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By H. B. Fuqua, B. E. Thompson

For a very brief description of the North Texas area, and the general geological features with which it is associated, the reader is referred to the opening paragraph of last year's summary1. A more complete discussion of the structure of the area, together with other interesting data concerning it, has been published recently by the Bureau of Economic Geology at the University of Texas2. It has been impossible for the authors to isolate the statistics for production for each of the many small pools of this district, as such statistics are not kept by operators except by counties or arbitrary divisions of counties. The total number of wells drilled in Archer, Wichita and Clay counties also has been subject to some estimate, as many of the shallower holes are not reported. While both routine development in proven or semiproven areas and exploratory drilling during 1935 showed an increase over the year 1934, the discovery of new producing areas of importance did not show improvement over that period. Several extremely local productive spots within semiproven areas were found in Archer, Cooke and Wilbarger counties; and extensions to older producing areas were developed in Archer, Baylor, Cooke, Montague, Wichita and Wilbarger counties. In Archer County, the Grace and Woods No. 1 Archer County (Fee), 4 miles northwest of Archer City, in the Thomas Glass survey, encountered a sand from 2836 to 2845 ft. of Pennsylvanian (lower Canyon) age, which showed an initial yield of 75 bbl. daily. While its production is of negligible importance, it is given special mention in this review because of the fact that it is producing from a new and deeper horizon than has been previously exploited in the county. Little deep development occurred in the district during the year. The Walter Gant No. 2 C. M. Worsham in J. M. Swisher survey, about 14 miles east of Henrietta, in Clay County, was abandoned at 5127 ft. in

Jan 1, 1936

By Frederick Crabtree

WHEN Professor Stock asked for a paper on the above subject, it was too late to prepare by June 1, or near that time, one that would involve any appreciable amount of experimental work or original research; but the suggestion was made that a review of the literature bearing on the subject might be submitted in good time, and that later this could be supplemented by any experimental data obtained during the summer, if experiments were carried out. In accordance with this suggestion, there are submitted the following notes on references found in the literature of recent years bearing on sulfur in gas. It is to be, understood that, ill general, these notes express the opinions of the authors whose papers are abstracted, not necessarily the opinions of the abstractors. Very little published information was found bearing directly on producer-gas sulfur, so this has been supplemented, in certain phases of the subject, by references to illuminating gas. Methods of analysis and processes for the elimination of sulfur from the gas are, without much doubt, very closely related in these two products. As in illuminating gas, sulfur is found in producer gas mainly as hydrogen sulfide, mixed with a much smaller and variable quantity of carbon bisulfide.1 The presence of minute quantities of other organic-sulfur compounds has been intimated, but no definite statement is made concerning these. The amount of sulfur present in producer gas is variable and depends on several conditions. The primary factor is the quantity of sulfur in the fuel, but the form in which the sulfur exists, the temperature of the producer, the air-steam ratio, and the efficiency of the scrubbing process are all determining factors. When the coal used contains less than 0.5 per cent. of sulfur, the sulfur in the gas will not exceed the quantity found in the average illuminating gas.2 Sulfur in producer gas may safely

Jan 9, 1919

By Henry Howe

THE data which are collected in Table 1 show that the ferrite of low-carbon steel and of electrolytic iron, like the network of hypo- and hyper-eutectoid carbon steel, inherits, either absolutely or relatively, the, grain size of the mother austenite from which it is born in cooling through the transformation range. This evidence is so abundant and concordant as to cast doubt on Prof. Jeffries' 1 hypothesis of what might be called reversed inheritance, by which he explains Mr. Ruder's observation2 that the grains of a "slug of pressed pure electrolytic iron powder"were coarser, perhaps 12,000,000µ2, after a 3-hr. exposure to 1000° C. than after a 3-hr. exposure to 1250-1300°, when they were about 35,000µs. His explanation implies a natural tendency of coarser austenite grains to yield finer ferrite ones than spring from finer austenite grains, so that the inheritance is reversed. What seems to me a simpler explanation is that the enormous grains which followed the 1000° heating were not inherited from the mother austenite, but were formed by the process of natal coarsening, by means of which Stead and Carpenter developed grains of this same order of magnitude in this same kind of material, on heating to 950° or to 1000°, the temperature used by Mr. Ruder, provided the exposure was not unduly prolonged, and it does not seem to have been in Mr. Ruder's case. That their coarsening was natal and not through inheritance is shown first by the fact that their grain coarseness was out of all proportion to their relatively low temperatures and short periods, and hence was very far in excess of the grain size which the mother austenite must have had, and second and more cogently by the fact that the shape of these coarsened grains was evidently determined by the temperature distribution which existed during and immediately after the Ar3 transformation, that during the passage from the gamma to the non-gamma state.

