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By Albert J. McIntosh

In discussing the petroleum products situation the first thing that comes to mind is "what is happening to gasoline." Is the consumption increasing? How is the export market? What about imports? Are stocks on hand too high? Have we produced too much? This paper will attempt to answer these questions. Consumption of gasoline (motor fuel) in the United States in spite of the depression and the chaotic conditions of many industries has increased during 1931 about 2 per cent over 1930. This favorable factor was offset by a severe contraction in exports, which fell off about 30 per cent from 1930. This drop in exports was so large that very little more export business was done than in 1926 or 1927. Taking all demand combined, there was a decrease from the peak year of 1930 of nearly 11,000,000 bbl., amounting to slightly over 2 per cent. The units of the industry, though, should have expected some decrease and governed themselves accordingly. Let us see what they did. They reduced imports over 3,000,000 bbl., which helped. Production was cut 3,000,000 bbl., but this was not enough, so that stocks increased 1,800,000 bbl. whereas during the previous year stocks were reduced 2,500,000 bbl. It is apparent, therefore, that something was done to keep the industry in balance in regard to gasoline, but not enough. If the year had ended on Sept. 30, we could have said that production had been cut 19,000,000 bbl. and stocks had been reduced from the previous year, but the excessive production during the last three months of the year changed everything. It is a strange thing and worthy of note that the price of gasoline fell to its lowest levels when apparently the greatest improvement was being made, and that during the last quarter of the year prices started to improve, when, in spite of an improvement in total demand which approximated 1930, an excessive production caused an uneconomic condition to set in. Stocks on hand on Dec. 31 were unquestionably too high, possibly 10,000,000 bbl. more than was needed for a strong condition to obtain. It seems almost unbelievable that the industry would continue to produce

Jan 1, 1932

By S. D. Michaelson, Eric Sinkinson

Many of the magnesite ores of the western part of the United States contain such large amounts of silica and hydrous silicate minerals that the value of the ores is either low or nominal. Expensive and carefully controlled mining methods are necessary to prevent excessive dilution of the higher grade ores by introduction in mining of small pieces of the hanging walls or footwalls of the deposit. This difficulty is further complicated by the various states of decomposition of the country rock of the deposits in which many of the ores occur. The problem the authors attempted to solve arose from a request to float an impure magnesite containing varying proportions of siliceous gangue with calcium carbonate. The ore is normally enclosed in serpentine masses, somewhat decomposed, and in mining it wall rock is incidentally added, so that variable amounts of siliceous material occur in the samples. The silica, alumina, and iron oxide are so closely associated with the magnesium carbonate in the magnesite that ordinary mechanical separation at coarse mesh sizes is of no avail. It is well known that calcium carbonate can be floated by suitable reagents, therefore it seemed reasonable to suppose that magnesium carbonate minerals would behave in a similar manner, but experimental trial proved that this supposition was unfounded. Therefore the first step in the problem was to find out what differences of behavior there were between magnesium and calcium carbonates under flotation conditions, or when suspended in water. In water at 18" C. magnesium carbonate is slightly more soluble than calcium carbonate; in fact, MgCO3 is soluble to the extent of 0.0106 grams in 100 c.c. of water at 18" C. and CaCO3 to the extent of 0.0013 grams. However, magnesium carbonate in water gradually changes to the basic carbonates of a composition (3MgCO3.Mg(OH)23H2O) or (4MgCO3.Mg(OH)25H2O), depending upon conditions, and calcium carbonate to calcium hydroxide, Ca(OH)2. The relative solubilities of these hydroxides in water are the reverse of the solubilities of magnesium and calcium carbonates. The range in published figures for solubility

Jan 1, 1938

By S. D. Michaelson, Eric Sinkinson

Many of the magnesite ores of the western part of the United States contain such large amounts of silica and hydrous silicate minerals that the value of the ores is either low or nominal. Expensive and carefully controlled mining methods are necessary to prevent excessive dilution of the higher grade ores by introduction in mining of small pieces of the hanging walls or footwalls of the deposit. This difficulty is further complicated by the various states of decomposition of the country rock of the deposits in which many of the ores occur. The problem the authors attempted to solve arose from a request to float an impure magnesite containing varying proportions of siliceous gangue with calcium carbonate. The ore is normally enclosed in serpentine masses, somewhat decomposed, and in mining it wall rock is incidentally added, so that variable amounts of siliceous material occur in the samples. The silica, alumina, and iron oxide are so closely associated with the magnesium carbonate in the magnesite that ordinary mechanical separation at coarse mesh sizes is of no avail. It is well known that calcium carbonate can be floated by suitable reagents, therefore it seemed reasonable to suppose that magnesium carbonate minerals would behave in a similar manner, but experimental trial proved that this supposition was unfounded. Therefore the first step in the problem was to find out what differences of behavior there were between magnesium and calcium carbonates under flotation conditions, or when suspended in water. In water at 18" C. magnesium carbonate is slightly more soluble than calcium carbonate; in fact, MgCO3 is soluble to the extent of 0.0106 grams in 100 c.c. of water at 18" C. and CaCO3 to the extent of 0.0013 grams. However, magnesium carbonate in water gradually changes to the basic carbonates of a composition (3MgCO3.Mg(OH)23H2O) or (4MgCO3.Mg(OH)25H2O), depending upon conditions, and calcium carbonate to calcium hydroxide, Ca(OH)2. The relative solubilities of these hydroxides in water are the reverse of the solubilities of magnesium and calcium carbonates. The range in published figures for solubility

