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By John H. Hollomon

In a recent paper,' a very early suggestion by Ludwik2 concerning the nature of the mechanical behavior of metals has becn reexamined and extended. In essence it was suggested that there exists, at least under certain conditions, a mechanical equation of state; that the stress required for flow depends upon the instantaneous values of the strain, strain rate, and temperature, and not upon their past values. It is proposed that under these circumstances thc stress does not depend upon past history of these variables, but is like the temperature of a gas that depends only upon the instantaneous values of the pressure and volume. This notion has not been applied to present-day studies of metals, though it is especially applicable to the study of creep. It is the purpose of this paper to analyze the significance and possible range of applicability of this idea and to determine how it influences the accepted ideas concerning creep. Stress-strain Relations It is wcll known that the stress-strain curves of metals are influenced by both train rate and temperature. For a fixed strain rate and temperature there is associated with each metal a stress-strain curve. If either the strain rate or temperature is changed a new stress-strain curve will be characteristic (Fig. I). A much more genera1 relation between the effects of these variables is possible, however. Consider the stress-strain curves of Fig. I determined at

Jan 1, 1947

By J. M. De La Garza Cárdenas

The total production of oil in Mexico in 1942 was 34,715,547 bbl.; that is, 8,179,254 bbl. less than the amount produced in 1941. The daily average for 1942 was 95,111 bbl., while that for 1941 was I17,520 barrels. The reduction of 22,409 bbl. per day in production was due to a decrease in exports because of the scarcity of tankers. This reduction has affected principally the Northern and Southern districts of the Tampico area; in December the Northern district (Panuco) was producing less than zoo0 bbl. per day with 445 wells shut down and the Southern district (GolJen Lane) less than $000 bbl. per day with 140 wells shut down. Drilling.—During the year 14 wells were drilled in Mexico, of which five were productive. Seven dry holes were drilled in Ebano, Tampico Northern district, in search for new producing fractures; plans are being made to explore this area by means of resistivity measurements. Three producing wells were completed in Poza Rica. Drilling in this important field will continue during 1943 to determine its extension to the west. In the Isthmus of Tehuantepec no wells were completed. Two gas wells were completed in northeastern Mexico. Wildcats.-—Two wildcat wells were completed during the year, to test the extension of the Golden Lane to the south; both were unproductive. In the Isthmus a deeper sand was found in the El Plan field* This discovery has made an important increase in the reserves in this field and will allow an increase in the production of the area during 1943. In December, three exploration wells were being drilled, two in the Tampico area and one in the Isthmus. Operating Technology.— Satisfactory progress has been made in Mexico in the application of petroleum engineering to the development and operation of the oil fields. Mud control is now an established practice and has lessened the number of fishing jobs and has allowed more open hole to be carried than formerly was possible. During 1942 the first effective use was made of determinations of bottom-hole pressure, and other modern production practices such as gun-perforating and squeeze-cementing are being introduced. Plans for 1943 The oil production during 1943 is expected to be slightly larger than that of 1942, especially if tankers are available for exporting crude and refined products. The Government proposes to increase exploration and drilling activities to increase the reserves and potential production of the country; about 50 wells will be drilled during the year, including wildcat wells in northeastern Mexico, Tampico and Isthmus areas and exploitation wells in the Ebano-Panuco, Poza Rica, El Plan and Cuichapa fields. Acknowledgment Mr. A. Barnetche, of the Production Department, "Petr6leos Mexicanos," assisted the writer in the preparation of the statistical data.

