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By C. Ernest Birchenall, Robert F. Mehl

Application of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion cocfficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner¹ derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smith5 on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 Activities in Brass9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by

Jan 1, 1947

By C. Ernest Birchenall, Robert F. Mehl

Application of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion cocfficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner¹ derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smith5 on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 Activities in Brass9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by

Jan 1, 1947

By C. C. McDermond, Others, B. N. Zavoico

Production of crude oil in Venezuela for the year 1937 was 186,653,-916 bbl., as compared with 155,228,982 bbl. produced in 1936, an increase of almost 31,500,000 bbl. The oil-field strike, which started on Dec. 14, 1936, lasted until Jan. 25, 1937, when a total of 10,000,000 bbl. of production was estimated to have been lost (5,750,000 bbl. in 1936 and the remainder in 1937). Of the total of 186,653,916 bbl. produced in 1937, the Lagunillas field contributed 45.6 per cent, a drop of approximately 10 per cent under 1936 figures; Tia Juana, 14.3 per cent; Quiriquire field, 14.0 per cent; La Rosa area, 13.3 per cent and the Mene Grande field, 7.6 per cent, these being the five leading contributors of the year's production. Detailed production figures by fields and by companies are shown on Table 1. Of the total production of Venezuela the following four major companies accounted for the greater proportion: Standard of Venezuela and Lago Petroleum Corporation together, 48.3 per cent; Shell, 37.4 per cent and Venezuela Gulf, 14.0 per cent. At the end of the year, 2491 wells were producing, of which number 1291 wells were pumpers, or about 52 per cent. Production The accompanying statistics of production record of Venezuela oil fields from its inception to Dec. 31, 1937, shown on Table 2, indicates that the cumulative production reached 1,503,283,228 bbl. In order of importance, Lagunillas leads all the fields, having accounted for about 50 per cent of Venezuelan production, followed by La Rosa area, which produced about 21 per cent; Mene Grande, which produced about 13 per cent, and Quiriquire, which produced 6.5 per cent. Table 3 shows the age of each field. Mene Grande is the oldest, having produced for 24 years; Tarra is next, 21 1/2 years old, and El Mene third, 171/2 years. The gravity of the crude from the various fields, also shown on Table 3, remained unchanged, the only addition being the new Tia Juana field, which averages 15.6' A.P.I. Table 4 shows the method of production by fields as of Jan. 1, 1938; at the end of the year 2491 wells were producing, compared with 2005 wells producing at the beginning of 1937, or an increase of 486 wells. The completions for the year reached 512. Of the 2491 wells producing crude oil, 1291 wells, or approximately 52 per cent, were pumping, 925 (approximately 37 per cent) were flowing naturally and 275 (11 per cent) were on

Jan 1, 1938

By J. J. Taber, I. S. K. Kamath, R. L. Reed

Alcohol floods of consolidated sandstone cores have shown the process to be strongly dependent on the phase behavior of the particular alcobol-oil-water system used. This means that in many cases the mechanism does not conform to the idea of a piston-like displacement. Instead, it is found that by changing the alcohol it is possible to change the relative velocities of the oil and water and, in fact, the entire mechanism of the process. The effects of rate, viscosity, initial saturation, distance travelled and hysteresis of relative permeability on the alcohol flooding mechanism are discussed. INTRODUCTION Reasons for interest in the use of alcohol to miscibly displace oil and water from a porous medium appear in the existing literature.l-7 The mechanism of the displacement has been considered and the apparent implications formulated into a theory which presumably would enable one to predict the essential features of the process.6 Unfortunately, most of the reported experiments have been performed with unconsolidated or artificially consolidated sands. With these systems some of the noteworthy facets of the process are obscured and resulting data appear uncertain. It is the purpose of this paper to show how the use of consolidated sandstones has led to revision of the mechanism and, hence, the theory of alcohol flooding. The practical result is increased pessimism toward the possibilities of commercial application of the simplest form of the alcohol-slug process. However, elucidation of the mechanism has made it possible to define the essential characteristics of a system of slugs which will behave in a nearly piston-like fashion and, thus, yield the best possible result. EQUILIBRIUM PHASE BEHAVIOR Fig. 1 is a diagram of the ternary system isopropyl alcohol (IPA)-Soltrol-calcium chloride brine. Brine was used to prevent plugging of the core and calcium chloride was used because sodium-chloride brine exhibits a solid phase with Soltrol and IPA. If alcohol is added in increments to the immiscible mixture of water and oil represented by Point A, the path followed by the successively equilibrated samples will be on the Line ABC and pass from the immiscible region to the miscible region by crossing the binodal curve at B. Consider the intersection D of this path with the tie Line EF. The quantity of oleic phase is proportional to the Segment ED and the quantity of the aqueous phase is proportional to DF. Compositions of the two phases are specified by Points E and F. It is clear that in the case shown the oleic phase is diminishing and entirely disappears when miscibility is achieved. Such will

