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By D. C. Porterfield

-4s a result of world economic conditions brought about by the European war and the consequent loss of European markets for Venezuelan crude, production in Venezuela decreased from 205,433,000 bbl. in 1939 to 186,134,000 bbl. in 1940, or 9.4 per cent. This decline interrupted a steady annual increase in production from the country, which had been continuous since 1932. The Maracaibo Lake Basin in western Venezuela accounted for 135,738,000 bbl. during 1940, or 73 per cent of the total, as against eastern Venezuela's production of 50,396,000 bbl., or 27 per cent of the total for the country. Corresponding figures for 1939 were 167,688,000 bbl., or 82 per cent of the total from the Lake Basin, and 37,744,000 bbl., or 18 per cent from the east. These comparisons indicate the increasing importance of the newer developments in eastern Venezuela, but it is unlikely that production from the east will ever exceed that from the west. In all, 429 new wells were completed in Venezuela during 1940 as compared to 438 in 1939. Of the 1940 completions, 411 were in proved areas and 18 were wildcats; 389 (95 per cent) of the exploitation wells drilled were producers, I was a gas well and 21 were dry holes, while 6 (33 per cent) of the wildcats drilled were producers and 12 (67 per cent) were dry; 263 of the exploitation wells and 4 of the wildcats were in the Maracaibo Lake Basin and 148 exploitation wells and 14 wildcats were in the east, mostly in the State of Anzoategui. Exploration of the light-oil areas in the Tia Juana and Lagunillas fields was con- tinued during the year with favorable results. Along the lake shore, drilling was confined principally to fill-in wells in the La Kosa, Tia Juana, Laguni!las and Bachaquero fields, although some important semi-exploratory drilling was done in the Pueblo Viejo area between Lagunillas and Bachaquero fields. The only other developments of particular interest in the west were the successful completion of a step-out well lying to the south of the former southern limit of Mene Grande field, which adds considerable proved acreage to that field; and the failure of two wildcats that were drilled near the Colombian border to determine whether the productive sands of the Petrolea field in the Barco Concession, Colombia, extend into Venezuelan territory. In the east no new fields were discovered during the year, although five wildcats were completed as producers. Three of these, Guario No. I, Jusepin-56 and LM-I (Leona), discovered important extensions to previously proved areas and the remaining two, Cantos-I and SPN-I (Socororo), were subsequently proved to have tapped productive sands of small extent and operations in these areas have been suspended. The greatest activity in the east was concentrated in the Oficina field, where 105 new wells were completed during the year and production was increased from 22,540 bbl. per day during January 1940 to 57,627 bbl. per day during December 1940. Important development work was also done in the Jusepin. San Joaquin and El Koble fields.

Jan 1, 1941

By D. C. Porterfield

-4s a result of world economic conditions brought about by the European war and the consequent loss of European markets for Venezuelan crude, production in Venezuela decreased from 205,433,000 bbl. in 1939 to 186,134,000 bbl. in 1940, or 9.4 per cent. This decline interrupted a steady annual increase in production from the country, which had been continuous since 1932. The Maracaibo Lake Basin in western Venezuela accounted for 135,738,000 bbl. during 1940, or 73 per cent of the total, as against eastern Venezuela's production of 50,396,000 bbl., or 27 per cent of the total for the country. Corresponding figures for 1939 were 167,688,000 bbl., or 82 per cent of the total from the Lake Basin, and 37,744,000 bbl., or 18 per cent from the east. These comparisons indicate the increasing importance of the newer developments in eastern Venezuela, but it is unlikely that production from the east will ever exceed that from the west. In all, 429 new wells were completed in Venezuela during 1940 as compared to 438 in 1939. Of the 1940 completions, 411 were in proved areas and 18 were wildcats; 389 (95 per cent) of the exploitation wells drilled were producers, I was a gas well and 21 were dry holes, while 6 (33 per cent) of the wildcats drilled were producers and 12 (67 per cent) were dry; 263 of the exploitation wells and 4 of the wildcats were in the Maracaibo Lake Basin and 148 exploitation wells and 14 wildcats were in the east, mostly in the State of Anzoategui. Exploration of the light-oil areas in the Tia Juana and Lagunillas fields was con- tinued during the year with favorable results. Along the lake shore, drilling was confined principally to fill-in wells in the La Kosa, Tia Juana, Laguni!las and Bachaquero fields, although some important semi-exploratory drilling was done in the Pueblo Viejo area between Lagunillas and Bachaquero fields. The only other developments of particular interest in the west were the successful completion of a step-out well lying to the south of the former southern limit of Mene Grande field, which adds considerable proved acreage to that field; and the failure of two wildcats that were drilled near the Colombian border to determine whether the productive sands of the Petrolea field in the Barco Concession, Colombia, extend into Venezuelan territory. In the east no new fields were discovered during the year, although five wildcats were completed as producers. Three of these, Guario No. I, Jusepin-56 and LM-I (Leona), discovered important extensions to previously proved areas and the remaining two, Cantos-I and SPN-I (Socororo), were subsequently proved to have tapped productive sands of small extent and operations in these areas have been suspended. The greatest activity in the east was concentrated in the Oficina field, where 105 new wells were completed during the year and production was increased from 22,540 bbl. per day during January 1940 to 57,627 bbl. per day during December 1940. Important development work was also done in the Jusepin. San Joaquin and El Koble fields.