Jan 1, 1943

By J. M. De La Garza Cárdenas

The total production of oil in Mexico in 1942 was 34,715,547 bbl.; that is, 8,179,254 bbl. less than the amount produced in 1941. The daily average for 1942 was 95,111 bbl., while that for 1941 was I17,520 barrels. The reduction of 22,409 bbl. per day in production was due to a decrease in exports because of the scarcity of tankers. This reduction has affected principally the Northern and Southern districts of the Tampico area; in December the Northern district (Panuco) was producing less than zoo0 bbl. per day with 445 wells shut down and the Southern district (GolJen Lane) less than $000 bbl. per day with 140 wells shut down. Drilling.—During the year 14 wells were drilled in Mexico, of which five were productive. Seven dry holes were drilled in Ebano, Tampico Northern district, in search for new producing fractures; plans are being made to explore this area by means of resistivity measurements. Three producing wells were completed in Poza Rica. Drilling in this important field will continue during 1943 to determine its extension to the west. In the Isthmus of Tehuantepec no wells were completed. Two gas wells were completed in northeastern Mexico. Wildcats.-—Two wildcat wells were completed during the year, to test the extension of the Golden Lane to the south; both were unproductive. In the Isthmus a deeper sand was found in the El Plan field* This discovery has made an important increase in the reserves in this field and will allow an increase in the production of the area during 1943. In December, three exploration wells were being drilled, two in the Tampico area and one in the Isthmus. Operating Technology.— Satisfactory progress has been made in Mexico in the application of petroleum engineering to the development and operation of the oil fields. Mud control is now an established practice and has lessened the number of fishing jobs and has allowed more open hole to be carried than formerly was possible. During 1942 the first effective use was made of determinations of bottom-hole pressure, and other modern production practices such as gun-perforating and squeeze-cementing are being introduced. Plans for 1943 The oil production during 1943 is expected to be slightly larger than that of 1942, especially if tankers are available for exporting crude and refined products. The Government proposes to increase exploration and drilling activities to increase the reserves and potential production of the country; about 50 wells will be drilled during the year, including wildcat wells in northeastern Mexico, Tampico and Isthmus areas and exploitation wells in the Ebano-Panuco, Poza Rica, El Plan and Cuichapa fields. Acknowledgment Mr. A. Barnetche, of the Production Department, "Petr6leos Mexicanos," assisted the writer in the preparation of the statistical data.

Jan 1, 1943

By E. H. Griswold

The efforts of petroleum production engineers during the past year have largely concentrated upon ways and means of reducing operating investments and expenses in order that the industry may survive a period of low crude oil prices. Major progress was made in outlining and solving the technical problems pertinent to unit operation in order that executives and legal staffs may actually arrange operating contracts to effect unit operation. Consequent savings in development and operating costs, accompanied by increased recovery, will thus be obtained. Well spacing has received considerable constructive thought and study, from which practical results are assured in the near future. The control of edge and bottom waters has advanced in technique through the engineering work done in Yates, Hobbs and East Texas, and there is evidence of greater cooperative efforts between engineers to increase recovery from pools by mutual gas conservation. The use of pressure control by surface and bottom-hole chokes has become general practice to reduce gas-oil ratios. The study of bottom-hole pressures has led to new conceptions of proper utilization of reservoir energy and maintenance of pressure by natural means. Pressure gradients of flowing wells have been measured in practice and strides made to develop workable formulas for the flow of oil and gas mixtures through vertical pipes. The information thus obtained will permit the intelligent design of flow tubing combinations. Gas-lit and repressuring advancements have been few, due to overproduction from naturally flowing wells. Satisfactory unloading valves for gas-lift wells have been developed and consistent progress made in gas-lift displacement pumps. The necessity for producing wells at high rates of flow while producing large quantities of sand has resulted in radical changes in Christmas tree and separator designs for the Oklahoma City pool. The opening of wells to obtain potential production for proration purposes has been eliminated in the Yates and Hobbs pools by the application of engineering principles.

Jan 1, 1932

By W. E. Coxe

In 1857 the Philadelphia and Reading Railroad Company, whose main line extended from Philadelphia to Pottsville, Pennsylvania, with branches into the coal regions of Schuylliill County, made a contract with the Fairmount Rolling Mill, at Philadelphia, for the rerolling of some four thousand tons of iron rails. The essential features of the agreement were that the old rails should be piled with puddled iron and rolled into flats for the rail pile, which latter was • to be of a section seven inches square, and after being heated, and reduced, by rolling, to a bloom of a section about fire inches by six inches, was to be reheated, before being finished into the rail of the T pattern, four inches high, weighing sixty-four pounds per yard. Great care was exercised in the execution of this contract, and the rails being distributed over all parts of the road, gave general satisfaction by their excellent wear. Five years afterward, the principal proprietor and manager of the Fairmount Rolling Mill was elected President of the Reading Railroad, and very many of the rails made under his supervision were still in use in the tracks of the company, of which he had just assumed the management. His first efforts were, therefore, directed to the procuring of more rails of the same quality wherewith to replace those worn out. Here he encountered some trouble, makers refusing to bid because of the details in the specification, the required reheating being the objectionable feature, for which it was generally intimated they would not be sufficiently remunerated for the increased labor, extra coal consumed, and the changes necessary from the established methods of working. Most of the new rails were, therefore, bought, and the old rails rerolled without regard to any particulars as to the manner of piling, heating, etc., each manufacturer furnishing what he deemed the best article possible for the money. As a consequence, rails of all imaginable grades were placed in the tracks, some giving out in six

