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By Maurice Rey, H. Brevers

THROUGH circumstances connected with the war, the senior author lost his records therefore it has been impossible to include numerical data in this paper. The arsenical quicksilver ore investigated had been roasted, with poor metallurgical results. The vapor-tension temperature curves of mercury and arsenious trioxide are similar, and the arsenical compound hampers the coalescence of mercury drops in the condenser and is the cause of large stack losses. The ore was a gray limestone carrying small amounts of carbon and mineralized with cinnabar and two arsenic minerals, realgar (As2S2) and arsenopyrite (FeAsS). The proportion of realgar often exceeded that of cinnabar; the proportion of arsenopyrite was smaller. The grade of the ore varied between 0.8 and 4 per cent Hg. The problem was to make a high-grade mercury concentrate, as free from arsenic as possible. The water used throughout the testing was hard, having a pH- of about 8. FLOTATION OF REALGAR Realgar showed a very strong tendency to float. It formed a film at the surface of the pulp and floated in abundance with only pine oil. Therefore an attempt was made to float the realgar before the cinnabar, but this was not very successful; the percentage of mercury in the realgar concentrate could never be brought below 2 or 3 per cent. Cinnabar slimed easily and floated with pine oil, so that some of it always accompanied the realgar. There was also the question of the cinnabar-arsenopyrite separation. On further investigation it was found that realgar can be floated not only with pine oil but even better with a combination of hydrocarbons and pine oil. Washing the ore with ether revealed that it contained hydrocarbons, which helped to float the realgar. In this connection it belongs to the same class as carbon, sulphur and talc. It can be floated also with a xanthate, when activated by a heavy-metal salt. The conditions favoring the two types of flotation are opposed, as activation by a copper salt facilitates xanthate flotation (in fact, is even necessary to it), whereas it hinders pine oil and petroleum flotation. One type of flotation can be termed nonpolar and the other polar, a distinction that has been stressed in a previous paper. DEPRESSION OF REALGAR AND FLOTATION OF CINNABAR Many chemicals were tested in an attempt to float the cinnabar and depress the realgar. Finally starch rendered soluble with caustic soda was tried, also several grades of commercial soluble starch, and dextrin was found to be the best and the most convenient reagent. Several of these starch preparations have a strong flocculating effect on the pulp, which is a distinct disadvantage. Dextrin, with its low flocculating power, is excellent. It is noteworthy that starch preparations are also depressants for carbon and talc, so that the fact apparently has a general

Jan 1, 1941

By William A. Johnson

The fundamental role of diffusion in many reactions occurring in solid metals has long been recognized, and there have been careful measurements of rates of diffusion in numerous alloy systems; but our understanding of the atomic mechanism by which diffusion occurs is scarcely in an advanced state.l-3 It is doubtful that this mechanism can ever be directly ascertained; rather, all imaginable mechanisms must be examined and the one that is in best accord with such data as can be obtained from suitably chosen experiments should be selected. Because of its relative simplicity, diffusion in a system containing only one kind of atomic species—commody called self-diffusion—is of considerable theoretical interest. It may be expected that diffusion theory will not be advanced appreciably until a wide variety of diffusion experiments—of which diffusion in a chemical concentration gradient and self-diffusion are two important types—are carefully performed and inter-compared. Aside from the purely theoretical interest in self-diffusion measurements, such studies will be of considerable engineering importance. The rate of any process in a pure metal requiring the movement of atoms, of which recrystallization and creep are two familiar examples, will be understood more readily with the aid of self-diffusion data.† Self-diffusion implies the diffusion of something into its exact counterpart; the detection of such a process is patently impossible, and it is necessary to substitute for it the diffusion of one isotope (in this case radioactive) into another isotope (in this case stable) of the same chemical element. There is, however, no reason to suppose that a radioactive atom will not diffuse at the same rate as its stable isotope, for all of the isotopes of the same element have exactly the same chemical properties; neither the difference in nuclear energy nor the difference in mass would be expected to exercise an important influence in this phenomenon. In this sense, self-diffusion may be thought of as the diffusion of radioactive atoms down a radioactivity concentration gradient, just as usual diffusion is the diffusion of one kind of atom down its chemical concentration gradient. The first measurements of self-difiusion were made by von Hevesy4-6 using the radioactive lead isotope thorium B in ordinary lead. The recent development of means for producing artificial radioactive elements has made possible similar measurements on gold,7, 8 copper,2, 9 and zinc.10, 11 Many of the data that have been obtained are rather poor, and no adequate reason has been given for their poorness; it appears, however, that the unsatisfactory results are characteristic of the particular experimental procedure employed, and not of self-diffusion measurements in themselves. The experimental technique that has yielded the poorer results is the deposition of a thin layer of radioactive atoms on the surface of a specimen and the determination of the rate of inward diffusion

