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By D. R. Miller

Internal friction and elastic modulus variations in electrorefined titanium, iodide refined titanium, and alloys of the latter material with oxygen, nitrogen, aluminum, and zirconium were investigated. No oxygen peak was detected with electrorefined titanium but, provided precautions were taken to prevent increases in background damping, an oxygen peak at about 410°C could be resolved with each of the other materials. An additional partially resolved peak was observed at 500°C in a Ti-N alloy. An anomaly in the variation of rigidity modulus with temperature was observed. Possible mechanisms for the formation of any oxygen peak have been discussed. PRATT, Bratina, and Chalmersl investigated the internal friction of commercial purity titanium and alloys of this material containing 1.5, 3.5, and 4.5 at. pct O. With commercial titanium the internal friction curve consisted of two components, a background which increased steadily with temperature and a peak at about 600" C which was due to grain boundary relaxation. In the Ti-O alloys, however, an additional internal friction peak was observed at 430" to 450°C and, since this peak increased in height as the oxygen content was increased, it was thought to be associated with the presence of oxygen. The diffusion of oxygen in titanium at temperatures between 300" and 500° C is believed to have marked effects in its tensile properties2'3 and the present internal friction measurements were undertaken to obtain further information on this diffusion, using material of higher purity than that of Pratt et d. and an apparatus of very much greater sensitivity. In the course of the investigation a number of important limitations on the work of Pratt et al. were revealed and results have been obtained which emphasize the need for ensuring that in this type of experiment, internal friction is independent of strain amplitude and that the values obtained are reproducible. 1) MATERIALS AND APPARATUS The basis material from which the majority of the specimens was prepared was iodide-refined titanium, the major impurities in which were oxygen and nitrogen—the metallic impurities being present at concentrations less than 0.001 at. pct. The hardness of this material after arc melting, forging, and swaging to rods 1/4 in. diameter was Dph = 110. Specimens 10 in. long and 0.020 in. (0.51 mm) diameter were prepared from these rods by further swaging and wire drawing and were finally annealed in vacuo (5 x 10-6 mmHg) for 24 hr at 800°C. The oxygen alloys were prepared from iodide-

Jan 1, 1962

By M. I. Jacobson, M. L. Hammond

The solid solubilities of high-purity silver, aluminum, chromium, copper, and iron in zone-refined beryllium have been determined. Diffusion couple sandwiches of beryllium with aluminum, copper, and silver foil and diffusion couples of beryllium with two-phase alloys in the Be-Cr. Be-Fe, and Be-Ag systems were analyzed by electron beam micro-probe techniques. This paper describes the material used, the experimental methods for preparing the diffusion couples and the alloys, the analytical techniques, and the results obtained. The results are compared with those of previous investigators who used materials of lower purity. ~NVESTIGATORS of beryllium phase diagrams have often been hampered in their interpretations of certain phase boundaries because of the relatively low purity of the beryllium used. This has sometimes resulted in the appearance of three phases in the regions where only two should exist. Advances in purification methods, specifically zone refining, have made available beryllium that is considerably purer than the material previously used for phase diagram studies. The primary object of this investigation was to reex-amine portions of the beryllium-rich end of the binary systems of beryllium with silver, aluminum, chromium, copper, and iron to determine more accurately the limits of terminal solid solubility. The five elements—silver, aluminum, chromium, copper, and iron—include some which are commonly found as the major impurities in beryllium, some of which are being used as solid-solution alloying elements, and some of which are used in ductile matrix alloys. They are thus of considerable importance to physical metallurgists who must work with beryllium but who must rely on the present inaccurate or incomplete diagrams. The determination of more reliable diagrams would aid researchers concerned with the problems of alloying, heat treatment, and ductility. MATERIAL The beryllium was acquired from the Franklin Institute in the form of a single-crystal, 6 in. long by 1 in. in diam, zone-refined in three passes from Pechiney SR-grade beryllium bar. The principal impurities, as determined by mass spectrography at Battelle Memorial Institute, are shown in Table I. Vacuum-melted copper, silver, and aluminum, and electron-beam zone-refined iron were obtained from the Materials Research Corp. in the form of 1/2-in.- diam bars. Iodide chromium was obtained as flakes from the Chromalloy Corp. Analyses supplied with these metals are shown in Table 11. EXPERIMENTAL PROCEDURE Preparation of Diffusion Couples. Two types of dif-fusion couples were used in this study. For the copper, silver, and aluminum systems, the couples were sand-