By R. J. Arsenault

The yield drop that occurs in tantalum, Cu-AZ. and Ag-Al was investigated as a function of strain rate and at several temperatures. From the strain-rate dependence of the yield drop an activation volume was calculated and found to agree with that obtained from differential strain-mte tests. The temperature dependence of the yield drop can he explained in terms of the parameter temperature divided by activation volume. The yield drop is attributed to the rapid multiplication of dislocations during their motion. THE yield-point or yield-drop (upper yield stress minus the lower yield stress) phenomenon has been the subject of numerous investigations1-9 in both bcc and fcc metals. Also, there is no dearth of theoretical explanations10-20 to account for the yield-point phenomenon. The present explanations can be divided into two categories: the concept of dislocation locking and subsequent unlocking and the concept of multiplication of dislocations due to their motion. The Vottrell10,11mechanism of locking and unlocking, as applied to bcc metals, is the best known of the three proposed locking mechanisms. The two additional mechanisms, short-range order (SRO)7,16,17 and Suzuki-type locking,14,15 have been employed to account for the existence of yield points in fcc metals. The experimental evidence supporting the locking of dislocations, especially in bcc metals, is well-established. The dependence of the yield point on interstitial concentrations,' the kinetics of strain aging,2 and the observations by electron-transmission microscopy18 are some of these experimental results. The number of experimental observations supporting dislocation locking in fcc metals is not as extensive as in bcc metals. The unlocking of dislocations, which actually is supposed to account for the yield drop, is by no means well-established by experimental results for either bcc or fcc metals. The similar temperature dependence6 of the yielding and plastic flow is one of the experimental factors that cannot be explained in terms of the unlocking of dislocations. The mechanism based on the rapid multiplication of dislocations has been proposed by several investigators. 18-20 Johnston and Gilman19 have proposed a detailed model of yielding, which was later employed by Hahn21 to predict quantitatively the yield drop in iron. This mechanism was discussed in a previous paper22 and several limitations were pointed out. In the same paper it was shown that an activation volume could be obtained from the strain-rate dependence of the yield drop and that a correlation existed between the activation volumes obtained from the yield-drop tests and from differen-

Jan 1, 1964

By E. C. Houston

The presence in the Tennessee Valley of extensive deposits of olivine, a silicate of magnesium and iron that contains approximatcly 28 per cent magnesium, has been recognized since 1896 when Lewis8 published a survey of basic magnesium rocks of western North Carolina. A recent field survey by T.V.A.7 showed that more than two hundred million tons of high-grade olivine occurs above local drainage levels in western North Carolina and northern Georgia. Except for sporadic attempts to work the olivine for its nickel and chromium contents,10 the ore received little attention industrially until 1926 when Goldschmidt3 suggested its use in the manufacture of refractories. Only one instance is recorded of an attempt to utilize the ore commercially for its magnesium content;11 in this case a process was used in which olivine was treated with sulphuric acid, the resultant mixture was leached with water, and the leach solution was purified and evaporated to form epsom salts, which was the end product. As a part of its program of contributing to the development of the natural resources of the region, the Tennessee Valley Authority became interested in the olivine deposits as a source of metallic magnesium because of their high magnesium content and proximity to hydroelectric power. Studies were undertaken to determine the feasibility of producing magnesium chloride by extraction of olivine. The experimental work was carried out successively at the T.V.A. Minerals Testing Laboratory, Norris, Tenn., at the Georgia State Engineering Station,* Atlanta, Ga., and at the T.V.A. laboratory at Wilson Dam, Ala. The present paper describes a process, developed through the pilot-plant stage, whereby magnesium chloride suitable for reduction to metallic magnesium can be prepared from olivine by extraction with hydrochloric acid and subsequent purification. Research on the magnesium-from-olivine process, originally intended for peacetime use, was given impetus by the shortage of magnesium that existed at the beginning of the current world war. By the time the process was sufficiently developed to justify a proposal for its inclusion in the war program, the shortage had been met by expansion and development of other processes. However, it is believed that the magnesium-from-olivine process may have advantages that will warrant consideration of its use after the war, when the. economics of the various processes rather than production on a wartime scale will be the criterion for commercial production of magnesium. Description of Process Metallic magnesium is produced electro-lytically by the Dow and the Elektron