By W. E. C. Coxe

IN 1857 the Philadelphia and Reading Railroad Company, whose main line extended from Philadelphia to Pottsville, Pennsylvania, with branches into the coal regions of Schuylkill County, made a contract with the Fairmount Rolling Mill, at Philadelphia, for the rerolling of some four thousand tons of iron rails. The essential features of the agreement were that the old rails should be piled with puddled iron and rolled into flats for the rail pile, which latter was to be of a section seven inches square, and after being heated, and reduced, by rolling, to a bloom of a section about five inches by six inches, was to be reheated, before being finished into the rail of the T pattern, four inches high, weighing sixty-four pounds per yard. Great care was exercised in the execution of this contract, and the rails being distributed over all parts of the road, gave general satis¬faction by their excellent wear. Five years afterward, the principal proprietor and manager of the Fairmount Rolling Mill was elected President of the Reading Railroad, and very many of the rails made under his supervision were still in use in the tracks of the company, of which he had just assumed the management. His first efforts were, therefore, directed to the procuring of more rails of the same quality wherewith to replace those worn out. Here he encountered some trouble, makers refusing to bid because of the details in the specification, the required reheating being the objectionable feature, for which it was generally intimated they would not be sufficiently remunerated for the increased labor, extra coal consumed, and the changes necessary from the established methods of working. Most of the new rails were, therefore, bought, and the old rails rerolled without regard to any particulars as to the manner of piling, heating, etc., each manufacturer furnishing what he deemed the best article possible for the money. As a consequence, rails of all imaginable grades were placed in the tracks, some giving out in six

Jan 1, 1877

By Robert L. Davidoff

INTRODUCTION The impact of taxation differs substantially from state to state in a complex fashion that depends on both the physical characteristics of a mineral deposit and on the price of the mineral commodity relative to its costs of production. A comparative analysis of the tax structures of eight states (Arizona, Colorado, Idaho, Montana, Nevada, New Mexico, Utah and Wisconsin) showed wide variations in rates of return for any given type of mineral property, with no state having either the most burdensome or least burdensome tax structure under all circumstances. Three hypothetical mineral operations were analyzed: a producing open-pit copper property, a non-producing underground platinum operation, and a non-producing underground gold operation. None of them corresponds exactly to an existing property. Each of these property types is further defined to have ore feed grades at three different levels, leading to three potential profitability levels, referred to in this paper as "economic", "marginal" and "subeconomic". Thus the differential impact of state tax structures is measured for mineral properties of different types, as well as for different profitability levels. Montana is used as the base case. This study does not address the topic of corporate structures or tax consolidation. There are no costs assumed external to the operation of the deposit (e.g. exploration to locate additional deposits). Two types of analyses were performed for this study. The first calculates the total cumulative tax payments in each state using all applicable taxes (including U.S. federal income taxes and examines the resultant differences in discounted cash-flows rate of returns DCFROR's amoung the eight states. The second is a sensitivity analysis that examines each type of state tax separately (i.e. state income, property, and severance taxes) in order to isolate and examine the differences in tax payments that are due to the difference in rates and methods of computing specific types of taxes in each state. The results of this study serve to illustrate the complex nature of interactions among various taxes. For example, property tax is a deduction in calculating severance tax in some state. Changes in property-tax and severance-tax payments both enter into the calculation of state and federal income-tax liability. This, in turn, could change the timing and usage of tax-loss carry forward amounts and investment tax credits. Additionally, the physical characteristics of a property, the method and costs at which the mineral will be extracted, and the profitability level at which each property operates will affect tax treatment. Each mineral operation was evaluated at three different predetermined profitability levels, referred to using the terms economic, marginal and sub-economic. These three profitability levels are defined by the ore feed grades of the primary commodity that yield in constant terms, approximately an "economic" 18% DCFROR, "a marginal." 10% DCFROR, and a "sub-economic" 5% DCFROR, respectively, under the Montana tax structure. In the analyses, the mining and processing parameters for each of the three types of properties were assumed to be identical for each of the eight states. It was assumed that each operation produces at full operating capacity throughout its life. This implies the level of mineral commodity demand will support the inferred commodity price, such that each operation will be able to sell all its output. The analyses performed for this study were done using a comprehensive economic evaluation simulator that is used in the Bureau of Mines, Division of Minerals Availability MAS program to perform DCFROR analyses. All economic evaluations performed upon these data (see appendix 2) were in constant January 1981 dollars. By-product prices used for the analyses were: [Gold $425.00/troy ounce Palladium$200.00/troy ounce Silver $ 10.00/troy ounce] Typical cash-flow calculation layout is given in Appendix 3. The initial step for each evaluation is to define an "economic" profitability level scenario. An 18% DCFROR rate in Montana was considered the