Jan 1, 1938

By David N. French

In a recent paper, Miyoshi, Hara, and sugimotoL have shown that hardness increases and crack resistance decreases with polishing time in tungsten car-bide-cobalt alloys. They attribute the changes in hardness and crack resistance to cold working in these alloys. More recently Exner2 explains the decrease in crack resistance with the amount of material removed (polishing time) by suggesting that polishing removes a high compressive residual surface stress due to the initial grinding operation. He cites previous work on steel to show grinding can induce surface compressive stresses but offers no direct experimental measurements to support this in cemented tungsten carbides. In recent work we have observed changes in residual stress in the W C phase as measured by X-ray diffraction techniques with changes in polishing conditions.3 As a result of the work of Miyoshi et al.,L a brief study was undertaken to investigate the effects of polishing and grinding on the residual stress in the WC phase and have been reported.4 A single composition of tungsten carbide —10 wt pct Co was used. Two initial conditions were studied: an annealed condition with about -30,000 psi residual stress from the differences in thermal coefficients of expansion of WC and cobalt and, on the same specimen, a surface ground with a 150 grit diamond wheel. Stress was measured in the WC phase using X-ray diffractometry as a function of the amount of material removed by metallographic polishing with 6 diamond paste. The results are shown in Fig. 1. Two things are noted, 1) polishing with 6 p diamond paste has little effect on the annealed sample and 2) the magnitude of the grinding stress is markedly reduced as material is removed. By the time 0.1 mil is removed the surface has a metallographic polish satisfactory for light microscopy examination. Thus the surface, even though polished, can still retain most of the stress due to grinding. Since WC is itself slightly ductile, it seems reasonable that high compressive stresses can be generated in the surface by the plastic deformation accompanying grinding. Exner2 suggests, by analogy with steel, that as a result of grinding both WC and cobalt in the

Jan 1, 1970

By B. B. Rath, Hsun Hu

Rates of migration of large-angle boundaries have been studied in zone-refined aluminum crystals, defonned 80 pct by rolling in the (110)[112] orientation at -78°C followed by a recovery anneal at 80°C. Artificially nucleated grains show a marked variation. by an order of magnitude, in their growth rates in different directions. The average activation energy for the migration of all boundaries was found to be about 16,000 cal per mole. The anisotropy of the boundary migration is rationalized on the basis of the boundary structure. It has been observed by Beck and HU,1 Kohara el al,2,3 and Czjzek and Haessner4 that recrystallized grains formed upon annealing Of deformed sing1e crystals of aluminum show anisotropic growth characteristics. Kohara et al. found that single crystals rolled in the (110)[112] orientation, when random nuclei were provided on one side of the crystal by rubbing with emery paper and annealing, developed a sharp recrys-tallization texture on the other side of the crystal upon further annealing. This sharp recrystallization texture consisted of four components, which were related to the deformation texture of the crystal, i.e. (110)[112], by rotations of ±40 deg around each of the two common [ 111] axes' They also noted that recrystallized grains were elongated in directions perpendicular to either of these two common [1111 axes. They attributed this anisotropic growth to the difference in the rate of self-diffusion or diffusion of impurity atoms along the tilt and the twist boundaries. A somewhat similar investigation was conducted by Czjzek and Haessner4 On strained single-crystal sheets Of alum- inum. These authors claimed that the matrix structure of the deformed crystal had a greater effect on the growth anisotropy of the recrystallized grains than did the boundary orientation itself. In the present investigation quantitative measurements of the rate of grain boundary migration in anisotropic growth have been made in zone-refined aluminum (99.9999+pct pure) crystals deformed 80 pct by rolling in the (110) 112] orientation. Crystals of this particular orientation were chosen because of the following desirable features: 1) the crystal does not change its orientation during rolling; 2) the rolling plane contains all the significant crystallographic directions; and 3) when annealed, following deformation, the crystal does not re-crystallize spontaneously but polygonizes to a stable and homogeneous structure. Hence, the initial orientation of the crystal and a constant strain energy in the matrix can be maintained during subsequent grain boundary migration studies. It is essential to keep the driving force constant for the study of boundary mobility.5 EXPERIMENTAL PROCEDURE A cylindrical single crystal of 1 in. diam was grown by the Bridgman method in a high-purity graphite mold. The resistance ratio, R(4.2°K) /R(298°K) , of the grown crystal was approximately 2.0 x 10-4. A number of slices, 1/4 in. thick, were cut from the crystal along the (110) plane and were mechanically and electrolyti-cally polished to remove the strained surface layer. The crystals were then rolled along the [112] direction to 80 pct reduction in thickness at -78°C. To minimize surface friction, the crystals were rolled between two layers of 0.005-in. teflon sheet. Rolling was interrupted, prior to completion, to remove the surface layers and the edges by electropolishing. These and similar precautions in handling the rolled crystals

