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By S. Brunauer

The hydration of portland cement is treated as a chemical reaction and the changes in matter, in energy and the rate of change of the process are discussed, Portland cement is a mixture of four major and at least as many important minor constituents. In the hydration process, the four major compounds (trical-cium silicate, dicalcium silicate, tricalcium alumi-nate and tetracalcium aluminoferrite), plus gypsum and water form five or six new compounds. In spite o the great complexity of the reaction, considerable progress has been made in its understanding, primarily with the help of such research tools as X-ray diffraction and electron microscopy. The rate of the reaction can be followed by direct and indirect methods of measurements. The effects o composition, particle size (or specific surface), temperature and water-cement ratio on the rates of hydration are discussed. The hydration of portland cement is a chemical reaction accompanied by such highly important physical phenomena as heat evolution, setting and hardening. It is a vast and complex subject, on which hundreds of papers have been published. At the time of the writing of this paper, in October 1962, a two-volume book, which alone contains dozens of papers pertaining to cement hydration appeared in print.' The present paper deals with a few aspects of this vast subject, and the selection was not easy. The work reported here deals with some of the most recent investigations in the field. In any chemical reaction, the physical chemist is primarily interested in three things: changes in matter, changes in energy and the rate of change of the process or the speed of the reaction. This is true also of the chemical reaction between portland cement and water, and all three aspects of the reaction will be discussed. These three aspects are of vital interest to the engineer as well. Portland cement is not a cementing material — the hydration products, the new materials which form in the reaction, have the cementing action. The energy changes manifest themselves in a considerable evolution of heat, which may be useful or harmful. It is useful, for example, in winter concreting, but in very large concrete structures like dams, a large evolution of heat, which cannot be easily dissipated, may produce distress in the structure. Primarily for such a purpose was the Type IV or low heat portland cement developed. The speed of the chemical reaction is important because it determines the time of setting and hardening. The initial reaction must be slow enough to permit placing of the concrete before setting occurs. On the other hand, after the placing of concrete it is often highly desirable to obtain as rapid chemical reaction as possible. For this purpose the Type 111 or high early strength portland cement was developed. CHANGES IN MATTER Portland Cement: In a basic investigation, before one begins to study a reaction, one either knows the quantities and compositions of the starting materials, the reactants, or one determines them. This is obvious; the chemist expresses the changes in matter that occur in a reaction by a chemical equation, which has the quantities and compositions of the reactants on the left side of the equation and the quantities and compositions of the reaction products on the right side. The first question is then what to put on the left side of the equation in the reaction between portland cement and water? It is not very easy to answer this question. Portland cement is not a single chemical compound but a mixture of many compounds. Four of these are considered the major compounds, and at least four of the minor compounds also play important roles in the hydration reaction. In order to avoid complicating matters, the present discussion will be restricted primarily to the four major compounds, which constitute usually more than 90% of a portland cement. The relative amounts of these compounds vary from cement to cement. Actually not only the amounts but the compositions of these constituents also vary to some extent, but the variation in composition of the individual components will be neglected for simplicity.

Jan 1, 1963

By E. E. Thurlow

The Geology Div. of Northern Pacific Railway Co. has adapted to its exploration efforts field procedures for geochemical sampling and semi-quantitative analysis which have been developed through research by the U. S. Geological Survey. The sampling is done in conjunction with reconnaissance geologic mapping on aerial photographs or during field checking of maps which have been prepared largely by photo-geologic interpretation. Stream sediment or soil samples are taken and readily soluble combined heavy metals are extracted with ammonium citrate followed by colorimetric titration with dithizone at the sample site. The effectiveness of this approach has been demonstrated both in positive and negative results, thereby assisting in the elimination of large areas of land from further immediate attention and in providing targets for followup exploration. An occa sional sample is submitted for spectrographic analysis as a check on the possible presence of other elements of economic significance. Field laboratory procedures are also being implemented for determining molybdenum, mercury, and other metals which may be valuable in themselves or useful as pathfinder elements in outlining mineralized areas. A lead-zinc occurrence in Oregon and a copper deposit in Montana were readily detected and outlined by stream sediment and soil sampling and a heavy metal anomaly that lacks obvious interpretation has been found in northwestern Montana. Detailed mapping and additional sampling are followed by other exploration techniques if warranted. Northern Pacific's program of reconnaissance mineral evaluation of company-owned lands and adjoining areas was outlined in a paper presented at the American Mining Congress meeting in Las Vegas four years ago. That report included policies and procedures with respect to mineral development on Railway Co. lands and may be referred to for information on these matters.1 In a sense this paper is a progress report on the use of geochemical prospecting in Northern Pacific's continuing mineral evaluation program. At this time there are positive results but as yet there is no real success story in the form of a minable ore body. GEOCHEMICAL PROSPECTING PROCEDURES The decision to use geochemistry as a reconnaissance exploration tool must be followed by research into sampling and analytical methods and into the interpretation of results. Various analytical methods were tried and evaluated by the Geology Div., including hot and cold acid extraction with and without fusion of the sample, panning and magnetic separation followed by dithizone testing of the magnetite, and cold aqueous extraction of metallic ions followed by indicator tests. Samples were first sent to the laboratory for analysis; later field laboratories were established and now virtually all testing is done at the sample site. It was concluded that, where applicable, the quickest dependable methods for reconnaissance use are the dithizone field tests for readily extractable heavy metals. This involves the simultaneous treatment of a sample, usually of soil or stream sediment, with two immiscible liquids; one a cold aqueous extractant (ammonium citrate) and the other a solution of dithizone in toluene or xylene.2 Dithizone is a colorimetric indicator that reacts quantitatively with copper, lead, zinc, and several other metals to form colored complexes in organic solvents. Results may be expressed in ml of 0.001 pct dithizone that are required to reach the blue end point, or calibration of the test results can be carried out with standard solutions of zinc; conversion factors would then be expressed in ppm, zinc equivalent. Calibration of dithizone solution with zinc standards indicates that 1 ml of 0.001 pct dithizone is equivalent to approximately 0.25 ppm of zinc. An authoritative report on dithizone field tests authored by H. E. Hawkes in the June-July 1963 issue of Economic Geology* states "The appeal of these techniques has been the simplicity and speed of the determinations as compared with more tedious laboratory determinations of trace metals in weathered rocks, soils, or plant materials. This obvious appeal, however, has often been more than matched by misuse of the method in such a manner that the results are