Jan 1, 1985

By David Sinclair, Philip B. Bucky

THE dimensions and shapes of mine structures may at present be determined by (1) field experience, (2) structural calculations, and (3) barodynamic tests.§ None of these, however, provide information as to the stresses, their direction and distribution in a mine structure. For the design of pillars, the placing of openings relative to working places such as gangways, haulage levels, etc., this information is desirable. Photoelastic methods provide this and, while relatively new, their application in all engineering fields is assuming increasing importance. This paper, therefore, will present the method with a few applications to mining, and with sufficient reference for further study by the reader. PART I THE PHOTOELASTIC METHOD The photoelastic method of stress measurement determines the stress distribution in a two-dimensional model by optical means. It makes use of the fact that when a piece of isotropic transparent material, such as glass, celluloid, or Bakelite, is stressed and viewed in polarized** light a picture is seen which indicates by its color bands of light, or fringes, the magnitude of the stresses, their direction and their distribution. GENERAL EXPLANATION The stress at any point 0 in a structure (Fig. 1), may be resolved into two components, P and Q, each a pure tension or compression, at right angles to each other, called principal stresses.1 To fully identify the stress, the values of P and Q and their directions or angle [0] must be known.

Jan 1, 1940

By John H. Hollomon

IN a recent paper,1 a very early suggestion by Ludwik2 concerning the nature of the mechanical behavior of metals has been reexamined and extended. In essence it was [ ] suggested that there exists, at least under certain conditions, a mechanical equation of state; that the stress required for flow depends upon the instantaneous values of the strain, strain rate, and temperature, and not upon their past values. It is proposed that under these circumstances the stress does not depend upon past history of these variables, but is like the temperature of a gas that depends only upon the I instantaneous values of the pressure and volume. This notion has not been applied to present day studies of metals, though it is especially applicable to the study of creep. It is the purpose of this paper to analyze the significance and possible range [ ] of applicability of this idea and to deter- mine how it influences the accepted ideas concerning creep. STRESS-STRAIN RELATIONS It is well known that the stress-strain curves of metals are influenced by both strain rate and temperature. For a fixed strain rate and temperature there is associated with each metal a stress-strain curve. If either the strain rate or temperature is changed a new stress-strain curve will be characteristic (Fig. I). A much more general relation between the effects of the sevariables is possible, however. Consider the stress-strain curves of Fig. I determined at

Jan 1, 1946

By V. N. Burnhart

After eight years of testing and development, the E. J. Longyear Co. has adapted the wire- line core barrel to small diameter drillholes. Field performance indicates that the apparatus for the BX hole will be an important supplement to the conventional techniques used in the diamond core drilling industry. Higher core recovery, faster drilling progress, and reduced diamond costs will provide substantial savings to the user of coring equipment. The wire-line principle is not new, having been successfully applied to the large-diameter holes of the petroleum industry. But scaling the practices of core recovery in oil well drilling down to the small BX hole presented a number of problems. The technique, difficult even for large holes, was complicated by the exacting limitations of the small diameter in which durable and foolproof mechanisms would be required to operate. Since the maximum benefits could be realized from this sys- tem in holes 1000 ft and deeper or in holes in badly fractured ground, the drill string would have to be able to withstand heavy stresses. Most vital to the success of the idea was the development of a positive latching mechanism to assure proper positioning of the inner tube of the core barrel when the tube is dropped into place. Lastly, little was to be gained from the wire-line method without diamond bits that would give optimum penetration rates and a long service life in the drillhole.

Jun 1, 1955

By T. E. Weirich

Although 1931 witnessed no new discoveries of oil or gas in Oklahoma, the year is especially outstanding because of price demoralization, political intervention, abandonment of marginal properties, a strict curbing of oil flow from wells in flush fields and an extension of proration into settled fields. In spite of a strict, adherence to proration agreements, the price per barrel of oil sank from 65c to $1.07 to a low level of 10c to 22c. Table 1 gives the price range for crude oil in Oklahoma during the year. Under a martial law order by the governor, a period intervened from Aug. 4 to Oct. 10, of complete shutting in of the flush fields. This condition created an abrupt decline in the production curve during the two months' period. Oklahoma, as elsewhere, is passing through a "transition period" of relieving expensive above-ground storage by maintaining the more copious supplies of crude oil in the natural reservoirs. For many years the thousands of small, nearly depleted wells have been considered as being the "backbone of the industry." A large number of wells of this type are now idle or completely abandoned. More than 1100 abandonments were recorded by the state Corporation Commission during the year. The industry is becoming less interested in these small wells, replacing the former attitude by the curbed potentialities of flush pools. Many of the major companies are grouping these marginal properties with those of adjacent owners, operating the whole