Jan 1, 1967

By T. L. Berger, M. C. lnman, M. F. Rose

AFTER shock loading, mechanical twinning has been observed by several authors1-4 for a variety of fcc metals and alloys. It has been shown2,3 that low stacking fault energy materials deform primarily by the formation of mechanical twins and stacking faults during dynamic loading. Further, Inman, Murr, and Rose2 have shown that a correlation exists between the average hardness and the volume percent of mechanically twinned material in stainless steel. It has been observed in nickel' that mechanical twins are produced during shock deformation if the peak pressure associated with the shock wave is greater than 350kbar. It is the purpose of this work to discuss shock-hardening mechanisms in nickel and to determine to what extent the initial condition influences the final response. The "flying plate technique" was used to generate planar shock waves with peak pressures as high as 710 kbar. The details of the technique5" have been discussed elsewhere and will not be repeated here. The material used in this study was polycrystalline nickel of 99.98 pct purity and had an initial grain size of 0.18 mm. Prior to any deformation, all samples were given a stress-relief anneal of 6 hr at 600°C in a vacuum furnace. After annealing, the initial condition of the samples was changed by cold rolling individual samples from 0 pct to a maximum of 80 pct reduction in thickness. This provided samples with controlled initial histories for shock deformation. Immediately after shock loading, the specimens were slowed and quenched by suitable arrangement of buffer material and water bath. This technique minimized specimen damage and the effects of shock heating on the samples. Since deformation twins in high stacking fault energy fcc metals are only produced at high stress levels, the initial defect configuration prior to mechanical twinning should greatly influence the number of twins formed. In fact, Zukas and Fowler7 have found that prestraining in iron and steel greatly suppresses the formation of mechanical twins during the shock deformation process. Following the methods of Warren and warekois8 and Cohen and Wagner,9 X-ray diffraction profile analysis was performed to determine the incidence of stacking faults and mechanical twins in the deformed nickel. Analysis was made on samples in the annealed, cold-rolled, shock-loaded, and cold-rolled—shock-loaded states. The estimated accuracy of the peak position measurements is *0.01 deg in 2?. Therefore the accuracy in the measurement of the relative peak shifts between the (400) and (222) diffraction line profiles is on the order of *0.04 deg in 2?. None of our measurements indicated peak shifts greater than 0.04 in 28. This would correspond to a fault density of -1 pct and sets the limit on the sensitivity of our instrument. Similarly, analysis of the shift in the center of gravity of the diffraction line profiles yields the minimum measurable value of the twin fault probabilitya to be -0.002. Fig. 1 shows mechanical twinning in nickel shock-loaded to 400 kbar. In this photograph, fault intersections are clearly visible. The thickness of the individual fault lamellae was determined from the image widths of their lines of intersections by the

Jan 1, 1968

By J. H. Jackson, P. D. Frost, C. H. Lorig, A. C. Loonam

THIS paper describes (1) the effect of sodium on the tensile ductility of magnesium-lithium base alloys, and (2) the precautions necessary to avoid sodium contamination. Effect of Sodium on Properties The harmful effect of sodium in magnesium-lithium base alloys has been recognized by other investigators.1,2 However, quantitative data on its effect have not hitherto been published. The effect of sodium on the ductility of an 87 pct Mg-9 pct Li-4 pct Zn alloy is shown in fig. 1. The sodium was introduced by adding sodium chloride to the flux, which consisted of 50 pct LiC1-50 pct KC1. Moderately high ductility was obtained at an indicated sodium content of about 0.05 pct. Actually, the value probably was less than 0.05 pct, be-cause analyses of the lithium, which were more accurate than those of the alloy, indicated that the highest ductility was obtained when its sodium content was 0.02 pct or less. In fact, in alloys having somewhat greater strength than this particular composition, the sodium content of the lithium must be under 0.01 pct to avoid embrittlement. The effect of sodium on the ductility of several alloys having fairly low strength levels is shown in fig. 2. These alloys were melted with a flux containing 75 pct LiC1-25 pct LiF, to which various quantities of sodium chloride had been added. Sodium had no significant effect in pure magnesium but markedly decreased the ductility of the magnesium-lithium-zinc alloy, even though the alloy contained only 3 pct Li. As the lithium content of the binary alloys was increased, the ductility of the sodium-free alloys also increased. However, the effect of sodium on ductility became progressively more pronounced. Sodium raised the minimum hot-rolling temperatures, particularly those of the high-strength alloys, but its effect, in this respect, was less critical than its effect on tensile ductility. For optimum cold roll-ability, a low-sodium content was required. No deleterious effect of sodium on the stability of properties at slightly elevated temperatures was found. Control of Sodium in the Alloys Optimum ductility is obtained in the magnesium-lithium base alloys when sodium-free materials are used. Commercial lithium was formerly the chief source of contamination. Now purified lithium is usually available. When lithium of ordinary purity is used, the effects of sodium can be minimized by using a flux consisting of 75 pct LiC1-25 pct LiF. Bubbling nitrogen through the melt also helps remove sodium. The damaging influence of sodium on the ductility of the magnesium-lithium base alloys was observed very early in the alloy development program. The discovery came about as a result of chemical analyses made on the lithium used in the alloys. Ductile alloys had been made from lithium containing about 0.2 pct Na, whereas the lithium used in the brittle alloys contained about 0.9 pct Na. The first magnesium-lithium alloys were melted under commercial fluxes ordinarily used in melting magnesium alloys. These fluxes were unsuited for scavenging the contaminating sodium, and the resulting alloys were not ductile. Next, a flux containing 50 pct KC1-50 pct LiCl was tried. This was somewhat more effective but still was not satisfactory. After a number of different experimental fluxes had been investigated, one containing 75 pct LiC1-25 pct LiF was adopted. This flux made it possible to obtain good ductility in the alloys. The

