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By E. B. Hunt

Paraffin deposition has been studied in the laboratory under conditions simulating deposition in well tubing. A theoretical analysis has been made of the cooling of the oil and the precipitation of paraffin from the oil as it flows up the well tubing and through surface flowlines. It is proposed that paraffin deposits are initiated by the precipitation of paraffin directly on or adjacent to the pipe wall and grow by diffusion of paraffin from solution to the deposit. This mechanism is consistent with laboratory and field observations, and has proved useful in the design and interpretation of laboratory paraffin-deposition tests. Tests have been made of the effect of plastic pipe coatings and chemical additives on paraffin deposition. INTRODUCTION Paraffin deposits which form in well tubing and surface flowlines interfere with production and must be removed. Over the years much progress has been made in developing and improving methods of removing these deposits after they form. Much less progress has been made in developing methods of preventing or inhibiting the formation of paraffin deposits. This is due, it is believed, to the lack of knowledge of the mechanism of paraffin deposition, the absence of satisfactory laboratory testing methods and the difficulties in evaluating the results of field tests of preventive treatments. The present investigation was undertaken to elucidate the mechanism of paraffin deposition and to develop suitable laboratory tests for studying the inhibition of paraffin deposition in well tubing and surface flowlines. Current theories on the mechanism of paraffin deposition have been evolved from field observations, from laboratory studies of various factors which might be involved in paraffin deposition, and from laboratory paraffin-deposition tests.1-9 Paraffin deposits have been formed in the laboratory by immersing a cold finger into a hot wax-oil solution and by flowing hot wax-oil solutions through cooled pipe or over cooled plates. These laboratory conditions differ in important features from field conditions, and the observed deposition behavior is not entirely field-like." Thus, there is reason to question the field applicability of the results of these tests. The present investigation was undertaken to determine how to perform and interpret laboratory paraffin-deposition tests to obtain information on the inhibition of deposition in the field. The paraffin problem in the broadest sense encompasses the formation of any predominantly organic deposit in well tubing, surface flowlines and other equipment in contact with crude oil or gas. The present investigation was limited to paraffin deposition involving the precipitation of paraffin wax from solution by cooling and its concentration in a deposit on a cooled surface. This probably excludes its applicability to those problems arising from asphaltic-base crudes, but not those arising from paraffin-or mixed-base crudes. This also excludes its applicability to emulsion and congealing oil problems which are often included as part of the paraffin problem. The phenomenon of cooling appears to be the controlling factor in paraffin deposition involving the precipitation of paraffin wax and its concentration in the deposit. Deposits of this type are usually found in the field only where cooling occurs. Early in this laboratory investigation, it was not found possible to form deposits under constant temperature conditions from a wax-oil slurry, either by steady flow through pipe or by gas-lift up a pipe. Thus, the investigation was limited to situations involving cooling. THEORY The relationships involved in establishing the temperature profiles in an oil stream as it flows up well tubing with a linear (geothermal) pipe-wall temperature distribution or through surface flowlines with essentially constant pipe-wall temperature are presented in the Appendix. The relationship between radial distance in the pipe and the rate of cooling of the oil is then combined with a relationship between cloud point and rate of cooling to develop the pattern of formation of a wax cloud in the oil. The following discussion of paraffin deposition under various laboratory and field conditions is based upon this development which is presented in the Appendix. PARAFFIN DEPOSITION IN SURFACE FLOWLINES The average temperature of the oil coming out of a well is somewhat higher than the ground temperature. Thus, the oil continues to cool on its trip through the surface flowline, and wax deposition can occur. The temperature distributions calculated from Eq. A-4 are given in Fig. 1. As can be seen, almost all the cooling occurs in the first 500 ft from the wellhead. In addition, the radial temperature gradient near the wall decreases rapidly with distance and becomes very small after a few hundred feet. Thus, growth of a paraffin deposit would be expected to decrease rapidly with distance from the wellhead and become negligible after a few hundred feet, since growth is dependent on concentration gradient. Wax precipitation and diffusion of wax to the already

By Jo. E. Sheridan

The Dawson coal-mines are owned aid operated by the Stag Canon Fuel Co., of which Dr. James Douglas is President and E. L. Carpenter general manager. The property is situated in Colfax county, N. M., and the openings now in operation are in townships 28 and 29 N R. 20 E., and township 28 N E. 21 E., shown in Fig. I. The mines are part of the southern end of the Raton coal-field, which extends north into Colorado and embraces many coal-camps of the Trinidad section. II. Geology. Geologically, the coal-measures, commonly known as the Laramie series of the Cretaceous system, have x thickness of about 800 ft. in the vicinity of Damson. The coal makes an excellent coke, and, according to some authorities, its coking properties are due to the action of intruded sheets and sills of igneous rock, the sheets occasionally thickening into masses resembling laccoliths, at such places making nearer approach to the coal and sometimes producing small areas of natural coke. There are but few dikes throughout the entire southern portion of the field and little or no faulting along the dikes. In some parts of this great coal-field the intrusive sheets are far removed in the green shales below the coal-measures, and are so much altered as to be difficult of identification. There is but little disturbance of the strata throughout the Raton coal-field in as far as it extends into New Mexico. There are two workable seams in the coal-measures, and two or three smaller coal-seams, ranging from 1 to 2.5 ft. in thick-