Jan 9, 1917

By R. G. Knickerbocker, A. G. Starliper, H. Kenworthy, C. H. Gorski

This report describes the progress made in the research work on the development of a new method for preparing lower-cost titanium tetrachloride and preparing titanium oxide pigment. One of the requirements for the commercial production of ductile titanium in the process used by the Bureau of Mines is a source of lower-cost titanium tetrachloride. The production of ductile titanium by a modification of the Kroll1 process, recently developed by the Bureau of Mines, requires such a source of lower-cost titanium tetrachloride to make it commercially feasible. This report describes the progress of work done at the Mississippi Valley Experiment Station at Rolla, Missouri, on the development of a new method for preparing titanium tetrachloride. During the course of this research a new method for preparing pigment-grade titanium oxide was developed. At present, the price of technical-grade titanium tetrachloride is $0.32 a pound, which makes the price of the contained titanium $1.28 a pound.2 In addition, the titanium tetrachloride must be purified further before it is suitable for processing into metal, thus making its cost still higher.3 There were 8,562 tons of rutile produced in the United States in 1947, which was 900 tons in excess of that consumed. In addition there were 13,937 tons in various stocks, exclusive of the stocks in the Government strategic stock pile. No estimates of the domestic production of rutile are given for any of the prewar years. However, in 1939, 442 tons of rutile were imported as compared to 14,307 tons in 1947. One of the reasons for the large increase in the production of rutile is the working of the Florida beach sands for ilmenite, during which a considerable amount of rutile is produced as a by-product. It would be of value to determine methods for utilizing the excess production of rutile. The Arkansas titanium deposits in Hot Spring County produced commercial-grade rutile concentrates from 1933 to 1942. These were sold mainly to England, Germany, and Russia.

Jan 1, 1950

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane' by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane' by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

L. S. Austin, Denver, Colo. (communication to the Secretary) : Mr Hartman says (p. 4 of the pamphlet) that the penetration of air into the crucible of the blast-furnace " is, of course, a function of the diameter of the nozzle." To this I would emphatically take exception. Fig. 1 represents a vertical ideal section of tuyere, cruciblewalls and charge, immediately at the tuyere, in which the currents of air are represented, both in quantity and in direction, by the tortuous black-lines emanating from the nozzle-opening and passing through channels of the least resistance. As an electric current, flowing by various conductors to a common point, is carried in quantity inversely as the resistance of those conductors, so here the air ramifies through the most open cavities or channels, relatively little of it passing where the resistance due to fine materials is great. This figure represents the course of currents in the vertical plane only. As a matter of fact, they pass away in every plane, as opportunity offers. The effect of blocking or decreasing the area of the nozzleopening would certainly only decrease the quantity of air entering by that particular tuyere, without assisting penetration. The large channels (b, b, Fig. 1, for example) would still carry the larger part of the air, while again the smaller channels (a, a, a) would continue small and take no larger percentage of the air than before. These channels momentarily change, however, with the slow descent of the coke. Further on (p. 5), Mr. Hartman describes the dispersive effect of a single lump of fuel. He has only to conceive the entire spaces before the tuyere-nozzles as filled with such lumps, in order to parallel the condition of affairs I have just explained. It is where the large pieces of the charge come down, that the mass is the most open, and the blast passes most freely. On the other hand, wherever the fine ore collects combustion proceeds slowly, because of the smaller supply of air. The

Jan 1, 1899

By W. B. Gogarty, W. C. Tosch

A new recovery process for producing oil under both secondary and tertiary conditions utilizes the unique properties of micellar solutions (also known as microemulsions, swollen micelles, and soluble oils). These solutions, which displace 100 percent of the oil in the reservoir contacted, can be driven through the reservoir with water and are stable in the presence of reservoir water and rock. Basic components of micellar solutions are surfactant, hydrocarbon and water. They may also contain small amounts of electrolytes and co surfactants such as a1cohol.r. The specific reservoir application dictates the type and concentration of each component. A salient feature of [he process is the capability for mobility control. Micellar solution slug mobility, by way of viscosity control, is made equal to or less than the combined oil and water mobility. Mobility control continues with a mobility buffer that prevents drive water from contacting the micellar solution. Laboratory and field flooding have proven that the process is technically feasible and that surfactant losses by adsorption on porous media are small. Introduction projects are under way to recover the maximum amount of oil under the most favorable economic conditions.' : New techniques are being developed to increase oil recovery,3" Polymer solutions are becoming an important means of controlling mobility in a waterflood. Thermal methods such as in-situ combustion and steam injection are being used in reservoirs containing highly viscous crudes. Surfactant flooding is receiving attention as a method of reducing interfacial tension to increase recovery.*'" Exotic recovery processes have been considered primarily for ' perations. Economics are unfavorable in most cases for tertiary recovery. studies at the Denver Research Center of the Marathon oil CO. have led to a new oil recovery method.* Micellar solutions (sometimes called microemulsions, swollen micelles, and soluble oils) are used to recover oil by miscible-type waterflooding. Basically, these solutions contain surfactant, hydrocarbon, and water. The method can be used in either secondary or tertiary operations. First, thc concept of thc process is considered in terms of the requirements for an effective miscible waterflood ing operation. Next, micellar solution properties are described including structure, composition, and phase behavior with reservoir fluids. Fluid characteristics are then considered as related to mobility control, and, finally, laboratory and field results are presented to illustrate the efficiency of the process. Concept of the Process Unit displacement efficiency and conformance determine the effectiveness of any oil recovery mechanism. In theory, a miscible waterflood should be capable of a 100-percent unit displacement efficiency with a correspondingly high conformance. Requirements for the slug of a miscible waterflood include (1) 100-percent displacement of oil in the reservoir contacted, (2) controllable mobility, (3) the capability of being driven through the reservoir with water, (4) a low unit cost to enhance economics, and (5) the ability to remain stable in the presence of reservoir water and rock. Micellar solutions satisfy requirements for the slug of a miscible waterflood process. Our discovery that these solutions acted as though they were miscible by displacing all fluids in the reservoir and by being displaced by water solved the miscibility problem. Adequate mobility control is possible by variations in solution viscosity through compositional changes. Economic requirements are met since micellar solution costs below $6/bbl appear possible, Mi cellar solutions stabilize surfactant in the presence of reservoir rock and water, thus reducing the importance of the problem of surfactant loss by adsorption. Fig. 1 illustrates schematically how these solutions are used. Operations start with injection of a micellar solution slug that serves as the oil displacing agent. Next, a mobility buffer of either a water-external emulsion or water solution containing polymer (thickened water) is injected to protect the slug from water invasion. Finally, drive water (water used in a regular waterflood) is injected to propel the slug and mobility buffer through the reservoir. Reservoir oil and water are displaced ahead of the slug, and a stabilized oil and water bank develops as shown in Fig. 1. Stabilized bank saturations are independent of original oil and water saturations. This means that, for a particular type of reservoir, the displacement mechanism is the same under secondary and tertiary recovery conditions. Oil is produced first in a secondary operation. For tertiary conditions, water is produced first. Movement of the slug through the reservoir is stabilized by the mobility buffer. An unfavorable mobility ratio usually exists at the interface between the buffer and drive