Jan 1, 1932

By L. W. Holm, G. G. Bernard

Laboratory experiments were conducted to determine the effect of foam on gas flow in porous media. Previous studies have indicated that foam may be applicable as a restrictive agent in influencing underground gas flow. Foam was found to be exceedingly effective in reducing the permeability of porous media to gas. Consolidated and unconsolidated sands with specific permeabilities of 100 to 146,000 md had, in the presence of foam, gas permeabilities that were less than 1 per cent of the specific permeability; in many cases the gas permeability was practically zero. Foam reduced the gas permeability of loose sand to a much greater degree than that of a tight sand. For example, the permeability of a 125,000-md sand was reduced to 3 md while the permeability of a 4,000-md sand was reduced to 7 md. This effect should cause, to some degree, selective plugging of high permeability channels in various oil displacement processes. The presence of oil in a porous medium decreased the effectiveness of foam in reducing gas permeability; apparently oil acts as a foam depressant. However, it was found that certain foaming agents were very effective in reducing permeability even. in the presence of oil. Also, continuous injection of other foaming agents increased their effectiveness, when oil was present. The effect of foam on permeability of porous media to gas was studied as a function of foaming agent concentration and injection rate, absolute permeability, total pressure, pressure gadient, length of porous system, brine concentration and time. INTRODUCTION The use of surface active agents in flood water to increase the recovery of oil has been studied in the laboratory and in the field for decades, with rather limited success. In recent years a new approach to the problem was proposed. Instead of using an aqueous solution of surfactant as an oil recovery agent, Bond and Holbrook2 proposed that the oil recovery agent be a mixture of surfactant solution and gas. In their method, a water-soluble surface active agent with foam-producing characteristics is injected into an underground formation as an aqueous slug. This slug is followed by gas to produce a foam within the rock. Foams are defined as "agglomerations of gas bubbles separated from each other by thin liquid films'! A foam is fundamentally an unstable system. The foam process for oil recovery has since been studied by other investigators. Fried 1 has shown that foam can displace from porous structures oil that normally is unrecoverable by conventional water or gas drives. This superior oil displacing action is believed to be the result of several factors: (1) foam introduces into the reservoir many resilient interfaces of various sizes and curvatures, which increase the probability that a proper combination of forces for oil displacement will be created; (2) foam has appreciable viscosity which improves mobility ratio and contact efficiency; (3) foam accentuates the trapped gas effect because high gas saturations are possible without producing high gas/oil ratios. Deming4 studied the effect of various foam properties on the displacement of liquid. He found that (1) high foaming ability favors high displacement efficiency; (2) high foam stability is not necessary for high displacement efficiency; (3) displacement efficiency decreases with increase in plasticity of foam and (4) displacement efficiency is unaffected by surface tension of foaming agent solution. One of the important aspects of this oil recovery process is the effect of foam on gas permeability. The simultaneous flow of gas and liquid in porous media has been studied by numerous investigators and a large amount of literature exists on the subject. In this previous work, gas and liquid have generally been considered as essentially independent phases, whose flow characteristics are related through the saturation parameter. Foam, however, is a material with properties that are considerably different from those of its components; for example, the viscosity of a foam is greater than either of its components. Gas flow in a porous medium in the presence of foam should be considerably different

Jan 1, 1965

By G. L. Simard, D. J. Salley, J. Chupak

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,', ' were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.' Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951

By J. Chupak, D. J. Salley, G. L. Simard

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,', ' were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.' Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951