Jan 1, 1964

By E. O. Bennett

When oil is takcn from a subsurface structure it is generally accompanied by gas. The gas thus produced represents the 1ighter hydrocarbons present in the original petroleurn accurnulation, which arc, insoluble at the reduced pressures created around a well when it is producing. In some cases the gas accompanying the oil may come from a gas-bearing stratum not in immediate contact with the oil. The amount of gas from the formation accompanying each barrel of oil is called the natural gas factor. Energy Causing Well to Flow The force causing the flow of fluid into a well when it is drilled into an oil-bearing structure is the pressure differential between the well bore and the formation. A pressure differential between the formation and the well may be set up in three different ways, as follows: (1) pressure due to gas in solution or in contact with the oil, (2) hydrostatic pressure due to water in contact with the oil (it may be either bottom or edge water); (3) pressure difference due to forcc of gravity. The greatest source of energy for producing oil from most oil fields, and the one over which the greatest control can be exerted, is the poten-tial energy in the gas under pressure in the formation. In any pool there is but a definite amount of gas available. Part of this gas may be in solution and a part in contact with oil. The amount of gas in solution in each bard of oil depends on the pressure and temperature in the formation and the characteristics of the oil. Whether the gas is in solution or in contact with the oil it is necessary to use the energy it, contains as efficiently as possible in order to obtain the greatest ultimate recovery from the pool. Bush1 states: Gas being the most efficient aid in moving the oil, it is important to prevent more of it from escaping than is necessary to remove the maximum amount of oil from the sands. The conservation of this energy is far more important to the producer of oil than his returns from sales of gas to distributing companies. The flowing life of the well is the most profitable period, and keeping the gas-oil ratio low, or keeping the

Jan 1, 1928

By T. Sekimoto, T. Kokubo, M. Yamamoto, K. Masuda, T. Moro, H. Sakamoto

The choking-free cyclone was developed primarily to remove solid particles suspended in a slurry containing fibrous materials, such as municipal solid waste. This cyclone is characterized by a screw conveyor at the underflow side of the cyclone. The screw conveyor has a hollow rotational shaft for air supply and is driven by a variable speed motor for discharge control. Even if the underflow discharge is highly concentrated, this type of cyclone can be stably operated without nozzle choking. High classification efficiency similar to that of a conventional cyclone can be obtained as a result of air introduction through the hollow rotational shaft. The recovery of organic matter and the removal efficiency of inorganic matter were actually improved by the application of this cyclone to municipal solid waste. After applying this cyclone to the desliming of fine sand, sand product of low water content was recovered.

Jan 1, 1980

By J. B. Davis

This paper has been prepared at the suggestion of Mr. Dunbar D. Scott, to supplement his " Evolution of Mine-Surveying Instruments."† Before entering into a detailed history of solar instruments, a few remarks will be made touching upon land-surveys in general, and on what has led to the development of these instruments.The oxidation of metals melted in contact with air takes place with dissimilar results. Tin, lead or zinc are examples of a class, the oxides of which float on the surface of the melted metal. First a film is produced, which covers the surface; then, if agitation from any cause exposes new metal to the action of the air, additional oxidation takes place, and the film is increased in volume. This change goes on until a considerable quantity of oxide (or " dross," as it is technically called) is formed; depending, of course, upon the duration of the exposure of the metal to the atmosphere. When such metals are poured, the dross may be skimmed off; and clean metal will be left underneath. The removal of such oxides is, therefore, merely a mechanical process. In the case of copper, however, the result is quite different. The sub-oxide of copper (Cu2O) is readily soluble in molten copper; and therefore, instead of the formation of a film of oxide, to be finally removed as dross, the surface of the metal remains bright and clear, because the oxide has been dissolved as soon as it was produced. It is customary in the process of copper-refining to leave a small quantity of oxide in the metal, in order to oxidize any traces of bismuth, arsenic or antimony which have not been entirely removed. As a result, these metals exist in the commercial product as oxides, and not as metals, which would form an