Jan 1, 1969

By D. N. Seidrnan

In the present note we present thermal-analysis data for the liquidus curve from 0 to 76 at. pct Se and for the selenium-rich monotectic reaction in the Pb-Se system. We have previously reported that no expey-imental eviderzce was found for a lead-rich monotectic reaction, at -860°C with a monotectic composition of -20.5 at. pct Se, as found by Nozato and Igaki.&apos; Our additional data substantiated this earlier finding and extended the composition range studied. The alloys were prepared from semiconductor -grade lead and selenium purchased from the American Smelting and Refining Co. Both elements were 99.999+ wt pct pure as determined by the supplier. The impurities for lead were Fe (1 ppm) and Cu & ppm) while for selenium the impurities were Cu (< 1 ppm), As (< 1 ppm), Te (1 ppm), and C1 (<1 ppm). The general procedures used for thermal analysis were those specified by the National Bureau of Standards. A Pt/Pt-10 pct Rh thermocouple calibrated against the freezing points of zinc and copper purchased from the National Bureau of Standards and antimony (99.985 pct pure) purchased from A. D. Mackay, New York, was used for all the thermal analysis. The thermocouple electromotive force was measured with a Rubicon Type B potentiometer used in conjunction with a galvanometer with a sensitivity of 0.5 pV (mm) -&apos;. The absolute accuracy of this thermal-analysis system was *0.5"C. One-hundred-gram alloys of the desired composition were sealed in quartz crucibles, with a central thermocouple well, at a pressure of less than 10"1 Torr. The alloys were initially heated well above the liquidus curve and shaken vigorously to insure homogeneity. Cooling curves were then taken by the direct method at cooling rates ranging from -0.5" to 1.5"C (min)-&apos;. The phase diagram from 0 to 76 at. pct Se as determined by direct thermal analysis is shown in Fig. l.* An extrapolation of the selenium-rich portion of the liquidus curve to the monotectic reaction isotherm (678.3"C) gave a value of 76.1 at. pct Se for the monotectic composition. A tabulation of all the thermal-analysis data is given in Table I. As we previously reported no experimental evidence was found Fig. l—The partial Pb-Se phase diagram from 0 to 76 at. pct Se as determined by direct thermal analysis. For the sake of clarity the points for the 49.00 and 49.16 at. pct Se alloys were not drawn on this phase diagram, see Table I. for the lead-rich monotectic reaction found by Nozato and Igaki.&apos; This result was further substantiated by the fact that none of twelve lead-rich alloys, see Table I, examined for this monotectic reaction exhibited a thermal arrest in the temperature range (849" to 863°C) cited by Nozato and Igaki for the lead-rich monotectic reaction. Hence, our results tend to support the earlier qualitative work of ~elabon&apos; and Friedrich and ~eroux" in the 0 to 50 at. pct portion of the phase diagram, though the selenium-rich monotectic composition and reaction isotherm temperature were in agreement with the approximate values (75 at. pct Se and 672" to 680°C) given by Nozato and ~~aki. &apos;

Jan 1, 1967

By F. Bahnemann

IN discussing the problem of abnormal magnetic polarization, C. A. Heiland1? emphasized the unfortunate fact that our knowledge of the geological and physical conditions relating to such occurrences is very limited and that a more detailed insight into their physical causes would be extremely valuable for interpreting measured anomalies. He also pointed out that to arrive at quantitative physical formulas that would express the conditions that cause abnormal polarization many more occurrences of the kind would have to be recorded. The first part of this paper is a contribution to such descriptions.

Jan 1, 1935

By Walter Rose

Theoretical expressions are presented to describe wetting and non-wetting phase relative premeability relations. These expressions have then been compared with existing published data, the conformance noted being sufficiently good to satisfy the requirements of some engineering use. As a consequence, it may be supposed that relative permeability characteristics of porous media now can be inferred from basic core analysis data, in a manner more convenient (although less direct) than presently available methods of experimental evaluation. INTRODUCTION This paper presents a new approach to the problem of relative permeability evaluation. A classification of published discussions of relative permeability concepts which have appeared in the petroleum literature will show that previously emphasis has been placed on methods of experimental measurement, on the interpretation of the data so obtained with respect to the variable properties of the system, and on theoretical and practical considerations which relate relative permeability to gross fluid behavior in petroleum reservoirs. Essentially, no detailed examination has appeared which treats the fundamental factors controlling the quantitative features of the relative permeability relation*, although cer- tain references can be Cited where a qualitative awareness of their existence and nature is indicated. This condition is explainable in terms of the recognized complexity of the problem, and in order to provide some basis for theoretical development, the general emphasis has been placed in the past on experimental procedures of evaluation, the validity of which, in principle, could be confirmed by the analysis of well and reservoir performance. However, because of the experimental difficulties which have been encountered (notably, difficulties due to the so-called "end effects"), and because of the general unreliability of field performance tests required to study the applicability of the data, relative permeability phenomena continue to be incompletely understood and described.? In this paper is examined the possibility of predicting relative permeabilities entirely from fundamental considerations. In addition, attention is called to certain important factors, previously unemphasized in the published literature, which now can serve as a basis for the eventual experimental confirmation of this and similar theoretical approaches, as well as the experimental solution of the problem in general. Therefore, the analysis presented herein has the dual purpose both of orienting future experimental activity and also of providing an immediate solution for the relative permeability porblem, sufficiently adequate for some engineering use. It will be seen that the conclusions reached are supported by theoretical and intuitive considerations, and they are not contradicted insofar as gross features are concerned by existing concepts and interpretations of published experimental data, except as specifically noted. Darcy&apos;s law, expressed simply as: k dp q = k/u dp/dx .......(1) where q is linear rate of flow (assumed horizontal), k is the † The poor comparison usually obtained between laboratory and field gas-oil ratios (c.f.. Fig. 4 of paper by L. E. Elkins) is illustrative of conditions which dimcourage unqualified acceptance of the results of previous studies except as presently useful approximations. In this connection, Evinger and Muskat have discussed in detail the discrepancy observed between field well productivity values and values obtained from the analysis of laboratory flow data.