By Charles C. Peterson, Ronald E. Enstrom

Significant improvements have been made in the ursine systern for epitaxial vapor gvowtlz of Gds. The electron concentration has been reduced to below 1015 cm-3 with electron-mobility values as high as 7200 sq on per v-sec at 30PK and 60,000 sq cw7 per v-sec at 77°K. These high-purity layers have been successfully gvown on n&apos; layers with thicknesses as snzall as 1 p and as large as 125 p. Furthermore, high-purity layers have been incorporated into an structure without degradation of electrical properties. Different impurity gradients at the n&apos; to n interface were achieved. Using these structures, Gunn oscillators have been operated at frequencies as low as 0.4 GHz and as high as 40 GHz, which equals the highest valzle yet reported. The frequencies nleasured are in reasonable apeenlent with those calculated fron7 the n-layer widths and the transit times. CW operatiolz has been achieved from 3 to 20 GHz. In Gunn devices for >40 GHz operation (i.e., witk an n-layer tkickness below 2.5p), the n layer has been generally too pure to permit oscillations to occuv. ThE mechanism of the Gunn oscillator&apos; is now generally understood.2-5 Electron transfer from the (000) minimum to the ( 100) minima leads to a voltage-controlled negative resistance, which results in the formation of domains of high and low electric fields which travel through the crystal with a characteristic velocity of about 107 cm per sec. When a constant voltage is applied to the sample, this domain motion generaliy leads to oscillations at the transit time frequency, fT = 107/L, where L is the thickness of the active n layer.&apos; In this case, a single high-field domain is nucleated at the cathode and grows until it reaches the anode, where it is absorbed; a new domain then forms at the cathode.5 There are related modes of oscillation of the same device in which a tuned circuit causes a periodic variation of the voltage across the device. The frequency then may be either above or below fT. It has been shown that oscillations will occur when n • L 2 1012 cm"2, where n is the carrier concentration in the active region. At lower doping densities, 10" 5 n . L 5 lo&apos;&apos;, the doping is said to be subcritical for oscillation and the description of the device operation changes since the domains become comparable in thickness to the device thickness, L. Nevertheless, such devices have been found to be "active" and, in fact, are useful as amplifiers.778 For CW operation, one wishes to minimize the power dissipation, which is related to the electric field, E, and the low-field resistivity, p. Below threshold, the power dissipation density is approximately Typically, at threshold where E -- 3 x 103 v per cm, the dissipation density is 107/p watts per cu cm, p in ohm-cm. Furthermore, it is desirable to provide good conduction of the heat generated in the active region. The temperature rise, AT, across the active layer of a sandwich structure, with a heat sink on one side, is given by AT = (E&apos;/P)(L~/~~) where it is assumed that the thermal conductivity, u, and resistivity, p, of GaAs do not vary appreciably over the range of temperature and electric fields existing in the layer. This expression shows that, subject to maintaining an appropriate (n . L) product, CW operation is favored by a higher resistivity, a lower threshold field, and a thinner device. The above device requirements place some severe restrictions on the materials to be used, especially for high-frequency (>10 GHz) operation. Here, it is necessary to prepare very thin (<10 µ) layers of GaAs, in a state of high purity (-1 ohm-cm), complete with very low-resistance ohmic contacts. Problems of handling such thin and fragile samples become inereasingly severe as the frequency is raised. Furthermore, while good low-resistance ohmic contacts are easily applied to low-resistivity GaAs, contacting difficulties are encountered for these higher-resistivity materials.