Jan 1, 1951

In the special number of the magazine Ocl und Kohle (Oct. 22, 1940) dedicated to the petroleum industry of southeastern Europe, there appeared several articles relating to Yugos1avia.t In the first article the author calls attention to the fact that there are two fields in Yugoslavia that have been explored and exploited by more than 100 wells at variable depths during the last 50 years. These are on the Island of Mura, at the confluence of the Mura and the Drave. Additional exploration drilling in various other parts of the country has been without result, but certain ones of these explorations have revealed the existence of gas horizons that have some value, which are being used for industrial purposes. Table I shows the production of oil and gas between the years 1900 and 1939. TaBle —Production of Oil ad Gas in Yugoslavia . n,i Natural Natural Years oil Years Gas, Cu. Years Gas, Cu. Meters Meters T900-1929 10,000 1923 507,000 1934 1,388,000 1930 277 1924 567,000 1935 1,401,000 1931 202 I92S 691,000 I936 1,483,000 t932 289 19261 1.472,000 1937 1,841,000 1933 629 1927! 1,732,000 193s 2,431,000 1934 324 1928 2,515,000 1939 2,628,000 1935 260 1929 4,700,000 1936 137 I93O 5.345,200 1937 463 1931 6,376,153 1938 1,091 1932 1,661,737 1939 1,114 1933 959,574 The number of wells drilled from 1884 to the present time was in the neighborhood of zoo and the total footage drilled was 65,000 m. up to July I940 They may be divided roughly as follows: 12 wells in the region produce natural gas; 134 wells in the two old fields of the Island of Mura and about zo wells for the exploration of the zone of the Flysch, in Bosnia. The depths of 50 of these wells was roo to 200 m.; the depths of 50 wells oil the Island of Mura ran from zoo to 500 m.; of 2 ; wells, 500 to I000 m.; of ro wells from rooo to 2000 meters. The deepest well drilling in Yugoslavia has reached 2000 in. In the Valley of Morave, in the region of Selnica, I00 km. south of Nish, there have been discovered asphalt-bearing limestones, which contain about 15 per cent asphalt and are associated with bituminous clays. Later, at Paclenica, important deposits of natural gas were found. A zone rich in gas and oil seepages runs through Pracec, Miklenska, Bujavica, etc. The author studied these regions from the point of view of stratigraphy and tectonics. The anticlines and gas-bearing domes are concentrated in two zones: the region of the Drave (Island of Mura) and the region of the Save, southeast of zagreb, which contains the gas field in exploitation in the region of Bujavica. A full description of the productive region of the Island of Mura has been given by Egon Bohm, a geologist, in the second article mentioned. This includes a history of the exploration and exploitation that took place under Hungarian rule in this region. The most important exploration was effected between 1884 and 1885 by Stavenov and Stinger, of Vienna. In 1927 work was done in the same region by Anton Raky, a well-known explorer who makes work of this kind his specialty.

Jan 1, 1941

In the special number of the magazine Ocl und Kohle (Oct. 22, 1940) dedicated to the petroleum industry of southeastern Europe, there appeared several articles relating to Yugos1avia.t In the first article the author calls attention to the fact that there are two fields in Yugoslavia that have been explored and exploited by more than 100 wells at variable depths during the last 50 years. These are on the Island of Mura, at the confluence of the Mura and the Drave. Additional exploration drilling in various other parts of the country has been without result, but certain ones of these explorations have revealed the existence of gas horizons that have some value, which are being used for industrial purposes. Table I shows the production of oil and gas between the years 1900 and 1939. TaBle —Production of Oil ad Gas in Yugoslavia . n,i Natural Natural Years oil Years Gas, Cu. Years Gas, Cu. Meters Meters T900-1929 10,000 1923 507,000 1934 1,388,000 1930 277 1924 567,000 1935 1,401,000 1931 202 I92S 691,000 I936 1,483,000 t932 289 19261 1.472,000 1937 1,841,000 1933 629 1927! 1,732,000 193s 2,431,000 1934 324 1928 2,515,000 1939 2,628,000 1935 260 1929 4,700,000 1936 137 I93O 5.345,200 1937 463 1931 6,376,153 1938 1,091 1932 1,661,737 1939 1,114 1933 959,574 The number of wells drilled from 1884 to the present time was in the neighborhood of zoo and the total footage drilled was 65,000 m. up to July I940 They may be divided roughly as follows: 12 wells in the region produce natural gas; 134 wells in the two old fields of the Island of Mura and about zo wells for the exploration of the zone of the Flysch, in Bosnia. The depths of 50 of these wells was roo to 200 m.; the depths of 50 wells oil the Island of Mura ran from zoo to 500 m.; of 2 ; wells, 500 to I000 m.; of ro wells from rooo to 2000 meters. The deepest well drilling in Yugoslavia has reached 2000 in. In the Valley of Morave, in the region of Selnica, I00 km. south of Nish, there have been discovered asphalt-bearing limestones, which contain about 15 per cent asphalt and are associated with bituminous clays. Later, at Paclenica, important deposits of natural gas were found. A zone rich in gas and oil seepages runs through Pracec, Miklenska, Bujavica, etc. The author studied these regions from the point of view of stratigraphy and tectonics. The anticlines and gas-bearing domes are concentrated in two zones: the region of the Drave (Island of Mura) and the region of the Save, southeast of zagreb, which contains the gas field in exploitation in the region of Bujavica. A full description of the productive region of the Island of Mura has been given by Egon Bohm, a geologist, in the second article mentioned. This includes a history of the exploration and exploitation that took place under Hungarian rule in this region. The most important exploration was effected between 1884 and 1885 by Stavenov and Stinger, of Vienna. In 1927 work was done in the same region by Anton Raky, a well-known explorer who makes work of this kind his specialty.