Jan 1, 1949

By Walter Rose

Theoretical expressions are presented to describe wetting and non-wetting phase relative premeability relations. These expressions have then been compared with existing published data, the conformance noted being sufficiently good to satisfy the requirements of some engineering use. As a consequence, it may be supposed that relative permeability characteristics of porous media now can be inferred from basic core analysis data, in a manner more convenient (although less direct) than presently available methods of experimental evaluation. INTRODUCTION This paper presents a new approach to the problem of relative permeability evaluation. A classification of published discussions of relative permeability concepts which have appeared in the petroleum literature will show that previously emphasis has been placed on methods of experimental measurement, on the interpretation of the data so obtained with respect to the variable properties of the system, and on theoretical and practical considerations which relate relative permeability to gross fluid behavior in petroleum reservoirs. Essentially, no detailed examination has appeared which treats the fundamental factors controlling the quantitative features of the relative permeability relation*, although cer- tain references can be Cited where a qualitative awareness of their existence and nature is indicated. This condition is explainable in terms of the recognized complexity of the problem, and in order to provide some basis for theoretical development, the general emphasis has been placed in the past on experimental procedures of evaluation, the validity of which, in principle, could be confirmed by the analysis of well and reservoir performance. However, because of the experimental difficulties which have been encountered (notably, difficulties due to the so-called "end effects"), and because of the general unreliability of field performance tests required to study the applicability of the data, relative permeability phenomena continue to be incompletely understood and described.? In this paper is examined the possibility of predicting relative permeabilities entirely from fundamental considerations. In addition, attention is called to certain important factors, previously unemphasized in the published literature, which now can serve as a basis for the eventual experimental confirmation of this and similar theoretical approaches, as well as the experimental solution of the problem in general. Therefore, the analysis presented herein has the dual purpose both of orienting future experimental activity and also of providing an immediate solution for the relative permeability porblem, sufficiently adequate for some engineering use. It will be seen that the conclusions reached are supported by theoretical and intuitive considerations, and they are not contradicted insofar as gross features are concerned by existing concepts and interpretations of published experimental data, except as specifically noted. Darcy&apos;s law, expressed simply as: k dp q = k/u dp/dx .......(1) where q is linear rate of flow (assumed horizontal), k is the † The poor comparison usually obtained between laboratory and field gas-oil ratios (c.f.. Fig. 4 of paper by L. E. Elkins) is illustrative of conditions which dimcourage unqualified acceptance of the results of previous studies except as presently useful approximations. In this connection, Evinger and Muskat have discussed in detail the discrepancy observed between field well productivity values and values obtained from the analysis of laboratory flow data.

Jan 1, 1949

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. &apos;This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. &apos;This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

