPLES Several sample rods, 8 to 10 in. long, were zone refined or were heat treated at several temperatures. Both types of operations were performed using 3 me-

Jan 1, 1962

By Jerome Strauss

IN his review of developments in 1943, Gilbert Seil, Chairman of this Committee on Reduction of the Ferroalloy Ores, tabulated the consumption of the alloying metals in relation to the steel production of that year. In the year just closed the approximate tonnage was of the same order, differing only to a minor degree or suffering some correction with more precise figuses available, as indicated in the following estimates: Consumption Metals in Tons Steel 92,000,000* Manganese 700,000 Silicon 200,000 Chromium 200,000 Nickel 75,000 Molybdenum 20,000 Tungsten 8,000 Vanadium 1,700 Titanium 1.600 Boron 10 `Production figure. The technologic studies instituted during 1942 and carried forward with such great vigor during 1943 continued into 1944 although in some instances were brought to a close either by completion of the specific development

Jan 1, 1945