Jan 1, 1948

By E. C. Houston

The presence in the Tennessee Valley of extensive deposits of olivine, a silicate of magnesium and iron that contains approximatcly 28 per cent magnesium, has been recognized since 1896 when Lewis8 published a survey of basic magnesium rocks of western North Carolina. A recent field survey by T.V.A.7 showed that more than two hundred million tons of high-grade olivine occurs above local drainage levels in western North Carolina and northern Georgia. Except for sporadic attempts to work the olivine for its nickel and chromium contents,10 the ore received little attention industrially until 1926 when Goldschmidt3 suggested its use in the manufacture of refractories. Only one instance is recorded of an attempt to utilize the ore commercially for its magnesium content;11 in this case a process was used in which olivine was treated with sulphuric acid, the resultant mixture was leached with water, and the leach solution was purified and evaporated to form epsom salts, which was the end product. As a part of its program of contributing to the development of the natural resources of the region, the Tennessee Valley Authority became interested in the olivine deposits as a source of metallic magnesium because of their high magnesium content and proximity to hydroelectric power. Studies were undertaken to determine the feasibility of producing magnesium chloride by extraction of olivine. The experimental work was carried out successively at the T.V.A. Minerals Testing Laboratory, Norris, Tenn., at the Georgia State Engineering Station,* Atlanta, Ga., and at the T.V.A. laboratory at Wilson Dam, Ala. The present paper describes a process, developed through the pilot-plant stage, whereby magnesium chloride suitable for reduction to metallic magnesium can be prepared from olivine by extraction with hydrochloric acid and subsequent purification. Research on the magnesium-from-olivine process, originally intended for peacetime use, was given impetus by the shortage of magnesium that existed at the beginning of the current world war. By the time the process was sufficiently developed to justify a proposal for its inclusion in the war program, the shortage had been met by expansion and development of other processes. However, it is believed that the magnesium-from-olivine process may have advantages that will warrant consideration of its use after the war, when the. economics of the various processes rather than production on a wartime scale will be the criterion for commercial production of magnesium. Description of Process Metallic magnesium is produced electro-lytically by the Dow and the Elektron

Jan 1, 1948

By R. M. Brick

Segregation can occur only in cast alloys that solidify over a range of temperatures with a difference in composition of liquid and solid phases within this range (ignoring monotectic systems and chemical reactions as in rimming steels). Thus a pure binary eutectic alloy should show no segregation unless undercooling occurs for one of the solid constituents of the eutectic; e.g., chill-cast Al-I2 per cent Si alloys. The phasial condition implicitly described above—solidification over a range of temperatures with a compositional difference between solid and liquid—is found in nearly all solid solutions or combinations of solid solutions and eutec-tics, Metastable conditions of solidification of these types of alloys cause coring; i.e., a difference in composition between the center of a dendrite and its periphery. This composition gradient can be detected usually only by microscopic examination of etched structures; it is a "micro" effect. The gradient of more immediate industrial concern is that between the center of a cast section and the surface layers. This gross (macro) effect is usually deter-minable only by sampling of the casting at different points, with chemical analyses of each sample. If the compositional difference is of the same type as in coring, the first parts to freeze being enriched in higher-melting-point constituents, and vice versa, the effect is called normal segregation. When what is apparently the first part of the casting to solidify shows a higher concentration of low-melting-point constituents, the effect is called inverse segregation. These macro effects are quite separate from the micro effect, coring, yet the latter must be described first because it is an essential part of the picture. Coring Solid Solution, Ni-Cu The nickel-copper phase diagram is reproduced in Fig. Ia, in which the solid lines represent the equilibrium liquidus I, 3, 7 and solidus 2, 5, 8, and where the vertical I, 4: 8 represents a 55 per cent Cu alloy. Upon moderately rapid solidification, the first dendritic axes of composition 2 (see Fig. Ib) start to form at a temperature somewhat under I. Solidification continues by growth of the dendritic nuclei, but at temperature 4 the increment solidifying is of composition 5. The rapidity of this crystal growth prevents diffusion of nickel and copper atoms from adjusting the composition of the entire dendrite at 5, which it would be under equilibrium conditions. The average composition of a specific dendrite, or the entire solid phase, at temperature 4 might be that indicated

Jan 1, 1945

By H. C. Burghard, F. R. Brotzen

Experiments were performed to determine the effects of mechanical vibrations on ordering in CuAu. The effects of 5, 10, and 15 kc vibrations were investigated over a range of ordering temperatures of 280° to 360°C. A decrease in the rate of ordering was observed at all frequencies and ordering temperatures. THE effects of mechanical vibrations on certain solid-state reactions have been noted by several investigators. In 1930, Mahoux' reported a substantial increase in the case depth of a steel sample nitrided under the influence of mechanical vibrations over that of an unvibrated sample. Similarly, an accelerating effect of vibrations on the diffusion of chromium in steel was noted. Guillet, in the same year, confirmed the results of Mahoux. More recently Schenck and schmidtmann3 studied the effects of low-frequency, alternating loads on the diffusion of carbon in steel. The results of their experiments, conducted at 500 cycles per min and large strain, (0.2 pct), indicated an acceleration of the process. These workers also reported an increase in case depth of a sample vibrated at 430 kc during a carburizing treatment. Effects of high-frequency vibrations on solid-state reactions have also been investigated by Gudzoff and Gavze6 and Fairbanks and Dewez.7 The former reported an acceleration of the age-hardening process in aluminum alloys. The latter noted changes in the structure and mechanical properties of steel annealed under the influence of vibrations. On the other hand, Altenburg4 and Ehringer5 have given some theoretical reasons and experimental evidence as to the improbability of any effect of vibrations on diffusion. Comprehensive surveys of the effects of vibrations on metallurgical reactions are given by Hiedemann' and Bergmann.9 None of the above investigations led to a physical description of the effects of mechanical vibrations on solid-state reactions. In the present study an attempt was made to gain an understanding of the influence of vibrations on nucleation and diffusion. The order-disorder transformation was chosen for investigation since its mechanism has been extensively discussed in the literature. Moreover, the progress of the transformation may be easily followed by observation of electrical resistance changes. EXPERIMENTAL PROCEDURE The specimens used for the experimental observation of ordering rates were prepared from 50 at. pct Cu-Au alloy wire.* Each specimen consisted of a 0.02-in. diam wire approximately 10 in. long to which two copper potential leads were silver soldered, 2 1/2 in. apart, near one end of the wire. A 1/8-in. diam by 1/4-in. long steel stub was silver soldered