Jan 1, 1941

By Paul A. Beck

IN several recent investigations1 ' considerable evidence was accumulated to show the predominance in various face-centered cubic metals of a certain relative orientation, corresponding to a rotation of 30" to, 40" around a [111] axis, between a matrix with a strong single orientation texture and grains growing in this matrix." This relative orientation was found to occur both in recrystallization and in coarsening, "secondary recrystallization", so that one is inclined to look for an explanation applicable in both cases. The abundance of growing grains in the described orientations proves that suitable "nuclei" are present in the matrix material and that they have the capacity to grow. The scarcity of growing grains in other orientations may be explained in one 'of two ways. Either the number of nuclei or the rate of growth must decrease strongly for orientations deviating from that predominating among the growing grains, Fig. 1. Both the "oriented nucleation" and the "oriented growth" theory found support in the literature. Because the frequency of nuclei as a function of orientation is in most instances not amenable to direct experimental investigation, a definitive decision is difficult to achieve. However, it is now known with great certainty that the rate of boundary migration is strongly dependent on the relative orientation of the two grains meeting at the boundary and that the orientation favored by high boundary mobility closely corresponds to that predominating in most cases of recrystallization and coarsening. Thus, it was found that, in general, the mobility is very low for boundaries between grains of nearly identical orientation, or for coherent twin boundaries. On the other hand, the boundaries between two grains of a relative orientation correspending to a [1111 rotation of 30" to 40" have the highest mobility in face-centered cubic metals. If a large variety of nucleus orientations are produced grow- by means of a highly inhomogeneous local deformation, nuclei close to the above orientation are found to grow fastest.z4 In view of this evidence and of the fact that the preferred orientation relationship is the same in recrystallization and in coarsening, the oriented growth theory appears by far the more promising one. Since the origin of nuclei in primary recrystallization is certainly different from that in coarsening, the occurrence of the same orientation relationship in the two processes would be difficult to explain on the basis of oriented nucleation. other advantages of the oriented growth theory are its capability of accounting for the often observed sharpening of the texture in coarsening, and its suitability for explaining the role in the formation of the ''cube texture,, of the most important variables, such as the degree of rolling, the penultimate grain size, and the time and temperature of the last anneal: No similarly consistent explanation of all these effects has ever been offered in terms of oriented nucleation. An important problem in connection with the oriented growth theory is the following: In the ce-c entered system there are four [111] axes and

Jan 1, 1952

By William A. Johnson

The fundamental role of diffusion in many reactions occurring in solid metals has long been recognized, and there have been careful measurements of rates of diffusion in numerous alloy systems; but our understanding of the atomic mechanism by which diffusion occurs is scarcely in an advanced state.l-3 It is doubtful that this mechanism can ever be directly ascertained; rather, all imaginable mechanisms must be examined and the one that is in best accord with such data as can be obtained from suitably chosen experiments should be selected. Because of its relative simplicity, diffusion in a system containing only one kind of atomic species—commody called self-diffusion—is of considerable theoretical interest. It may be expected that diffusion theory will not be advanced appreciably until a wide variety of diffusion experiments—of which diffusion in a chemical concentration gradient and self-diffusion are two important types—are carefully performed and inter-compared. Aside from the purely theoretical interest in self-diffusion measurements, such studies will be of considerable engineering importance. The rate of any process in a pure metal requiring the movement of atoms, of which recrystallization and creep are two familiar examples, will be understood more readily with the aid of self-diffusion data.† Self-diffusion implies the diffusion of something into its exact counterpart; the detection of such a process is patently impossible, and it is necessary to substitute for it the diffusion of one isotope (in this case radioactive) into another isotope (in this case stable) of the same chemical element. There is, however, no reason to suppose that a radioactive atom will not diffuse at the same rate as its stable isotope, for all of the isotopes of the same element have exactly the same chemical properties; neither the difference in nuclear energy nor the difference in mass would be expected to exercise an important influence in this phenomenon. In this sense, self-diffusion may be thought of as the diffusion of radioactive atoms down a radioactivity concentration gradient, just as usual diffusion is the diffusion of one kind of atom down its chemical concentration gradient. The first measurements of self-difiusion were made by von Hevesy4-6 using the radioactive lead isotope thorium B in ordinary lead. The recent development of means for producing artificial radioactive elements has made possible similar measurements on gold,7, 8 copper,2, 9 and zinc.10, 11 Many of the data that have been obtained are rather poor, and no adequate reason has been given for their poorness; it appears, however, that the unsatisfactory results are characteristic of the particular experimental procedure employed, and not of self-diffusion measurements in themselves. The experimental technique that has yielded the poorer results is the deposition of a thin layer of radioactive atoms on the surface of a specimen and the determination of the rate of inward diffusion

Jan 1, 1941

By C. E. Birchenall, M. H. Davis

The rate of oxidation of titanium in the temperature range 650° to 950°C has been measured. 'The linear rate law obtained is explained by interface reaction control of the process. Tracer experiments indicate the oxygen diffuses in at least one phase of the scale. THE kinetics of oxidation of titanium, principally at low temperatures and under varying oxygen pressures, have been reported.¹,² In the present investigation the rates of oxidation of titanium have been determined by the gravimetric method in the temperature range 650" to 1000°C under 1 atm of oxygen. Some of the scales formed were powdered and an endeavor was made to identify the phases present by X-ray diffraction. Alexander and Pigeon1 ascribe a logarithmic rate law to the growth of thick films formed at temperatures up to 565"C, and Gulbransen and Andrew' suggest that the parabolic rate law holds up to 600°C. In both cases large initial deviations from those relationships are apparent and no explanation is offered. In the present experiments it is shown that a linear rate law holds in the temperature range 650" to 1000°C, and it is suggested that the initial deviations observed are due in part to a spurious surface area effect and also to the high solubility of oxygen in titanium metal. Positive information on the mechanism of oxidation is not available, but oxygen ion diffusion through the lattice is inferred from the re- sults of trace experiments. X-ray analysis of the scale confirms Gulbransen and Hickman's' observation on the presence of rutile TiO². Experimental Details The titanium used in these experiments was prepared by the reduction of titanium tetrachloride with magnesium and was used in the form of rolled sheet. Samples approximately 0.040x0.5x0.75 in. were cut and polished to a fineness of 4/0 on metal-lographic polishing papers. Individual samples, suspended on a platinum wire, were lowered into the hot zone of a furnace, in vacuo, by means of a winch, and oxygen was admitted after the desired temperature was attained. The increase of weight of single samples oxidized for fixed times at certain temperatures was determined by weighing the sample before and after oxidation on a chemical balance. In these instances the sample was used for only one time at one temperature. In some cases the course of oxidation was followed by attaching the sample to a sensitive spring balance and noting periodically the extension of the spring with time of oxidation. Kirkendall type experiments were carried out by marking the surface of the titanium prior to oxidation with a solution containing radioactive silver. After drying, the specimen was heated in vacuo to decompose the silver nitrate used, leaving a small amount of metallic radioactive silver on the surface. Following oxidation, these samples were mounted, ground, and then placed in intimate contact with