Jan 1, 1901

By E. A. Steigerwald, G. L. Hanna

The influence of work-hardening exponent on the variation of fracture toughness with material thickness was studied for high-strength steel, aluminum, and titanium alloys. The results indicate that, when materials are compared at similar fracture toughness to yield strength ratios, the material with the lower work-hardening exponent undergoes the transition from flat to slant fracture at a larger thickness than material with a high work-hardening exponent. In the thickness range where complete slant fracture is obtained the reverse is true and a lower work-hardening exponent results in a lower fracture toughness. The influence of work-hardening exponent on fracture toughness is, therefore, dependent on the particular fracture mode. In the transition region a low work-hardening exponent is beneficial for fracture toughness while in the 100 pct slant region it is detrimental. THROUGH the use of fracture mechanics analyses, the influence of geometric variables on the crack propagation resistance of structures can be interpreted with reasonable consistency. However, in order to gain a more complete understanding of the fracture process, the influence of material parameters on crack propagation must be defined and coupled to the macroscopic fracture mechanics approach. The work-hardening exponent, which characterizes specific material behavior, may serve as an effective parameter to allow some degree of coupling to be accomplished. In the extension of a crack in a specimen of suitable dimensions the propagation process occurs in a stable manner when the crack extension force is balanced by the resistance to crack extension, which exists in the material at the crack tip. As the applied stress, and therefore the crack extension force, on the specimen increases, the resistance also increases primarily because the effective plastic zone at the crack tip, which is the main energy absorption process, becomes larger. Since the work-hardening rate of a material influences the stress-strain relationship, it will also influence the energy absorption process in the plastic enclave at the crack tip and hence should have an effect on crack propagation. A number of studies have been made correlating the strain-hardening exponent or the strain to tensile instability with the ability of a material to resist fracture. Gensamer1 concluded that a low-strain-hardening exponent would result in a steep strain gradient at the base of a notch. He reasoned that a large work-hardening coefficient would result in high-energy ab- sorption due to the increased area under the stress-strain curve. Larson and Nunes2 experimentally observed in Charpy tests on steels heat-treated to below 200,000 psi yield strength that the energy to failure in the fibrous mode, i.e., above the brittle-to-ductile transition temperature, was logarithmically related to the strain-hardening exponent. In order to avoid the complicating effects present in studying materials which undergo a brittle-to-ductile transition, Ripling evaluated the notch sensitivity of a variety of fcc metals with varying work-hardening exponents.3 The results indicated that the relative notch sensitivity, as determined from tests on specimens with a sharp notch, decreased with increasing values of strain hardening. Although the energy required for ductile or fibrous fracture increases with increasing work hardening, high-strength steels often exhibit improved crack propagation resistance when heat-treated to obtain low values of strain hardening.4,5 An analysis of whether low strain hardening is beneficial or detrimental to crack propagation resistance must depend on the particular fracture criterion involved. At temperatures where the material is relatively ductile and the development of a critical strain is required for fracture, high strain hardening increases the energy required to produce failure. In the transition region and below, however, a critical stress law appears to be valid6 and a low rate of work hardening may produce superior resistance to semibrittle crack propagation. The experimental program is aimed at studying these possibilities and determining the specific influence of strain hardening on the crack propagation resistance of several high-strength materials. MATERIALS AND PROCEDURE The alloys, chosen as representative of various classes of high-strength materials, are summarized in Table I. The heat treatments evaluated along with the smooth tensile properties are presented in Table 11. Pin-loaded sheet tensile specimens were employed to determine the smooth tensile properties. A strain gage extensometer (measuring range 0.200 in.) was used at a strain rate of 0.02 in. per in. per min. The work-hardening exponents were determined from the stress-strain curves generated in the smooth tensile tests and the assumption that the portion of the stress-strain curve beyond the yield point can be described by the power relationship: where a is the true stress, P is the true plastic strain,

Jan 1, 1969

Discussion of the paper of L. C. Graton and Joseph Murdoch, presented at the New York Meeting, February, 1913, and printed in Bulletin No. 77, May, 1913, pp. 741 to 797. THOMAS T. READ, New York, N. Y. (communication to the Secretary *) :-At the meetings of English technical societies it not infrequently happens that, during the discussion of a paper, someone will arise to say that although he highly appreciated the material presented, nevertheless he believed it would have been better if some other phase of the question had been more highly emphasized. Assuming that this form of discussion is permissible in the Institute, I should like to reiterate the point made by Prof. A. J. Moses that conclusive proof of the identity of the minerals in question is an essential feature of the study of ores in this way. This is also expressed by Paul Krusch in his recent valuable paper 1 on the sulphide ores (in which he arrives at conclusions diametrically opposed to those of Mr. Graton), as follows : ?The diagnostic properties of the various ore minerals are known to but a limited circle of investigators." Many earlier investigators began the study of ores beneath the microscope by reflected light, but discontinued their work, in most cases, because they were unwilling to undertake the great amount of preliminary work necessary to securely establish a basis for their inferences. It is evident that Messrs. Graton and Murdoch realize that the promised later paper on diagnostic characters will be the more important of the two, but the point should be emphasized to forestall a flood of literature from other investigators who may gain the impression that the brief survey of polished specimens is a wade mecum to incontrovertible conclusions as to any given ore deposit.

Jan 10, 1913

By E. C. W. Perryman

The wide grooves formed at the grain boundaries when high purity aluminum is attacked by hydrochloric acid or sodium hydroxide have been attributed by earlier workers to the high energy of the grain boundary material. The effect has been investigated for high-purity AI-Fe alloys with up to 0.055 pct Fe as a function of iron content and heat treatment. It is shown that the explanation given above is untenable, but that the results can be explained on the assumption that iron segregates to the grain boundary in solid solution. IN 1934, Rohrmann¹ showed that aluminum of 99.95 pct purity suffered intercrystalline corrosion when immersed in 10 to 20 pct hydrochloric acid, and that the susceptibility to intercrystalline corrosion depended upon the heat treatment given. The greatest susceptibility was found for specimens quenched from a high temperature (600°C) and the lowest susceptibility for specimens cooled slowly from that temperature. Lacombe and Yannaquis2 have shown that super-pure aluminum (99.9986 pct) annealed at 600°C suffers intercrystalline attack in 10 pct hydrochloric acid and that this attack is intensified by anodic dissolution in the same solution at a current density of 10 milliamperes per sq dm. No difference in extent of intercrystalline attack was found between the 99.993 and 99.986 pct Al, which led the authors to suggest that impurities played only a secondary role in the mechanism of intercrystalline corrosion. It was found, however, that the attack at the grain boundaries depended upon the relative orientation of the grains, large differences in orientation favoring rapid attack. Boundaries where the two neighboring grains were similarly orientated showed high resistance to attack as did boundaries between grains which were in twin relationship. These observations led Lacombe and Yannaquis to suggest that the intercrystalline attack was due to lattice discontinuities present at grain boundaries. Assuming that the grain boundary is a layer three to five atoms thick and has a crystal structure which is a compromise between the two neighboring grains it is clear that the discontinuities will increase with increasing difference in orientation between the neighboring grains and hence the increasing tendency to intercrystalline attack. Roald and Streicher³ investigated the effect of heat treatment of aluminum alloys ranging in purity from 99.2 to 99.998 pct on the corrosion resistance in 20 pct hydrochloric acid and 0.30N sodium hydroxide. They found that in hydrochloric acid the intercrystalline attack appeared to be determined by the type and quantity of impurities present and by the relative orientation of the grains. No difference in the susceptibility to intercrystalline attack was observed between specimens quenched and those furnace cooled, from 575°C. In 0.30N sodium hydroxide some materials exhibited intercrystalline attack, this taking the form of V-notches. Rohrmann¹ offered no explanation for the greater susceptibility to corrosion of material quenched from 600°C. It seems possible that this difference is connected in some way with a different distribution of impurity elements in the quenched and slowly cooled specimens. The fact that Roald and Streicher8 observed no difference between quenched and slowly cooled specimens may possibly be due to differences in either rate of cooling or silicon content or possibly both. Both these would be expected to have an effect on the distribution of impurity elements. Although the rate of cooling used by Rohrmann was slightly more rapid than that used by Roald and Streicher the position cannot be clarified because Rohrmann does not give the silicon content and Roald and Streicher give the silicon contents of only a few of their alloys. That Lacombe and Yannaquis2 found no difference in corrosion behavior attributable to impurities between the two materials they used may be because both were of high purity compared with the aluminum used by Rohrmann.¹ Although they found no difference in the corrosion behavior of their two materials it is possible that the results obtained by Lacombe and Yannaquis may, nevertheless, have been influenced by impurity distribution, since, on the transition lattice theory of grain boundary structure, it would be expected that sparingly soluble impurities would tend to segregate to boundaries where the orientation difference is such that there is a greater density of atomic sites of suitable size to contain them. It was considered worth while, therefore, to examine the corrosion properties of a series of materials of differing impurity content with the objects of confirming the experimental observations made