Jan 1, 1910

By R. G. Aspden

The cold rolling and annealing textures were studied for 3 pct Si-Fe grains initially (001) [hkl]. A concentration of (001) [loo] primaries were observed only in the annealing textures of crystals initially having [loo] within 8 deg of the rolling direction. Eke annealing textures of the (001) [I101 cold rolling textures were sensitive to the initial orientation of the grains. Single crystal data were used to explain the formation of (001) [loo] in poly-crystalline malerial. CUBE texture formation in 3 pet Si-Fe sheet occurs during the final high temperature anneal. Its formation is dependent on the proper distribution of (001) plane primaries with reference to the rolling direction&apos; and on the growth of these primaries by secondary recrystallization. The selective driving force for these primaries with (001) within 7 deg of rolling plane is derived from the difference in surface energy between the annealing atmosphere and the crystallographic planes exposed at the surface of the sheet.&apos;-= The alignment of [loo] directions of (001) secondaries with the rolling direction is required for optimum magnetic characteristics7 and is dependent on processing.&apos; A high degree of alignment has been observed when the final cold rolled texture has a strong (111) [ll2] type component3 and the normal grain growth texture prior to secondary recrystallization has components with a [loo] parallel to the rolling direction and planes from (001) to (110) parallel to the rolling plane.1,3,8,9 Generally, this (001) component is much weaker than the (110) component. The growth rate of (001) plane primaries to secondaries has been found to be independent of the orientation of the primaries with reference to the rolling direction, i.e., the secondaries have the same degree of alignment of [loo] directions with the rolling direction as the (001) primaries.&apos; Hence, the rolling and annealing textures of individual grains or single crystals are of interest in understanding the development of the (001) [loo] secondary recrystallization texture. (001) components have been observed in the annealing textures of cold rolled grains initially having a [loo] parallel to the rolling direction and an (001) rotated up to 30 deg from the rolling plane. Crystals initially near the (001) [loo] orientation when rolled under the influence of constraints imposed by neighboring grains form deformation bands and ro- tate in both directions toward (001) <110>.10,11 Deformation bands have been reported also for crystals initially with an (001) within 1 deg of the rolling plane and a [loo] within 1 deg of the rolling direction when rolled as a free single crystal.12 These crystals have weak recrystallization textures and contain near an (001) [loo] component.10-12 When near (001) [loo] crystals are rolled as free single crystals no deformation bands form and the crystals rotate by a single rotation toward (001) [110]. Recrystallization after a 70 pct cold reduction yielded near an (001) [loo] component13 and after a 90 pct cold reduction an (001) [I201 component." Crystals initially near (210) [001] had a texture after a reduction of 70 and 84 pct which was similar to the (111) [li2] but rotated 10 to 15 deg in the transverse direction. These crystals recrystallize to (210) [OOl] or (410) [001] and contain an (001) [loo] component.10,13 An (001) component has not been detected in the normal grain growth textures of other single crystals. Crystals initially having orientations between (110) [001] and (111) [ll2] have a cold rolled texture of principally (111) [ll2] .10>16 Other crystals with a [I101 parallel to the cross direction rotate to (111) [112] and/or (001) [110] stable end orientations. Crystals initially having from (001) [110] to (111) [lie] retain this orientation after cold rolling.15 The cold rolled textures having [I101 directions parallel to the rolling direction had components in the annealing textures related to the deformation textures by 25 to 30 deg rotations about common (1 10) poles. Cold rolled textures of the (111) (112) type recrys-tallized to (120) [001] or (110) [00l]. The purpose of the present work was to further the understanding of the alignment of [loo] directions of (001) secondaries with the rolling direction. The cold rolling and annealing textures of grains initially (001) [hkl] were studied. These data were applied to the formation of (001) [loo] by secondary recrystallization. PROCEDURES AND EXPERIMENTAL TECHNIQUES The (001) poles near the sheet normal and rolling direction are given in Fig. 1 for the 10 grains studied. Each of these grains was located in the center of a polycrystalline specimen approximately 25 mm wide and 50 mm long. The lower case lettered grains, a through dl were about 1.2 mm in diam and near the (001) [loo] orientation. Specimens containing these grains were from a commercial 3 pct Si-Fe alloy with the principle orientation of (110) [001] as obtained by impurity inhibition of growth with manganese sulfide inclusions.17,18 Upper case lettered grains, A through F, were about 6 mm in diam and had (001) planes near the rolling plane and [hkl] di-

Jan 1, 1963

By Hsun Hu, R. S. Cline

The effect of rate of deformation on texture formatiotz has been studied with cube-oriented single crystals of 3 pct Si-Fe, compressed 80 pct at two widely different rates. Compression at a low rate (crosshead speed, 0.1 ipm) produces large orienta-tional changes and coarse deformation bands, whereas little change in orientation is observed, particularly at the surface of the crystal, when compressed at a high rate (impact velocity, -500 ips). Thin plates of mechanical twins are produced at the high rate, but their contribution to the deformation texture is practically negligible. The crystal deformed at a high rate has a lower hardness and a more uniform dislocation structure and is morc resistant to recrystallization. There is also a dilference in the recrystallization texture between the slowly and rapidly compressed crystals. These results indicate that plastic flow is less "turbulent" at high strain rates than at low strain ratcs. THE behavior of metals under high-speed deformation has been the subject of wide study in the past decade. Most of these works were concerned with mechanical properties during testing at high rates of loading, the resulting structures, and the theoretical aspects of the observed phenomena. The present status of knowledge and research activities in this field has been documented in recent publications.17&apos; There is, however, very little information available in the literature concerning the effect of high-speed deformation on the texture formation in metals. The possibility of an effect of rate of deformation on texture is suggested by the microstructural differences observed between normally and very rapidly deformed samples. Aside from the strong tendency for twinning (and phase transformation in certain metals) in high-speed deformation, the slip-line patterns and the dislocation configurations show marked differences as a result of large differences in the strain rates. For instance, in mild steel in static and dynamic compression, Campbell and co-worker3,4 observed that coarse slip occurred on several systems in specimens deformed at normal strain rates, whereas specimens deformed rapidly showed only fine slip on fewer systems, the slip-line pattern being very similar to that in specimens deformed at low temperatures and at normal strain rates. The absence of multiple slip was also noticed by Dieter5 in shock-loaded nickel. The dislocation configuration in an iron shock loaded at 70 kbar pressure was shown by Leslie et al.6 to be similar to that produced by light rolling at low temperature—the dislocation lines were mostly straight and uniformly distributed. These observations suggest that the mode of deformation at high strain rates is notably different from that at low strain rates. Consequently, the nature and the extent of lattice reori-entation during deformation should also be different. This investigation was undertaken to test this idea. MATERIAL AND METHOD The remaining part of a single-crystal ingot of a 3 pct Si-Fe alloy,* prepared for an earlier investi- gation,1 was used in the present studies. Specimens 9/16 in. square and 0.365 in. thick were cut from this ingot with (001) planes parallel to the square surfaces, and the [loo] and 1010] directions parallel to the edges of the specimen, within ±1 deg. These machined crystals were etched to remove distorted metal, and annealed at 1300°C for 24 hr in a purified helium atmosphere. The annealed crystals had a hardness of 161 Dph. The crystal orientation was rechecked with X-ray back-reflection techniques. In high-strain rate experiments the crystal was compressed in a Dynapak machine to approximately 80 pct reduction in thickness (from 0.360 to 0.070 in. with an impact velocity of -500 ips). Thus, the duration of loading was approximately 6x 10-4 sec, and the average strain rate was about 103 sec-1. As a result of this rapid, severe deformation, the specimen became a roughly circular thin disc. The original shape of the crystal, however, could still be recognized by a diffusely outlined square area in the center of the disc. For compression at a low speed, the crystal was deformed in a universal testing machine at a rate of crosshead movement of 0.1 ipm. Compared with