Jan 1, 1941

By R. W. Raymond

ALL history testifies that the mineral resources of a region have furnished both the impulse for its first development by man, and the foundation for its subsequent occupation by civilized and prosperous communities. In the pre-historic ages, the hunters, fishers, shepherds and gardeners of the world may have wandered or tarried without regard to the attractions of the mineral deposits which they could not utilize, and therefore did not value. But with the rise of civilization, as expressed in manufactures and commerce, the national value of such deposits began to be realized. Barbarous and remote tribes, possessing the sources of such supplies, won recognition in trade long before they could attain it through any other means. Thus, the North American Indians of Lake Superior exchanged their native copper for the mica of North Carolina; the ships of Tyre sailed all the way to Spain for lead and to Britain for tin; and the fleets of Solomon brought gold from Tarshish. In more modern times it has been chiefly the precious metals that have stimulated exploration and conquest. The inherent qualities and the traditional value of gold and silver sufficiently explain this historic fact, the continued existence and potency of which is evidenced, even in our own times, by the occasional rush of eager adventurers to new districts where gold and silver have been discovered. The history of North and South America has been peculiarly influenced by this factor. It was the prospect of obtaining gold and silver that led the Spanish adventurers to the shores of America, and the conquests of Mexico by Cortez and of Peru by Pizarro were inspired by the stories of the wealth of the Aztecs and the

Mar 1, 1909

By W. van der Knapp

A theoretical and experimental ana1ysis is given of the change in volume of a porous medium due to changes in external and internal pressures. The result enable one to deduce directly the effect of large increlents in stresses. It is shown that the three-dimensional representation of the volume of a nonlinear porous system is a cylindrical rules surface, the generating lines of Which have a slope according to the solid rock compressibility. Analytical expression for such a ,surface is very simple. It follows that the bulk and pore compressihilities depend only on the difference between pore fluid and external hydrostatic pressure, i.e., the effective rock frame pressure. From measurements on a number of sandstones as well as limestones it can be conduded that for practical values of this effective frame pressure the pore compressibility falls in the range between the compressibility of water and that of undersaturated crude oil. In general, pore compressibility is found to be higher the lower the porosity. For a particular limestone reservoir pore compressibility and porosity could he related by means of a simple empirical formula. Results from the described study find a direct applicxtion in material balance calculations and in prob1ems of liquid flow through porous media. Since the elastic constants of the rock bulk material enter into equatiorls for velocity of acoustic waves, the results are also of importance for calculating rates of wave propagation in these media. It is shown for sandstones with 1.5 to -10 prr cent porosity that laboratory measured porosities may differ from those lender reservoir conditions by about I per cent of their value. The difference for low porosity limestotnes can be of the order of 10 per cent. The subsidence caused by elastic deformation of reservoir rock is shown to he very small. General formulas relating pore and bulk volume to external and internal pressure can be derived, as has been shown by Biot1, Gassmann2 and Geertsma.2 Their theories describe the differential change in volume caused by a variation in pore fluid tension and external hydrostatic tension. It has been known for a long timei that the stress-strain relations of a packing of spheres are essentially noninear. Our experiments show that for almost all reservoir rocks which arc elastically deformable the relation between volume and loading is also a nonlinear one, resembling that of a packing of spheres very closely. The behavior of these media is often described by using the linear stress-strain relations for small incremental stresses and strains in the vicinity of a pre-stressed condition." The present study differs from these considerations in that it enables one to deduce the effect of large increments in the stresses directly. In analogy to the stress tensor for a homogeneous body the stress tensor for a porous body can be written in the conventional way: where the tensor components, o, and t, represent the total forces acting on the faces of a unit cube of porous material. This tensor can be split into two parts. a hydrostatic and a deviatoric part, as follows2,3,1 where the component of the hydrostatic stress system, a. equals The hydrostatic stress causes a change in volume whereas the deviatoric stress system gives rise to a change in shape only. One of the difficulties in describing changes of volume occurring in reservoir rocks is that the relations connecting these volume changes with external and internal stresses are essentially non-linear. A complete description requires the bulk volume, V,,, as well as the pore volume,V,,. to be known as a function of both the changes in pore fluid tension (v) and the hydrostatic tension on the outer boundary.