Jan 1, 1954

By Pol Duwez

The effect of the rate of cooling on titanium, zirconium, and thallium has been measured. For titanium-molybdenum alloys, it has been shown that for molybdenum concentration up to 8 pct the rate of cooling has no effect on the transformation temperature, but this temperature decreases progressively with increasing molybdenum content. HIGH strength to weight ratio and remarkable corrosion resistance have often been advanced as the main reasons for the present widespread interest in titanium. For the physical metallurgist, the existence of an allotropic transformation in titanium is another important factor. As in the case of iron, an allotropic transformation may be the fundamental property upon which the response of Ti-base alloys to heat treatment will depend. It is therefore important to study the mechanism of the allotropic transformation in pure titanium and the effect of alloying elements on this transformation. The existence of an allotropic transformation in titanium was reported in 1931 by Schulze.' Later, De Boer et al.' determined the transformation temperature from a discontinuity in the electrical resistivity at 882"42O°C. According to recent work," the transformation temperature is 882.5"&1°C. The crystal structure of the room temperature a phase is hexagonal close-packed and the high temperature fi phase is body-centered cubic.' It is well known that the high temperature /3 phase of pure titanium cannot be retained by quenching to room temperature. Several investigators'-' have shown that in alloys of titanium with metals which are soluble in the @ phase (for example, nickel, molybdenum, chromium, or manganese), the /3 structure can be retained, providing the concentration of the alloying element is greater than a certain critical value. Below this critical value, the alloys transform during quenching, at least partially, into a supersaturated solid solution having the a. structure. This behavior is very similar to that found in some iron binary alloys (Fe-Ni and Fe-Mh, for example) and is an indication that the transformation might occur by means of a shear mechanism analogous to that observed in the austenite-martensite reaction. The present investigation is mostly concerned with the effect of the rate of cooling on the /3 to a transformation. In the first portion of this paper, the results obtained on pure titanium are described. Two other pure metals, zirconium and thallium, were also investigated, because they both have an allotropic transformation like titanium, from an hexagonal close-packed to a body-centered cubic structure. For purposes of comparison, the effect of rate of cooling of the y to a transformation of iron was included in the experimental program. The second part of this paper deals with Ti-Mo alloys. The equilibrium phase boundaries involving the solid state reactions on the Ti-rich side of the system were determined and a study was made of the effect of the rate of cooling on the transformation of the high temperature /3 solid solution. Experimental Procedure Since the main object of the present investigation was the determination of the effect of the rate of cooling on a transformation temperature, the best technique available was that used by Greninger" in his study of the martensite arrest in carbon steels. This method consists of heating a very small sample of metal to which fine thermocouple wires are .attached, cooling the sample rapidly by means of a blast of helium, and recording the temperature vs. time curve on an oscillograph. The apparatus used in the present experiments was very similar to that described by Greninger, except that the heating coil was made of molybdenum wire (0.040 in. in diam) and the assembly was placed in a bell jar under vacuum of 10" mm Hg or less. The specimen con-

Jan 1, 1952

By Alec M. Crowell, J. W. Sanders

While the production of crude oil and condensate in South Arkansas increased only 1.7 per cent over the 1940 figure, complete utilization of gas produced with the oil and condensate, and heretofore wasted, was beginning to be evidenced. There were 26,229,264 bbl. of oil and condensate produced in South Arkansas during 1941, as against 25,790,380 bbl. for the year 1940. (Fig. I.) Since 1936, deep producing sands have been discovered in 18 fields and during that period only 40 per cent of the total state production has come from Upper Cretaceous formations while 60 per cent came from the Lower Cretaceous and Jurassic formations. The gas produced with crude oil and condensate from the latter formation contains large quantities of hydrogen sulphide, the maximum being 6900 grains per 100 cu. ft. in the Patton pool of Lafayette County. Gas Utilization During the latter part of 1940 and the early part of 1941, pilot plants were placed in operation to determine whether the hydrogen sulphide and deleterious material in South Arkansas gases could be removed economically. The Federal Government desired to build a large aluminum plant in the Ouachita Valley and was seeking cheap fuel for the generation of electricity. The fact that the gases were produced with appreciable quantities of crude oil and condensate made it available at a very low price, since the state's conservation law prohibits the flaring of any gas. As a result of these experiments the first large-scale unit for the processing of gases containing hydrogen sulphide was placed in operation on Sept. I, 1941. The plant is in the Magnolia oil field, Columbia County. It processes residue gas from the Shell Oil Company's gasoline plant in that field and also raw gas from the Village field, 6 miles east of the Magnolia field. The gas entering the desulphuri-zation unit is laden with approximately 1400 grains of hydrogen sulphide per 100 cu. ft. and is stripped to a content of 4 grains per 100 cu. ft. The capacity of the plant is 15 million cu. ft. of gas treated daily under a pressure of 160 lb. per sq. in. The cost of treatment, exclusive of depreciation, is appreciably less than I per 1000 cubic feet. Two other plants of much greater capacity have been announced and priorities have been granted, which should bring the total amount of gas treated to 150 million cu. ft. daily. The gas to be treated will have a maximum hydrogen sulphide content of 4500 grains per 100 cu. ft. and will be processed under a pressure of 600 lb. per sq. in. These developments are something entirely new in field practice for the industry. The fact that this heretofore wasted gas is available at very low cost has led to the location of some eight war industries within the state, in addition to the alu-minum plant. Recovery OF Sulphur The Susearch Corporation and the Southern Acid and Sulphur Co. placed in operation during 1941 pilot plants to de-