Jan 1, 1969

By T. E. Watkins, M. D. Nelson

INTRODUCTION Deeper drilling for oil is becoming more and more the rule rather than the exception. With deeper drilling come additional problems, perhaps the greatest being those brought on by the higher temperatures encountered down the hole. particularly in the Gulf Coast region of Texas and Louisiana. Temperature gradients of the order of 1.8° to 2.0°F/100 ft are not unusual, and a gradient of 2.3"F.'100 ft is found in some areas of Texas. With a mean surface temperature of 74oF, the following temperatures could be expected for a geothermal gradient of 2.0°F; 100 ft: at 10,000 it. 271°F. 12,000 ft, 314°F: 14,000 ft, 354,oF; and 16.000 ft. 394°F. Severe gelation of lime-base drilling fluid in wells that have high bottom hole temperatures has become perhaps the most serious difficulty enconntered in drilling under such conditions. Lime-base drilling fluids have been very succesefully and widely used in the drilling of wells in the Gulf Coast region because of their inherent stability toward contaminants. their ability to suppress the swelling dispersion of bentonitic shales, and their ease of maintainance. The gradual recognition: during the past few years, that these muds were. in themselve. the cause of many difficulties experienced in drilling has led to wide-pread efforts by the drilling industry. to determine the reasons for the failure of these mud systems and to develop mud systems capable of performing satisfactorily under high-temperature conditios. MANIFESTATIONS OF HIGH-TEMPERATURE GELATION it is generally possible to recognize the symptons of high-temperature gelation early enough that advance predictions can be made of serious difficulties. in mud control, and the useful life of the drilling fluids can be extended by proper treatment. Following i.; a list of the manifestations of high-temperature gelation: (1) The drill string 'takes weight' while going in the hole after a trip. In early stages of high-temperature gelation it is possible to notice a slight reduction in drill string weight as the drill pipe is lowred near the bottom of the hole. (2) Excessive pump pressure is required to .tart the circulation of drilling fluid at or near the bottom of the hole when going hack to bottom after a trip. As the severity of the gelation increases it may be necessary to break circulation a number of times when going in the hole. (3) The drilling fluid from the bottom of the hole is thick and often granular or lumpy when pumped up after making a round trip. In a severely gelled drilling fluid system such a condition may be irreversible; that is, it cannot be stirred or chemically treated to produce a satisfactory drilling fluid. (4) Completion tool.. such as logging tools or perforating guns will not sink to the bottom of the hole. On some occasions completion tools will become stuck and require a fishing job to retrieve them if the wire line attached to them is broken. It is often difficult to determine whether the condition of the drilling fluid is responsible for sticking the tool or whether the wire line becomes key seated in a crooked hole and causes the allow difficulty. When there are 110 other symptoms of high-temperature gelation. then the difficulty may usually be attributed to the latter cause. (5) In extreme cases of high-temperature gelation it is necessary to "wash" and "ream" when going back to bottom after coming out of the hole. (6) In many -instance. it has been found to be extremely difficult and expensive to 1111 production packers 2nd tubing in moderately deep oil wells which had been drilled with a lime-base drilling fluid. In such instances-the original mud had apparently "set" to a consistency approaching that of a weak cement. CAUSES OF HIGH-TEMPERATURE GELATION Extensive test; have indicated that a lime-base mud does not develop a highly gelled condition at temperatures below 250°F. whereas above that temperature such condition often develops rapidly. (Fig. 1) concurrently. the following changes are evident ill the mud: (1) The alkalinity of the mud decreases to a very low value. with both caustic soda and lime being consumed. (2) The quartz content of the mud decreases sharply. (3) The bentonitic content of the mud decreases or di-appears, with concurrent decrease or loss of base exchange capacity of mud solids. (4) New compounds formed in the mud have been found to be cal-cium silicate, calcium aluminum silicate, and calcium sodium aluminum silicate. (5) The mud loses the ability to form a filter cake of low permeability. The above characteristics have been discussed, in part. by other authors