Jan 1, 1960

By William D. Klopp

A study was conducted of the tensile and creep properties of are-melted and electron-beam-melted tungsten over the temperature range 2250° to 4140°F. The tensile and creep strengths vary with pain size, the finer -grained materials being stronger. The activation energy for transient creep at 2250° to 3500°F is 95,000 cal per (g)(mole), while that for steady creep at 3300o to 4000°F is 141,000 cal per (g)(mole). At 2875o to 3300°F the apparent activation energy for steady creep decreased with decreasing temperature. It is suggested that cross slip is rate controlling during transient creep, while dislocation climb is rate controlling during steady creep above 3300° F. ALTHOUGH considerable data have been generated on the high-temperature tensile properties of powder-metallurgy tungsten,1 relative few data have been published on the properties of are-melted2 or electron-beam melted tungsten.3 Furthermore, the available data show a fairly large amount of scatter at high temperatures. The effects of structure and purity have not yet been defined, aside from observations that high-purity electron-beam (EB)-melted tungsten3 and single-crystal-plasma-flame tungsten4 are weaker than less pure powder-metallurgy tungsten. The creep behavior of powder-metallurgy tungsten has been studied, but no data are available on the creep behavior of tungsten consolidated by melting. Green5 found that powder-metallurgy tungsten exhibited linear creep at 4082° to 5072°F with an activation energy of 160,000 cal per (g) (mole). The similarity of this activation energy to that of 153,000 cal per (g)(mole) for volume self-diffusion6 suggests that recovery of strain hardening by dislocation climb is rate controlling in this temperature range. In studies at 4800°F, Sutherland and Klopp7 concluded that grain size significantly affected the creep behavior of commercial powder-metallurgy materials. This grain-size effect was suggested by sherby,8 although the opposite relation had been reported for aluminum.' The purpose of the present study was twofold: first, to provide baseline data on high-temperature tensile and creep properties of are-melted and EB-melted tungsten for concurrent tungsten alloy studies, and, second, to determine the phenomenolo-gical effects of structural and purity variables on the high - temperature mechanical properties of tungsten. EXPERIMENTAL The are-melted tungsten materials were prepared by melting sintered 1-1/4-in.-diam electrodes into 2-1/2-in.-diam by 5-in.-long ingots. The are-melting facility has been described previously.' Eight ingots were melted, machined, and hot-extruded at

Jan 1, 1965

By Thomas E. Leontis

INTRODUCTION THE importance of magnesium alloys in the manufacture of aircraft engines has been realized for many years. A concentrated effort has been exerted in the laboratories of the Dow Chemical Co. to develop magnesium-base alloys with improved properties at elevated temperatures whereby greater advantage can be taken of the inherent lightness of these materials. In an earlier publication,1 attention was called to the superior tensile properties and resistance to creep of cerium-containing magnesium alloys at temperatures up to 700°F. More recently, additional data on magnesium-cerium alloys have been furnished by Murphy and Payne.2 The present paper deals with the mechanical properties of sand-cast magnesium alloys containing zinc, at temperatures up to 500°F. The study includes binary Mg-Zn† alloys containing up to 10 pct zinc and several ternary and some polynary alloys based on the Mg-1Zn,†Mg-3Zn, Mg-4.4Zn, Mg-6Zn, and Mg-10Zn binaries. The compositional variation in the tensile properties, hardness, and creep at room and elevated temperatures, and in the electrical conductivity at room temperature has been determined. The results of these tests show that many zinc-containing magnesium alloys exhibit resistance to creep at elevated temperatures significantly higher than that of present commercial magnesium alloys, but lower than that of alloys of the magnesium-cerium type. In addition, they have high tensile properties at room and elevated temperatures and high conductivity. This combination of mechanical properties and conductivity indicates that these alloys should be given serious consideration for commercial applications involving exposure to temperatures higher than those to which present commercial magnesium alloys can be taken safely. LITERATURE The properties of sand-cast magnesium alloys containing zinc as a principal alloying element have not been investigated very extensively, especially at elevated temperatures. The following remarks, which are confined to sand-cast alloys, will serve as a summary of the most important references on this phase of magnesium metallurgy. The first recorded determination of the tensile strength of binary Mg-Zn alloys as a function of zinc content was reported by Aitchison.3 Similar studies, including the measurement of elongation and hardness, have been performed by Gann and Winston,4 Dumas and Rockaert,5 Haughton and Prytherch,6 and by Spitaler, the last being reported by Beck.7 A slight superiority in the tensile strength of chillcast Mg + 8 Zn alloy over the sand-cast alloy was noted by Maybrey 8 That alloys of magnesium containing 5 to 12 pct zinc