Jan 1, 1942

By Alec M. Crowell, J. W. Sanders

While the production of crude oil and condensate in South Arkansas increased only 1.7 per cent over the 1940 figure, complete utilization of gas produced with the oil and condensate, and heretofore wasted, was beginning to be evidenced. There were 26,229,264 bbl. of oil and condensate produced in South Arkansas during 1941, as against 25,790,380 bbl. for the year 1940. (Fig. I.) Since 1936, deep producing sands have been discovered in 18 fields and during that period only 40 per cent of the total state production has come from Upper Cretaceous formations while 60 per cent came from the Lower Cretaceous and Jurassic formations. The gas produced with crude oil and condensate from the latter formation contains large quantities of hydrogen sulphide, the maximum being 6900 grains per 100 cu. ft. in the Patton pool of Lafayette County. Gas Utilization During the latter part of 1940 and the early part of 1941, pilot plants were placed in operation to determine whether the hydrogen sulphide and deleterious material in South Arkansas gases could be removed economically. The Federal Government desired to build a large aluminum plant in the Ouachita Valley and was seeking cheap fuel for the generation of electricity. The fact that the gases were produced with appreciable quantities of crude oil and condensate made it available at a very low price, since the state's conservation law prohibits the flaring of any gas. As a result of these experiments the first large-scale unit for the processing of gases containing hydrogen sulphide was placed in operation on Sept. I, 1941. The plant is in the Magnolia oil field, Columbia County. It processes residue gas from the Shell Oil Company's gasoline plant in that field and also raw gas from the Village field, 6 miles east of the Magnolia field. The gas entering the desulphuri-zation unit is laden with approximately 1400 grains of hydrogen sulphide per 100 cu. ft. and is stripped to a content of 4 grains per 100 cu. ft. The capacity of the plant is 15 million cu. ft. of gas treated daily under a pressure of 160 lb. per sq. in. The cost of treatment, exclusive of depreciation, is appreciably less than I per 1000 cubic feet. Two other plants of much greater capacity have been announced and priorities have been granted, which should bring the total amount of gas treated to 150 million cu. ft. daily. The gas to be treated will have a maximum hydrogen sulphide content of 4500 grains per 100 cu. ft. and will be processed under a pressure of 600 lb. per sq. in. These developments are something entirely new in field practice for the industry. The fact that this heretofore wasted gas is available at very low cost has led to the location of some eight war industries within the state, in addition to the alu-minum plant. Recovery OF Sulphur The Susearch Corporation and the Southern Acid and Sulphur Co. placed in operation during 1941 pilot plants to de-

Jan 1, 1942

By Eugene S. Perry

The most outstanding event in oil and gas development in Montana during 1936 was the discovery of oil in the Baker-Glendive gas field, in the extreme eastern part of the state. Other notable achievements were small extensions in the Cut Bank oil field; continued favorable results of acidization in the Kevin-Sunburst oil field; and the discovery of oil and gas in commercial quantities about 20 miles southwest of Billings, on what is known as the Mosser dome. Several wildcat wells were drilled. For the coming year of 1937, it is anticipated that the main activities will be confined to drilling in or near known fields. During 1936 Montana had seven fields producing oil, but over 95 per cent of oil production came from four fields, which in order of importance are: Cut Bank, Kevin-Sunburst, Cat Creek and Pondera. Total production for the state was 5,850,893 bbl., which is 1,251,761 bbl. more than the total for 1935. Natural gas was produced and marketed from eight fields, most important being Cut Bank, Baker-Glendive, Kevin-Sunburst and Dry Creek. These four fields accounted for over 85 per cent of total state gas production, which is slightly greater than the 1935 production of nearly 18 billion cubic feet. Increase in gas consumption is due in part to increase in smelter operation. More detailed information pertaining to the various fields is given in Table 1. In the Baker-Glendive field a test 8186 ft. deep, 15 miles southeast of Baker, was completed by the Montana-Dakota Utilities Co. in 1936. The first gas-bearing sandstone (Judith Hiver horizon, Upper Cretaceous) was found at a depth of 528 ft., and a second sand at 1167 ft. Sandstones of the Dakota formation, in which occurred water, were found from 3724 to 3853 ft. White sandstone correlated with the Tensleep (Minnelusa) formation of Pennsylvanian age was found from 5631 to 5751 ft. deep. The lower 1900 ft. of the well (below 6278 ft.) was essentially in limestone and dolomite, and information on correlation of formations in this mass of sediments is not available at this time. The upper portion of this part of the well contained much anhydrite. Cherty and dolomitic limestone below 7000 ft. may be equivalent to limestones of the Madison formation. The thickness of strata beneath the Dakota formation was