Jan 1, 1968

By C. F. Gates, H. J. Ramey

Recent literature shows that pronounced increases in oil recovery can result from the use of miscible systems in recovery operations. This literature also points out certain problems associated with maintaining miscibility, e.g., compositional changes resulting from alterations in pressure and temperature or from zone dilution. The purpose of the work described in this paper was to study miscible zones for possible use in waterflooding operations and examine the manner in which these zones break down. The fluid system selected for study was oil—terNary-butyl alcohol—water, which, because of its narrow range of miscibility, is ideally suited for investigation in short, linear systems. The laboratory-observed effects on oil recovery and zone stability of a number of variables are reported. Among the variables investigated were miscible zone size, viscosity ratio, length of travel, and interstitial water saturation. Results obtained with this system show that interstitial water adversely affects recoveries because of premature phase break. Salinity of the water further aggravates Ais situation. This effect, although pronounced for this system, would probably occur in any fluid system containing an alcohol. As expected, viscosity ratio has a decided influence on recovery efficiency and zone stability. The results also show that use of a suficieno zone size, even though the system has poor phase characteristics, yields higher oil recoveries than are obtained from straight water floods. Length-of-travel studies showed a square root relationship between zone growth and path length for favorable viscosity ratios. No such clear-cut dependence was observed under unfavorable viscosity conditions. INTRODUCTION As new oil reserves have become increasingly more difficult and expensive to find and develop, the oil industry has devoted more and more time and money to finding more efficient methods for exploiting known reserves. The increasing number of water floods is one manifestation of this attempt to improve oil recoveries from existing fields. Since considerable quantities of oil are by-passed by the waterflood process, it is only a partial answer to the problem. The search continues. Of late, several proposed processes have received the critical attention of investigators. Among them are gas drives, in situ thermal reactions and miscible displacements. The present paper is concerned with miscible displacements in conjunction with water floods. Recent literature1- reports that, under proper conditions, oil recoveries from LPG floods, propane sweeps, condensing gas drives, etc., approach 100 per cent of the oil in place in the region contacted by the flood. This literature also points out some of the problems associated with these processes, one of the main ones being the maintaining of miscibility. Compositional changes resulting from pressure and temperature variations or from zone dilution give rise to phase breaks and loss of miscibility, the conclusion being that, after loss of miscibility, much of the beneficial influence of the zone is lost.&apos; The results of the subject work show that, if sufficient zone material exists ahead of a phase interface, considerable improvement in oil recovery can be obtained. In order to increase our understanding of the behavior of miscible systems as they degenerate into immiscible processes, a laboratory system having rapid deterioration characteristics was needed. The fluid system oil—ter tiary-butyl alcohol (TBA)—water possesses these properties and was the system investigated. Although these fluids are different from those generally employed in miscible studies, an understanding of their behavior can be applied to other miscible slug processes. However, under conditions where mass transfer maintains a miscible system through multiple contacts, e.g., enriched gas drive or high pressure gas drive, the observed behavior of alcohol zones would not be applicable. The variables of interest were zone size, viscosity ratio, length of travel, initial water saturation, rate and core characteristics. Of these, only the effects of the following on zone breakdown and oil recovery are reported in detail: (1) zone size, (2) path length, and (3) initial water saturation. The effects of viscosity ratio and core characteristics are discussed in conjunction with other variables. Although initial water saturation is not envisioned as important to the phase behavior of hydrocarbon systems, e.g., LPG, it is important in alcohol systems. The properties of the fluids and cores used are given in Table 1. As previously stated, this fluid system was selected because of the limited range of miscibility

C. A. ROSE, New York, N. Y. (written discussion *).-Without doubt the excellent results obtained at Ajo will cause surprise among metallurgists; 75 per cent. average capacity and 80 per cent. extraction during the first year of operation of a plant using a new metallurgical process are figures that speak for themselves. It is obvious that the most troublesome feature of the process is the fouling of solutions. The effects of this are most evident in the electrolytic tank house; but apparently the solutions are so heavily loaded with salts that their dissolving power is also impaired. This is indicated by the fact that copper comes into solution during washing after the leaching of the ore is completed, as shown by the decreasing ratio of acid to copper in the various washes tabulated in Table 4, and also by the fact that 4.9 per cent. of the total copper in the ore remains in the tailings in a soluble form. Even though the extraction in leaching and the ampere efficiency in electrolysis would be benefited by keeping the salts in solution at a lower concentration, it is doubtful whether it would pay to decrease these salts by discarding more electrolyte without other changes in the, process, since this would increase the amount of cement copper produced, which is already very large. If, however, it would not disturb the process otherwise, this object could be accomplished by increasing the range of electrolysis, so that solution going to the tank house would contain, say, 4 per cent. copper and 1 per cent. acid, and the solution returned to the leaching plant 1 1/2 per cent. copper and 4.8 per cent. acid, and by increasing the volume of solution to be discarded, this to be taken from the electrolyzed solution returned to the leaching plant. By this arrangement, more salts will be removed from the system per ton of cement copper produced; and if sufficient solution is discarded to keep the iron content down to 1 1/2 per cent. it would he feasible to recover the copper from

Jan 4, 1919

By E. T. Peters, L. E. Tanner

In the course of a study concerned with the rnechanical behavior of the intermetallic compound CO3V, both structural observations and anomalous electrical-resistivity behavior indicated the presence of a new high-temperature phase in an alloy with the stoichiometric composition, Co-22.4 wt pet V. The evidence, which is given below, suggests that the new phase is situated between the low-temperature ordered hexagonal phase, k,1, 2and the high-temperature disordered fee solid solution, a,3 within a small range of temperature in the vicinity of 1070°C. Structural studies included X-ray diffraction analysis* and electron-transmission microscopy examination* of stoichiometric composition speci- mens homogenized for 1 hr at 1200oC and either air-cooled or water-quenched. The air-cooled specimens yielded X-ray diffraction evidence of the k phase, while electron microscopy revealed a microstructure of both heavily and moderately faulted regions as shown in Fig. 1. The high density of stacking faults (or fine twins) in region A is reminiscent of hexagonal cobalt following its allotropic transformation.4 Selected-area diffraction from this region revealed distinct superlattice reflections of the ordered hexagonal phase, as well as continuous rel-streaks which were normal to the fault planes in the micrograph. The latter is indicative of extremely small spacings between the faults.&apos; Regions such as ß were found to be only partially transformed to the k phase. Attempts to study the antiphase domain structure by either bright- or dark-field techniques were unsuccessful in these initial studies. This was due to the low intensity of the superlattice reflections arising from the closeness of the cobalt and vanadium scattering factors. Quenching Co3V from above Tc appears to suppress the formation of the k phase. Both X-ray and electron-diffraction results indicated that the disordered phase, a, was partially ordered during severe cooling and that the structure of the ordered phase was of the L12 (Cu3Au) type,6 designated here as a&apos;. As in the case of the hexagonal phase, examination of the domain structure was unsuccessful; however, significant information concerning the morphology of this condition was revealed by the appearance of dislocation arrays. In particular, it