Jan 1, 1952

By H. R. Hendricks

THE ore of the Iron King Mine, being very hard and having a very fine crystalline structure, presents many problems in milling that are not present in ordinary lead-zinc ores. This very fine crystallization causes much interlocking of minerals and is most prevalent between the gold and pyrite and the sphalerite and pyrite. The recovery of gold is extremely important in the economic value of the ore and therefore constitutes a large part of the metallurgical problem to be solved. All of the gold is free but it has not been observed in any of the mill products except under very high magnification. Some of the gold is tarnished, and this condition also makes recovery difficult. The gold values have been determined to be highest in association with chalchopyrite and arsenopyrite. The silver occurs mostly in association with galena and tennantite. A small amount of native silver has also been observed occasionally. The galena, being softer than the other minerals, frees much better in grinding. Some oxidation of galena is present in the ore, as the nonsulphide lead content amounts to approximately 10 pct of the total lead. Some oxidation of sphalerite is also present in the ore. Microscopic examination of the zinc concentrate shows many grains in the minus 325-mesh to be half pyrite, together with the fact that some of the zinc is marmatite, makes production of a high-grade zinc concentrate very difficult unless recovery is sacrificed. In the grinding, it has been determined that the flotation feed must be maintained at 85 pct minus 200-mesh to free the minerals sufficiently to make the best economic recoveries. Table I illustrates the effect of fine grinding. It shows that the bulk of the recovered minerals is in the minus 325-mesh size and is the part of the minerals that is more readily freed. The pyrite concentrate is not given in the table because it contains practically no minus 325-mesh. DEVELOPMENT OF PRESENT FLOWSHEET AND MILLING PRACTICE The first milling operation started in 1938, with a mill capacity of 140 tons daily, producing a bulk gold-silver-lead concentrate. After several stages of expansion and changes of the mill flowsheet, the mill is currently treating 380 tons of ore daily and three separate concentrates are produced. In order of their importance and value, these are: (1) lead concentrate, (2) zinc concentrate and (3) pyrite concentrate. The present average grade of mill heads is: gold 0.11 oz, silver 4.00 oz, lead 2.50 pct, zinc 7.60 pct, copper 0.22 pct, iron 22 pet and 30 pct insolubles. Specific gravity of the ore is 3.8. During the period when bulk flotation was practiced, the flowsheet was very simple. The ore was ground fine enough to liberate as much gold, silver and lead as possible. Necessary collectors and frothers were added in sufficient quantity

Jan 1, 1947

By A. W. Bitner, A. W. Asman

An analysis is made of three different types of section production units that represent the manner in which most of the nation's bituminous coal is produced. The general delays and production characteristics of these sections are presented along with a method for evaluating section performance based on actual and theoretical production characteristics. THE forerunner of the modern mechanical loading machine first entered the mines in 1890—a Stanley header with a conveyor. Since then progress has been substantial, both in the design and application of mechanized production units. Mechanization is almost a necessity for survival in the economy of today. In this paper an analysis is made of three types of sections, and a method for evaluating section performance based on present production characteristics and theoretical characteristics is presented. In mechanical loading mining sections the loading machine is the unit directly responsible for production. If the face preparation units provide a plentiful supply of properly prepared coal and the transportation system is coordinated and adequate, the loader will be idle a minimum of time. If either of the above do not perform adequately or other delays occur, the effect on production will be reflected in the performance of the loading machine. Therefore, attention is focused on the loading machine and factors that affect the overall performance of the production unit. Three complete mechanized production units are presented for analysis: A track section, a trackless section using battery-powered shuttle cars, and a trackless section using cable-reel shuttle cars. These particular sections were chosen for the following reasons: 1—The daily tonnage and mining conditions are approximately the same. 2— Production in each is 10 to 20 pct above the daily average. 3—The production characteristics and delays are average and typical. 4—They represent the manner in which the most of the nation's bituminous coal is produced. A. W. ASMAN, and A. W. BITNER, Members AIME, are Chief, and Research Assistant, respectively, Div. of Mining, The Pennsylvania State College, State College, Pa. Discussion on this paper, TP 3140F, may be sent to AIME by Oct. 31, 1951. Manuscript, Feb. 22, 1951. St. Louis Meeting, February 1951. Section A Fig. 1 is a layout for the track mining section showing the development to date, the projected plan and the cuts loaded on the shift studied. The seam mined averages 96 in. in thickness with a fireclay bottom and a roof of 10 in. of drawslate topped by sandstone. The mineability is considered good, and roof support is not a difficult problem. Two locomotives are used in the section to minimize the losses occurred in trip changing. The places are driven 20 ft wide, and the crosscuts are angled to permit fast tramming of the equipment. Table I lists the equipment and labor that make up the section. ANALYSIS Production Characteristics: The average loading rate for eight loading machines studied of this type is 1.81 tons per min. This one at 2.78 is considerably above average.