Jan 1, 1941

By R. M. Waterstrat, E. C. van Reuth

BINARY- alloy phases having the A15-type crystal structure have been described as occurring at a simple and more or less invariant stoichiometric composition (A3B) which corresponds to the relative number of atoms occupying each of the two crystallographi lattice sites in this structure.1,2 It is frequently assumed, therefore, that each crystallographic site is occupied exclusively by one kind of atom. In most cases, however, there have been insufficient experimental data to establish whether atomic ordering is, in fact, complete. Recent studies have shown that binary A15-type phases are sometimes stable over an appreciable composition range3''* and, occasionally, the composition range of stability does not even include the "ideal" A3B stoichiometric composition.5-7 We have observed the existence of nonstoichiometric A15-type phases in the binary systems Cr-Pt and Cr-Os. This has not been reported in previous work on these alloy systems.1,8-11 A series of alloys, each weighing approximately 30 g, was prepared by are-melting in an Ar-He atmosphere using 99.999 pct Cr, 99.999 pct Os, and 99.99 pct Pt as starting materials. Each alloy was melted four times with a total weight loss of less than 1 pct. The stoichiometric (A3B) alloys were sealed in evacuated quartz tubes and annealed at 1200°C for periods of time ranging from 3 days to 2 months. Examination of the alloy microstructures revealed that little change had occurred over this time interval and it was therefore assumed that the microstructures were fairly representative of equilibrium conditions. No evidence of contamination was observed although there was apparently some loss of chromium which was confined to a thin layer at the surface of the specimens. The quartz tubes were quenched from the annealing temperature into cold water. X-ray diffraction and metallographic examination of the stoichiometric alloys revealed an estimated 10 to 30 pct of second phases which were tentatively identified as phases previously reported in these binary-alloy systems.8-11 A second series of alloys was prepared by mixing -325 mesh metal powders having a nominal purity of 99.9 pct and compressing these mixed powders in a cylindrical die at a pressure of 43,000 psi. These alloys, each weighing 15 g, and some of the arc-melted alloys were annealed in a high-temperature vacuum furnace heated by tantalum strips at a pressure of 10-8 Torr and were rapidly cooled by turning off the furnace power. X-ray and metallographic examination of both series of alloys served to establish the composition ranges of the A15-type phases. Although some chromium losses occurred during the vacuum annealing, they were largely confined to a thin layer on the outer surfaces of the samples. It was established that the A15 phases occur in the Cr-Pt system at 21 ± 1 at. pct Pt after 1 week at 1200°C and in the Cr-Os system at 28 ± 1 at. pctOs after 1 day at 1400°C (see Table I). We also observed that an arc-melted stoichiometric (A3B) alloy in the Cr-Ir system was single-phase (A15-type) in the "as-cast" condition in agreement with previous work.8,13 In addition we obtained a sample of the Cr-Os A15-type phase from Argonne National Laboratory. This alloy contained less than 1 pct second phase12 and was submitted to a density measurement. The density measurement yielded a value of 11.14 g per cu cm in comparison to a theoretical value of 11.25 g per cu cm calculated using the observed lattice constant (4.6806Å) of this alloy. The uncertainty in measurement was 0.1 pct but the sample may have contained some cracks or minor imperfections which could account for the low experimental value. We have also studied the atomic ordering in these phases by means of integrated line intensity measurements using thick, flat, rotating powder samples and CuK a radiation in an X-ray diffractometer. We have obtained order parameters of 0.90 for the Cr-Pt phase, 0.89 for the Cr-Ir phase, and 0.64 for the Cr-Os phase using the formula: where s is the usual Bragg and Williams order parameter, ra is the fraction of chromium atoms in A sites, and FA is the fraction of chromium atoms in the alloy. The values obtained are estimated to be accurate within ±4 pct. If the unusually small value for the order parameter of the Cr-Os A15 phase were due to the existence of lattice vacancies on the "B-atom" sites, then a density of 10.04 g per cu cm would be expected in contrast to the observed value of 11.14 g per cu cm. We, therefore. conclude that the fraction of lattice vacan-