Jan 1, 1965

By Charles Y. Clayton

Cast-steel runners, while not interesting from a commercial standpoint, furnish valuable material for microscopic study. Folcyl found not only the usual ingot structure, but zones of Widmannstättian structure, which he explains as due to differential crystallization. The writer, in examining nickel-steel runners, found a type of pro-eutectoid ferrite that is unusual and most probably new. The runner in question was 8.75 cm. (3.5 in.) in diameter and analyzed at its center 2.69 per cent. nickel and 0.350 per cent. carbe a and at its edge 2.62 per cent. nickel and 0.359 per cent. carbon. Th macrostruc-ture, which is the usual type, is shown in Figs. 1 and 2, which are a cross-section and the longitudinal surface, respectively. Slight segregat&apos;ion of ferrite can be seen near the center of the segment and at other points near the edges of polyhedral grains. Stead&apos;s reagent brings out the dendritic structure within the grains as shown in Figs. 3 and 4. This texture is what would be expected of such a steel. Figs. 5 to 10 show the peculiar swirls of pro-eutectoid ferrite, the finding of which prompted this paper. These swirls, or eddies, if such a term can be applied, occur in all parts of the runner and in all parts of the individual grains. The upper left-hand figure shows this ferrite at a grain boundary; the middle left-hand figure shows the inner portion of a grain; and the lower left-hand figure shows these swirls at the edge of a grain which is also the outer edge of the runner. Straight-lined ferrite associated with swirls is found in the areas of Figs. 11 and 12. The texture of the carbon-bearing constituent of the runner is shown to some extent in Fig. 12, the pearlite being very fine or sorbitic. Higher magnification does not bring out any new features either in the peculiar ferrite or in the pearlite. Figs. 13 and 14, at 240 diameters, show the curved and straight-lined ferrite.

Jan 1, 1922

By Charles Y. Clayton

Cast-steel runners, while not interesting from a commercial standpoint, furnish valuable material for microscopic study. Folcyl found not only the usual ingot structure, but zones of Widmannstättian structure, which he explains as due to differential crystallization. The writer, in examining nickel-steel runners, found a type of pro-eutectoid ferrite that is unusual and most probably new. The runner in question was 8.75 cm. (3.5 in.) in diameter and analyzed at its center 2.69 per cent. nickel and 0.350 per cent. carbe a and at its edge 2.62 per cent. nickel and 0.359 per cent. carbon. Th macrostruc-ture, which is the usual type, is shown in Figs. 1 and 2, which are a cross-section and the longitudinal surface, respectively. Slight segregat&apos;ion of ferrite can be seen near the center of the segment and at other points near the edges of polyhedral grains. Stead&apos;s reagent brings out the dendritic structure within the grains as shown in Figs. 3 and 4. This texture is what would be expected of such a steel. Figs. 5 to 10 show the peculiar swirls of pro-eutectoid ferrite, the finding of which prompted this paper. These swirls, or eddies, if such a term can be applied, occur in all parts of the runner and in all parts of the individual grains. The upper left-hand figure shows this ferrite at a grain boundary; the middle left-hand figure shows the inner portion of a grain; and the lower left-hand figure shows these swirls at the edge of a grain which is also the outer edge of the runner. Straight-lined ferrite associated with swirls is found in the areas of Figs. 11 and 12. The texture of the carbon-bearing constituent of the runner is shown to some extent in Fig. 12, the pearlite being very fine or sorbitic. Higher magnification does not bring out any new features either in the peculiar ferrite or in the pearlite. Figs. 13 and 14, at 240 diameters, show the curved and straight-lined ferrite.

Jan 1, 1922