Jan 1, 1965

By Frank Rieber

THE discovery that strongly magnetic bodies localized near the surface of the earth could be detected by the distortion which they produced in the resultant magnetic field marked the beginning of magnetic surveying methods. From an original ability to detect bodies of magnetic iron ore and the like when located very close to the, surface, these methods have been extended until today they promise to give much information with regard to the structure of such slightly magnetic material as sedimentary rock containing only a very small proportion of iron.1 The recent extensions have been made possible through the development of more delicate instruments, and of methods for their use. From the original compass and dip needle, the design of apparatus has progressed until equipment Is typified by magnetic balances capable of measuring the components of the earth&apos;s field to an extremely high degree of accuracy. It seems unlikely that the limit of such instrumental development has been reached. Just as the change from compass and dip needle has enabled the location of relatively minor changes in magnetic materials, so additional developments in the direction of increased sensitivity, as well as in greater dependability and constancy of operation, should reveal positively many slight changes which either escape notice in the present surveys or are so small that they cannot with certainty be separated from uncontrollable errors due to inconstant operation of the equipment. The ability to read smaller and smaller variations does not mean, of course, that deductions as to the causes of these variations will be made as accurately and definitely as -is possible with the more pronounced anomalies.

Jan 1, 1928

By L. A. Norman

ANOTHER chapter in the history of Mother Lode mining is being written by operations in the Old Eureka mine near Sutter Creek, Amador County, California. During a two-year period (1938-1939), 85,517 tons of ore averaging 0.62 oz. gold per ton were mined and milled, as compared to the production of approximately 210,000 tons of 0.315-oz. gold ore during the preceding seven years. This is a repetition of mining history in the Mother Lode, where a period of prosperity has followed a long period of lean production. The location of this new ore in the hitherto unproductive hanging-wall greenstones and its mining and geological developments are most interesting. HISTORY OF THE OLD EUREKA MINE The Old Eureka mine, also known as the Hayward, Eureka, Hetty Green and Amador Consolidated, is in the most productive 10-mile length of the 120-mile long Mother Lode of California. The mine was first opened in 1852 with operations more or less continuous for the next 30 years. Production during this period amounted to $12,000,000 from an ore shoot 500 ft. long, which bottomed 1700 ft. below the surface. The shaft was continued as a prospect to 2065 ft. on the incline, where work was stopped in 1881. The mine was sold in 1916 by Hetty Green and the shaft deepened to the 3500-ft. level (3212 ft. vertically) by the new owners. Drifts were run on the 1700, 2100, 3000 and 3500-ft. levels, together with approximately 1500 ft. of crosscuts. No ore was found and work was abandoned in 1921. The present owners, the Central Eureka Mining Co., purchased the mine in 1924 after threatened litigation over rights to the rich ore shoot being mined from the lower levels of the Central Eureka mine on the south. Rehabilitation of the shaft commenced in 1926 and in 1930 mining on the old 2100-ft. level was started. While efforts of the previous owners had been directed for the most part toward the area south of the Old Eureka shaft and adjacent to the productive Central Eureka mine, the present owners started drifting northward on the old 2100-ft. level. On the 2000-ft., 2100 and 2300-ft. levels, drifts were run in part along the

Jan 1, 1939

By George D. Graffin.

The first use of graphite is lost in the mists of time. It was used by primitive man to make drawings on the walls of caves and by the Egyptians to decorate pottery. As early as 1400 A.D. graphite crucibles were being made in the Haffnerzell district of Bavaria. Through the Middle Ages graphite was confused with other minerals, especially galena and molybdenite. Two common names that are still used for the mineral are "Plumbago," meaning leadlike, and "Black Lead." The latter name implied that graphite is either composed of lead or at least contains a large percentage of it. Gessner is credited with having recognized it as a separate mineral in 1565, but its composition was not determined until 1779, when Scheele demonstrated that graphite oxidized to carbon dioxide, thus proving its carbon constitution. In 1789, Werner named it "graphite" from the Greek word "graphein," meaning to write. The United States has long relied on foreign countries for its graphite supplies. This reliance has been due more to the lack of suitable domestic graphites than to any particular preference for buying minerals overseas. Ceylon (now Sri Lanka) graphites were imported as early as 1820, and Madagascar graphites have been imported since the properties on that island were opened up about a hundred years later. Mexico has long supplied the United States with most of its requirements for amorphous graphite. Physical Properties and Classification Graphite is found in laminated, flaky aggregates disseminated in schistose rocks. It also occurs in veins and exhibits a foliated or fibrous structure. Graphite is a black lustrous mineral that crystallizes in the hexagonal system, with rhombohedral symmetry. The crystals have tabular form and are six-sided; the faces are commonly striated. The flakes have perfect basal cleavage and are opaque. When well crystallized, the flakes have a black metallic luster while the amorphous material is black and earthy, with a microcrystalline compactness. The flakes feel greasy. Graphite is an excellent conductor of heat and electricity. It melts at approximately 3550°C at a triple point under 1250 psi. It sublimes between 3300-3500°C at 14.7 psi. At 3726°C a second triple point occurs at approximately 100,000 atmospheres. Thermal oxidation in the presence of oxygen begins at 300°C and the rate increases with temperature. The three forms of carbon (charcoal, graphite, and diamond) are distinguished by chemical and physical tests. The specific gravity of charcoal is 1.3 to 1.9, of graphite 2.266 g/ cm3 (crystal density), and of diamond 3.5. Graphite has a hardness of 1 to 2 (Mohs&apos; scale). Natural graphite can be divided into three classes: disseminated flake, crystalline vein (fibrous or columnar), and amorphous. Flake graphite is a lamellar form found in metamorphic rocks, such as marble, gneiss, and schist. Each flake is separate, having crystallized as such in the rock. Crystalline vein graphite is found in the form of well defined veins or as pocket accumulations along the intrusive contacts of pegmatites with limestones. The graphite of such deposits is of two types, foliated and columnar. The important Sri Lanka (Ceylon) deposits are vein type. Amorphous graphite is commonly found as minute microcrystalline particles more or less uniformly distributed in feebly metamorphic rocks, such as slates and shales, or in beds consisting practically entirely of graphite. The latter usually are metamorphosed coal seams and carry as much as 80-85% graphitic carbon, while the former, being altered carbonaceous sediments, commonly range from 25 to 60%