Jan 1, 1967

By B. Chalmers, S. Wojciechowski

THE structure of the equiaxed zone of several A1-Cu samples mechanically stirred during unidirectional solidification was examined. The stirring was produced by rotary oscillation of the mold about its vertical axis.' It was found that in Some samples the structure is not of the same type over the whole of the equiaxed zone; it consists of regions with two different etching responses. Fig. 1 shows this structure in a Al-1 wt pct ku sample. The lighter etching regions with a coarse structure form something like a network and the darker etching regions with a finer structure can be observed as the continuation of the coarse structure inside this network. The difference in size and shape of the dendrite branches (they are rounded in the coarser structure) is similar to that found by Williamson and Chalmers in ice crystals solidified in undercooled water: when the amount of undercooling was small, the ice crystals were more rounded and coarser than these solidified with a larger amount of undercooling.' It seems justified to conclude that the observed structure resulted from solidification under different thermal conditions: the coarser structure solidified first out of the "purer" liquid and with a smaller amount of undercooling and the finer was formed later out of solute-enriched liquid under conditions of much more rapid heat extraction. A considerable change in the heat flow conditions at the later stages of solidification can be easily understood by taking into account that the coarser crystals form a continuous network and the amount of trapped liquid is relatively small; hence the contribution of latent heat is much smaller in the later stages of solidification. The difference in structure and etching characteristic reflects a difference in composition between these two regions. It was found that the darker etching re- gions are harder (30.4 to 31.3 HV5) than the lighter etching ones (25 to 26 HV5). A similar type of structure was found in a A1-4 wt pct Cu sample grown by Czochralski method. Fig. 2 shows the structure in the lower part of a sample grown slowly and then decanted by a rapid removing of the sample from the melt. In a few places trapped liquid solidified in the same manner as in the sample shown in Fig. 1.

Jan 1, 1968

By Y. Dardel

Since the first determination of Dumas1 in 1880, many authors have tried to measure the solubility of hydrogen in solid aluminum, or at least the amount of dissolved gas in it. However, the interpretation of the results which have been obtained is still difficult. Sieverts? then Baukloh and Oesterlen,a during their gassing experiments could not determine any solubility of hydrogen in solid aluminum. On the other hand, Portevin, Chaudron and Moreq4 leaving the determination of the hydrogen solubility beyond the scope of their experiments, measured only the amount of gas that they could extract by high voltage positive ion bombardment and found up to 151 cm3 of gas per I00 g of metal. Winterhager,6 by repeated vacuum extraction during severe cold rolling, extracted up to 161 cm3 per 100 g. In both series of experiments, the extracted gas contained chiefly hydrogen with a small amount of nitrogen, carbon monoxide, carbon dioxide and methan. Later, Schmidt and von Schweinitze as well as Chaudron and Moreau7 showed the importance of the adsorbed layer of hydrogen, the extracted quantities being proportional to the surface and not to the weight of the sample, when its cleaning was not perfect. In earlier experiments, Steinhausers extracted from more massive samples nothing but a little amount (< 0. 5 cm3 per I00 g) of hydrogen, carbon monoxide and methane. Thus, according to these experiments the quantity of dissolved gas is probably very small and the effect of the surface could falsify the results of the extraction. However, owing to the care taken by Chaudron and his coworkers, it was clear that all the hydrogen extracted could not come from the superficial layer, or that the links which bound hydrogen to the surface were so strong that the usual method of cleaning could not destroy them. After the main parts of the experiments reported here had already been carried out, Eborall and Ransley9 published the results which they obtained with an analysor having an accuracy of 0.03 cm3 per I00 g, while that of the usual apparatus was only about 0.2 cm3 per I00 g. During all their experiments the adsorbed layer would have been a difficulty, for the value of the adsorbed hydrogen was approximately equal to that of the dissolved amount. Table i—Amount of Adsorbed and Dissolved Hydrogen (After Eborall and Ransley) Extraction Hz Adsorbed „ h2 dissolved Temperature Calculated Extraction OCcma 500 0.057 0.050 600 0.062 o.096 Since always keeping the same adsorbed layer is very difficult, an error in the correction for the adsorption can be made when using the apparatus of. Eborall and Ransley, as well as the earlier apparatus.

Jan 1, 1949

By Francis Foley

FROM the point of view of the metallographist, the adaptation of x-rays to the study of the crystal structure of metals is of the greatest importance. While one may hardly consider the findings resulting from x-ray study as revolutionary, their positive nature, compared with the deductions we have been forced to accept from the work that had gone before, gives firmer ground on which to build and furnishes new fields for speculation. Prior to the advent of the crystallogram, the best work on the crystal structure of steel was that of Osmond and Cartaud.1 They concluded, from their investigation with percussion figures formed at various temperatures, that alpha, beta, and gamma irons belonged to the cubic system and that they showed well-marked specific characteristics and could not have the same internal structure. What the internal structures were, they had no direct method of determining; but from a consideration. of the fact that the 001 plane (that parallel to the cube face) is a plane of perfect cleavage and minimum hardness in alpha iron and that the 111 (octahedral) plane is by far the most important in the crystallography of gamma iron, they were led to suggest the simple cubic arrangement as that of alpha and the face-centered cubic arrangement as that of gamma iron. They suggested the body-centered cubic arrangement as that of beta iron. The atomic arrangement of the various crystal forms of iron has been quite definitely determined in recent years by means of x-rays and the work of Westgren2 and Westgren and Phragmèn3 has been rather conclusive. They not only determined the atomic arrangement of alpha, beta, and gamma iron but also that of the high-temperature modification delta.