Jan 1, 1952

By John T. Galey

An intensified search for gas, because of the shortage in the area, led to the completion of 482 wells in southwestern Pennsylvania during 1944. This number was 27 more than the number in 1943, but 118 of the wells were nonproductive. Shallow Development Oil The initial production of the 25 producers completed was slightly less than was obtained from four wells above last yearJs total. The largest well, 20 bbl., was found in the Big Injun (Miss.) sand in Morris township, Washington County, at a depth of 2085 ft. It is currently producing about 3 bbl. per day. Outside the main producing area, a well drilled in Nicholson township, Fayette County, obtained 15 bbl. per day from 1864 to 1866 ft. in the Gantz (U. Dev.) sand. The Federal subsidy of 75¢ per barrel, effective , 1, 1944, which increased to $3.40 the current pipe-line price in this area, seems to have been insufficient stimulus to materially increase drilling for oil, although more repressuring operations are contemplated. Gas The volume of initial open flow of gas developed is off slightly over 10 million cu. ft. from 36 more wells than were completed a year ago, and the average rock pressure of this new gas is more than 100 lb. less than that obtained a year ago. Apparently the best find of this year was reported in Patton township, Allegheny County, where an initial volume of over 4 million cu. ft, was encountered in the Speechley (U. Dev.) sand at a depth of from 3293 to 3303 ft. The rock pressure there, 1190 lb. per sq. in., is nearly virgin. However, this area is fairly well delimited by dry holes and docs not seem nearly so promising from the standpoint of reserves as the Armbrust area, which was discovered several Years ago. In the patton township locality another fair well with 1303 M cu. ft. open flow and 400 lb. Per 59. in. rock pressure completed in the Hundred-Foot (U. Dev.) sand at a a depth of 2125 feet. Armstrong County, as usual, leads in number of producing wells completed with lowest percentage of failures but ranks only fou th in volume of production developed. Only two wells here had more than one million cubic feet capacity, but the rock pessure was under 200 Ib. Per sq. inch. In Fayette County, where the largest portion of new gas was found, activity appears to be shifting eastward. In Luzerne township, four producers having a total combined initial open flow in excess of 10 million cu, ft, were found in the Big Injun (Miss.) sand. The best well was found also in the same area in the Speechley sand (U. Dev.) at a depth of 3460 ft. This was a 2500-M CU. ft. well in Georges township. Several wells of more than a million cubic feet capacity were found in Jackson, Washington, Wayne and Whitley townships, Greene County. None of these, however, was in a new pool.

Jan 1, 1945

By Louis Ware

At the beginning of the present war, the United States faced the need to multiply its production of magnesium metal almost roo times within the shortest possible period. Urgently needed for construction of military aircraft, incendiary bombs, and other war uses, magnesium was at the top of the list of critical war materials. Up to that time only one Producer, employing Only One process and using One raw material in a single plant, represented this country's entire Production capacity. It was immediately desirable to plan a numher of plants located strategically over the Count'Y and to expand an industry more rapidly and to a greater extent than ever before had been attempted in so short a time. In '939 this American producer, the Dow Chemical .9 was making about 7 million Pounds of magnesium metal. It utilized as a raw material brine containing magnesium chloride, which was pumped from wells in Michigan. The logical ap-preach to certain increased production was to employ the same process on the same raw material in other sections of the United States. In Europe and other countries, different processes had been used and different raw materials were being utilized, but all of the skill and knowledge for production in this country was that of using the Dow type of cell and magnesium chloride as a raw material. The Government was testing other processes, but none then had been proved commercially feasible. Development OF New Process The International Minerals and Chemical Corporation had available a large quantity of magnesium ,chloride at Carls-bad, New Mexico, contained in the end liquor produced from its potash plant sillce the buildng of the plant in 1941 It was the only company mining commercially a magnesium ore and having anything like this quantity of magnesium chloride liquor. The magnesium ore, langbeinite, was being mined from the 800-ft. level for its content of potassium sulphate. This ore, a potassium magnesium sulphate, was reacted in a base exchange plant with potassium chloride to produce potassium sulphate, the discharge liquor having a high content of magnesium chloride. Three potash-producing companies are in the Carlsbad area, but only International has developed and is commercially producing the potash-magnesium ores. The lower, or No. 4, veil, in that area is potassium chloride ore, and is continuous through all the properties. The langbeinite, or No. 2, vein is minable at the International property, but occurs sparsely, if - at in other areas being mined in that vicinity. It is understood that most of the mag. nesium produced] by Germany comes from magnesium and magnesium-potassium ores obtained from potash mines. It was logical for International to pro-pose to make available this magnesium material and to offer its technical staff to design, construct and manage a magnesium plant for the account of the Government. The plan that finally was adopted by the