Jan 1, 1948

By C. E. Berry

NATURAL stone or manufactured porcelain pebbles are used as the grinding elements in pebble mills and the mills are lined with stone or porcelain blocks. Steel balls usually form the grinding medium in ball mills, and the mills may he lined with steel. Pebble mills are used to avoid contamination by metal of the material being ground, to avoid rapid wear due to corrosion, and for other specialized reasons. Belgian silex (silica) blocks formerly were used widely for lining pebble mills, because of their good resistance to wear, light color, and low cost, but the importation of these blocks was suspended early in the war. The stocks of Belgian silex diminished so rapidly that it was found desirable to compare the properties of a number of domestic substitutes for use in critical operations. Accordingly, a study was made to determine the best substitutes for fine grinding of white pigment and for certain heavy-chemical process work such as the disintegration of phosphate rock in weak phosphoric acid solution. A comprehensive survey of substitute lining materials was not contemplated. It was stipulated at the beginning of the investigation that only materials on the market, available in large quantities, would be tested and that these should be reasonable substitutes from a wear-resistance viewpoint as determined from known physical characteristics. Marble and limestone, for example, could be eliminated immediately. Quartzite, granite and porcelain were selected as likely substitutes for Belgian silex and were subjected to quality tests. MATERIALS TESTED I. Belgian Silex.-Sample blocks of a standard grade were taken from crates in which they had been imported. The stone was light gray in color and contained inclusions of small clusters of quartz crystals as well as light colored portions that might be calcite. This was a siliceous rock which appeared to be of igneous origin. 2. Quartzite.-Samples of quartzite were obtained from a quarry in Minnesota. The blocks exhibited a crystalline fracture. The stone was pink in color and composed of fine quartz crystals bound together with a siliceous cement. 3. Granite A was a fine-grained granite quarried in South Carolina. 4. Granite B was coarse-grained granite quarried in South Carolina. 5. Granite C was a coarse-grained granite quarried in North Carolina. 6. Porcelain A.-Sample blocks of the pebble-mill lining material were obtained direct from the manufacturer. It was white in color and of lower specific gravity than the natural materials. It did not have a crystalline structure. 7. Porcelain B.-Sample pebble-mill lining blocks of the porcelain were received direct from the manufacturer. It was white

Jan 1, 1946

By C. E. Nelson, T. E. Leontis

THE properties and casting characteristics of sand-cast Mg-Al-Zn alloys, used commercially in this country and abroad, have been discussed in a number of articles during the past few years.'-" In addition, broad surveys of many compositions in the magnesium corner of the Mg-Al-Zn diagram between 0 and 12 pct A1 and 0 and 6 pct Zn have been presented by Busk and Marande7 and by Fox." The purpose of this paper is to furnish a comprehensive survey of the changes in tensile properties, micro-structure, and dimensional stability of two magnesium alloys, AZ92A and AZ63A,+ as a function of aging time and temperature after solution heat treatment. Rates of precipitation in Mg-Al-Zn alloys are slow enough so that a substantially homogeneous, supersaturated solid solution can be maintained even when these alloys are air-cooled from the heat-treating temperature. Consequently, even though it has been demonstrated9 10 that significantly higher strengths can be developed in some alloys in the aged condition by quenching rather than air cooling from the heat-treating temperature, general practice is to air-cool magnesium alloys. All the work discussed in this paper is based, therefore, on aging studies performed on material air-cooled from the heat-treating temperature. This investigation was intended to be a study of commercially practical aging cycles; the tensile properties were determined, therefore, up to aging times of 25-hr duration. The alloys, used in this investigation were prepared in the laboratory by remelting commercial ingots of the appropriate composition according to the procedures described in a previous paper" as the "crucible method." All melts were given the standard superheating treatment in order to insure the maintenance of a uniform grain size of 0.003 to 0.004 in. Standard test bars, 61/2 in. long with a 2½ in. long reduced section having a diameter of Y2 in., were cast from these melts in green-sand molds using a four-bar pattern. The alloys were heat treated according to the following schedules: AZ92A alloy: 500" to 780°F in 2 hr + 780°F (24 hr) AZ63Aalloy: 500" to740°Fin2 hr + 740°F (16hr) In commercial practice," AZ92A alloy is heat treated at 770°F for 18 hr and AZ63A alloy is heat treated at 730°F for 10 hr. The slightly higher temperatures and longer periods of heat treatment were used in order to obtain as homogeneous a solid solution as possible and thus to minimize inconsistencies in the