Jan 10, 1925

By H. I. Aaronson

Isothermally formed plates of proeutectoid a, lengthen at approximately the rates predicted by the Zener-Hillert equation, indicating that their lengthening kinetics are controlled by the volume diffusion of chromium in the ß matrix. Solution annealing treatments in the vicinity of the transus introduce a second mode of transformation, in which the lengthening rate is at least 1.8 x 104 faster than predicted by this equation. Little or no volume diffusion appears to accompany the latter transformation. The Presence of oxygen is evidently a Prerequisite for the occurrence of this reaction. X HE effects of thermal history prior to the initiation of transformations which proceed by nucleation and diffusional growth are currently evoking considerable interest. The rate of nucleation (but not the rates of growth) of pearlitel and of bainite,2 and the over-all rates of aging reactions in Al-cu3 and Al-si4 alloys have been shown to be appreciably dependent upon thermal history in the solid-solution region"&apos; or in the two-phase region prior to the onset of pre~ipitation.3,4 In none of these reactions, however, was the transformation mechanism changed by variations in the temperature-time path used to reach the reaction temperature. Preliminary experiments reported by M. K. McQuillan5,8 and a systematic investigation by Farrar and Margolin7 have disclosed that the transformation behavior of hypoeutectoid Ti-Cr alloys is considerably more sensitive to thermal history. Qualitative evidence strongly suggests that not only the rate of nucleation but also the rate of growth and even the mechanism of the ß — a reaction can undergo remarkable changes when a solution annealing treatment in the vicinity of the ß/a +ß, or transus temperature, is interposed between a high-temperature solution anneal (conventionallq at 1000°C) and the isothermal reaction treatment. The present investigation was undertaken in an attempt to ascertain the nature and origin of these effects. Study of the changes in the kinetics and morphology of the ß - a, reaction produced by varialtions in thermal history was the primary means employed for this purpose. EXPERIMENTAL PROCEDURE The compositions of the alloys used in this in~esti~ation are given in Table I. These alloys were homogenized for 5 days at 1050° C in evacuated (2 x 10 -5 mm of Hg), zirconium-gettered fused quartz capsules. The capsules themselves were enclosed in a porcelain chamber evacuated with a mechanical pump during the homogenization anneals. Upon completion of homogenization, the alloys were cooled to room temperature and then reheated to 550°C for 3 1/2 days in order to transform the alloys to a finely divided mixture of a and TiCr2, and thus provide an approximately constant initial mi-crostructure. Individual specimens were sealed in evacuated and internally gettered Vycor capsules and heat treated as previously described.8,9 EXPERIMENTAL RESULTS Ti-10.64 Pet Cr. This investigation was largely performed on the 0.64 pet Cr alloy. The "base"

Jan 1, 1962

By K. P. Sinha, J. F. Schatz, T. F. Borschel, S. Demou

Triaxial creep behavior of oil shale was investigated in the laboratory at simulated in-situ conditions. A range of temperature and stress conditions were chosen to represent those within the inter-chamber pillars of a modified in-situ retorting operation. Oil shale in grades up to 60 gallons per ton have been tested. Experimental data and a constitutive model have been presented here.

Jan 1, 1982

By Robin O. Williams

The increase in internal energy as the result of deformation has been measured for lead, aluminum, silver, nickel, iron, and zirconium by using rapid, adiabatic compression. The stored energy increase is roughly Proportional to the strain; the propor-tionality constant increases rapidly with increasing melting point. The fraction of the mechanical energy which is stored increases more slowly, since the strength of the metals also increases with melting point. The values of the stored energy are considered accurate to about 10 pet. The present values appear about 50 pet larger than the more reliable published results where comparisons are possible. It is possible that this difference is due to the high strain rate used in this investigation. Immediately after deformation all these metals release energy at a rate roughly proportional to (time)-&apos;. This release is considered to be associated with dislocation motion but in aluminum (and copper) some additional process seems to be present. This release can represent 20 pet or more of the stored energy. WHEN pure metals are plastically deformed, most of the mechanical energy is converted into heat. The energy remaining within the metal is significant in that it is the energy of the disorder produced and thus detailed knowledge of this energy is a powerful tool in understanding the nature of deformational disorder. While much effort has been expended on this problem, the amount of information available is limited. The situation as of 1958 has been carefully reviewed by Titchener and ever.&apos; The present results have been obtained by a new experimental approach to this problem. The method necessitates high-strain rates which make comparisons with published results less certain, but a high-strain rate is an advantage in that the energy release immediately after deformation can be followed. EXPERIMENTAL PROCEDURE In the experimental method used, the internal (stored) energy is given as the difference between the mechanical work used in deforming the sample and the heat which is released (the first law of thermodynamics). The work is supplied by two identical hammers swinging freely from a fixed height, the available energy being the product of the mass, the gravitational constant, and the distance through which the center of gravity moves. The initial temperature rise of the sample represents the heat produced by the deformation. The sample temperature is determined by a small thermocouple embedded in and supporting the sample. This process can be repeated over and over to produce increased strains. Most samples are run through about five cycles to a total strain of around 0.7. Further details are covered elsewhere. The determination of the heat is dependent upon the sample weight, its specific heat, the rise in temperature, and any gains or losses to the surroundings. One is dependent on published results for specific heals (the values were taken from a collection).3 The values must be accurate to about 0.1 pet in order that they not affect the results. The best values thus do not contribute to the uncertainty, but this is probably not always the case. The accuracy of the temperature rise is limited primarily by knowledge of the thermocouple characteristics over short temperature intervals, but careful calibration eliminates this as an important factor. One can calculate readily the heat flow between the sample and hammers if the time of contact and the sample temperature are known and if there were no oil at the interface. Assuming the maximum temperature difference, upper values for this interchange have been calculated (the time of contact is determined from the decrease in sample length) and it may or may not be significant. However, no correction is colnsidered necessary because of the presence of a thin oil film which has a thermal conductivity much less than the metals. Except for the possible uncertainty in specific heat, the heat is considered to be adequately known. The mechitnical losses which are recognized as important are: 1) friction between the sample and the hammer:;, 2) the kinetic energy in the hammer suspension system which may not be entirely usable, 3) the rebound energy of the hammers, and 4) the vibration of the hammer heads. All these have been covered in detail elsewhere2 and only the more significant points are made here. The friction turns out to be small except for soft materials (lead)