Jan 1, 1953

By G. L. Kehl, Emilo Jaraiz F., J. S. Brett

The transformation of eutectoid beryllium bronze has been quantitatively investigated at 550° and 592°C, the temperature region where the products of p decomposition are a fine lamellar eutectoid and a coarse lamellar aggregate which replaces the fine eutectoid with prolonged annealing. Metallographic evidence indicates that the coarse lamellar aggregate forms preferentially in the most densely lamellated regions of the fine eutectoid and favors the hypothesis that the development of the coarse lamellar aggregate in the fine eutectoid is due to the occurence of a cellular segregation reaction. WHEN eutectoid beryllium bronze (Cu-94 pct, Be-6 pct) is isothermally transformed at high temperatures in the and y region after quenching from the fl field, the principal initial decomposition process is G one of growth of approximately spherical nodules composed of a number of lamellar colonies of the a and y phases. After the initial reaction has proceeded substantially or completely, depending on the transformation temperature, a second reaction occurs wherein the fine lamellar eutectoid is replaced by a coarser lamellar aggregate composed of the same oand yphases.' This reaction is not simply a spheroidization of the initial fine eutectoid but the nucleation and growth of a coarser, structurally different, and more stable distribution of the @and yphases. Fig. 1 illustrates the replacement of the initial fine lamellar structure by a coarse lamellar aggregate. The a phase is the dark mottled constituent; the light constituent the y phase. The phase diagram for the copper-rich end of the Cu-Be system2 is shown in Fig. 2. The a phase has the face-centered cubic structure characteristic of copper-rich solid solutions. The B phase is a disordered body-centered cubic structure, while the y phase is body-centered cubic, ordered (CsC1, B2 type). A. viswanathanS investigating Debye patterns of Cu-6 pct Be discovered that a transitory phase appeared on very rapid quenching from the /3 region which was absent when the quenching velocity was moderate. The phase could be assigned a body-centtred cubic structure with a lattice parameter of 2.876. Tempering at 100°C for 2 hr after quenching resulted in complete disappearance of the phase. The work of Fillnow and Mack' is the only previously published study of the isothermal transformation of eutectoid beryllium bronze. Their study elucidated the nature of decomposition at various subcritical temperatures in an exploratory fashion. The purpose of the research reported in this paper was principally to obtain quantitative information on the isothermal decomposition of the fl phase and to clarify the relationships existing between the fine lamellar eutectoid and the coarse lamellar aggregate. EXPERIMENTAL PROCEDURE The material used in this investigation was an almost eutectoid Cu-Be alloy bar furnished by D.J. Mack. The alloy had been melted under a protective carbon cover and centrigugally cast into a graphite mold preheated to 490 "C. Segregation was minimized by violent agitation during melting and pouring. The analysis of the casting was 93.85 pct Cu, 5.60 pet Be with traces of Si, Mg, Mn, Co, and Al. To determine the minimum soaking time necessary to insure specimen homogeneity, a number of specimens were held in the P region at 788OC for times fron 1 min to 12 hr and isothermally transformed at 550°C. Specimens betatized less than 12 min exhibited partial transformation at times shorter

Jan 1, 1961

By A. J. Teplitz, R. J. Goodwin

A new type water shut-off for use in air drilling has been developed. The method has been 99 to 100 per rent effective in several different formations of inter-ranular-type porosity. Since costs for materials, time and equipment used are relatively small, the process should extend economies of air drilling to many new areas. The treatment involves a new technique for forming a water-inroluble precipitate within the pores of a rock. Advantage it taken of the difference in mobility of a liquid and a gas in porous media to achieve the greatest volume of precipitate in a given pore. Reactants selected for the laboratory (2nd field tests were aluminum sulfate solution and gaseous ammonia. This process has been tested in both intergranular and fractured-type porosities. It has consistently shut-of between 99 and 100 per cent of the water flowing from formations having intergranular-type porosity and perrlreuhilities ranging from a few millidarcise to over a darcy The treatment is not particularly suitable for shutting-off water from fractured formations although plugging of the order of 50 per cent or greater has been achieved in all such applications. Among advantages of the treatment are: (I) no reaction waiting rime after a relatively short placement time, (2) a low mate-rials cost of about $3/f1 of hole treated, (3) use of common service-type equipment for treatment, and (4) no unusual requirements for mixing and placement. INTRODUCTION In rotary drilling with air or gas it has been possible to increase bit life by tenfold and more than double rate of penetration over corresponding performance when drilling with mud. These factors have amounted to as much as 22 per cent savings on total cost of drilling a well. However, these advantages are rapidly lost when water is encountered in an air- or gas-drilled well because water interferes with the removal of cuttings from the hole and also gives rise to other difficulties. In attempting to combat water troubles, operators have commonly resorted to such measures as mist drilling, treatment with cement or chemicals, converting to conventional mud drilling, or setting casing. In many cases these measures have either been costly or ineffective. In an effort to overcome this problem, studies were undertaken to develop an effective and economical water shut-off technique for use in formations possessing inter-granular-type porosity. Extensive laboratory experimentation finally led to a unique method for producing a water-insoluble precipitate within the pores of a sandstone. The unique part of the treatment is use of a liquid and a gas to form the precipitate, and in this case the reactants used were aluminum sulfate solution and gaseous ammonia. The reaction between these two materials is shown in the following equation. Al2 (SO1)3 - 18 H20 6NH2? saturated Water- Solution Cat 2A1(OH)3 . n H20 3(NH4)2SO • n H20 Solid Solid That is, a solid precipitate consisting of aluminum hydroxide and ammonium sulfate is formed when ammonia reacts with aqueous aluminum sulfate. The aluminum hydroxide is insoluble in water and the ammonium sulfate, though soluble, can only be removed from the formation pores by diffusion—an extremely slow process. Although the precipitate formed by the reaction is not particularly firm, great strength is not needed for a precipitate to bridge and plug intergran-ular-type porosity. A flow path in such a system is extremely tortuous and involves a great variety of pore