By Lester L. Hirst, Arno C. Fieldner, Henry H. Storch

EXPERIMENTAL work on liquefaction of coal was taken up by the Bureau of Mines in 1936 when it became evident that a prudent policy from the national point of view should include preparation for the time when gradual exhaustion of petroleum resources would require supplementing the growing demand for motor fuel with gasoline and diesel oil from coal. At that time (1936) certain foreign nations that had no home sources of petroleum, especially Germany, England, and Japan, were conducting active research and at least two of them were producing liquid fuel from coal on a commercial scale. Germany was reported to have an annual producing capacity of 800,000 metric tons of gasoline per year, and England had just put into operation the Billingham plant of Imperial Chemical Industries for the hydrogenation of bituminous coal and tar by the Bergius-.I.G. process. The annual capacity of this plant was about 150,000 long tons of gasoline per annum (3500 bbl. per day). With these developments taking place in foreign countries, it seemed important to undertake a long-range program of fundamental research in this country to establish a sound groundwork for the evaluation of foreign work on synthetic liquid fuels and at the same time to obtain data on the oil yields and operating difficulties using various kinds of American coals and lignite to the hydrogenation process. The results of such research would be useful in determining the yields and quality of liquid products obtainable from various coals so that American industry would be in position to select the most suitable coals and make rapid progress in establishing this new industry when the commercial need should arise. It was hoped, also, that progress in a better understanding of the chemistry of coal hydrogenation would reduce the cost of the process materially. To carry out this program, a small continuous unit capable of hydrogenating 100 lb. of coal in 24 hr. was installed at the Central Experiment Station of the Bureau of Mines at Pittsburgh, Pa. Small steel autoclaves or bombs of 0.3 gal. (1.2 liters) capacity also were used for batch-hydrogenation experiments in the study of the chemical fundamentals of the process. Much valuable assistance was obtained in planning the experimental program and designing the equipment from the Fuel Research Station of Great Britain and the Fuel Laboratories of the Mines Department of Canada, where such investigations had been in progress for several years. EQUIPMENT AND GENERAL PROCEDURE OF RESEARCH The industrial liquefaction of coal by the Bergius-I.G. hydrogenation process as practiced at Billingham, England, from

Jan 1, 1944

By Joseph Kelly

DEPLETION of anthracite resources in Lackawanna County, Pennsylvania, has forced the recovery of coal tracts formerly considered unminable. Chief among these are the large areas of outcrop coal lying on a heavy pitch on the mountain sides, abandoned thirty or forty years ago as too costly and too hazardous to mine. The old companies, in many instances, stopped their chambers 80 or 100 ft. hack from the actual outcrop, and then dropped back another 100 ft. before starting to rob the pillars, thus leaving large areas of coal. Recovery of this coal naturally leads to mining hazards not encountered years ago. The first step is to sink a slope from the surface with the pitch of the vein, and then drive counters across the pitch as close to the robbed area as proper protection for the lower side of the -counter will permit. Next, the old chambers are advanced or new ones driven in the solid, as the conditions require. As these chambers approach the outcrop the real safety work begins-that of preventing the miner from being buried or locked in by an avalanche of mud.

Jan 1, 1936

By Y. C. Liu, G. A. Alers

measurements of the anisotropy in Young&apos;s modulus produced in copper by rolling 95 pct reduction in thickness below room temperature have been carried out in order to study the dependence of the texture on rolling temperature. The results clearly show the transition from a copper-type texture to a brass-type texture as the temperature of rolling is lowered. The intermediate textures observed can be described very well as a simple mixture of the two terminal textures. These results cormbined with other texture measurements make possible afresh review of the experimental facts velating to rolling textures in fee metals and, as a consequence, a critical examination of the current theories is presented. PREVIOUS experiments have shown that the transition from the copper- to the brass-type rolling texture is clearly displayed and can be quantitatively analyzed by measurements of the anisotropy of Young&apos;s modulus.&apos; Application of this method to the Cu-Zn alloy system showed that the description of the texture transition as a gradual rotation of the grains from the orientation characteristic of the copper texture to the {110}(112) texture of brass2 was inconsistent with the data. Instead, the data suggested that the texture within the transition region could be described as a simple mixture of the two terminal textures.5 Unfortunately, it was difficult to establish this point conclusively because of the inadequacy of corrections for the composition dependence of the single-crystal elastic constants. Since a rigorous establishment of the nature of this texture transition is essential to our understanding of the formation of rolling textures in fee metals, it is clearly important to undertake an investigation in which the composition dependence of the elastic constants would not enter. A suitable composition-independent texture transition is provided by the well-established variation in the rolling texture of copper with rolling temperature. This temperature-dependent texture transformation has been studied by smallman&apos; in several fee alloys and by Müller5 and others"&apos; in copper. They observed that the texture characteristic of copper rolled at room temperature changed to a brass-type texture when the rolling temperature was lowered to 77°K. Although it is not possible to decide unequivocally from the published pole figures whether or not the 77°K rolling texture of copper is entirely of the brass type,&apos; this complication does not affect the main purpose of the present investigation. In addition to establishing the nature of the texture within the transition region, the modulus data should also provide a determination of the temperature at which the transition occurs as well as the temperature range over which the transition extends. This information when combined with the modulus data on Cu-Zn alloys would then provide a considerable body of new information on textures in fee metals. Since these modulus results and the data obtained from pole-figure studies must be internally consistent, it is appropriate to compile a brief summary of the experimental observations based on all available methods rather than on the pole-figure data alone as has been done in the past. The primary purpose of such a summary would be to yield a more precise definition of the experimental facts on the rolling textures of fee metals, and thus greatly facilitate our evaluation of various proposed theories in this field. The final section of this paper is devoted to this compilation of consistent, experimental facts and their application to the various theories. EXPERIMENTAL PROCEDURE Two 18-lb ingots of cathode copper of 99.99 pct purity were induction-melted under a nitrogen atmosphere in a graphite crucible and chill-cast into a steel mold. The ingots were repeatedly cold-rolled and annealed (I hr at 500°C) into slabs about 1 1/8 in. thick. Blocks 3 1/4 in. wide, 2 1/4 in. long, and 1.000 in. thick were machined from each slab. The rolling schedule used was the same as in the previous investigation1 and the final thickness of the sheet was 0.050 in. with a rolling reduction of thickness of 95 pct instead of 97.5 pct as in the previous work.&apos; The compositions and temperatures of the cold baths used for the low-temperature rolling were as shown in Table I. After each pass the rolled strip was immediately immersed in the cold bath for about 1 min or until the bubbling of the bath had subsided. The modulus data were taken within 2 hr after the rolled strip was warmed to room temperature for the first time, so that effects due to recrystallization were minimized. The modulus specimens were in the shape of flat bars, 3 in. long, 4 in. wide, and 0.050 in. thick, cut with their long dimensions oriented at 15-deg intervals between the rolling direction and the transverse direction. The values of Young&apos;s modulus were deduced from measurements of the frequency at which these long narrow bars were set into longitudinal, resonant vibration as previously described.9 To excite the mechanical vibrations in the specimen, an electromagnetic drive similar to that employed by Thompson and lass" was used. The maximum in the amplitude of