By J. E. Miller, W. E. DeVaney, L. Stroud

During a recent phase study of a natural gas, two stable equilibrium liquid phases were observed at temperatures below —200°F and pressures above 200 psi. This paper reviews the published literature on the occurrence of multiple equilibrium liquid phases and presents analytical data for the vapor and two equilibrium liquid phases of the liquefied natural gas at five experimental conditions. In addition, data for 30 conditions of two-phase equilibria are included. INTRODUCTION The low-temperature phase behavior of gases, most of which contained helium, has been investigated in the laboratories of the Helium Activity for many years. Since 1952, experimental studies of these systems have been continuous as part of the research program at Amarillo, Tex. Because of their value to private industries interested in participating in the Helium Conservation Program, several "Open File" reports containing phase equilibria data for heliurn-bearing natural gases have already been released by the Helium Activity. A paper containing information on the general phase behavior, operating criteria and extensive vapor-liquid data for two helium-containing systems was recently published.2 Additional publications presenting experimental data on the phase relationships of various gas systems are now in process and will be available in the near future. PREVIOUS EXPERIMENTAL WORK Although the formation of multiple liquids has been reported for various systems, to our knowledge this paper is the only substantiated evidence of a vapor-liquid-liquid equilibria in a naturally occurring gas. In 1940, Vink, Ames, and others13 reported the presence of two liquid phases in a hydrocarbon system consisting of mixtures of crude oils, solvents and natural gas. Eilerts and co-workers; published data on the recombined fluids from a gas-condensate well. This condensed gas, containing approximately 76 per cent methane and 24 per cent ethane-plus, exhibited two distinct liquid phases. Weinaug and Bradley 14 observed "unusual" phase behavior in a reservoir mixture. These workers postulated that the anomalous phase behavior was due to the "imminent formation of a second liquid phase". Botkin, Reamer, Sage and Lacey 1 studied two California crude oils that exhibited multiple phases. Kohn and Kuratal0 recently reported two equilibrium liquid phases in the methane-hydrogen sulfide system. Roof and Crawfordl1 and Eakin, et a16 also have reported experiments with binary systems that formed two stable equilibrium liquid phases. APPARATUS AND PROCEDURE A U. S. Bureau of Mines Phase Equilibrium Apparatus was used in conducting this study. The apparatus and procedures employed in its operation have been previously described3 and will not be repeated in detail ill this report. Briefly, the apparatus consists of a windowed cell which can be maintained within ±0.5°F for temperatures between room temperature arid -320°F. Pressure within the cell can be maintained within 0.1 per cent of gauge reading up to 800 psig. Equilibrium vapor and liquid samples are obtained in special containers4 for analysis by a mass spectrometer. Although the accuracy of the analyzer is about ±0.1 mol per cent, the reproducibility of the phase-equilibrium apparatus is considered relatively poor. Values reported from methane and nitrogen are considered accurate to ±l.0 and ±0.6 mol per cent. Data for ethane-plus in the vapor are accurate within 0.2 mol per cent; liquid-phase data for this aggregate compolnent are accurate within 1.5 mol per cent. For helium in the vapor phase, the analytical data are accurate within 0.2 mol per cent; liquid-phase analyses for this component were obtained by the charcoal adsorption method described by Frost8 and are accurate within 0.006 mol per cent. All of these references to the accuracy of reported values are conservative estimates based upon a statistical treatment of reproducibility data obtained with the apparatus.

By Stanley Gill

The apparatus is composed of sections of small diameter, seamless steel tubing welded into a continuous flexible tube. At the bottom end a 1/4-in. pipe nipple with a 10 to 15-lb. weight is attached, together with a registering thermometer and a pair of ball check valves. The entire length of tubing is coiled in a single layer upon a drum 4 ft. in diameter which can be attached to the platform of a truck and provided with devices for winding and unwinding the tubing. Connections are made with the upper end of the tubing through a stuffing box, thence to a gas manifold to which a pressure gage is connected. Hydrogen gas is carried in standard 2-ft. cylinders and readings are taken by admitting gas into the tubing from one (or both) of the hydrogen cylinders until the pressure has been built up above that to be measured. At this time the gas supply is cut off. Excess gas escapes through the open end of the tubing and when equilibrium is reached, the pressure is read at the surface gage. Corrections are made for the weight of the column of gas. The advantages claimed for the apparatus include accuracy and the ability to measure the pressures at any number of points without removing the gage. Among the disadvantages of the apparatus are the somewhat bulky size of the equipment and its relatively high initial cost.

Jan 1, 1933

By I. Cornet

With the greatly expanding use of magnesium during the war, it appeared necessary to the War Metallurgy Committee that the notch sensitivity of magnesium alloy extrusions be further investigated and the influence of various factors upon notch sensitivity be noted. Accordingly, the National Defense Research Committee of the Office of Scientific Research and Development placed a research contract with the University of California, supervised by the War Metallurgy Committee. The work discussed herein was done under "Restricted" Project NRC-21, reported in Dec. 1943~; it has been released for publica-tion by the O.S.R.D. Scope of the Investigation The notch sensitivity of various magnesium alloy extrusions was determined under axial tension, and also under several conditions of nonaxial tension. Hardness, grain size and other metallographic features were observed; stress-strain data were obtained, and the chemical compositions of the alloys were determined, in order to correlate these quantities with thc notch sensitivity. Notch sensitivity under axial tensile load was determined for a few specimens which had been cold worked to various degrees by tensile prestraining. Magnesium alloy extrusions studied included Dowmetal 0, X, J, and A(. For comparison, extrusions of aluminum alloy 24s-T, cast bars of aluminum alloy 122-T2, and cast bars of magnesium alloy C were also tested. The specified chemical composition of these alloys is given in Table I. All bars tested were within specification limits of composition. Investigation of thc tensile notch sensitivity of various magnesium alloy extrusions, under conditions of axial and eccentric load, showed little or no correlation with stress-strain or other conventional data. Since the many uncontrolled variables present might mask significant relationships, one alloy was selected for intensive study. Magnesium 0 alloy extrusions were subjected to experimental heat treatments, and the ,Changing hardness, tensile strength, microstructure, and notch sensitivity observed. Experimental Techniques and Procedures Tensile Testing Bars used for axial loading were machined with % in.- and with 34-in. minimum diam1 and included specimens with 60" V notches (Fig I and 2). Each V-notched specimen was roughed out carefully and then finished with a honed tool. These Y-notched bars were sampled frequently, sectioned, polished, and examined at 500 X magnification to control