Jan 1, 1944

By E. P. Valby

A method is presented in which the hydrocarbon weight fractional analyses of the well effluents from a true gas-tip-portion well and a true dark-oil-ring well furnish the basic data for determining the properties of any mixture of production from the two sources. The effect of injected gas on these properties can be computed. Comparison of similar properties of a given well effluent to the properties of mixtures of the basic well effluents will give the relative amounts of production from the two sources and injected gas. Presentation of Problem Oil fields having an area of gas-cap, or light-oil production, over the dark-oil area present a problem of increasing gas-oil ratios during the production of an oil well. The use of pressure maintenance in a field such as above, or a cycling project, wherein residue gas from an absorption plant is injected into the reservoir, adds to the problem, because a part of the increased gas-oil ratio may be due to the production of injected gas. The usefulness of a means to determine the amount of injected gas in a well effluent led to the development of a method in which well-effluent analyses of a true gas-cap-portion well and a true dark-oil-ring well furnish the basic data needed to determine whether injected gas of a known composition is present in a given well effluent. Development op Method The method presented herein is based upon the principle that if two fluids, or well effluents, having different properties are mixed in known proportions by weight, • the properties of their mixtures can be computed. Conversely, if these basic data are known, the properties of a mixed well effauent can be used to compute the relative amounts of each type of well effluent in the mixture. A convenient way of making these computations is to have the fractional analyses of the base well effluents and mixtures expressed in weight fractions The mathematical equations expressing the properties of mixtures will be developed for a two-component system consisting of the well effluents from the dark-oil ring and the gas-cap area. The added effect of injected gas, a third component, will also be developed. The following assumptions have been made in developing the method: 1. The gas-cap and dark-oil fluids exist initially in separate portions of the reservoir. 2. The fluids in each portion exist in a single phase at pressures above the saturation pressure for the dark-oil fluid. 3. The composition of each fluid is substantially constant throughout its respective portion of the reservoir. 4. Changes in reservoir pressure and temperature will not change the composition of the fluid entering the well bore. 5. The injected gas displaces original gas-cap fluid 100 per cent. •• 6. AS the injected gas travels through a

Jan 1, 1945

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice-chairman for Production of the Petroleum Division, and revised in 1939. Generally in Table 1 the unit for prescntation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions—several units of continuous productive reservoirs of distinctly different structure and of distinctly different stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and /or commercial value. As to each spacc in the tabulation, it is citller (1) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert x; in spaces where the proper entries are detcrminable but not detcrminable from data available to the author, the author will please insert y; in spaces where the proper entries are determinable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries arc not subject to precise determination. In such rases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use x. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report 1,8xx,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations

Jan 1, 1939

By J. H. Frye, J. W. Caum

ONE of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium,, germanium; and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, II, III, IV, and V, respectively and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-solution hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have. been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? PREVIOUS WORK Theories have been advanced to account for the hardness of solid solutions,, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Angier2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter, change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately

Jan 1, 1943

By William A. Johnson

THE fundamental role of diffusion in many reactions occurring in solid metals has long been recognized, and there have been careful measurements of rates of diffusion in numerous alloy systems, but our understanding of the atomic mechanism by which diffusion occurs is scarcely in an advanced state 1-3 It is doubtful that this mechanism can ever he directly ascertained, rather, all imaginable mechanisms must be examined and the one that is in best accord with such data as can be obtained from suitably chosen experiments should be selected Because of its relative simplicity, diffusion in a system containing only one kind of atomic species-commonly called self-diffusion-is of considerable theoretical interest It may be expected that diffusion theory will not be advanced appreciably until a wide variety of diffusion experiments-of which diffusion in a chemical concentration gradient and self-diffusion are two important types-are carefully performed and inter-compared Aside from the purely theoretical interest in self-diffusion measurements, such studies will be of considerable engineering importance The rate of any process in a pure metal requiring the movement of atoms, of which recrystallization and creep are two familiar examples, will be understood more readily with the aid of self-diffusion data † Self-diffusion implies the diffusion of something into its exact counterpart, the detection of such a process is patently impossible, and it is-necessary to substitute for it the diffusion of one isotope (in this case radioactive) into another isotope (in this case stable) of the same chemical element There is, however, no reason to suppose that a radioactive atom will not diffuse at the same rate as its stable isotope, for all of the isotopes of the same element have exactly the same chemical properties, neither the difference in nuclear energy nor the difference in mass would be expected to exercise an important influence in this phenomenon In this sense, self-diffusion may be thought of as the diffusion of radioactive atoms down a radioactivity concentration gradient, just as usual diffusion is the diffusion of one kind of atone down its chemical concentration gradient The first measurements of self-diffusion ii ere made by von Hevesy4-6 using the radioactive lead isotope thorium B in ordinary lead The recent development of means for producing artificial radioactive elements has made possible similar measurements on gold,7,8 copper,2,9 and zinc 10 11 Many of the data that have been obtained are rather poor, and no adequate reason has been given for their poorness, it appears, however, that the unsatisfactory results are characteristic of the particular experimental procedure employed, and not of self-diffusion measurements in themselves The experimental technique that has yielded the poorer results is the deposition of a thin layer of radioactive atoms on the surface of a specimen and the determination of the rate of inward diffusion