Jan 1, 1937

By M. Kitada, U. Kawabe, F. Ishida, T. Doi

The relations between micros tructures and critical current density in transverse magnetic field were experimentally investigated due to each transformation of the 0 to 0' + P" phases at 700' C for superconductmainly examined using replication electron microscopy. The ß' or a precipitates were found to pin down magnetic flux lines in these alloys. The effects of precipitation upon the critical current density were discussed in relation with the size, spacing, and characler of these precipitates. HIGH magnetic field superconductors, such as Nb-Zr, Nb-Ti, and Nb-Zr-Ti alloys, have been recently put to extensive practical use as winding materials for superconducting magnets.13 The critical current density of these hard superconductors under an applied magnetic field is an important characteristic for magnet materials and is very sensitive to metallurgical structure. It is generally known that the critical current density is increased by introducing dislocations and precipitates into a superconductor; that is, dislocations and precipitates are presumed to be barriers that hinder quantized flux lines from moving.4'5 Theoretical6'7 and experimental analyses of the motion of flux lines and the interaction between flux lines and various defects have already been reported by many authors. Metallographic analysis of high magnetic field superconductors such as Nb-Zr and Nb-Ti is difficult, so that no quantitative relationship between microstruc-ture and critical current density has been established yet. In this paper, the effect of precipitation on the critical current density in magnetic field was investigated for two superconducting alloys, Nb-40Zr-10Ti and Nb-5Zr-60Ti. In these alloys the resistive critical field H, at 4.2oK was about 100 kG and the critical current density Jc at 80 kG was of the order of 104 amp per sq cm.13-l5 The superconducting properties were examined in relation to the microstructural changes due to transformation of i) the ß to ß' + ß" phases at 700°C for Nb-40Zr-10Ti alloy and ii) the ß to a + ß phases at 500°C for Nb-5Zr-6OTi alloy. The effect of size, spacing, and character of precipitates on flux line pinning was in particular examined. The microstructures were studied by means of residual resistivity, microhardness, and tensile strength measurements as well as by X-ray diffraction, optical, and replication electron microscopies. I) EXPERIMENTAL PROCEDURE Pure niobium, zirconium, and titanium, in the form of rods 0.8 cm in diam, served as raw materials. Results of chemical analyses of these rods are given in Table I. Ingots of the alloys, 0.4 cm in diam and 3 cm in length, were prepared by means of levitation melting, utilizing a copper mold in an argon-gas atmosphere. Samples from the ingot then were cold-worked by grooved mill to 0.2 cm in diam, heat-treated homogeneously (in the ß phase region) for 5 hr at 1100° in a vacuum of 1 x 106 Torr, and finally cold-drawn to 0.025 cm in diam. For heat treatments, samples were wrapped in niobium foil and sealed in an argon-gas atmosphere in fused quartz capsules. Water quenching was done after each heat treatment. Subsequently H-J, were performed at 4.2° by slowly transporting the current through the samples 4 cm long, under transverse magnetic field, until the least detectable resistive terminal voltage was observed. The resistive critical field H, was taken as the field at which 100 pv appeared at 4.2°K across a sample 3 cm in length, with a current of 5 ma. The critical temperature T, was measured by means of a conventional four-probe resistivity technique and taken as the temperature at which the sample resistance reached one-half of full restoration of the normal-state resistance with a current l ma flowing through a sample 2 cm in length. Precipitates were observed by means of optical microscopy and carbon replication electron microscopy. The etching solution consisted of 5 ml HF, 10 ml H2SO4 10 ml H2O2, and 50 ml H2O, and shadowed carbon replicas were examined in a itachi HU-11 electron microscope operated at 50 kv. X-ray diffraction photographs were taken by a 11.46-cm-diam Debye-Scher-rer camera using copper Ka radiation. The micro-hardness was measured under a load of 200 g using

Jan 1, 1969

By G. G. Priest, B. E. Morgan

The production of oil and gas from wells is often seriously hindered by the compaction of solids in the perforations during the perforating process. To realize the full productive capacity of a well, it is necessary either to remove the plugging material from the perforations or to perforate in a manner which does not cause plugging of the perforations. The latter method can be accomplished by having a non-plugging fluid in the casing at the time the well is perforated. This paper describes the results of laboratory tests, perforating tests, and experimental field tests which demonstrate that certain emulsions serve effectively as non-plugging perforating fluids. The principal components of these emulsions are two liquids: an aqueous phase consisting of a solution of either sodium chloride or calcium chloride, and an oil phase consisting of diesel oil, tetrachloroethylene, or a combination of both. Small amounts of other agents which serve to stubilize the emulsions, to reduce the fluid loss, and to inhibit corrosion are also present. The density of the emulsions is controllable within the range of 7.5 to 12.5 lb/gal; no insoluble solids are present, the filtration rate is low, and the thermal stability is satisfactory at temperatures as high as 200°F. The corrosion of steel by these emulsions is negligible. Tests conducted under conditions which simulate the temperature and the pressure in an actual well demonstrate that these emulsions fulfill the requirements of a non-plugging perforating fluid. In addition, lirnited field experience furnishes evidence that these emulsions remain in position after they are spotted, that they are retained in the casing after the perforations are made, and that they are easily removed from the perforations when the well is opened for production. When the pressure in the borehole is greater than the formation pressure at the time a well is perforated, plugging of the perforations can be avoided by spotting an emulsion adjacent the interval to be perforated. This procedure should eliminate low well productivity caused by plugging the perforations. INTRODUCTION Nature of Problem The most widely used method for the completion of oil and gas wells is to set and cement casing through productive horizons, and then to obtain production by gun-perforating the section of casing opposite the desired interval. This method is gen- erally successful and it was thought at one time that those failures which did occur were due to insufficient penetration by the perforator. Despite recent improvements in perforators which assure ample penetration, unsatisfactory fluid production continues to be a problem. Evidently, the trouble comes from some other source. Recent results obtained by Allen and Worzel1 demonstrated that low fluid productivity may be caused by the perforating process and/or by the fluid in the wellbore at the time of shooting. They found that perforations are often completely plugged by debris from the perforator, pulverized sand from the formation, and compacted solids from the drilling mud when the pressure in the wellbore is greater than the pressure in the formation at the time of perforation. In some cases a differential pressure in excess of 400 psi was required to initiate flow into the well through these plugged perforations. The plugging of perforations by solids not only causes low productivity from wells, but it creates simultaneously other problems in the production of oil and gas. For example, when most of the perforations are plugged, high rates of flow must occur through the few perforations that are open. The resulting high pressure drop may cause production