Jan 1, 1952

By P. W. Bakarian, John C. McDonald

Three magnesium alloys were processed in various ways to exhibit a wide variation in the ratios of yield strength and tensile strength in the rolling direction compared to the cross-rolling direction. Basal-plane pole figures were prepared from several specimens. A fair correlation was observed between the property ratios and the ratio of percent of poles oriented in the cross-direction quadrants compared to the percent oriented in the rolling-direction quadrants of the pole figures. THE modes by which magnesium crystals deform are such as to lead to marked preferred orientations in all forms of wrought products. The effect of the active modes at room temperature, coupled with these orientations, is often to produce a lower compressive yield stress compared to the tensile yield stress. The phenomenon is due to easy twinning in compression, and has been well-related to the preferred orientations as described by basal-plane pole figures of the hcp magnesium single crystal. The literature contains some information on the variation with test direction of the tensile properties of sheet, but no quantitative relationship to the observed pole figures has been established. These effects have been reviewed in the few com- prehensive treatises in English which have been written on magnesium technology and metallurgy.1°3 Roberts presents several pole figures, but no tensile-property data in the plane of the sheet. Raynor has no pole figures, but quotes Frommer's4 results. The information in Beck's compendium more or less parallels the results of Jones and powell.5 In both a Mg + 1.5 Mn alloy and a Mg + 4.6 A1 alloy, cold rolling was found not to change the general situation of higher properties in the cross-rolling direction,* than in the rolling direction. Thomas'6 X-ray studies of Jones and Powell's specimens did not permit correlation of properties and preferred orientation. Ansel and Betterton7 report tensile and compressive properties on three other alloys as a function of degree of cold rolling, plus a recrystallizing anneal. As rolled, there was a change in anisotropy with degree of reduction, but all alloys were reasonably isotropic in tension when annealed. X-ray diffraction photograms illustrated the kinds of orientations present, but were not correlated with the properties. Bakarian8 has described a method of determining quantitatively a preferred orientation, and illustrated the method by applying it to pure magnesium and two of its alloys. This method was used in the present work as a basis for correlating the strength properties with the texture.

Jan 1, 1965

By E. C. Houston

THE presence in the Tennessee Valley of extensive deposits of olivine, a silicate of magnesium and iron that contains approximately 28 per cent magnesium, has been recognized since 1896 when Lewis8 published a survey of basic magnesium rocks of western North Carolina. A recent field survey by T.V.A 7 showed that more than two hundred million tons of high-grade olivine occurs above local drainage levels in western North Carolina and northern Georgia. Except for sporadic attempts to work the olivine for its nickel and chromium contents,10 the ore received little attention industrially until 1926 when Goldschmidt3 suggested its use in the manufacture of refractories. Only one instance is recorded of an attempt to utilize the ore commercially for its magnesium content;" in this case a process was used in which olivine was treated with sulphuric acid, the resultant mixture was leached with water, and the leach solution was purified and evaporated to form epsom salts, which was the end product. As a part of its program of contributing to the development of the natural resources of the region, the Tennessee Valley Authority became interested in the olivine deposits as a source of metallic magnesium because of their high magnesium content and proximity to hydroelectric power. Studies were undertaken to determine the feasibility of producing magnesium chloride by extraction of olivine. The experimental work was carried out successively at the T.V.A. Minerals Testing Laboratory, Norris, Tenn., at the Georgia State Engineering Station,* Atlanta, Ga., and at the T.V.A. laboratory at Wilson Dam, Ala. The present paper describes a process, developed through the pilot-plant stage, whereby magnesium chloride suitable for reduction to metallic magnesium can be prepared from olivine by extraction with hydrochloric acid and subsequent purification. Research on the magnesium-from-olivine process, originally intended for peacetime use, was given impetus by the shortage of magnesium that existed at the beginning of the current world war. By the time the process was sufficiently developed to justify a proposal for its inclusion in the war program, the shortage had been met by expansion and development of other processes. However, it is believed that the magnesium-from-olivine process may have advantages that will warrant consideration of its use after the war, when the economics of the various processes rather than production on a wartime scale will be the criterion for commercial production of magnesium. DESCRIPTION OF PROCESS Metallic magnesium is produced electrolytically by the Dow and the Elektron