Jan 1, 1962

By E. W. Dewing

The nature of solid solutions of sodium in non-paphitic carbon at temperatures near 1000°C has been investigated by an electrolytic technique. The activity coefficient is found to vary strongly with the heat-treatment temperature of the carbon, and an analysis of the energy terms involved suggests that this is due to variations in the Fermi level. The diffusion coefficient for sodium is in the range implying that the sodium atoms (or ions) are not bound to specific sites on the carbon, in agreement with lack of evidence for specific compounds in the activity -composition curves. In the light of These results phenomena occurring in aluminum reduction cell linings are dis-cussed. It is concluded that sodium migrates by diffusion through the carbon lallice and not the pores, and that A14C9 is formed within the lining hy The excess of NaF invariably found in used linings is formed by this reaction and by air oxidation: There has recently been much interest in the swelling of carbon which occurs when it is made cathodic in an aluminum electrolysis cell, and there is general agreement that the phenomenon is due to the penetration of sodium atoms, derived from the reaction on the carbon lattice. (NaF and AlF3 are constituents of the fused-salt electrolyte.) The low-temperature lamellar compounds of potassium with graphite are well-known, and one compound between sodium and graphite has been reported.4 There is, however, virtually no information on the basic chemistry of the interaction of sodium with nongraphitic carbon at high temperatures, although Dell3 has made some fundamental studies of rates of penetration. At the time the present work was carried out these were not available. Rapoport and samoilenkol had measured rates of physical expansion in a dilatometer, using the fractional increase in length of a carbon specimen after electrolysis in a cryolite bath for 2 hr as an index of susceptibility to cathodic swelling. Work here with a similar apparatus showed that expansion (of a 1.5-in.-diam cylindrical specimen) ceased in less than 20 hr, and that the final expansion was much more reproducible than the value at some intermediate time. This suggested that an equilibrium was being set up, and that a thermodynamic approach was required. The results obtained are not as accurate as had been hoped, but they are the only ones of their type available and have enabled useful conclusions to be drawn. The experimental work was divided into two parts: an investigation of the activity-concentration diagram for sodium in carbon, and a rough determination of the diffusion rate. For the former, most of the experiments were made with petroleum coke even though this is not a form of carbon used in cell linings. It has the advantages, however, that it is a homogeneous material, that it is low in ash, and that its structure is reasonably well understood. Anthracites and coal cokes gave results of the same type as obtained with petroleum coke, but the reprodu-cibility from specimen to specimen was extremely poor. EXPERIMENTAL 1) The Activity-Composition Diagram for Sodium in Carbon. The petroleum coke was ground, pressed at 40,000 psi into plates 19 by 9 by 2 mm without added binder, and heat-treated. The sodium activities were established by an electrolytic technique. The carbon was made anodic in a cryolite bath with an aluminum cathode, and a controlled potential, E, applied so that the sodium activity at the anode was given by ln Na = 1n asa - EF/RT [21 where as, is the sodium activity generated by Reaction [I]. The relative activity is sufficient for many purposes and is simply given by The value of Na not at present known, but when the thermodynamics of the Na-A1 system have been worked out it can be derived from the equilibrium

Jan 1, 1963

By H. De Cizancourt

France.—Pechelbronn remains about the only producing field, 41 per cent of the 1937 output of 496,525 bbl. being mined by shaft and 59 per cent produced from pumping wells. At present Gabian has only a very small production. During 1937 there was no private undertaking for petroleum research. Only the Office National des Combustibles Liquides has done any drilling, unsuccessfully, at Pezenas and Frangy-Chilly. Algeria.—No new research has been made and Tliouanet, a small acreage pool that has been declining for several years, gave only 2193 bbl. in 1937. Morocco.—The SociCt6 Chhrifienne des Petroles continues active work. First tests of production made on the Jurassic structures of the Tselfat and Bou Draa must be mentioned for 1937. In connection with these tests, which have yielded 16,495 bbl., 14 new wells have been located