Jan 1, 1983

By M. B. Ramachandra Roa

This paper records the results of the earth resistivity surveys made in the Godavari River in connection with the Ramapadasagar project. After describing the topographical and geological features of the area, the results of the investigation at the several sites have been mentioned. Further, a detailed account has been given of the resistivity methods adopted, the apparatus used and the interpretation of the curves. The resistivity measurements carried out over the water course have been specially outlined, and a review of the verification of the electrical indications by drilling in a number of cases, has also been presented. Introduction The Government of Madras has under consideration the Ramapadasagar project which is estimated to cost some Rs.660,-000,000 (about two hundred million dollars). The most essential feature of this project is the construction of a high dam across the Godavari near Polavaram for impounding the waters of this great river of South India, whose maximum discharge is 2 million cu secs in flood time. It is estimated that when the proposed reservoir is constructed, about one million tons of rice could be produced annually under irrigation. To those who have had any acquaintance at all with the recent distressing famine conditions which India has passed through and is still undergoing, the Lounteous effects which this project will bring about to the country in the future, are obvious. In the region of the proposed reservoir, the river flows for several miles through a hilly tract, hemmed in between flanks of hard, solid rock; but the river bed is mostly sandy. A few bore holes put down in this sandy bed touched rock at a depth of 180 to 200 ft. The river bed is about jo ft above the mean sea level (m.s.l.) and the bedrock was found at —125 to —160 ft m.s.l. The crest of the dam is proposed at +162 ft m.s.l. The proposed dam mould therefore be about 120 to 130 ft above the river bed, and the foundations would have to reach down nearly zoo ft below the bed at the deepest part. A number of alternative sites were proposed for investigation, and it became necessary to quickly ascertain the bedrock topography at these sites. Dr. M. S. Krishnan,* who was consulted in the matter, furnished a detailed account of the geological features of the region and suggested a geophysical investigation which the writer carried out from February to April 1944, employing solely the electrical resistivity methods. The total length of the survey lines for the electrical measurements amounted to 62,600 ft and the number of resistivity determinations was about 2500. Altogether nine alignments for the dam were inten-

Jan 1, 1949

By William H. Shockley

There was an extensive mining and industrial exploitation of Russia, about 20 years ago, by Belgian, French and British capitalists; but the results were discouraging. It is said that the Belgian and French public together lost approximately $400,000,000, chiefly in the coal and iron industry of southern Russia. This loss is largely accounted for by the fact that most of the companies were formed, as usual in " boom" times, to sell stock; and that thorough investigations were not made. I11 1906, renewed interest was taken in Russian mines, especially in those of gold and copper, and a considerable literature is growing on this subject; but as yet I have seen no account of one of the large Russian mining estates. The following notes on such property, where the conditions are so different from those in the mining regions of the United States, should be of interest: This inadequate and probably somewhat inaccurate account is made up, partly from my own notes made on the ground, in the summers of 1904 and 1905, and partly from a volume on the geology and resources of the estate issued several years ago, containing surface- and mine-maps, and from a pamphlet published in 1904, giving a general account of the condition and prospects of the property. This pamphlet includes a report made in 1899 by Arthur L. Pearse, a member of this Institute. Both these books are in Russian, and were prepared by the Bogoslovsk Mining Co., which owns and operates the property. Articles in many other languages have appeared dealing with various matters connected with the estate; but I know of no other general account of it. In numerous books and articles on the Urals and Siberia, however, localities are described in which somewhat similar conditions prevail. Recent papers by

Jan 1, 1909

By G. W. P. Rengstorff, L. E. Olds

High purity molybdenum ingots containing controlled amounts of a single impurity element (oxygen, nitrogen, or carbon) were prepared. These ingots were tested for ductility by bending test specimens at various temperatures. The relationship between the plastic behavior of the ingots and their chemical composition has been determined. MANY proposed applications for molybdenum require ductility at or near room temperature. At the present time, it is possible to obtain wrought molybdenum with considerable ductility only if special fabrication techniques are used to control the grain structure. Starting with are-cast or powder metallurgy ingots, the usual methods for obtaining ductility rely on fabrication procedures that result in fibered microstructures in the finished product. Recently, it has been found that the ductility of either powder metallurgy or are-cast molybdenum can be improved by uniform recrystallization of the metal to a very fine equiaxed grain structure.&apos; The need for a fibered or a fine grained structure may limit the practical usefulness of molybdenum. For example, welding. which may be used in fabricating the metal, generally produces coarse grained structures that lead to brittleness. This applies, certainly, to currently available commercial molybdenum. Although commercial molybdenum is brittle when the grains are coarse, it has been shown experimentally that fine grained structures are not always essential for ductility. For instance, as-cast molybdenum with a coarse columnar grain structure is ductile if it is sufficiently pure.&apos; Because high purity cast molybdenum has good ductility even when coarse grained, it is probable that the brittleness in coarse grained commercial molybdenum is caused by the impurity content of the metal. Although the general effects of impurities on the cold ductility of molybdenum have been known in a qualitative manner for some time, no quantitative evaluation of these effects has been available. The present investigation was made in order to determine more accurately the effects of oxygen, nitrogen, and carbon on the cold ductility of cast molybdenum. Oxygen has long been known to be detrimental to ductility, although the minimum amount which will embrittle molybdenum has been open to speculation. Parke and Ham" showed that ingots with oxygen contents above 0.003 pct could not be forged. Maringer and Schwope have described the embrittle-ment of molybdenum wire by oxygen. A discussion on the effects of heat treatment on the distribution of oxygen in molybdenum has been given by Perry, Spacil, and Wulff." Although nitrogen would also be expected to have harmful effects on ductility, no extensive work has been done previously to determine whether this is so. However, Tury and Krausz" found that wires presumably with less than 0.007 pct N were brittle. Carbon is added to commercial cast molybdenum for deoxidation. Parke and Ham" have shown that molybdenum containing as much as 0.06 pct C could be forged if the oxygen was kept below 0.003 pct. Also, Bruckart and others&apos; found that the room temperature ductility of sintered molybdenum improved with carbon contents up to 0.84 pct. However, Rengstorff and Fischer&apos; found that residual carbide particles in cast molybdenum apparently had an unfavorable effect on room temperature ductility.