Jan 1, 1945

By O. D. Sherby, J. L. Lytton, C. R. Barrett

Randomly oriented polycryslalline copper of 99.995 pcl was tested in tension at temperatures of 626o, 496o, and 406o. The gvain-size mnge investigated was from 0.03 to 0.7 mm. Grain sizes were produced by two techniques: 1) varying the amount of prior cold work and the amealing time at constant annealing temperature so as to obtain various vecrystallized grain sizes with minimum grain growth, and 4 holding the prior cold work constant while varying the annealing time or temperature so as to obtain varying grain sizes by grain growth. Polycrystalline samples (grain size of 0.03 mm) with a strong. [001](100) texture were also studied. The relationship between the steady-state creep rate, Es, and pain size was found to be the same indepentent of the technique used to prepare the various grain sizes. For specimens with grain diameters above about 0.1 mm ea zuas esse)ztiallj~ independent of grain size, while for smaller grain diameters Cs increased slightly with decreasing grain size. Strongly textured polycrystalline copper, which contained low-angle grain boundaries, exhibited steady-state creep rates that were slightly lower than those observed in randomly oriented copper, of the same gain size. The results are explained by conside?%ng- the contribution of grain boundary shearing to the total strain and the effect of grain size on the resulting creep substructure. EXPERIMENTAL observations concerning the influence of grain size on steady-state creep rates are varied and oftentimes conflicting. Numerous early investigators found that an increase in the grain size resulted in a decrease in the high-temperature steady-state creep rate, i,.'-" Other workers have foundthat ef decreases with increasing grain size up to some optimum grain size and then increases with a further increase in grain size.'- '' It has been suggested that es, decreases with an increase in grain size only because the range of grain sizes studied normally lies to the left of the grain size for optimum creep resistance. However, sherbyl2 and Feltham and his co-worker13, 14 have found that even for small grain sizes 2, does not always decrease with an increase in grain diameter but may be proportional to the square of the grain diameter. A possible explanation for the different creep rate-grain size relationships which have been observed is that in most experimental studies different grain sizes have been prepared by annealing at various temperatures. For metals in which the impurity concentration is high (greater than about 0.1 at. pct) this type of

Jan 1, 1968

By Edwin Hopkins

THE year 1923 started a few days after the Venezuelan Oil Concessions, Ltd., discovered a 140,000-bbl. well at. La Rosa and a well of between 2500 and 5000 bbl. at La Paz, on the opposite side of Lake Maracaibo. These nearly simultaneous events changed, overnight, the general aspect of oil affairs in Venezuela. Up to that time, big things had been expected by the companies then in the district, but many major companies had shown little interest in the country. Within a few weeks the Pure Oil. Co. and the Gulf Oil Corpn. entered the field and acquired large properties. The Texas Co. purchased several concessions and the Standard of California, Atlantic Refining Co., and Mexican Petroleum Co. established offices. Representatives of many other companies visited the district during the first few months of the year. The sudden influx of buyers naturally caused a great rise in prices and this, together with overproduction in the United States, doubtless caused the slowing up of concession transfers in the latter part of the year. The following property transfers occurred: (1) The Gulf Oil Corpn. contract with the Maracaibo Oil Exploration Corpn., whereby the Gulf acquired the right to select 100,000 acres from the Maracaibo's zones. (2) The Gulf Co. purchase of one-quarter interest in seven concessions of the New England Oil Corpn., Ltd. (3) The Gulf Oil Corpn. purchase of several concessions of Kunhardt and others in the Perija district. (4) The Gulf Oil Corpn. purchase of certain portions of the one-kilometer Lake zone that were not covered by parcels or Government reserves (namely the "sobrantes"). (5) Pure Oil Co. purchase of all Government reserves turned back by Maracaibo Oil Exploration Corpn. in the districts of Mara and Miranda. (6) Standard Oil Co.: of New Jersey deal with the British Controlled Oilfields, Ltd., for control of approxi-mately the eastern third of the .district of Buchivacoa, state of Falcon. (7) Royal Dutch deal with the British Controlled Oilfields, Ltd., for the control of the central third of the district of Buchivacoa, Falcon. (8) The Texas Co. purchase of several concessions in Perija and one west of Mene Grande on the east side of Lake Maracaibo. (9) Purchase by the British Equatorial Oil Co., Ltd., of Goverment reserves corresponding to certain Creole Syndicate parcels under the margin of Lake Maracaibo near La Paz. (10) The Lago Petroleum Co. acquired a concession on all of Lake Maracaibo except a 1-Km. strip along the shore.

Jan 3, 1924

By H. C. Lukens, E. V. Potter

The volume of hydrogen released from electrolytic manganese at various temperatures and pressures was determined in a previous investigation1 as part of a study to determine the most practical procedure for removing the hydrogen from electrolytic manganese metal. No attempt was made to determine the absolute volume of gas in the metal at any temperature and pressure; the volume of gas released showed only the variation in solubility with temperature and pressure. The results were very similar to those obtained by Sieverts and Moritz.² Both sets of data show a minimum solubility between 500' and 700°C., but they differ in certain respects; on cooling from 500°C., our results showed an increase in solubility of about 7 C.C. as compared with an increase of 34 C.C. per 100 grams shown by Sieverts. Furthermore, the transition temperatures, as indicated by sharp breaks in the solubility curves, did not agree well with Sieverts' data. This information was of secondary importance in the earlier investigations, and the solubility at low temperatures and the transition temperatures were subject to considerable error. Therefore, a subsequent investigation, reported in this paper, was made to measure the absolute solubility at temperatures from room temperature through the melting point and make more accurate observations of the transition temperatures. Apparatus and Method The apparatus and method were essentially the same as those described in the previous work,' as shown in Fig. I. At high temperatures, the small tube containing the thermocouple in the sample container A frequently broke off, so for some of this work the thermocouple was placed outside the sample container and protected by a quartz tube of about the same wall thickness as the sample container. No significant difference was found in the transition temperatures obtained in the two ways. The automatic temperature controller was used in these tests in the regions where there was little change in solubility with temperature. In the neighborhood of the transition points a continuously variable autotransformer was used instead of the automatic controller, and the power input to the furnace was adjusted so that the temperature increased or decreased at a very slow, uniform rate through the transition range. This procedure was followed because the temperature oscillations produced by the controller were too great compared with the transition range, and the transi- . tion points determined under such conditions were less accurate. Absolute Solubility Procedure ad Results The absolute solubility of hydrogen in manganese could be determined most