Jan 1, 1938

By A. C. D. Chaklader, Ashok K. Kakar

The basic density equation originally dericed &apos; to predict the increase in density of a compact of spherical particles with the progressive deformation at the points of contact has been further modified to include the yield strength of the material. This has been done by assuming that the contact areas grow to stable sizes under a fixed stress which is equal to three times the yield strength. The final equation has the form: where Do and D me the initial and final bulk densities of the compact, u is the applied pressure, and Y is the yield strength of the material. This equation was tested with the data obtained on spheres of lead, K-Monel, and sapphire. The calculated yield strength t~alues for lead and sapphire are within the range of values reported in the literature. A few of the earliest hot pressing models proposed to explain the mechanism by Murray, Livey, and williams2 and then by McClelland3 are based on a plastic flow mechanism. However, more recent investigations suggest that the overall densification process is a combination of several mechanisms, such as particle rearrangement, fragmentation, plastic flow, and stress-enhanced diffusional creep. While fragmentation and particle rearrangement are considered to be responsible for the densification in the early stages,"475 it has been concluded that the final stages of hot pressing are controlled by stress-enhanced diffusional creep.516 The manner in which the densification takes place, i.e., by fragmentation, particle rearrangement, plastic flow, or stress-enhanced diffusional creep, would depend upon the type of material, the temperature, and the stress level used during the hot-pressing experiments. Metal compacts can be expected to have a much greater contribution from plastic flow than ceramic oxides. Also, plastic flow would be a significant contributing factor to densification at high temperatures and high stresses. Most of these works, directed towards elucidation of densification mechanism, have dealt with kinetics of the process. The results of most of the authors vary from one another and they have proposed either new empirical or semiempirical equations to fit their data. The densification rate was found to vary with the type of the powder, shape and size of the powder, initial packing density of the compact, and a few other factors such as rate of heating, pressure, and so forth. Beyond the initial stages, the densification process has been considered to be as time-dependent flow, controlled by a diffusional process, e.g., Nabarro-Herring creep. Palm our, Bradley, and johnson&apos; have attempted to use modified creep rate equations to interpret the data of densification under hot-pressing conditions. Beyond the initial stages, however, the densification would be controlled by a process depending upon the temperature, pressure, and size of the powders. It is the authors&apos; belief that such densification cannot be exclusively controlled by a single process and so attempts should be made to study some observable phenomenon like microstructure, yield strength, and so forth. The emphasis of this work has been toward studying the densification problem from a more fundamental point of view. Some of the principal variables, like initial packing density, mode of packing, and size of the powders, have been controlled to a great extent. The total strain produced on pressure application (instantaneous) in such a case can be considered to be due to plastic and elastic deformation. The elastic component of the strain can be determined by decreasing the load to the initial value. The strain remaining then can be correlated with the contact areas produced by deformation and the corresponding applied load. In a previous paper,&apos; the possible deformation behavior of spheres in a compact has been theoretically analyzed and experimentally tested. The change in contact area radius a relative to the particle radius R was related to the bulk density and the bulk strain for simple and systematic modes of packing. Tt was found that a density equation relating the above parameters can be represented by: where D and Do are the bulk densities of the compact at any value of a/R and a/R = 0, respectively. This basic equation should hold for any material as it was derived from geometrical considerations alone. An attempt has been made in this work to include the yield strength in the above density equation, so that a knowledge of the properties of any material can be used in predicting the densification behavior during the hot-pressing process. THEORETICAL CONSIDERATTONS The deformation of two spheres in contact under a static load can be compared to the deformation occurring between a hard spherical indentor and the flat face of a softer metal. Tt has been shown theoretically by both ~encky~ and lshlinskyg and experimentally by ~abor" that, for a material incapable of appreciable work hardening, the mean pressure required to produce plastic yielding (for deformation occurring between flat face and a hemispherical indentor) is approximately equal to three times the elastic limit, Y, of the material (in tension or compression experiments). Tabor has further observed that the same relationship is valid in the case of work-hardening materials, if the elastic limit at the edge of the indenta-