By D. J. Schmatz

DISCUSSION OF RESULTS The qualitative correlation between low-temperature ductility and prior high-temperature creep strain in nickel obtained in this investigation confirms the result obtained on high-purity brass by Chen and Machlin. However, the quantitative effect is much smaller in nickel. Comparison can be made on the basis of a prior high-temperature strain that is a certain percentage of the total high-temperature elongation to rupture. In the research of Chen and machlin, the prior high-temperature strain of 1/2 pct equaled 8.5 pct of the total high-temperature elongation at rupture. For nickel, in our experiments, 8.5 pct of 21.2 pct equals 1.8 pct. For eh = 1.8 pct, the loss in ductility in percent equals x 100 = b.5 pct. That is, for equivalent bo Formation of Beta Manganese-Type Structure in Iron-Aluminum-Manganese Alloys D. J. Schmatz IRON-aluminum alloys have gained much interest in the past few years for use as a base material for elevated-temperature alloys because of their excel- high-temperature strain the loss in low-temperature ductility is 8.5 pct for nickel as compared to 60 pct for pure a, brass. It is also interesting to note the observation that in nickel the low-temperature fractures, even at the most extreme high-temperature pre-strain, were partly trans crystalline and partly intercrystalline. In the case of a brass, these fractures were completely intercrystalline. According to the data on the percent of the grain boundary area that is cracked, at 22 pct high-temperature elongation, about 12.5 pct of the grain boundary area does not carry load. Thus, the inter-crack areas are carrying a stress that is about 11 pct higher than the nominal stress. A simple model predicts that the overall elongation, which is primarily the elongation in the bulk of the specimen, will correspond to the nominal stress when the stress in the intercrack area equals the tensile strength. Quantitatively this model predicts the equation The form of this equation will agree with that found if the strain-hardening exponent, n, equals unity. Actually this model is too gross an approximation to yield good quantitative results. The question naturally arises as to whether in ordinary hot-working, such as hot-rolling, intercrys-talline cracks are introduced that affect the low-temperature properties. It appears that the answer is that such a possibility cannot be overlooked, if the hot-working induces tensile stresses at temperatures above the equicohesive temperature and if the material tends to be notch sensitive at low temperature. ACKNOWLEDGMENT This research was supported by the Aeronautical Research Laboratory, Directorate of Research, Wright Air Development Center, United States Air Force. REFERENCES lC. Zener: Fracturing of Metals, 1948, Cleveland, ASM. 'H. C. Chang and N. J. Grant: Mechanism of Intercrystalline Fracture. AIME Trans., 1956, voL 8, p. 544; lownal of Metals, May, 1956. 'E. S. Machlin. CreepRupt ure by Vacancy Condensation, AIME Trans., 1956, vol. 8, p. 106; lownd of Metals, February, 1956 'C. Chen and E. S. Machlin: On a Mechanism of High-Temper at ure Inter-crystalline Cracking, lownd of Metals, July. 1957. p. 829. Alloys lent oxidation resistance. Binary alloys of aluminum in iron are ferritic and consequently have poor hot strength. Alloys of iron-aluminum-manganese were made in an attempt to produce an austenitic alloy containing sufficient aluminum to retain the oxidation resistance of binary alloys of iron-alumi-