Jan 1, 1968

Duval Corporation, the owners of the Sierrita, Esperanza, and Mineral Park copper operations in Arizona, first acquired the mineral rights to their Battle Mountain, Lander County, Nevada, property in 1962. Development of the mine commenced in mid - 1965, and the copper operation began at the end of 1968. The ore, a mixture of chalcocite and chalcopyrite, was milled and floated at a rate of 3, 175 mtpd (3,500 stpd). Because of low copper grade and price, the plant was shut down after about ten years of operation. Attention was then turned to an adjacent low-grade precious metal ore body which contained 2.74 g Au and 3.4 g Ag per mt (0.08 oz Au and 0.10 oz Ag) and minor amounts of copper. Test work revealed recovery by Carbon-In- Pulp treatment would amount to approximately 2.8 mt (90,000 oz) each of gold and silver per year. A rapid engineering and construction schedule resulted in the world&apos;s largest, as of late 1980, Carbon-In- Pulp plant being put on-stream in January 1979, with a capacity of 2.720 mtpd (3,000 stpd). Fortunately, the original crushing and grinding plant with all its infra structure was available, and the only modification needed was the addition of a gravity circuit to remove coarse free gold ahead of Carbon- In-Pulp treatment. One of the four primary 500 mm (20 in.) cyclone underflows in the primary ball mill circuit is directed to a secondary ball mill where its product is again cycloned. The cyclone underflow is screened at 3,360 microns (6 mesh) with the undersize being treated on two Pan American 1.07 m by 2. 14 m (42 in. by 84 in.) jigs. Hutch product is further concentrated on two Wilfley tables, a magnetic separator, and on a third Wilfley table where approximately 930 g (30 oz) of gold are recovered each day for amalgamation, retorting, and smelting. Returning to the grinding circuit, the final cyclone overflow is sent to the original plant tailings thickener to obtain proper pulp density for Carbon-In-Pulp treatment. Thickener underflow, at about 40% solids, is then conditioned with air and lime in a series of two 8.5 m by 9.75 m (28 ft by 32 ft) 15O cone bottom Pachucas for oxidation of pyrrhotite. The pulp is then split into two streams for cyanidation for 48 hours in two lines of eight Pachucas of the same size. Pulp is transferred from tank to tank by auxiliary air lifts. Cyanided pulp is then sent to a series of six C. I. P. mechanically agitated tanks with one hour retention in each tank. Originally these