Jan 1, 1941

By Stuart E. Buckley, C. R. Hocott

The viscosity of the oil in the reservoir is one of the properties that influence its movement through the sand to producing wells. Measurements of viscosity, therefore, are pertinent to problems associated with well behavior and with the estimation of recoveries, and afford an indirect means for partial evaluation of various methods of controlling reservoir behavior. The effect of dissolved gases on the viscosity of crude oil has been determined,ls2 but no data have been published on the viscosity of representative samples of reservoir oils. This paper describes a simple instrument that has been used to determine the viscosities of a number of subsurface oil samples at the temperatures and pressures existing in the reservoirs, and presents the results of the determinations for typical fields. Construction oF the Apparatus The principal requirements of any instrument used for the examination of subsurface samples are that it be strong and simple both in design and in method of operation. Accuracy beyond that of the degree of reproducibility of subsurface Sam-~les from various wells in a reservoir or exceeding that of the common measure-merits of reservoir temperatures and Pressures is not required. Because of the expense of procuring subsurface samples, it is necessary also that the instrument operate on a relatively small fraction of a sample, leaving the remainder for other tests, and that there be few or no failures of the equipment to cause undue delay or loss of a sample. After preliminary experiments with a falling bullet, the results of which were not satisfactory, a simple viscosimeter was built of the rolling ball type first proposed by Flowers3 and later used by several investiga-tor. 5.8 The apparatus consists essentially of a removable, accurately bored cylindrical barrel of 1/4-in. nominal internal diameter, 8 in. long, in which a closely fitting steel ball rolls through the oil with the barrel inclined at a definite angle. The ball makes contact at one end of the barrel with ail insulated electrode, closing an electrical circuit, which actuates a buzzer. The meas-urements consist essentially in determining the time required for the ball to travel the length of the barrel. The details of the construction are shown in Fig. I. The barrel in which the ball rolls was made from a section of 25-caliber blank rifle barrel, specially bored to an exact uniform diameter and polished. The barrel slides snugly into a hole bored in a solid stainless-steel cylinder, an upper external shoulder of the barrel compressing a small spring, and is held in place by a hollow nut. The spring prevents the barrel from seating against the bottom of the bored hole in the cylinder, while narrow external longitudinal slots in the barrel permit fluid to flow around it and through the bottom. The upper part of the recess in the steel cylinder is enlarged to form a tapered chamber, which acts as a reservoir for the oil and affords space for agitation to ensure

Jan 1, 1941

By Jr. D. C. Williams, D. V. Carter

The four new oil-field discoveries made in the East and East Central Texas districts during 1941 were the East Long Lake field, Anderson County; Pickering field, Shelby County; Pleasant Grove field, Rusk County, and Tri-Cities field, Henderson County. The discovery of oil production in the Pettit lime of the Lower Glen Rose was made in the Groesbeck (Barron) field in Limestone County and the Willow Springs field in Gregg County. Important extensions were made to the Pittsburg field, in Camp County, the Chapel Hill field, in Smith County, and the Hawkins field, in Wood County. The Hawkins field was extended sufficiently to more than double the number of proved surface acres. As usual the East Texas field led the district in the number of completions for the year. The second most active field during the year was the Hawkins field, with 250 new wells completed. The third most active was the Long Lake field, in which 50 wells were completed. Approximately 964 wells were completed in the district during 1941. Production and Probation The district is credited with having produced 163,566,695 bbl. of oil and distillate during the year. This represents a decrease of 4 per cent from the 170,424,685 bbl. of oil and distillate produced during the preceding year. The production of 130,378,620 bbl. of oil and distillate from the East Texas field represents 79.7 per cent of the total production of the district; that is, 6.3 per cent less than the production for the year 1940, The district had an estimated basic daily allowable of 614,982 bbl. of oil on Dec. 31. Approximately 33 per cent of the state's annual production was produced in the district, compared with 34.9 per cent for 1940. Since the majority of the fields in this district are subject to proration, any change in the annual production is attributable largely to changes in proration schedules and number of shutdown days. Fields subject to shutdown days were closed in for 113 days during the year, with the exception of the East Texas field, which was shut down 111 days. An order was promulgated by the Oil and Gas Division of the Texas Railroad Commission for encouraging the disposal of salt water and reservoir-pressure maintenance in the East Texas field. Discoveries Tex Harvey Oil Company'sNo. I S. E. J. Cartmel was completed as the discovery well for the East Long Lake field, Anderson County. Production was found in the Woodbine sand, the horizon from which the Long Lake field produces. The Pickering field, Shelby County, secures its production from the Nacatoch sand, found at an approximate depth of 1510 ft., in A. E. McKiernan's No. I, Pickering Lumbering Co. This field is in an area near the state line in which a number of relatively unimportant and