Jan 1, 1957

By L. D. Jaffe, R. K. Pitler

IT would clearly be advantageous to produce molten titanium, suitable for alloying and casting, directly from the relatively inexpensive tetra-chloride, without using a metallic reducing agent. Accordingly, a preliminary investigation has been made of the production of titanium by hydrogen reduction of the tetrachloride in an electric arc furnace. For the reaction: TiCl4(g) + 2H2(g) ? Ti(s) + 4HCl(g), Lockhart and his colleagues&apos; have calculated equilibrium constants at 800" to 1500°K, based on tables of Brewer.&apos; Extrapolating these data on the assumption that the heat of reaction varies linearly with temperature, and using Brewer&apos;s value for the heat of fusion, there is obtained for the reaction: TiCl4(g) + 2H2(g) ? Ti(l) + 4HCl(g) an equilibrium constant at 2100°K (100" above the melting point) Kp = (PHCl)4/pTlcl4 (Ph2)2 = 0.167 atm. If this is correct, starting with hydrogen saturated with TiC14 at 25°C, where the vapor pressure of the latter3 is 12.6 mm, and maintaining the overall pressure at 1 atm, 99 1/4 pct of the TiC14 would be reduced to Ti at equilibrium. An arc furnace designed for the melting of titanium and lined with water-cooled copper was used for the preliminary experimental check. Its inside diameter was 2 7/16 in. and height 6 in. The water-cooled electrode was tipped with 3/4 in. diam tung-sten. In the one run carried out, the furnace was charged with a starting batch of 293.35 g of scrap titanium,&apos; analyzing 99.24 pct Ti. After the system was twice pumped out and flushed with argon to remove air, the arc was struck in argon and kept at 400 amp dc, electrode negative, for 1 min to melt the starting batch. Commercial tank hydrogen, dried by passing over silica gel and bubbled through technical grade TiC14 at room temperature, was then admitted to the furnace. The inlet tube directed this gas downward toward the arc and melt; the gas outlet was at the top of the furnace. The quantity of gas passed through was not measured accurately but is estimated to be about 50 liters per min at a few mm of mercury above atmospheric pressure. The arc was held in the H2-TiC14 mixture at 400 amp with little difficulty. After 10 min the arc burned through the copper lining above the melt, admitting water and ending the run. (This had happened frequently in straight melting runs under argon, and is not thought due to the atmosphere used.) In the furnace were found an ingot, several small pieces, and a little metallic powder, evidently formed when water entered the hot furnace. Some titanium also clung to the electrode. The portions were weighed and separately analyzed for titanium. Their total weight was 321.76 g of 94.82 pct overall purity. Much of the impurity consisted of tungsten broken off when the titanium was removed from the electrode. No detailed impurity analysis was made because the starting materials were impure and flooding the furnace introduced further contamination. Thus, the metal recovered contained 305.08 g Ti, as compared to 291.12 g in the starting batch. Titanium could not have been carried over from previous melting runs in the furnace, as the interior was sandblasted and the electrode ground clean before the run. Evidently at least 13.96 g of Ti were produced from TiCl4. Since this would require complete reduction of 430 liters of TiCl, gas at 12.6 mm of Hg, the efficiency of the process must have been rather high. Experimental work is continuing. No reason is seen why the process could not be scaled up to the size of a 30-ton steel-melting arc furnace. In a large unit there would be a large molten pool from which liquid metal could be withdrawn for alloying and casting. The problems of electrodes and power supply are similar to those arising in arc furnaces for melting titanium. Unreacted TiC14 and the HC1 in the exhaust gases could be recovered; unreacted H2 could be dried and re-used. The melt would be saturated with hydrogen, whose solubility in liquid titanium is unknown. Small amounts of hydrogen seem to have little effect on the properties of titanium.5 If the amount introduced was so large as to impair properties or cause casting difficulties, it could be reduced by holding the melt under an inert gas or by pumping on it, prior to casting. Acknowledgment The authors would like to thank I. Preble and M. Goldman for their valuable aid in the experimental work and the thermodynamic calculations, respectively. References 1R. J. Lockhart, J. J. Ward, M. J. Hussey, and J. W. Clegg: In unpublished report, "U. S. Air Force Project Rand. Titanium and Titanium Base Alloys." Battelle Memorial Institute (1949) 37-44. 2 L. Brewer et al: Chemistry and Metallurgy of Miscellaneous Materials—Thermodynamics. Ed. by L. L. Quill. pp 13-39, 60-192. (1950). McGraw-Hill Book Co. 3 K. Arii: Scientific Reports. Tohoku Imp. Univ. (1933) 22, 182. 4 R. S. Dean, J. R. Long, F. S. Wartman, and E. L. Anderson: Transactions AIME (1946) 166, 369-381; Metals Technology (Feb. 1946) TP 1961E. * R. I. Jaffee and I. E. Campbell: Transactions AIME (1949) 185, 646-654; Journal of Metals (Sept. 1949) TP 26813.

Jan 1, 1951

By William D. Klopp

A study was conducted of the tensile and creep properties of are-melted and electron-beam-melted tungsten over the temperature range 2250° to 4140°F. The tensile and creep strengths vary with pain size, the finer -grained materials being stronger. The activation energy for transient creep at 2250° to 3500°F is 95,000 cal per (g)(mole), while that for steady creep at 3300o to 4000°F is 141,000 cal per (g)(mole). At 2875o to 3300°F the apparent activation energy for steady creep decreased with decreasing temperature. It is suggested that cross slip is rate controlling during transient creep, while dislocation climb is rate controlling during steady creep above 3300° F. ALTHOUGH considerable data have been generated on the high-temperature tensile properties of powder-metallurgy tungsten,1 relative few data have been published on the properties of are-melted2 or electron-beam melted tungsten.3 Furthermore, the available data show a fairly large amount of scatter at high temperatures. The effects of structure and purity have not yet been defined, aside from observations that high-purity electron-beam (EB)-melted tungsten3 and single-crystal-plasma-flame tungsten4 are weaker than less pure powder-metallurgy tungsten. The creep behavior of powder-metallurgy tungsten has been studied, but no data are available on the creep behavior of tungsten consolidated by melting. Green5 found that powder-metallurgy tungsten exhibited linear creep at 4082° to 5072°F with an activation energy of 160,000 cal per (g) (mole). The similarity of this activation energy to that of 153,000 cal per (g)(mole) for volume self-diffusion6 suggests that recovery of strain hardening by dislocation climb is rate controlling in this temperature range. In studies at 4800°F, Sutherland and Klopp7 concluded that grain size significantly affected the creep behavior of commercial powder-metallurgy materials. This grain-size effect was suggested by sherby,8 although the opposite relation had been reported for aluminum.&apos; The purpose of the present study was twofold: first, to provide baseline data on high-temperature tensile and creep properties of are-melted and EB-melted tungsten for concurrent tungsten alloy studies, and, second, to determine the phenomenolo-gical effects of structural and purity variables on the high - temperature mechanical properties of tungsten. EXPERIMENTAL The are-melted tungsten materials were prepared by melting sintered 1-1/4-in.-diam electrodes into 2-1/2-in.-diam by 5-in.-long ingots. The are-melting facility has been described previously.&apos; Eight ingots were melted, machined, and hot-extruded at