Jan 1, 1958

By Charles E. Wait

It is said by some that the occurrence of a deposit of sulphide of antimony in Southwestern Arkansas has been known for fifteen or twenty years. Whether or not such is the case I am not prepared to say, but I am not able to find any record of such a discovery, or any analysis of antimony ore obtained from that section, published at so early a period. The present discoveries, that seem to be attracting some attention, date back to the winter of 1873-74. At that time a vein of ore was found by Mr. Robert Wolf, in honor of whom the vein was named, and still is called, "the Wolf lode." At the time of the discovery the ore was unknown to the prospector, and its composition was not thoroughly understood in that locality until samples were sent to several analytical chemists, who pronounced it sulphide of antimony—stibnite. Since the discovery of this ore there have been three mines opened, and a number of interesting minerals of the antimonial series have been found. I have had an unusually good opportunity to collect specimens from these mines; and it is owing to the constant inquiry concerning the character of these ores that I have collected for publication the results of quite a number of analyses, sufficient I trust to clearly point out their composition. This is one of the few localities in the United States where antimony ore is found in workable quantities ; I say workable quantities, because two different shipments of ore have been made to English reduction works, and in both cases excellent returns were made. The discovery of these deposits will, it is hoped, give rise to a prosperous and remunerative industry at no distant day, and when fully developed they may yield ore in sufficient quantity to supply the regulus for the home demand, thus adding wealth not only to those interested, but also to the State of Arkansas. The three mines are situated in the northern part of Sevier County, and may be reached by the St. Louis, Iron Mountain and Southern Railway to Fulton, thence by wagon-road to Columbus, Nashville, Centre Point, and to the mines. During most seasons of the year the

Jan 1, 1880

By Charles E. Wait

IT is said by some that the occurrence of a deposit of sulphide of antimony in Southwestern Arkansas has been known for fifteen or twenty years. Whether or not such is the case I am not prepared to say, but I am not able to find any record of such a discovery, or any analysis of antimony ore obtained from that section, published at so early a period. The present discoveries, that seem to be attracting some attention, date back to the winter of 1873-74. At that time a vein of ore was found by Mr. Robert Wolf, in honor of whom the vein was named, and still is called, "the Wolf lode." At the time of the discovery the ore was unknown to the prospector, and its composition was not thoroughly understood in that locality until samples were sent to several analytical chemists, who pronounced it sulphide of antimony-stibnite. Since the discovery of this ore there have been three mines opened, and a number of interesting minerals of the antimonial series have been found. I have had an unusually good opportunity to collect specimens from these mines; and it is owing to the constant inquiry concerning the character of these ores that I have collected for publication the results of quite a number of analyses, sufficient I trust to clearly point out their composition. This is one of the few localities in the United States where antimony ore is found in workable quantities; I say workable quantities, because two different shipments of ore have been made to English reduction works, and in both cases excellent returns were made. The discovery of these deposits will, it is hoped, give rise to a prosperous and remunerative industry at no distant day, and when fully developed they may yield ore in sufficient quantity to supply the regulus for the home demand, thus adding wealth not only to those interested, but also to the State of Arkansas. The three mines are situated in the northern part of Sevier County, and may be reached by the St. Louis, Iron Mountain and Southern Railway to Fulton, thence by wagon-road to Columbus, Nashville, Centre Point, and to the mines. During most seasons of the year the

Jan 1, 1880

By D. S. Sanders, E. W. Witcomb

FLOTATION tests, from which the flowsheet for the concentrator was determined, were made in a pilot mill at Chuquicamata and later comparative testing of full size flotation cells was done at the Andes Copper Mining Co. concentrator in Potrerillos. The principal sulphide copper mineral is chalcocite with varying amounts of covellite, enargite, and chalcopyrite. The oxidized portion is principally antlerite, a green basic copper sulphate. The gangue minerals include quartz, sericite, pyrite, feldspars and kaolin. Chuquicamata pit ores have proved to be hard grinding. The results of the flotation and metallurgical work prove that good extraction and concentrate grade can be obtained under a rather wide range of conditions. Metallurgy In general the metallurgy of the ore requires a fairly close control of the grind to the primary rougher flotation and of the regrind of the primary rougher concentrate before cleaning. Regrinding is necessary to reduce the insoluble content of the final concentrate since a large part of the middling combinations are between the copper and silica minerals. The alkalinity of the pulps can vary between wide limits and control of the percent solids gives the desired grind. Alkalinity Control Arroyo Salado water is supplied to the concentrator head tanks. It contains about 5000 ppm of salts but test work shows no deleterious effect. Actually this water permits a decrease of as much as 1 lb of lime per ton of ore as compared to San Pedro water, which is used for leaching oxide ore. About one quarter of the water flow through the concentrator will be new water from the reservoir. The remainder will be reclaimed from the thickeners. For primary grinding and rougher flotation, new and reclaimed water are combined in the head tanks. To avoid erratic results, only new water is used in the regrind system. Milk of lime is added to the rod mill feed chute to obtain the maximum benefit of mixing with the ore. This protects the equipment from corrosion due to entrained acids and soluble copper salts. Lime consumption is 3 to 5 lb per ton of ore. Grinding and Flotation The six bin gates over each belt feeder are opened in controlled combination and sequence to keep a live bed of ore in the bin to prevent arching and to obtain mixing. The milk of lime added ahead of the rod mill is regulated to suit rougher flotation requirements. The primary promoter reagent, Aerofloat 238, is added to the 10-mesh discharge of the rod mill as it is laundered to the ball mill scoop box. The classifier overflow is regulated to produce a grind of about 12 to 15 pct +65 mesh and 60 pct -200 mesh. A secondary promoter Z-4 (aml zanthate) and the pine oil frother are added in the overflow launder where a pH of 10 to 11 is maintained. Comparatively heavy beds of froth on the