Jan 1, 1981

By J. G. Thompson

Determinations of the hydrogen content of irons and steels invariably are subject to two serious difficulties: (I) the determination of amounts of 0.001 per cent or less of any constituent requires an analytical procedure of unusual precision and accuracy, and (2) the hydrogen content of many samples is dccidedly not stable; i.e., there is no assurance that the content at the time the analysis is made is the same as it was when the sample was taken or at some previous time in the history of the piece. In respect to both the precision and speed of the determination, the vacuum-extraction procedure for the determination of hydrogen possesses advantages over the vacuum-fusion procedure, which has been the recognized standard for the detcrmination of other gaseous elements in sted-— oxygen and nitrogen for example. The basic facts upon which the vacuum-extraction procedure is based—i.e., the evolution of gas from solid steel when it is heated in vacuum, and the fact that the evolved gas is rich in hydrogen—were observed by Graham1 many years ago. Subsequent investigations have shown that hydrogen exists in steel chiefly as interstitial solid solution (i.e., in atomic dispersion) and perhaps to some extent as hydridcs that are unstable and decompose to form atomic hydrogen. In either case practically all of the hydrogen in steel at elevated temperatures exists in the atomic condition and consequently is able to diffuse readily through the metal. In contrast to this, other gaseous elements, such as oxygen and nitrogen, normally are present in steel chiefly in the form of relatively stable compounds such as oxides or silicates and nitrates; i.e., the oxygen and nitrogen atoms are fixed in stable combinations and are not free to migrate. The only oxygen or nitrogen that can diffuse in steel is the small amount in solution (atomically dispersed) and the rate of diffusion of these atoms is much less than that of hydrogen because of their greater atomic volume and lower mobility. Consequently, it is possible to extract most or all of the hydrogen from solid steel in a reasonable time at moderately elevated temperatures, but the procedure is not applicable to the determination of oxygen or nitrogen. It is only within the last decade that these observations have been developed into an analytical procedure for the determination of hydrogen. Apparatus and Procedure The apparatus used at the National Bureau of Standards,6 for the determination of hydrogen by the vacuum-extraction procedure, is shown schematically in Fig. I. The specimen, freshly cleaned and dried,* is suspended on a fine wire within the quartz furnace tube that is connected to the reservoir system and analytical train.

Jan 1, 1945

By Don B. Carson, Donald L. Katz

NATURAL gases under pressure form crystal-line hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methane-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbonrich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. INTRODUCTION Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villard1 and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies.2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Deaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on temperatures and pressures of hydrate formation for pure methane, ethane, propane, n-butane, methane-ethane mixtures, methane-propane mixtures, methane-butane mixtures, and some 15 natural gases, all in the presence of excess water. However, up to the present time no method has been available for predicting the temperature at given pressures or the pressure at given temperatures at which natural gases will form hydrates if saturated with water. This paper pre¬sents data on the methane-propane-water, methane-pentane-water and methane-hexane water systems in four phases, one of which is the hydrate. The application of the phase rule to the methane-propane-water data proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1941

By Leonard D. Jaffe, Donald C. Buffum

THE importance of temper brittleness in alloy steels has long been realized in Europe, In the United States recognition of its importance has developed within the last several years. Many brittle failures encountered in parts made of alloy steel are undoubtedly attributable, wholly or in part, to temper brittleness. These failures have occurred particularly at low temperatures, under shock loading, and in the presence of notches, restraints and combined stresses. It has been almost universally accepted that plain carbon steels are not susceptible to temper brittleness. As a result, considerable effort has been expended in attempts to discover the manner in which alloying elements introduce temper brittleness. It is desired to raise the possibility that plain carbon steels are not only susceptible to temper brittleness, but are much more susceptible than alloy steels, in the sense that they embrittle much more rapidly. It is suggested that previous views, (that plain carbon steels are not susceptible), are based upon an erroneous interpretation of the experimental results. INTERPRETATION OF PREVIOUS DATA For many years the standard criterion for susceptibility of a steel to temper brittleness consisted of comparison of the energy absorption, in a notched-bar impact test at room temperature, of specimens that had received two heat treatments.1 One specimen (or group of specimens) was quenched, tempered, and quenched from the temper. The other specimen (or group) differed only in having received an embrittlement treatment, which might consist of a slow cool from the tempering temperature, or of an isothermal hold in the range 450-550°C subsequent to quenching from the temper. If the energy absorption of the specimen receiving the embrittlement treatment was lower than that of the specimen not given this treatment, it was said that the steel was susceptible to temper brittleness, If the energy absorptions were the same, it was said that the steel was not susceptible. Several investigators2,3 found that plain carbon steels showed negligible difference in energy absorption in such tests (at least when their manganese content was below 0.60 pct), and concluded that plain carbon steels are not susceptible to temper brittleness. Recently the deficiencies of the criterion mentioned above have been pointed out.4-6 The criterion now generally used for susceptibility to temper brittleness retains the heat treatments used in the earlier scheme, but instead of the notched-bar impact tests being made only at room temperature, they are made over a range of temperatures, covering the transition from ductile to brittle fracture, If the transition temperature of the specimens receiving the embrittlement treatment is higher than those