Jan 1, 1965

By J. W. Pugh, J. D. Nisbet

THIS study of the ternary has been made as one phase of a metallurgical investigation which began nearly four years ago in the General Electric Company&apos;s Research Laboratory in Schenectady, N. Y. The objective of this program is the discovery of new metallurgical information which will lead to the development of better high-temperature materials. Combinations of the four pure base elements—iron, chromium, nickel, and cobalt—are being studied at the present time. It is essential in an investigation such as this to know as much as possible about the constitutional diagrams involved. The study of the iron-chromium-nickel system has been made to this end. Preliminary Explanation of Experimental Procedure: In all, fifty-five alloys at steps of 10 at. pct were made for the investigation of this ternary. Several ternary alloys in the chromium rich corner had to be omitted because their extreme brittleness made testing impractical. All alloys were vacuum melted with hydrogen reduction and centrifugally cast. The apparatus and technique of this process has been described in detail by Nisbet.1,2 The purity of the alloys prepared in this way is considered to be quite good. Impurities are listed as follows: Pct Carbon.............................0.02 Oxygen................................0.02 Nitrogen.........................0.005 Magnesium..................0.03-0.05 Sulphur...........................trace Hydrogen....................trace Phosphorous..................trace Silicon........................ trace After casting, all samples were given a homo-genization treatment which consisted of holding them for 15 hr at 1150°C (2100°F) and water quenching. Testing was begun with the samples in this condition. The tests employed in the study of this system were (1) dilatometer, (2) hardness versus aging temperature, (3) tensile strength and elongation versus temperature, (4) microstructure analysis, and (5) electrical resistance versus temperature. Dilatometer tests were made at the rather rapid heating rate of 1093°C (2000°F) in one hour on a Bristol-Rockwell type instrument. Hardness data were taken on specimens cooled from 204", 427", 649°, 760°, 871°, 982°, and 1093°C under conditions which are thought sufficient to bring the specimens to equilibrium in all but the cases of the very sluggish transformations. Electrical resistance data for several specimens were taken for both heating and cooling conditions in a vacuum furnace especially designed for this work by D. W. Bainbridge, formerly of this laboratory. Provisions were made for heating and cooling standard specimens at a constant rate, while autographic records of resistance and temperature were made simultaneously. Micrographs of all the alloys were made in the quenched condition. Some question may exist as to how such physical values as hardness, tensile strength, and elongation were interpreted to indicate a change in phase. Original data were recorded on physical property versus temperature graphs, each of which was made from the data of a single alloy (fig. la). From these, another series of graphs were plotted with the physical property as a function of composition for constant temperatures (fig. 1b). Sharp deviations in the slope of these composition versus hardness curves often indicate a change in phase. The example of fig. 1 will serve to describe this experimental technique. The plotting of a single point from graph "a" to graph "b," and finally to the phase diagram "c," is illustrated. The location of the point on graph "b" is indicated as point (1). If all the alloys of the A-B binary system were solid solutions at temperature X, the hardness in this curve would be expected to rise at a fairly even rate as A is diluted with B to a maximum at some intermediate value between A and B, as

Jan 1, 1951

By D. M. Kehn

A method has been devloped for chromatographic analysis Of the vapor and liquid phases Of a a system containing methane to components having 20 or more carbon atoms. The method uses a windowed equilibrium cell in which volumetric phase behavior of the system can be observed accurately and from which small samples of gas or liquid can be withdrawn for analysis. Analyses are made using two chromatographs, one for the lighter and one for the heavier components in a sample. Combination of the two analyses yields a detailed analysis of the gas or liquid sample. The complexity of the condensate heavy ends is evident from the chromatograms of these fractions, and the predominance of the paraffin hydrocarborn serves as a useful marker in interpreting the chromatograms. The K-values obtained in this analytical method are presented for a high-pressure condensate system and predict closely the observed volumetric behavior of the system. INTRODUCTION Quantitative analysis of hydrocarbons from natural gas reservoirs is necessary for several reasons—to calculate the amount of sales gas produced, to calculate the amount of natural gasoline produced, to plan a liquid recovery system, or to calculate the potential economic value of a reservoir produced under one or more of several different conditions. Analysis of natural gas fluids produced to the surface consists of identifying and computing the mol fraction of each component of the mixture. Although methane is the predominant component, varying amounts of ethane, propane, butane, pentanes and heavier components are also present. Materials containing up to 30 carbon atoms occur in amounts which decrease with increasing molecular weight. However, the quantities of components in the 20 to 30 carbon atom range are usually so small that their importance is negligible, and they are undetect-able in natural gas by ordinary analytical methods. All the components up to those having 20 carbon atoms may sigsficantly affect phase behavior, however. Commonly, only the methane-through-pentane fraction is analyzed quantitatively for each component, while components heavier than Pentane are lumped and repored as "hexane- plus". Expensive, tedious techniques are required for analysis of this fraction. Consequently the detailed analyses needed for prediction of reservoir behavior are usually undertaken only when major gas fields are being developed. The need for complete analyses of condensate systems is apparent when it is recalled that most gas fields are produced by pressure depletion. As the pressure declines, some of the heavier hydrocarbons are lost as liquids which are in the reservoir. In many instances the amount of liquid in equilibrium with the gas phase at high pressure constitutes only 1 or 2 mol per cent of the total system. Flash calculations generally must predict the actual amount of liquid with an accuracy of a few per cent in order to be useful. This retrograde condensation has been understood for years, but accurate correlation methods to permit quantitative prediction of phase behavior in the retrograde region are not presently available. The increasing importance of natural gas has made accurate prediction of phase behavior and composition of produced natural gas streams an economic necessity. The work reported here was undertaken to provide a rapid, economical method for obtaining the vapor-liquid equilibrium information needed to predict accurately the composition of the fluids produced from a gas reservoir throughout its life. TO develop this method, a pressure cell equipped with windows was designed and built for observing the volumes of liquid and gas present at reservoir pressures and temperatures. Use was made of established chromatographic methods for rapid and detailed analysis of both phases. This paper describes the equipment and techniques developed for obtaining vapor-liquid equilibrium data, presents the results of analyses of a condensate system, and indicates the usefulness of these data in predicting hydrocarbon phase behavior. DESCRIPTION OF EQUIPMENT USED The equipment used in obtaining the required information on phase behavior and the complete analysis of hydrocarbon mixtures through C, will be described first, followed by a discussion of the operation of the equipment. It will be helpful, however, to consider first a brief outline of the technique used. A sample of separator gas and liquid is charged to the windowed cell (see Figs. 1 and 2) where volumetric equilibrium phase behavior at reservoir pressures and temperatures can be determined. Then samples of the coexisting phases are withdrawn. The methane-through-pentane fraction is analyzed with a chromatograph equipped with a hot-wire detector, and the pentane-plus fraction is analyzed with a second chromatograph equipped