Jan 1, 1960

By James A. McGurty, Walter J. Koshuba, Samuel G. Gordon, Gilbert E. Klein

ONE of the problems encountered in working with metals at elevated temperatures is the instability resulting from solid-solid diffusion at a -common interface. A determination of the nature and magnitude of this phenomenon is important as related to structural properties of materials potentially useful in high temperature applications. This paper is concerned with the solid state reaction between metallic molybdenum and beryllium at elevated temperatures. In the older literature,' there were no known inter-metallic compounds in the system Be-Mo, and the list of beryllium intermetallics was rather small. New compilations have been made by Smithells' and by Taylor," listing all the then known beryllium binary intermetallic compounds. In addition to these, some new phases have just been reported' in the system Zr-Be and some further compounds of the type MBe,3 have been currently described. The new compound MoBe,, which is reported upon in this paper differs considerably from the above mentioned MBe13 group, and will be discussed in detail. Diffusion Study The nature of the solid diffusion at a Mo-Be interface was determined by sealing a beryllium rod inside a molybdenum capsule and heating at a temperature of 2000°F' (1100°C) for 100 hr. The molybdenum capsule was fabricated from % in. swaged molybdenum rod obtained from the Fansteel Metallurgical Corp. The beryllium metal was obtained from Brush Beryllium Corp. as % in. cold-drawn rod. This material assayed 99.05 pct Be and contained as impurities 0.84 pct Be0 and 0.19 pct Be2C. The molybdenum capsule was % in. in OD x 2 in. long. To prepare it, a concentric hole 0.250 in. + 0.001 in. — 0.000 in. in diam was drilled and reamed in one end of a rod to a depth of 1 '/2 in. A 1 in. long beryllium rod 0.250 in. + 0.000 in. — 0.001 in. in diam was pressed into the molybdenum capsule. A molybdenum plug 0.250 in. & 0.001 in. in diam x 9/16 in. long was then used to seal the beryllium in place. The capsules were placed in a molybdenum resistance furnace and heated at 2000°F (1100°C) for 100 hr. On cooling, the specimens were cut and examined metallographically. Fig. 1 is a micrograph at X250 of a portion of the interface from a transverse section. Four phases are clearly visible, with sharp boundaries between them. Phase A is a section of the molybdenum capsule; phase B is the molybdenum-rich intermetallic composition MoBe,; phase C is the beryllium-rich compound MoBe13; phase D is a section of the beryllium rod. All phases were readily polished to a high metallic luster. The molybdenum-rich phase has a pronounced purple tinge. The beryllium-rich phase (C) is only slightly darker than the pure beryllium. In polarized reflected light, however, it shows striking birefringence between crossed Nicols. The black areas represent flaws or pores in the material. A small representative amount of powdered material from each of the phases was carefully removed under the microscope with a diamond tool. With this material, powder X-ray diffraction patterns were made for the identification of each phase. Table I lists the X-ray diffraction spacings and corresponding indexes characteristic of these intermetallic compounds. Synthesis To establish the formula of the new intermetallic compound, X-ray diffraction patterns were made from powders obtained from solidified melts of known composition. The syntheses were made by

Jan 1, 1952

By B. N. Webber

During World War II the Pocos de Caldas bauxite deposits of Minas Gerais in Brazil yielded some 60,000 tons. Since then they have maintained a small but almost continuous production. Known for many years, the deposits have been reconnoitered by a number of geologists,1-4 but no dimensional study has been possible because there have not been enough exposures to show clearly the depth, bedrock, and habit of occurrence. The deposits are somewhat unorthodox in their occurrence mainly on steep slopes of mountainous terrain. Although the parent rocks are a sequence of alkalic intrusions that bauxitize readily under the proper conditions, bauxitization has not been the dominant weathering process in the area. It is limited to certain localities where important volumes of bauxite have formed by laterization of several rock types, each yielding a distinctive type of bauxite. Bauxitization may be observed in several stages and in both direct and indirect cycles of formation. The deposits are unique in being of demonstrably recent age, so that the conditions under which the bauxite formed are essentially those of the present time. The bauxitization sequence is postulated in Fig. 1. Pocos de Caldas district is situated at approximately 21" 50' south latitude and 46" 30' west longitude in southwestern Minas Gerais, near its boundary with the state of Sao Paulo. It lies within the Eastern Plateau physiographic province of Brazil, occupying a prominent highland area that rises some 2000 ft above the surrounding country. The central portion of the Pocos de Caldas highland is characterized by gently undulating topography, with generally sluggish drainage, and is surrounded by a rim of hills rising above 1000 ft above it. In cross section the highland resembles a truncated cone with a depressed central area. The rim has been sculptured into a more prominent and abrupt topographic pattern than the central area, and streams that are of low to moderate gradient in the central plateau plunge over the rim in a spectacular series of cascades and falls. GEOLOGIC SETTING The Pocos de Caldas highland owes its physiographic expression mainly to the differential erosion of a complex intrusion of alkalic rocks into gneiss and sandstone. Erosion was guided somewhat by faulting. The highland is almost circular, and its limits, except in one locality, coincide with the periphery of the intrusion. The alkalic intrusions largely control its shape and extent, aided by some subsidence through faulting of the central portion. The mountainous rim of chilled phase, the later intrusions, and the indurated intruded rocks have resisted erosion more effectively than the central portion of the intrusion, which is composed of more coarsely crystalline alkalic rocks that form a central basin in the highland. Gneiss and sandstone are found coincident in elevation with the topographically highest intrusions. BAUXITE TYPES Most of the bauxite, which varies in physical type, is on the top and steep slopes of the northern rim. The only alumina mineral is gibbsite, definitely crystalline but iron-stained unless of secondary origin. Clay particles occurring with the bauxite are kaolinite. Some types of bauxite are an index to their origin. There are four general physical types of bauxite or bauxite laterite: 1) Surface Rubble: This partly nodular and partly fragmented type, usually less than 3 ft thick, results from surface weathering of massive bauxite or may form by superficial enrichment of nodular bauxite with a clay matrix when the interstitial clay is removed by surface runoff.