Jan 1, 1948

By D. L. Martin, E. R. Parker

IN a previous paper, one of the authors observed that the rate of cooling from the anneal prior to testing greatly influenced the life of copper under sustained load at 200°C. Furnace-cooled bars of oxygen-free copper (with, and without silver) had a life four to twenty-five times that of the water-quenched specimens. The addition of 0.054 per cent silver to the oxygen-free copper increased the life at a stress of 20,000 lb. per sq. in. from about 2 hr. to 50 hr. Fractures in these bars were intercrystalline. An explanation was advanced to account for the profound influence of cooling rate on the rupture properties at 200°C. The suggestion offered was that at the high annealing temperature the minor constituents are distributed at random. By water quenching, this condition is maintained at room temperature, whereas furnace cooling permits some segregation at the grain boundaries. The higher concentration of the minor constituents in the grain boundaries results in a strengthening, so that a longer life at a given stress and temperature results. Small amounts of cadmium or manganese have also been found to increase the life of copper at 200°C., and to a much greater extent than silver .2 The increase in the long-time strength of copper resulting from small additions of cadmium or silver appears to be related, indirectly at least, to the higher softening temperatures of such alloys. The elements, such as silver or cadmium, which greatly increase the rupture life of copper also cause large increases in the softening temperature. As little as 0.05 per cent of cadmium or silver is sufficient to raise the softening temperature more than 100°.3,4 The effects of cooling rate and of minor constituents on the rupture properties are of considerable fundamental as well as practical interest; therefore a more detailed study of their nature was conducted and is reported in this paper. EXPERIMENTAL PROCEDURE Materials The materials studied in this investigation may conveniently be classified in two groups: one consisting of a wide variety of commercial coppers, and the other composed of special high-purity, laboratory-prepared coppers. The commercial materials were tested to determine whether or not the effect of cooling rate occurred with all coppers, whereas the high-purity coppers were investigated in order to establish a basis for evaluating the effect of minor constituents on the rupture properties. In Table I are given the analyses of the coppers tested. The samples I to 6 are commercial materials and were obtained for the most part from stock supplies.*

Jan 1, 1943

By M. E. Wadsworth, I. B. Cutler, R. W. Bartlett

The oxidation kinetics of ZrC was studied between 450" and 580°C in oxygen pressures from 6.5 x 10-to 1 atm using a ther mogravimetric apparatus and sized powder samples. Two parallel rate controlling processes were observed. A surface reaction occurring at the ZrC-ZrO2 phase boundary accounted for most of the oxidation and had an activation enthalpy of 46 kcal per mole. The other process, believed to be diffusion of oxygen into the ZrC lattice partially replacing carbon, had an activation enthalpy of 53 kcal per mole. The enthalpy for chemisorption of O2 on ZrC was determined to be —13 kcal per mole. Water vapor in the presence of oxygen accelerated the surface reaction rate. THERE has been little reporting of formal rate studies or attempts to ascertain the mechanism of oxidation of carbides. MacDonald and Ransley1 studied the oxidation of titanium carbide which has the same structure as zirconium carbide, fcc. They observed an initial increase in rate with increasing temperature followed by a rapid decrease through a rate minimum and a subsequent second increase at higher temperatures. The discontinuity in the rate rise was attributed to a phase change in the oxide which changed the rate determining step from the surface reaction at the carbide-oxide interface to diffusion through the oxide layer. Samsonov and Golybera 2 studied titanium carbide and reported that during the initial period of oxidation a dense film of Tic-TiO was formed followed by the formation of less adhering layers of higher oxides. The purpose of this investigation was to study the kinetics of oxidation of zirconium carbide and to attempt to gain some knowledge of the mechanism by which oxidation occurs. EXPERIMENTAL PROCEDURE Measurement of the weight gain associated with the oxidation of ZrC was used to determine oxidation rates. The principal experimental parameters were surface area, temperature, and oxygen pressure. Although moderately sized crystals of ZrC can be grown by the Van Arkel method, the only commercially available ZrC is a powder. In using powders, the surface area must be controlled either by fabricating the powder into a sintered pellet with a measurable surface area, relatively fixed during oxidation, or by using sized unconsolidated powder and applying appropriate geometric considerations to the shape of the grains to correct for their diminishing surface areas as they oxidize. Both techniques involve some difficulties. pellets of binder-free zirconium carbide can be made by hot pressing, but it is difficult to obtain densities greater than 90 pct of

Jan 1, 1963

By Charles H. Snow

The engineer has often to penetrate difficult or unknown regions. Mineral, irrigation, boundary and railway problems frequently necessitate journeys through, or long residence in, localities whence sustenance cannot be drawn. The selection and conveyance of provisions, outfit and implements thus become a matter of the first importance. Scientific skill, even of the highest order, is powerless unless supported by the proper appliances and foods. The advance of civilization favors the engineer, in that it is constantly enlarging his facilities and thus reducing his difficulties. Notwithstanding this fact, many are yet brought face to face with the problems considered in this paper. Distinction must be made between parties which are to be in constant or even occasional touch with a base of supplies, and those which will be for a long time dependent on their original outfit. Again, the requirements of a party on the march are different from those of a fixed camp. The district, season, cliinate, size and personnel of party also influence the character of the outfit. A party that is to be detached from its base of supplies for some time requires a greater variety of food than if it is to be gone for a short time. Much less in proportion need be taken where the journey is not long, so that privation is confined to a limited period. The ability to establish a fixed camp permits a larger outfit than would be possible if the camp mere to be moved from day to day. Transportation, climatic and other conditions are thus so varied that lists prepared for one work could hardly be applied to any other without some modification. Lists that have proved successful in some instances may, however, serve as bases to be added to, or otherwise altered, for the case in hand. The mistake usually made is in providing too large an outfit. Every emergency cannot be provided for; so that it is well to take, not what may be needed, but what cannot be spared.