Jan 1, 1965

By Ray W. Carpenter, Ralph Hultgren, Raymond L. Orr

Heats of formation of Au-Zn alloys of compositions Au3Zn and AuZn were rneasured at several temperatures by liquid tin solution calorimetry. The data for Au3Zn show that much smaller heat and entropy effects are associated with the a2- a1 transformation than for the a1 - a transformation. This result is consistent with reported X-ray diffraction studies which indicate that the a1 and (a2 phases have ordered structures which only slightly differ, whereas the a phase is disordered. The heat of formation of AuZn(ß&apos;) does not change significantly between 322o and 8000 K, confirming that the ß&apos; alloy remains highly ordered to high temperatures. Not many measurements have been made of the energies of order-disorder transformations in alloy phases. In many cases these energies may be conveniently determined by measuring heats of formation as a function of temperature. Many alloy phases approximately obey Kopp&apos;s law of additivity of heat capacities; as a consequence their heats of formation do not change with temperature. In ordered alloys, however, a decrease in degree of order with increasing temperature will contribute an endothermic component to the heat of formation. Thus, for ordered phases where other anomalous contributions to heat capacity in the alloy or its pure components are absent, a measured change in the heat of formation may be attributed to the energy of disordering. A portion of the Au-Zn phase diagram1" is shown in Fig. 1. The composition AuZn(ß&apos;) has a well-ordered superlattice structure of the CsCl type at room temperature. The alloy is considered to remain ordered to its melting point,1 although, from X-ray diffraction data and electromotive force measurements of zinc activities, Terpilowski3 concluded that considerable disordering began at -673°K. The Au3Zn composition is a disordered fee solid solution (a) at high temperatures. Between 693o and 543oK, the ailoy orders to form the a1 phase, having a structure based on the L12(AuCu3) type, but with a regular distribution of ordering faults in the c direction, making it tetragonal. Below 543oK, the alloy orders further by means of slight atomic shifts, without diffusion, yielding a complex long-period orthorhom-bic superlattice structure, a2.4-7 Heats of formation of Au3Zn(a2) and AuZn(ß&apos;) were measured at 363°K by Biltz et al.8 by aqueous solution calorimetry. Heat capacities of several alloys between 14.9 and 38.4 at. pet Zn in the range from 373" to 723°K were measured by Iwasaki ef al.6 Stoichiometric Au3Zn, however, was not included in the alloys measured, the nearest composition being 26.1 at, pet Zn. Also, the heating rate used for the measurements, 2 deg per min, may not have permitted equilibrium to be reached in the neighborhood of the transformations. Heat contents of solid and liquid AuZn were measured between 488o and 1138°K by Kubaschewski.9 It was decided to determine the ordering energies of Au3Zn and to check on the possible disordering of AuZn by measuring the heats of formation of these alloys at several temperatures. The present paper reports measurements by liquid tin solution calorimetry of the heats of formation of the three phases of Au3Zn at temperatures within their regions of stability, and of AuZn at a low (322°K) and a high (800°K) temperature. EXPERIMENTAL Alloy Preparation and X-Ray Examination. Ten-gram ingots of Au3Zn and AuZn were prepared by melting weighed amounts of gold (99.95 pct Au) and zinc (99.99 pet Zn) together in sealed evacuated Vycor tubes at 1060°K, followed by rapid quenching. The resulting ingots were homogenized at 900°K for 10 days. The Au3Zn alloy lost no weight in preparation, the loss from the AuZn alloy was enough to introduce an uncertainty of only 0.1 at. pet in its composition. Filings for X-ray examination were taken from various parts of each ingot and strain-annealed at 723°K for 20 min in vacuo. The Au3Zn filings were quenched rapidly to retain the disordered phase. Diffraction patterns were determined with an X-ray dif-fractometer using copper Ka radiation.

Jan 1, 1968

By C. S. Matthews, J. L. Mahaffey, W. M. Rutherford

This paper gives results of an experimental study of the sweep efficiency of a miscible displacement in a five-spot. The study was carried out in a parallel-plate glass model in which effects of diffusion were scaled at or near the molecular diffusion level. The experiments show that very early breakthrough (25 to 35 per cent of pore volume (PV) injected) may be expected in miscible floods because of the unfavorable viscosity ratio. However after 1 PV of displacing fluid is injected, the sweep rises to a reasonable value (50 to 60 per cent). Photographs show that small slugs of less than 10 per cent of PV tend to dissipate before breakthrough. A minimum slug size of 15 per cent of PV would appear to be necessary even in a relatively homogeneous formation. Presence of a slug whose viscosity is inter-mediate between that of oil and gas increases the sweep efficiency of the oil-gas system. In a typical system the sweep at breakthrough rose from 26 to 37 per cent of PV for a 25 per cent slug. The increase in sweep brought about by use of a large slug could well pay for the extra deferment cost of the additional slug material. INTRODUCTION Most miscible displacement processes involve the displacement of oil with fluids of much lower viscosity and density. The displacement process at these adverse viscosity and density ratios is dominated by instability phenomena, i.e., viscous fingers and gravity tongues. These phenomena have highly adverse effects on oil recovery. Although a number of laboratory studies have been made to determine the effect of adverse viscosity ratios on five-spot sweep patterns,l,2 the scaling of diffusion effects is uncertain. In the series of scaled model studies reported herein, an attempt was made to scale diffusion. Model studies of miscible displacements in which molecular diffusion predominates are per-mitted by controlling the parallel plate spacing which reduces convective mixing to arbitrarily small levels. To decide how this scaling relates to any particular Geld displacement necessitates an estimation of diffusion effects for the natural rock being considered and conditions under which displacement will be conducted. The approach normally taken is to extrapolate data obtained from stable miscible displacements performed in the laboratory, such as those presented by Brigham et al.3 The validity with which such an extrapolation can be applied to an unstable flow system has yet to be established. If this approach is accepted, a family of oil recovery curves can be generated for a single viscosity ratio based on Brigham&apos;s observation that the magnitude of the dispersion coefficient is dependent, among other things, upon specific rock properties. Objective of our test was to define the lower limit of this range by presenting the case where dispersion effects were reduced to the molecular diffusion level in both the transverse and longitudinal directions.