Jan 1, 1960

By R. W. Coughlin, W. U. Ault

Experiments in laboratory and mine have clearly demonstrated the usefulness of radioactivity detection for directly measuring the potassium content of potash ore as mined. This paper presents the results of these tests and documents the design of a system for automatically grading and sorting potash ore on the basis of radiation detection. It is shown how the experimental results in the subject mine lead directly to the design of this kind of an automatic control system. The system is capable of grading the ore with an accuracy of approximately ±2% K20 content or better. Due to the usual stratification of the ore body, mining potash seldom presents an extreme problem of gangue separation. Nevertheless, it is frequently necessary to transport within a potash mine and even hoist to the surface considerable quantities of halite and other valueless materials. Up to recent times it has been customary to recognize and route these materials by simple visual and manual techniques. However, the work reported here clearly demonstrates that it is now practical and economical to improve upon these techniques by continuous measurement1 of the naturally occurring radioactive isotope, potassium-40. It was the purpose of the work reported here to investigate this technique and assess its applicability. LOCALE OF EXPERIMENTS The work described here was carried out in a potash mine in Carlsbad, N.M. At the working face of this mine the potash ore is freed by blasting; it is then transported a short distance by shuttle car to a moving-belt system which conveys it to the main shaft where it is hoisted to the surface. Quantities of gangue which are also produced in the mining operation are disposed of in mined-out sections of the mine where possible. Otherwise, this material which contains only a small percentage of potassium (as K2O) must also be transported by the conveyor-belt system to the main shaft and then hoisted to the surface and discarded. With this situation, any measuring device for automatic control purposes must be capable of clearly distinguishing between gangue containing insignificant amounts of K2O and ore containing larger percentages of the same mineral. The conveyor-belt system transports the material from the mine face to a rotary crusher and then to temporary storage pits at the main shaft. This is shown in Fig. 1. Upon leaving the conveyor belt the material enters either one of the two storage pits according to the position of a manually operated gate. It was decided that all experiments should be carried out at the conveyor belt between the crusher and gate with a view to the possibility of providing a signal which could operate the gate automatically. THEORETICAL BASIS AND LABORATORY EXPERIMENTS In principle it is possible to grade potassium-bearing ore on the basis of radioactivity. Natural potassium contains 0.012% K40, which is radioactive with a half-life of 1.3 x 10' years. Although about 89% of the K40 disintegrates to Ca40 by beta decay, the other 11% changes to Ar40 by electron capture and the emission of gamma rays. Unlike the ß-rays which are readily absorbed in the first few millimeters of ore surrounding the disintegrating nucleus, the y-ray photons will escape from an ore sample several inches in size. A detector rigidly mounted under a conveyor belt loaded with potash ore will intercept some constant fraction of all the photons emitted from the ore within its field of view. Under these

Jan 1, 1968

Edgar Hall, Silverspur, Queensland, Australia (communication to the Secretary*):—Dr. Douglas has written on this subject before, and his influence has had a powerful effect on the eide of freedom among the' younger generation of engineers. Moreover, it is not the first time that he has attributed the decline of the copper-smelting industry in Swansea to the secrecy maintained by the firms there engaged in smelting-operations. In this latter statement I think his conclusions are open to criticism. Whether the firms mentioned have suffered by their secrecy is their own business—I hold no brief for them ; but that the decline of the copper-industry at Swansea was inevitable seems to me to he proved conclusively by Dr. Douglas's own writings. In his paper on The Copper Situation,' Dr. Douglas says : "In comparing iron and copper mining,...it must be remembered that 2 tons of average iron ore from the most prolific source now available ... will make 1 ton of metal; whereas from 33 to 75 tons (say an average of 50 tons) of copper ore must be mined to produce 1 ton of copper." And further: "Last year's production of iron was made from approximately 50,000,000 tons of ore. Our copper mines, to yield a production of 900,000,000 pounds, must have handled approximately 22,000,000 tons of ore, or nearly half the quantity raised from our iron mines." Is not this the key to the whole situation ? In transporting the 50,000,000 tons of iron-ore, 25,000,000 tons of the metal iron were carried so much nearer to the market, but the transportation of 22,000,000 tons of copper-orc would have carried only 450,000 tons of the metal copper nearer to its ultimate destination. The small percentage of copper available in its ores makes

Jan 1, 1909

By Robert M. Yonco, Irving Johnson, Martin G. Chasanov

The thermodynamics of the cadmium-rich portion of the Pu-Cd system has been studied with a high-temperature galvanic-cell method. The partial phase diagram of the Pu-Cd system was determined. The existence of the intermediate phases PuCd11 (cubic BaHg11 structure, ao= 9.282) and PuCd6 (cubic, CeCd6 structure, a, = 15.59) was established. The existence of at least one other intermediate phase richer in plutonium was indicated. PuCd11 was found to peritectically decompose into PuCd6 and liquid at 406" * 2°C. The solubility of plutonium in liquid cadmium may be represented by the equations: (355' to 399°C) log (at. pct Pu) = 6.223 -4282T-1 (399° to 632°C) log (al. pct Pu) - 5.148 - 5277T-1 > 1.156 x 106 T-2 The free energy of formation values (kcal per mole) of the two intermetallic phases are given by the equations: (PuCd11), ?Gf= -45.9 + 35.7 x 10-3 T (PuCd6), ?Gf0- -39.27 + 25.86 X 10-3T The excess free energy (kcal per mole) of plutonium in liquid cadmium may be represented by the equation: -(-16.72 * 29.54 NPu) 10-3T in which Npu and Ned are the atom fractions of plutonium and cadmium. The thermodyanamics of the U- Cd and Pu-Cd systems are compared. THERMODYNAMIC information on systems of the actinide metals with low-melting metals, such as zinc and cadmium, is useful in the design of pyro-metallurgical processes for the purification of nuclear reactor fuels. The thermodynamics of the Pu-Zn,1 Th-Zn.2,3 U-Zn,4-5 and U-Cd6 systems have been reported. The present report on the Pu-Cd system concerns the liquidus composition in the cadmium-rich region, the characterization of the two most cadmium-rich intermetallic phases, and the thermodynamic properties of these intermetallic phases and dilute liquid solutions of plutonium in cadmium. EXPERIMENTAL Phase Studies. The liquidus composition was determined by analysis of filtered samples of the liquid phase withdrawn at a series of temperatures. The apparatus and procedure were identical to that used in the previous study of the Pu-Zn system.' Briefly. a sample of the melt was withdrawn into a tantalum tube fitted with a porous tantalum filter (30-µ pore). the entire sample dissolved in hydrochloric acid (to avoid errors due to segregation