Jan 1, 1952

By Margaret G. Scroger, Luke L. Y. Chang, Bert Phillips

Using the sealed-system technique, isothermal sections at 1000°, 1400°, and 1700°C for the system Co-W-O hare been determined. The equilibrium data were obtained by microscopic and X-ray diffraction examination of samples winch had been equilibrated in pellet form fit sealed capsules and subsequcelly quenched. The only ternary phase in the system is CoWO, which mells congruentlly at approximately 1280°C. At 1000°C, this ternary phase exists in equilihrinm with all the allows and oxide compounds in the hounding binary systems. At 1400°C, liquid forms in thin oxygen-rick region near the CoWO4 composition and only one phase assemblage in the system (W + WO2 + H'5CV7) contains no In order for tungsten to be used to its full potential as a refractory metal. it is necessary that coatings be developed which will preclude oxidation of the metal. It is true that coatings now in use do protect tungsten for short periods at temperatures near 1700 °C. but no coating has been developed which protects adequately at or above this temperature where the use of tungsten is most required. This situation exists despite the great effort in recent years to develop such coatings. and it has become evident that success in this area can be achieved only after a more fundamental knowledge of the thermochemical and therrnophysical propertics of tungsten oxidation and tungsten -metal oxidation is obtained. In our 1aboratories. a project liclrriel. At 1700°C, tungsten is the ouly solid phase which is stctble, and a large range of compositions melt to two liquids, one metallic and one oxidie. The sealed-system method of etjuilibra lion prevents the determination of the partial pressure of oxygen and the total gas pressure orer the condensed phases at equilibrium. This data is not available and can be obtained only by some other method. We can generalize on these unknowns and indicate that both partial pressure of oxygen and total pressure of the gas phase must increase as compositions change from the W-Co binary toward the oxygen apex and as temperatures increase. has been initiated which is directed at providing some of this fundamental information through a study of metal-tungsten-oxygen reactions and equilibria and the properties of any intermediate phases which result. This paper is based on a part of this program in which the system Co-W-O was studied between 1000° and 1700°C. I) RELEVANT INFORMATION FROM THE LITERATURE A) The Notable Lack of High-Temperature Work on Metal-Tungsten-Oxygen Systems. It should be pointed out that there has been no published report (of which we are aware) which deals with the study of a metal-metal-oxygen system at 1700°C. Also, there has been no report on a complete metal-luugsten-oxgen system at any temperature. As a matter of fact. before this program started. The

Jan 1, 1965

By Lewis W. MacNaughton

The North Texas district, as herein defined, includes the counties of Archer, Baylor, Clay, Cooke, Foard, Hardeman, Knox, Montague, Wichita, and Wil-barger. This area covers generally the crest and south flank of a system of buried mountains known as the Red River uplift. The oil and gas accumulations along this feature are in traps, which, although localized by structures incident to the regional uplift, are usually modified by stratigraphic changes in the sediments. Excepting the fields in southeastern Baylor, southern Archer, and southwestern Clay Counties, all the fields within the district are on this Red River uplift. These exceptions, which have the same type of oil and gas accumulation as the other fields, are on the extreme north end of the Bend arch, which is a broad anticline plunging northward from the Llano uplift in central Texas to Archer County. The larger part of past oil and gas production has come from Pennsylvanian strata, with less important amounts from the Permian, and minor but increasingly important quantities from the Ordovician. Developments during 1940 The encouraging outcome of exploration and development in Montague and Cooke Counties and generally greater activity throughout the district resulted in the drilling of some 1700 wells during 1940, about 350 more wells than were drilled in 1939. Approximately 1250 of these tests were completed as oil wells. Production likewise increased during I940 to the extent of 8 million barrels more than the 25 1/2 million barrels produced in 1939. In spite of this large increase in production, known oil reserves again increased substantially. As is usually characteristic of this district, the new reserves were from a large number of fields, none of which were of such magnitude as to be important to the oil industry. Nevertheless, the Fargo field, Wilbarger County, deserves mention as one of the more important discoveries in this district during 1940. Following seismic surveys, the hmerada Petroleum Corporation located its No. I Goodpasture in sec. 35, block IS, H. and T. C. R. R. Co. survey, and drilled it to a total depth of 6717 ft. This well was completed in July 1940 through perforations in the casing from a pay between 3230 and 3252 ft. for an initial production of 241.5 bbl. on an 8-hr. pumping test. Other potential producing horizons were found in the Pennsyl-vanian at depths of 3960 to 3995 ft., 4208 to 11.234 ft., 4407 to 4422 ft., and in the Ordovician at 6300 ft. Wells completed to date in the several Pennsylvanian horizons have an average daily potential of 600 bbl. of oil. Although no wells have yet been completed in the Ellenburger dolomite (Ordovician), the discovery well swabbed I5 bbl. per hour from this formation before plugging back for completion in an upper horizon.

Jan 1, 1941

By Lewis W. MacNaughton

The North Texas district, as herein defined, includes the counties of Archer, Baylor, Clay, Cooke, Foard, Hardeman, Knox, Montague, Wichita, and Wil-barger. This area covers generally the crest and south flank of a system of buried mountains known as the Red River uplift. The oil and gas accumulations along this feature are in traps, which, although localized by structures incident to the regional uplift, are usually modified by stratigraphic changes in the sediments. Excepting the fields in southeastern Baylor, southern Archer, and southwestern Clay Counties, all the fields within the district are on this Red River uplift. These exceptions, which have the same type of oil and gas accumulation as the other fields, are on the extreme north end of the Bend arch, which is a broad anticline plunging northward from the Llano uplift in central Texas to Archer County. The larger part of past oil and gas production has come from Pennsylvanian strata, with less important amounts from the Permian, and minor but increasingly important quantities from the Ordovician. Developments during 1940 The encouraging outcome of exploration and development in Montague and Cooke Counties and generally greater activity throughout the district resulted in the drilling of some 1700 wells during 1940, about 350 more wells than were drilled in 1939. Approximately 1250 of these tests were completed as oil wells. Production likewise increased during I940 to the extent of 8 million barrels more than the 25 1/2 million barrels produced in 1939. In spite of this large increase in production, known oil reserves again increased substantially. As is usually characteristic of this district, the new reserves were from a large number of fields, none of which were of such magnitude as to be important to the oil industry. Nevertheless, the Fargo field, Wilbarger County, deserves mention as one of the more important discoveries in this district during 1940. Following seismic surveys, the hmerada Petroleum Corporation located its No. I Goodpasture in sec. 35, block IS, H. and T. C. R. R. Co. survey, and drilled it to a total depth of 6717 ft. This well was completed in July 1940 through perforations in the casing from a pay between 3230 and 3252 ft. for an initial production of 241.5 bbl. on an 8-hr. pumping test. Other potential producing horizons were found in the Pennsyl-vanian at depths of 3960 to 3995 ft., 4208 to 11.234 ft., 4407 to 4422 ft., and in the Ordovician at 6300 ft. Wells completed to date in the several Pennsylvanian horizons have an average daily potential of 600 bbl. of oil. Although no wells have yet been completed in the Ellenburger dolomite (Ordovician), the discovery well swabbed I5 bbl. per hour from this formation before plugging back for completion in an upper horizon.

Jan 1, 1941