Jan 1, 1967

By Aureal T. Cross

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

Jan 1, 1952

By Arthur Smith

THE Verde mining district is in Yavapai County, in north-central Arizona. Jerome, the principal town, has a population of 6000 and the two important mines of the district-the United Verde and the United Verde Extension-lie almost within its limits. Perched high on the southwest side of the Verde valley, at elevations of 4800 and 5500 ft. (1463 and 1676 m.) respectively, both mines have long tunnels from their lower levels through which the ore is hauled to the smelters. Clarkdale, the smelter town for the United Verde mines, lies in the Verde valley 4.1 miles (6.5 km.) distant in an air line from Jerome and at an elevation of 3560 ft. The two towns are connected by the standard-gage railroad of the Verde Tunnel and Smelter R. R., a subsidiary of the United Verde Copper Co. This road is 11 miles long and has a compensated grade of 4 per cent. At Clarkdale it connects with the Verde valley branch of the Santa Fe railroad. Clemenceau, the smelter town for the United Verde Extension mine, lies 3.5 miles (5.8 km.) in a southeasterly direction from Clarkdale, at an elevation of 3420 ft. It is connected to the Verde Valley branch of the Santa Fe railroad at Clarkdale by the Arizona Extension R. R., . a subsidiary of the United Verde Extension Mining Co. The portal of the haulage tunnel, at an elevation of 3757.5 ft., is also connected with the smelter town by 4 miles of standard-gage track belonging to? the same company. In the vicinity of Jerome, the great southern escarpment of the Arizona plateau forms the northeast side of the Verde valley. The general level of this escarpment, or "rim" as it is called, is about 4000 ft. above the Verde River. A corresponding elevation is reached only by the highest peaks of the Black Hills, which bound the valley to the southwest. Two lava-capped mesas, known as "Mingus" and "Wood chute mountains," form the culmination of the Black Hills. That part of the Old Black Hills mining district which lies between their crests and the Verde River is now known as the Jerome, or Verde, mining district. If the . smelter towns are not included, a strip about 7 miles long by 3 miles (11 by 5 km.) wide, embraces practically all of the properties belonging to the Jerome district. This strip lies parallel to and along the side of the Verde valley from First View, 2 miles northwest from Jerome, to the vicinity of Allen Springs, at the south end of Mingus mountain and all within the boundaries of the Prescott national forest reserve.

Jan 3, 1924

By J. M. W. Mackenzie, M. H. Buckenam

Flotation experiments using stearic, oleic, linoleic, linolenic, and ricinoleic acids and naturally occuring products rich in these acids as collectors for calcite are described. The results confirm the validity of the rule of Hukki and Vartiainen relating the collecting power and unsaturation of the C18 acids. Reasons for this relationship are discussed and a close relationship between mineral depression and critical micelle concentration is reported. It has long been recognized that the unsaturated fatty acids are in general superior flotation collectors to their saturated homologues. Whereas earlier workers concentrated on saturated and monoethe-noid acids, recent investigations have centered on oleic, linoleic, linolenic, and the substituted mono-ethenoid acid: ricinoleic. From studies of the collecting properties of palmitic, oleic, linoleic, and linolenic acids on ilmenite, rutile, hematite, and magnetite, Hukki and Vartiai-nenl concluded that the collecting power of fatty acids increased with unsaturation of the hydrocarbon chain. Sun, Snow, and Purcel12 investigated the collecting properties of unsaturated fatty acids as collectors for phosphate ores and concluded that the collecting power increased with increasing unsaturation of the hydrocarbon chain up to two double bonds and that further unsaturation decreased the collecting power. More recently Sun3 studied the collecting power of the C18 fatty acids stearic, oleic, linoleic, and linolenic on 37 minerals. The results of these experiments with a few exceptions showed that the collecting power of the acids increased in the order stearic, oleic, linoleic, and linolenic. The relative collecting powers of linoleic and linolenic acids were in many cases altered by the cleanliness of the mineral surface prior to flotation. Sun concluded that linolenic acid may become oxidized by atmospheric oxygen during flotation, a reaction which would reduce its effectiveness as a collector. This deduction is supported by Gaudin and Cole4 who concluded that oleic and linoleic acids do not undergo appreciable oxidation of the double bonds during flotation but that the linolenic acid double bonds are measurably affected. The most complete investigation on the influence of hydrocarbon chain unsaturation on the collecting properties of fatty acids is that of Kivalo and Lehm~svaara.~ These workers using linolenic acid of a higher purity than Hukki and Vartiainen showed that this acid was superior to oleic and linoleic acids as a collector for magnetite. They also found that ricinoleic acid was a more effective collector for this mineral than the other acids investigated, an observation particularly apparent at high collector concentrations. Seeking to explain the superiority of the unsaturated acids these authors considered the effects of critical micelle concentration, surface activity, hydrolysis, and cross sectional area of the hydrocarbon chain in relation to unsaturation. Using what, according to the results of Caviere are erroneous surface tensions of the soap solutions of these acids, they concluded that the surface activity decreases and the critical micelle concentration increases with increasing unsaturation. In view of the data of Cavier, whose results show that surface activity of these soaps increases with unsaturation, the deductions of Kivalo and Lehmusvaara are open to criticism. The degree of hydrolysis of the soap solutions as measured by Kivalo and Lehmusvaara decreases as the unsaturation of the fatty acid increases, a result which helps to explain the superiority of unsaturated acids as collectors. In view of the superiority of unsaturated acids as collectors for many minerals, attention has been directed towards the utilization of fatty acid raw materials such as tall oils and linseed oils which contain considerable quantities of these acids. This paper describes test work to determine the effect of unsaturation of the hydrocarbon chain on the collecting properties of fatty acids on calcite, and includes comparable test work using natural products rich in unsaturated acids. TEST WORK Reagents: The pure fatty acids used were oleic, linoleic, and linolenic. Of these, oleic was supplied by British Drug Houses Ltd. and the others were produced by the Hormel Inst. When not in use these

Jan 1, 1961

By M. C. Udy, C. H. Lorig

THROUGH the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the general effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. LITERATURE Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H20, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H20, FeO¬Fe-CO-C02 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnas1 published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at one temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1942