Jan 1, 1949

By Henry Howe

W. E. RUDER, Schenectady, N. Y.-In 1913 I presented a paper before this society on Grain Growth, and at that time it seemed to me that the only explanation for grain growth was that of critical strain. I do not think I published the photographs at the time, but I made some experiments on the effect of stretching sheets of metal. This allowed for fairly accurate determinations of the amount of cold deformation, At the time I worked-with silicon steel because one could see the change in grain growth with the naked eye. I stretched about 10-samples from 0.5 per cent. to 10 per cent., and, after heating to 1,050° C., I found that the maximum grain growth occurred at about 2 ½ per cent. cold deformation. This I designated "the critical strain" for maximum grain growth. About a year ago I talked with Prof. Jeffries, who explained to me his ideas of grain growth. It occurred to me that it would be a very easy thing to check the strain hypothesis against the strain and temperature hypothesis, if we took a certain number of these strips, strained exactly alike and heated to different temperatures; in that case the maximum grain growth ought to appear at a different percentage of deformation for each temperature. These experiments showed that there was, as Mr. Jeffries shows in his present paper, a decrease in germinative temperature with increased cold deformation. The samples were stretched from ½ to 8 per cent. and heated for 10 hr. in hydrogen. Samples were introduced into a furnace previously heated to temperature. A maximum grain growth was obtained at 5 per cent. deformation, when heated to 750° C.; at 2 ½ per cent. when heated to 800' C.; at 1 1/4 per cent., if heated at 950°C.; and at 5/8 per cent.. when heated at 1,100° C. This shows very clearly that the germinative temperature decreases with the increase in cold deformation. The growth was very much more marked, however, at the high temperature, i.e., the grain grew more rapidly and attained a much larger size than at lower temperature. In considering the photographs (Fig. A) those along the lateral edges should be ignored because.

Jan 4, 1917

By D. L. Wood, J. H. Westbrook

The tensile behaviors of the CsCl structure compound AgMg are extensively documented in terms of strain, strain rate, temperature, composition, and metallurgical processing treatment. The observations lend themselves to presentation in terns of three regimes of deformation behavior; 1) low temperatures where deformation is primarily by slip; 2) intermediate temperatures where the deformation mode is also slip but with the detailed behavior dominated by dislocation interactions with solute atoms; 3) high temperatures where defomation is primarily by diffusion controlled processes. Of all the material groups of potential interest as high-temperature structural materials, the inter-metallics have been the least studied, particularly with respect to their mechanical behavior. Moreover, the application and processing of intermetallics for uses which exploit their often unique physical properties have been impeded by a lack of understanding of their mechanical properties. Previous work in this area* has been largely *For a recent review, see Westbrook.' exploratory, aimed on the one hand at the direct empirical development of materials of engineering utility and ,on the other at identification of the important parameters affecting the mechanical behavior of inter metallics. As a consequence, there has not been available, heretofore—for any inter-metallic—data, sufficient in extent or precision to provide an adequate phenomenological description of the effects of metallurgical variables on deformation behavior. Such documentation is prerequisite to intelligent application or processing design and is also necessary for testing present and future theoretical analyses of mechanical behavior. It was therefore an objective of the present investigation to document the deformation behavior of a simple ordered intermetallic over as wide a range as possible of all the usual metallurgical variables. The compound AgMg was chosen as the subject of this investigation because it met all of a group of desired criteria, namely: 1) congruent but moderate melting point; 2) simple crystal structure; 3) ordered structure persisting to the melting point; 4) broad solubilities for the component elements. The first and last criteria were expected to aid in the preparation of homogeneous single-phase specimens: the second and third to help simplify the

Jan 1, 1962

By I. Cornet

INTRODUCTION WITH the greatly expanding use of magnesium during the war, it appeared necessary to the War Metallurgy Committee that the notch sensitivity of magnesium alloy extrusions be further investigated and the influence of various factors upon notch sensitivity be noted. Accordingly, the National Defense Research Committee of the Office of Scientific Research and Development placed a research contract with the University of California, supervised by the War Metallurgy Committee. The work discussed herein was done under "Restricted" Project NRC-21, reported in Dec. 1943 1; it has been released for publication by the O.S.R.D. SCOPE OF THE INVESTIGATION The notch sensitivity of various magnesium alloy extrusions was determined under axial tension, and also under several conditions of nonaxial tension. Hardness, grain size and other metallographic features were observed; stress-strain data were obtained, and the chemical compositions of the alloys were determined, in order to correlate these quantities with the notch sensitivity. Notch sensitivity under axial tensile load was determined for a few specimens which had been cold worked to various degrees by tensile prestraining. Magnesium alloy extrusions studied included Dowmetal 0, X, J, and M. For comparison, extrusions of aluminum alloy 24S-T, cast bars of aluminum alloy I22-T2, and cast bars of magnesium alloy C were also tested, The specified chemical composition of these alloys is given in Table I. All bars tested were within specification limits of composition. Investigation of the tensile notch sensitivity of various magnesium alloy extrusions, under conditions of axial and eccentric load, showed little or no correlation with stress-strain or other conventional data. Since the many uncontrolled variables present might mask significant relationships, one alloy was selected for intensive study. Magnesium 0 alloy extrusions were subjected to experimental heat treatments, and the changing hardness, tensile strength, microstructure, and notch sensitivity observed. EXPERIMENTAL TECHNIQUES AND PROCEDURES Tensile Testing Bars used for axial loading were machined with 3/8 in.- and with 1/4-in. minimum diam, and included specimens with 6o° V notches (Fig I and 2). Each V-notched specimen was roughed out carefully and then finished with a honed tool. These V-notched bars were sampled frequently, sectioned, polished, and examined at 500 X magnification to control