Jan 1, 1942

By M. van Swaay, C. E. Birchenall

Palladium has a large capacity for the dissolution or occlusion of hydrogen; the gas also diffuses very rapidly through the metal. Palladium thimbles are widely used in the laboratory for purification of hydrogen by diffusion. The use of palladium filters could be extended to several large-scale applications if greater stability of the permeation process could be attained. In this paper a number of aspects contributing toward this goal are discussed, and new data on solubility and diffusivity are given. Palladium sheets of 0.005, 0.010, or 0.020 in. thickness were prepared by three procedures: casting and rolling, sintering palladium powder, and sintering palladium powder to which 0.1 pct thorium oxide had been added. Half-inch diam circular specimens were cut and clamped in a stainless steel holder provided with knife edges to seal the palladium sheet with soft copper gaskets. The seals were tested for leaks at l0-5 mm Hg. No difficulties from this source were encountered even after many temperature cycles in the system. The holder was silver-soldered to Kovar-glass seals and attached to the system through glass ball joints. Each joint was sealed with Apiezon wax and was adjacent to a cold trap. In several experiments the holders were fused directly into the system, eliminating the ball joints, to show that the wax did not affect the filter. Three filter holders were supported in holes in a stainless steel cylinder, which also acted as a temperature equalizing block inside the resistance wound furnace. The measuring thermocouple was inserted in one of the holders. A potentiometric controller with control thermocouple on the furnace heater winding maintained ± 0.2oC. Electrolytic hydrogen was purified and stored as shown in the flow diagram, Fig. 1. It could be admitted to either or both sides of the palladium specimens. Only a mechanical pump was used, for even high pumping speeds would not bring the pressure on the off-gas side of the filter below 10 to 50p Hg owing to the rapid hydrogen flow through the filters. A series of steady-state permeability studies allowed identification of several conditions of permeability loss. A constant fore pressure was maintained while the low-pressure face was pumped. After enough time had elapsed for a steady flow to be established the pump was cut off, and the rate of pressure increase in a thermostated bulb was measured to determine the flow rate. The time delay method of Daynes1,9 was adopted since it offered the possibility of determining solubilities and diffusivities. For each measurement both sides of the filter were evacuated for 15 min, which gave about 10-4mm Hg residual pressure. Hydrogen was admitted to one side or the other of the filter at a fixed pressure. The pressure on the off-gas side was observed as a function of time. A

Jan 1, 1961

By David Turnbull

In most reactions involving solids the transformation kinetics may be represented by the combination of two processes —those of nucleation and of growth. For example, Mehl and his coiq-orker in their studies on the transformation of austenite to pearlite in steels have been able to describe the kinetics in terms of the rates of nucleation and of growth. By micrographic examination of their specimens they determined the nucleation rate (rate of appearance of pearlite colonies) as a function of time, of percent transformation, and of temperature. They observed that after an incubation period in which no nuclei are observed, the number of nuclei appearing per unit time per unit of untransformed grain boundary area, increases at an increasng rate with time. When recrystallization rates have been interpreted in terms of rates of nucleation and growth and the rate of nucleation determined, an incubation period followed by an increasing rate of nucleation has also been reported. Among the studies in which this phenomenon has been observed are those of Kornfeld and coworkers3 on cold-drawn aluminum wire, of Anderson and Mehl4 n the recrystallization of aluminum sheet, and of Stanlcy and Meh15 on the recrystallization of silicon ferrite sheet. The existence of an incubation period during which no nuclei are observed does not appear to have been reconciled with the generally accepted Volmer-Becker theory of nucleation in condensed systems. This theory ostensibly requires the rate of appearance of nuclei to be independent of time. Volmer-Becker Theory In order to form a stable nuclcus of a new phase B in a mother phase A, the molecules or atoms of the mother phase must surmount a free energy barrier whose height is determined by the volume free energy change accompanying the transformation and the energy of the surface separating the two phases. The free energy difference between nuclei of various sizes and the molecules or atoms of the mother phase is plotted schematically in Fig I as a function of the radius of the nucleus r. This free energy difference is plotted for two values of the change of free energy per atom, (Jb — ja) accompanying the transformation when the volumes of the two phases are infinite. One of these values of (Jb—Ja) corresponds to a temperature above the temperature To at which the phascs A and B are in equilibrium, and the other to a temperature below To. In order for a nucleus of phase B to be stable at a temperature T² < TO, its radius must be equal to or greater than the critical value r* for which the free energy of formatioil of the nucleus is a maximum, the of phase B having radii equal to or less than r* will be called embryos hfehl and Jetter," in discussing the kinetics of nucleation in solid systems, suppose that embryos of critical size are formed

Jan 1, 1949

By Morris Muskat

The detailed analogy between flow systems in porous media and the corresponding poten-tiometric model systems is developed under conditions where it may be desirable to take into account variable pay thickness, variable porosity, and permeability, and also the dependence of the fluid density on pressure. It is shown that in such models it is only necessary that the electrolyte thickness be made everywhere proportional to the millidarcy-feet of the formation. In contrast to the iso-vol type model, previously suggested as a basis for the analogy, the porosity does not enter directly in the construction of the model. It is introduced only in translating the electrical voltage gradient measurements into the equivalent fluid travel times. A discussion of this procedure is given. I NTRODUCTION It is now some 50 years since it was pointed out&apos; that on the basis of Darcy&apos;s law Laplace&apos;s equation must govern the steady state flow of homogeneous fluids through porous media. It is 16 years since the obvious implication of this fact, namely, that such steady state homogeneous flow systems in porous media could be simulated by electrical analogies, was first applied2 to problems of practical interest with respect to oil production. In these initial studies major emphasis was placed on the use of electrolytic models, made of blotting paper, to give a direct and graphic history of the fluid particle motion in regular and infinite well networks. However, it was also noted there that the basic requirement of the model was that it give a potential distribution similar to the pressure distribution in the flow system, and that from the electrical measurement of the potential distribution the fluid particle motion could be graphically or numerically determined. This was demonstrated by application to the five-spot infinite network, for which a conducting metallic sheet was used to establish the equipotential contours. As anticipated, the fluid particle motion computed from these contours agreed well with that given directly by the blotting paper model. For irregular well distributions it was found more convenient to use electrolytic bath analogs rather than metallic sheets. Several investigations,3&apos;4 as applied specifically to cycling well patterns, have been reported with these models, which have become known as "potentiometric models." However, the extremely laborious nature of both the electrical measurements by direct probing and the associated interprctive computations retarded the widespread use of these procedures. The electrical measurements can be accelerated by using a four-probe electrodc,5,6 which provides a means for simultaneously determining the streamline paths along which the fluid particles must move and the voltage gradients along these paths which are proportional to the fluid velocitics. With the increasing frequency of discovery of condensate pools, as drilling depths are becoming greater, the applicability of the potentiometric model to production problems, and especially to the study of well patterns for cycling, has been given a fresh impetus. Although the formal theory for determining the motion of fluid particles in porous