Jan 1, 1969

Discussion of the paper of W. G. MATTESON, presented at the New York meeting, February, 1918, and printed in Bulletin No. 134, February, 1915, pp. 429 to 468. WILLIAM KENNEDY, Fort Worth, Tex. (written discussion*). -In his discussion of this paper, Mr. Sherburne Rogers offers voluminous figures to show that the salt forming the. cores of the various domes could not have been derived from sea water, and gives as an illustration the immense quantity of water required to form the salt found in the Humble dome. He refers to the theory advanced by Van der Gracht apparently in support of this contention, and claims to have disposed of the views held by some that the domes were, in a great measure, formed by lateral secretion. Van der Gracht says the immense salt plugs found throughout North Germany and other countries in that region were apparently formed by orogenic movements acting upon what he calls the Mother Bed of Salt, which he gives a thickness of about 1000 ft., and an extent of several thousand square miles. The age of this "mother bed" is given as Permian. Harris, in addition to his growing-crystal theory, also says probably a great portion of the salt found in the Coastal dories may have been derived from the salt water of Permian time. Both of these theories require an abundance of water, and consequently oppose Mr. Rogers&apos; idea that the immensity of water required disproves the formation of the salt from that source. I do not suppose, however, that either Van der Gracht or Harris absolutely limits his view to the Permian as being the only source from which the salt could have come, but would probably agree to consider any other age as being the beginning. Although the Permian is very strongly represented throughout North Texas, we have none anywhere throughout the region from which the salt may be considered as having been derived. Many deep wells have been drilled along the eastern outcropping of the Carboniferous and each has passed directly from Cretaceous to Carboniferous formations. Thus we may eliminate the Permian as a source of salt in this region. But, although the Permian may be absent, we have with us the Carboniferous with probably a thickness of 3000 to 4000 ft., and something like 3000 ft. of Cretaceous, to say nothing of approximately 8000 ft. of Tertiary and later beds, all of which, if we may judge by the quantity and density of the waters obtained from the numerous wells drilled, carry immense quantities

Jan 7, 1918

By Walter B. M. Davidson

Phosphorus is one of the elements having the widest distribu tion, and phosphoric acid plays an important part in the composition of the crust of the earth. It is allied in various chemical combina- tions with many bases, of which lime, alumina and iron are the most common. It is difficult to state in what chemical combination phosphoric acid predominates in the crust of the earth, for while phosphate of lime, as the mineral which is sought for and found in deposits of economic value is the most familiar, it is probable that the phosphates of alumina and iron are the most usual forms in which phosphoric acid exists in all soils not essentially calcareous. It has been shown by thousands of analyses that all fertile soils contain from a trace to 0.5 per cent. of phosphoric acid. All limestones, dolomites and chalks contain it in proportions which, though usually small, are large enough to make careful analysis necessary in the selection of limestone as flux for iron-smelting. It is generally Trenton limestones that are found best for this purpose, the more recent strata being more phosphatic. In some places phosphoric acid replaces carbonic acid, and the limestone or chalk becomes phos phatic to a large degree, or sometimes pure phosphate of lime. The waters of the ocean, from very early periods, have contained phosphoric acid. Different analyses show varying contents; it is asserted that some portions of the Gulf Stream are more phos phatic than the surrounding waters of the Atlantic. Many springs, usually from limestone regions, contain soluble phosphates in vary ing quantities. I think it safe to assert that phosphorus is nearly the most widely and evenly distributed element on the surface of the earth, and probably the most subdivided. This can be readily understood when the important part which phosphoric acid plays and has played in the vital cosmos is taken into consideration. Phosphorus was on the earth in gaseous, liquid or solid form before the dawn of life, and since then all animal and vegetable creation have combined with the

Jan 1, 1893

By W. J. Babyak

The habit planes for hydride precipitation in large grains of alpha zirconium and Zircaloy-4 were determined in specimens containing 161 and 136 ppm hydrogen, respectively. In zirconium, the hydride platelets precipitated on various pyramidal planes inclined to the basal plane at angles ranging from 10 to 50 deg and 75 to 90 deg. Hydrides were most frequent at inclinations of about 20 deg and 90 deg. In Zircaloy-4, hydride plates were inclined to the basal plane at angles vanging from 5 to 25 deg with the predominant inclinatioiz equal to 12 deg; no platelets were found near the prism plane position. In both zircoinium and Zir-caloy-4, hydrides were principally, but not exclusively, parallel to (1011) type planes. When the Zircaloy-4 gmins were subjected to tension stresses of 12,100 psi and 19,400 psi during hydride precipitation, the hydride habit was unchanged except that precipitation favored those habit planes which were inore nearly perpendicular to the stress direction. The stress-orientatioiz effect increased with the magnitude of the stress. THE hydride habit plane in a zirconium has been determined by several investigators. Langeron and Lehr1 in 1956 found platelets parallel to (1010) slip planes. In 1962, Westlake and Fisher2 confirmed these findings and showed that hydride precipitation on twin planes, as reported by Kunz and Bibb,3 was probably due to incomplete removal of worked metal from specimen surfaces. Secondary habit planes, ( 1011) and (1015), were also found by Westlake and Fisher under particular charging conditions where a hydride layer may have existed at the hydrogenation temperature. Most recently, walters4 and westlake5 again observed the (1010) habit exclusively in zirconium. Louthan and hgermans have reported that hydrides precipitate on various ( 101l ) and (112l) planes positioned 31.5 to 90 deg to the basal plane in Zircaloy-2. The present investigation was concerned with the hydride habit in Zircaloy-4 in relation to that in zirconium and the possible change in habit when precipitation occurs under stress. The latter consideration was prompted by the stress-orientation phenomenon originally reported by Marshall and Louthan.7, 8 I) EXPERIMENTAL Materials and Specimens. Chemical analyses of all materials are given in Table I. The zirconium specimen was a 1 by 4 in. section cut from wrought crystal bar that was hot-rolled at 790°C to 0.300 in. and cold-rolled to a final thickness of 0.095 in. All surfaces were mechanically polished and then chemically polished with a solution of H2O, HNO3, and HF (10:10:l by volume) prior to annealing. Grains as long as 0.25 in. were grown by thermally cycling the specimen three times (in 10-5 mm Hg vacuum) between 825" and 1000°C at approximately 125°C per hr. The specimen was isothermally annealed at 825°C for 24, 40, and 120 hr after each cy-