Jan 1, 1900

By H. l. Burghoff, C. H. Mathewson

THE study of the creep of metals under conditions of prolonged loading has received the attention of many investigators for several years and almost innumerable papers have been published on the various aspects of the subject. As it appeared that much could still be learned from a study of single crystals, the present work was carried out to study the effects of temperature and conditions of loading upon the properties and deformation in tension of single crystals of alpha brass containing about 70 per cent copper and 30 per cent zinc. In particular, it was hoped to obtain information from tests below and above the recrystallization temperature of the material, so that properties such as elastic limit, yield point or critical stress, and manner of deformation might be compared for tensile tests at an ordinary loading rate and for prolonged. loading. Accordingly, short-time tensile tests and creep tests were made at room temperature, 300º, 500° and 700°F. The two latter temperatures are above the lowest possible recrystallization temperature of polycrystalline 70-30 brass. PREVIOUS WORK Clarke and White1 have made creep tests of some copper-zinc alloys, including 70-30 brass, and copper-zinc-tin alloys at temperatures both below and above the recrystallization temperature of the materials considered. Hanson and Wheeler have studied the flow and fracture of single crystals of aluminum for short-time and prolonged tensile loading over a range of temperature extending from room temperature to 400°F., their experiments being made without consideration of the orientations of the test specimens. Extensive creep and fracture tests on single crystals of lead at room temperature have been made by Betty3 and by Baker, Betty & Moore.4 Results of the last-named investigation were published while the present work was in progress. Millers examined the elastic limit of zinc single crystals at and above room temperature by means of creep tests, while Miller and Milligan6 reported the results of tests designed to show the influence of temperature on elastic limit of single crystals of aluminum, silver and zinc. The behavior, of iron crystals under static tensile loading at room temperature was reported by Gensamer and Mehl7 while the present investigation was in progress. Their specimens exhibited a well-defined yield point, below which no appreciable creep could be detected. The manner of yielding proved interesting, as the shape of the creep-time curve for the iron crystals differed from the common type of creep curves. Elongation did not begin immediately, or at least was initially very slow. The rate of elongation then increased continuously and finally decreased to zero. This S-shaped type of elongation-time

Jan 1, 1941

By R. P. Carreker, J. G. Leschen, J. H. Hollomon

The external appearance of a crystal which has undergone plastic flow suggests that adjacent blocks of the crystal have glided bodily past one another along the slip planes. However, the great discrepancy between the shear stresses calculated to effect such a movement and those actually observed has for many years stimulated searches for more satisfactory interpretations of the slip process. Appreciable success in these efforts has been realized by assuming the presence in the crystal of various sorts of imperfections and by considering the consequences of the presence of these flaws when stress is externally applied. The theory that has received the most attention recently—that of dislocations—postulates the occurrence of small, mobile imperfections or dislocations which move through the crystal along the slip direction, each dislocation being attended by a local shear displacement of one interatomic distance. Thus only that portion of the crystal through which the dislocation has passed may be said to have slipped. Since each dislocation produces a displacement of only one interatomic distance, an avalanche or train of many dislocations would be necessary to account for the observed displacements of several hundred or thousand interatomic distances. The salient point of the theory of dislocations is the concept that a slip band does not suddenly appear in its entirety. On the contrary, it grows progressively across the slip plane as the individual dislocations successively appear and advance in a train through the crystal. However, the concept of growth is not intrinsic only to the theory of dislocations, since atomistic mechanisms other than that postulated by the dislocation theory can quite probably also describe the growth of a slip band. For instance, a slip band might resemble a disc-like interface that appeared and then grew continuously from a small size, producing a displacement that increased with the size of the disc. Whatever the precise mechanism, the concept of growth is in itself consistent both with the observed low values of critical shear stress and with the experimental observation that slip bands frequently do not traverse the entire crystal. The likelihood that slip bands grow implies that they must first be nucleated and that the initiation of slip can therefore be analyzed in terms of the general concepts of nucleation. Indeed, this suggestion was advanced1 several years ago, but the matter does not appear to have been further pursued. Recent advances in the theory of nucleation 2,3,4 have encouraged such a treatment of the slip process. As will presently be demonstrated, this approach to the problem not only accounts successfully for the incubation periods that have been observed 5,6 to precede slip but also predicts certain transient effects in the deformation process. The existence of these transients apparently has not hitherto

Jan 1, 1949