Jan 1, 1965

By Walter Harvey Weed

The notes given in this paper, the result of observations made during recent brief professional trips to the northern States of Mexico, are offered as a slight contribution to the geological knowledge of a region little known, but long famous for its rich gold- and silver-mines. They are not detailed geological studies, but they contain, I believe, the salient facts. The following districts were visited: 1. Santa Eulalia (silverlead) ; 2. Parral (silver-lead); 3. Las Vigas (copper); 4. Jimenez (copper); 5. Guadalupe y Calvo (gold); 6. La Cumbre (gold); 7. Palmarito (silver); 8. Cananea (copper); 9. Sierra Pinitos (gold); 10. Sierra Azul (gold). 1. The Santa Eulalia Silver-Lead Deposits. Seventeen miles SE. of Chihuahua is the mining district of Santa Eulalia, to which that city owes its origin and long prosperity. Discovered in 1703, this district has been, and still is, one of the great silver-lead producers of the world. For 86 years after its discovery, the total output upon which the crown tax was paid amounted to $112,000,000. Worked until within the last 20 years by the most primitive methods, without machinery of any kind, the deposits continued to yield a vast treasure of silver; at present the yearly tonnage far exceeds that of former times. A broad-gauge road runs from Chihuahua up the valley of a small creek to the village of Santa Eulalia, which is situated within the borders of the mountains of that name. A few miles out of Chihuahua a narrow-gauge railway, owned by the Chihuahua Mining Co., branches off to the mines. This road ascends a smooth but steeply-rising plain to the base of the mountains, and winds about the slopes until the mines are

Jan 1, 1902

By Carl Benedicks

IT is well known by every one who has had to deal with boiler tubes that these are often seriously affected by a sort of corrosion, occurring as a local pitting, that frequently causes a perforation of the tube in a rather short time. The characteristic appearance of this corrosion is shown in Fig. 1. A very similar corrosion occurs in condenser tubes (Fig. 2).1 A study of the microstructure or local chemical composition of the metal (iron; 70 :30 brass) fails to reveal any cause for this pitting. Of course one might possibly assume the starting point-to be some oxide particle, causing an electrolytic local action, but this in no way explains the continued corrosion, progressing even when the assumed oxide particle must have disappeared. By the excellent work done by the Corrosion Research Committee of the Institute of Metals, and communicated, in October, 1923, to the Institution of Engineers and Shipbuilders in Newcastle-on-tyne, stress was laid on the fact that a content of entangled air has a very obnoxious effect. In the following correspondence, Sir George Goodwin stated that "engineers have, for a long time past, regarded air as the big enemy to be fought against in all questions of corrosion"2 and Kenneth Fraser pointed out that the most vital point is "the avoidance or removal of possibly the chief cause of present day corrosion, i. e. entrapped air and gases brought out of solution."' In their reply, however, the authors state that they had "never for a moment believed that entangled air was responsible for the beginnings of corrosion, and express the opinion that the gradual liberation of air could not account for localized corrosion."4 On consulting the many textbooks on corrosion, as that

Jan 4, 1925

By Walther Mathesus

INTRODUCTION THE use of high blast heats on furnaces melting Mesaba ores is still the exception, the average blast temperatures carried on Mesaba stacks seldom reaching 1,100° F. Some 15 years ago, when the use of fine Mesaba ores in larger proportions to the total burden first came into practice, it was found difficult to employ even those blast heats which it had been possible to carry with the Old Range ores. The furnaces refused to "take" high heats, and would persistently labor with irregular stock movement, which impaired the practice and increased the coke consumption. By lowering the blast temperature, the working of the furnace became smoother, and experience taught that with the softer and more easily reduced Mesaba ores, satisfactory practice could be obtained with comparatively low blast heats. Therefore a large number of Mesaba furnaces have ever since been operated on very low blast temperatures, ranging between 800° and 1,000° F. In the face of these difficulties, furnace men were slow to recognize that furnaces could be so designed as to permit a free movement of the charges in combination with the use of higher heats. Since higher blast temperatures did not seem to offer great advantages in the smelting of Mesaba ores, investments in hot-blast stoves were not as attractive to the furnace man as labor-saving devices and means of obtaining greater tonnages. The effect of this preference is keenly felt at the present time. It has brought about the peculiar situation, that the majority of our furnace plants (among them some of the most progressive) lack modern and efficient stove equipment. The result is that, even where the proper furnace lines have been adopted and conditions are now favorable to the successful employment of higher blast temperatures, the heats required for the greatest fuel economy are not available.

Jan 3, 1915