Jan 1, 1949

By Jr. D. C. Williams, D. V. Carter

The four new oil-field discoveries made in the East and East Central Texas districts during 1941 were the East Long Lake field, Anderson County; Pickering field, Shelby County; Pleasant Grove field, Rusk County, and Tri-Cities field, Henderson County. The discovery of oil production in the Pettit lime of the Lower Glen Rose was made in the Groesbeck (Barron) field in Limestone County and the Willow Springs field in Gregg County. Important extensions were made to the Pittsburg field, in Camp County, the Chapel Hill field, in Smith County, and the Hawkins field, in Wood County. The Hawkins field was extended sufficiently to more than double the number of proved surface acres. As usual the East Texas field led the district in the number of completions for the year. The second most active field during the year was the Hawkins field, with 250 new wells completed. The third most active was the Long Lake field, in which 50 wells were completed. Approximately 964 wells were completed in the district during 1941. Production and Probation The district is credited with having produced 163,566,695 bbl. of oil and distillate during the year. This represents a decrease of 4 per cent from the 170,424,685 bbl. of oil and distillate produced during the preceding year. The production of 130,378,620 bbl. of oil and distillate from the East Texas field represents 79.7 per cent of the total production of the district; that is, 6.3 per cent less than the production for the year 1940, The district had an estimated basic daily allowable of 614,982 bbl. of oil on Dec. 31. Approximately 33 per cent of the state&apos;s annual production was produced in the district, compared with 34.9 per cent for 1940. Since the majority of the fields in this district are subject to proration, any change in the annual production is attributable largely to changes in proration schedules and number of shutdown days. Fields subject to shutdown days were closed in for 113 days during the year, with the exception of the East Texas field, which was shut down 111 days. An order was promulgated by the Oil and Gas Division of the Texas Railroad Commission for encouraging the disposal of salt water and reservoir-pressure maintenance in the East Texas field. Discoveries Tex Harvey Oil Company&apos;sNo. I S. E. J. Cartmel was completed as the discovery well for the East Long Lake field, Anderson County. Production was found in the Woodbine sand, the horizon from which the Long Lake field produces. The Pickering field, Shelby County, secures its production from the Nacatoch sand, found at an approximate depth of 1510 ft., in A. E. McKiernan&apos;s No. I, Pickering Lumbering Co. This field is in an area near the state line in which a number of relatively unimportant and

Jan 1, 1942

By J. H. Brophy, A. L. Prill, H. W. Hayden

An error lzas been found in the conventional way of determining the time exponent of linear shrinkage for the solution-precipitation stage of liquid-phase sintering. Large amounts of shrinkage due to initial rearrangenzent result in erroneously low exponents and tni si dentification of the rate-controlling process. Two alternative, mathematically correct, methods of calculation are applied to existing data on Fe-Cu, WC-Co, and Tic-Ni-Mo. This results in reidentifi-cation of the rate-controlling process and somewhat better agreement with related data. In each case the solution-precipitation process is solution-controlled and not diffusion-controlled. THE liquid-phase sintering process has been the object of a considerable amount of research for many years. Linear shrinkage vs time data at various sintering temperatures have been used recently in an attempt to identify the prevailing mass-transport processes in a number of metallic and nonmetallic systems. There is an analytical error inherent in the methods previously used for handling data during the "solution-precipitation" stage of shrinkage which must be recognized before the correct rate-controlling processes can be determined. It is the purpose of this paper to show how the error has affected previous conclusions and to suggest corrections. A number of mechanisms have been proposed to explain experimental observations during sintering in the presence of a liquid phase. The earliest of these is due to Price, Smithells, and williamsl who attributed the observed growth of the solid phase to the simultaneous solution of smaller particles and growth of larger particles. From the work of Lenel et al.2,3 and Gurland and Norton4 has come the suggestion that the liquid-phase sintering process may be divided for analysis into three steps: 1) rearrangement upon formation of the liquid phase; 2) solution and reprecipitation of the solid phase in the liquid; and 3) "coalescence" or a final stage of sintering, characteristically slower than the solution-precipitation process. The sequence of steps is shown schematically in Fig. 1. Kingery5 presented a thermodynamic and kinetic analysis of the first two "stages" of the liquid-phase sintering process in which the functional dependence of lineal shrink- age on time at temperature was used to identify the rate-controlling mass-transport process. Table I summarizes the time dependences and processes considered by Kingery.5 This method of data presentation has been employed by Kingery and coworkers for Fe-CU,6 WC-Co, and a number of nonmetallic systems," and bv Whalen and Humenik for Tic-Ni-Mo and Fe-cu.8 In each of these studies, the rate-controlling step during the "solution-precipitation" stage was identified from the slope of the curve in that stage on a logarithmic plot such as Fig. 1. However, in all of the previous studies, at a certain composition, relatively large amounts of shrinkage due to rearrangement preceded the solution-precipitation stage. Under these conditions, the larger the amount of rearrangement shrinkage the

Jan 1, 1965