Jan 1, 1947

By E. V. Potter, H. C. Lukens

The volume of hydrogen released from electrolytic manganese at various temperatures and pressures was determined in a previous investigation1 as part of a study to determine the most practical procedure for removing the hydrogen from electrolytic manganese metal. No attempt was made to determine the absolute volume of gas in the metal at any temperature and pressure; the volume of gas released showed only the variation in solubility with temperature and pressure. The results were very similar to those obtained by Sieverts and Moritz.² Both sets of data show a minimum solubility between 500' and 700°C., but they differ in certain respects; on cooling from 500°C., our results showed an increase in solubility of about 7 C.C. as compared with an increase of 34 C.C. per 100 grams shown by Sieverts. Furthermore, the transition temperatures, as indicated by sharp breaks in the solubility curves, did not agree well with Sieverts' data. This information was of secondary importance in the earlier investigations, and the solubility at low temperatures and the transition temperatures were subject to considerable error. Therefore, a subsequent investigation, reported in this paper, was made to measure the absolute solubility at temperatures from room temperature through the melting point and make more accurate observations of the transition temperatures. Apparatus and Method The apparatus and method were essentially the same as those described in the previous work,' as shown in Fig. I. At high temperatures, the small tube containing the thermocouple in the sample container A frequently broke off, so for some of this work the thermocouple was placed outside the sample container and protected by a quartz tube of about the same wall thickness as the sample container. No significant difference was found in the transition temperatures obtained in the two ways. The automatic temperature controller was used in these tests in the regions where there was little change in solubility with temperature. In the neighborhood of the transition points a continuously variable autotransformer was used instead of the automatic controller, and the power input to the furnace was adjusted so that the temperature increased or decreased at a very slow, uniform rate through the transition range. This procedure was followed because the temperature oscillations produced by the controller were too great compared with the transition range, and the transi- . tion points determined under such conditions were less accurate. Absolute Solubility Procedure ad Results The absolute solubility of hydrogen in manganese could be determined most

Jan 1, 1947

By Jr. W. L . Phillips

The deformation and fracture characteristics of lithium-fluoride single crystals stressed in compression at room temperature have been studied. In as-cleaved specimens the stress-strain curves were variable; two types of {110} fractures were observed in the vicinity of kink bands. The stress-strain curves of annealed crystals were reproducible; {100} cracks formed which propagated along the (100) and (110) planes. The deformation and fracture characteristics were affected by quenching and X-ray irradiation. STUDY of the mechanical behavior of nonmetallic materials has received considerable impetus in recent years because of the need to overcome the problem of brittleness before the refractory properties of nonmetallics can be fully exploited. Ionic crystals provide a convenient and simplified starting point from which to study the deformation and fracture processes in nonmetallic materials. Early investigations of the mechanical behavior of non-metals were restricted largely to determinations of the crystallographic indices of the cleavage and fracture planes and the glide and twinning elements. Until recently, only occasional systematic studies of the deformation characteristics of non-metals have been made; and investigations of the forces necessary to initiate plastic deformation and the factors which affect the flow characteristics have been restricted largely to studies of sodium chloride'-7 , magnesium oxides-l3 and lithium fluoride. 14-22 Fracture studies on alkali halide and metal oxide single crystals have been limited despite the fact that these materials have a number of advantages for fracture studies. Because they are transparent, the cracks which form can be viewed in three dimensions instead of in two dimensions as in metals. Also, they exhibit stress birefringence under polarized illumination, which enables the internal stress pattern and, therefore, the distribution of dislocations to be examined in the vicinity of the fracture. Early workers1-4 have shown that ionic crystals with a cubic structure fracture in tension along the (100) plane normal to the applied stress. These fractures were brittle at room temperature and propagated very rapidly across the cross section of the crystal. More recently, Stokes, Johnston, and Lil0 have studied crack formation in compressed magnesium-oxide single crystals. They found that the cracks, which were observed after about 3 pct strain, formed in the region of a kink band and lay on conjugate (110) slip planes instead of the usual(100) cleavage plane. Two different types of cracks were noted: stroh23 and secondary. The Stroh cracks did not exist merely on the surface but extended through the specimen in the form of tiny slits. A secondary

Jan 1, 1962