Jan 1, 1948

By R. E. H. Pomeroy

THE statistical data given in this paper are taken from the actual performance of the No. 2 reverberatory furnace of the Nevada Consolidated Copper Co., Me Gill, Nev., for a period of four months, from April to July, 1914. The principal furnace dimensions are: Length, 132 ft. ½ in. at the skim-line level; average width, 18 ft., 10 in. at the skim-line level. The roof is 7 ft. above the skim-line level at the firing end. The average area in the uptake flue is 36 sq. ft., and the area above the skim line under the vulcatory arch is 24.3 sq. ft. Fig. 1 shows a diagrammatic plan and sectional elevation of this furnace. The furnace is equipped with two 400-b.h.p. Stirling waste-heat boilers set in parallel. California crude petroleum is used for fuel and has a specific gravity of 16.5° B., flashing in open test at 199° F. The oil is heated to about 200° F. in a steam heater before going to the burners, requiring about 9 b.h.p. per furnace day to heat it from the line temperature to the burning temperature. Measurement is made by oil meter, checked daily by reservoir readings. The oil is fed by gravity (34 lb. static pressure) to seven low-pressure blast burners of the Steptoe type (Fig. 2). The blast for these burners is supplied at about 40-oz. pressure by a motor-driven Connersville blower of 42 cu. ft. capacity per revolution. The air supplied by the blower through the burners for atomizing the oil amounts to about 10 per cent. of the theoretical air necessary for complete combustion of the oil. The remainder of the necessary air enters the furnace through the burner openings in the firing wall. No checker holes are provided, and the charge holes in the roof are equipped with slide gates and "dog houses? to minimize air leakages. The combustion of the fuel, as shown by gas analysis at the front of the furnace, is practically complete, the carbon monoxide in the gases being less than 0.5 per cent.

Jan 2, 1915

State of California, Division of Mines, Ferry bldg., San Francisco, Calif. Walter W. Bradley, State Mineralogist. A list of publications available will be sent upon request. Bulletin 77 is a list of publications complete from 1880 to 1917 and contains synopses It is sent free. Bulletin 105, California mineral production and directory of mineral producers for 1930, brings the complete list up to date, sent free on request The Division of Mines issues principally (1) A series of Reports, (2) Bulletins, (3) Preliminary Reports, and (4) maps. The Reports were first issued biennially, later annually, and for the past few years they have taken the form of quarterly reports. The yearly subscription price for the quarterly reports is $1, payable in advance Reports and separate chapters available are Report 2, First Biennial (1892), $1, 14 (1913-1914), Chapter on mines and mineral resources of Colusa, Glenn, Lake, Mann, Napa, Solano, Sonoma, and Yolo counties, 50 cents, 15 (1915?1916), Mines and mineral resources of Butte, Lassen, Modoc, Sutter and Tehama counties, 50 cents, and Mines and mineral resources of Monterey, San Benito, San Luis Obispo, Santa Barbara and Ventura counties, 65 cents, 16 (1917-1918), Nevada County, 75 cents, Plumas County, 50 cents, Sierra County, 50 cents; 17 (1920), Mining in California during 1920, $1 75, 18 (1922), Mining m California, chapters for Aug , Sept , Oct , Dec , free, 19 (1923), Mining in California, chapters for Jan , Feb , Mar, Sept , free, 20 (1924), Quarterly chapters on mining in California (except July, out of print), 25 cents, 21 (1925), Quarterly chapters containing county reports- Jan (Sarcramento, Monterey, Orange) 25 cents, April (Calaveras, Merced, San Joaquin, Stanislaus, Ventura), 25 cents, July (Del Norte, Humboldt, San Diego) 25 cents, Oct (Siskiyou, San Luis Obispo, Santa Barbara), 25 cents; 22 (1926), Quarterly county reports: Jan. (Santa Cruz, Trinity), 25 cents, April (Shasta, San Benito, Imperial), 25 cents, July (Mann, Sonoma) and Copper in California, 25 cents, Oct (El Dorado, Inyo) Minarets District, 25 cents, 23 (1927), Quarterly county reports- Jan (Contra Costa), 25 cents, April (Aniador, Solano) Bibliography of clay

Jan 1, 1933

By F. Keller, E. H. Dix

The desirable high strength and hardness of the heat-treated strong aluminum alloys result from two distinct structural changes: (1) the formation of a solid, solution by heating at the required temperature for a sufficient period, and the substantial retention of this solid solution by rapidly quenching; (2) precipitation of particles of constituent and coalescence to a critical size to produce maximum strength and hardness. In alloys of the duralumin type, that is, alloys containing both copper and magnesium silicide precipitation takes place at normal atmospheric temperature, whereas in alloys containing copper without magnesium silicide or magnesium silicide without copper, maximum properties are obtained only after an accelerated aging treatment consisting of heating for 15 to 20 hr. at temperatures of about 150" C. The mechanical properties of these alloys subsequent to quenching but prior to aging are ideal for forming operations. Unfortunately, however, the alloys of the duralumin type age very rapidly during the first 24 hr. and aging is substantially complete after four days. For severe forming, such as the heading of rivets, it is desirable that this be accomplished within ½ hr. or at the most 2 hr. after quenching. Alloys containing magnesium silicide without copper also age at normal temperatures but the aging is less rapid and the material can be satisfactorily worked within several weeks after quenching. Some slight aging of alloys containing copper alone also takes place at room temperature but it is unimportant from the standpoint of workability. Any method of retarding the aging at room temperature of the duralumin type of alloys would be of considerable advantage in that the period during which the material could be worked successfully would be lengthened. For instance, in aircraft plants it is customary to supply the workmen with small lots of rivets that should be used within ½ hr . after heat treatment. Such procedure has the obvious disadvantage of being uneconomical, and furthermore there is always the possibility that the workmen would use the rivets after the time limit had expired, or the supply being depleted might use some that had not been heat-

Jan 1, 1931