Jan 1, 1968

By R. W. Guard

ALTHOUGH etching techniques have been developed for revealing dislocation sites in several metals and ionic crystals,h t is valuable to extend the technique to new metals. An etch pit method for nickel has been developed on the basis some suggestions of Dr. John R. Cuthill of the National Bureau of Standards who had observed etch pits in creep specimens of nickel. The etchant used was proposed first by wensch2 for revealing grain size in nickel. The present paper describes the evidence that the technique can be used to reveal dislocations and gives the conditions under which etching can be carried out. The specimens examined were vacuum melted high-purity Ni (99.985 pct Ni) and commercial "A" nickel (99.8 pct Ni). Both materials contained greater than 0.008 pet C and had been annealed in nitrogen or dry hydrogen at 1100o to 1200°C. This gave a grain size of 1.5 mm in the high-purity nickel and 0.050 mm in "A" nickel. Tensile specimens (0.254 in. diam) were deformed from 0.25 to 10 pct at room temperature and then heated for 1/2 hr at different temperatures from 400" to 900°C. The specimens were sectioned longitudinally then polished electrolytically in 60 pct H2SO4 and etched in 35 pct H3PO4 solution at 0.2 to 0.4 v for 30 sec to 3 min. The best method for setting the proper voltage for etching is to increase the voltage until gas bubbles are evolved vigorously from the specimen and then cut it back by 10 pct. It is necessary to heat the specimen above 500°C after deformation in order that etch pits will be formed. This "decoration" treatment permits carbon to segregate to the dislocation rendering them sensitive to etching. It was demonstrated that carbon was the decorating impurity by decarburizing some specimens in wet H2 at 1200°C. The susceptibility to etch pitting was lost following this treatment but could be restored by carburizing in contact with graphite. Some rearrangement of the dislocations in the as-deformed structure occurs on heating at 500oC and above so that the technique can not be used to study the nature of dislocation patterns in deformed specimens. Extended etching does not change the number of pits although the background becomes rough and the pits quite large. The polycrystalline specimens with various strains were examined after annealing at different temperatures. Typical patterns are shown in Figs. 1 and 2. In the unstrained specimen, Fig. 1, the density of pits is 2.5 X 10&apos; per sq cm. All grains show pits regardless of their orientation although there is a

Jan 1, 1961

By C. G. Dunn

Many investigations have been made concerning the nature of plastic deformation and recrystallization of metals either in the form of polycrystalline materials or in the form of single crystals. However, similar work on strip materials composed of large grains as thick as the strip and having a high degree of preferred crystal oricntation has not been carried out extensively. Such materials are ideal not only for studying changes in single crystals under conditions where neighboring grains exert their influences but also for obtaining the complete change in orientation of a grain or group of grains during the course of plastic deformation and subsequent recrystallization. It is well known that first-order twins in the form of Neumann bands may be produced during the plastic deformation of ferrite crystals, particularly silicon ferrite crystals.l--3 Furthermore, it is believed that high-stress regions exist in the vicinity of these bands4. and it has been said that these banded regions would be active in recrystallization processes.5 Evidence to that effect in silicon ferrite had already been presented with photomicrographs showing recrystallization among Neumann bands during the early stages of recrystallizati~n.5,6 Similar evidence has been published for nonferrous metals5 Merging of fine parallel deformation bands during annealing to form twin bands of ordinary appearance in alpha brass has been offered not only as evidence of an active role being played by mechanical twins but also as evidence that such twins cxisted prior to recrystalli~ation.5 Proof that such new structures are actually first-order twins, or even twins at all, must be considered inadequate except for those cases where X-ray or optical data have been obtained to confirm the necessary oricntation relationship.7,8 A. B. Greninger has obtained excellent iliustrations of annealing twins in alpha iron.9 Since his material was previously deformed by sharp hammering, a process that generally induces Neumann bands, the existence of twins following annealing might suggest that they grew from mechanical twins. In connection with transformation twins in alpha iron, Greninger reported that grains containing three twin orientations occurred rarely and none occurred with three sets of well-developed bands.9 The work at the Pittsfield Works Laboratory on silicon ferrite in the form of large-grained strip steel deformed a small amount and annealed to partially recrystallize the grains indicates that the deformation and recrystallization processes that lead to annealing twins involvc more complex processes than the formation of Neumann bands and the growth of such bands. Some groups of annealing twins are obtained which contain not only three well-developed twin structures, but also contain more than one order of twins. It is also shown, in one case, that an interrelated group of twins did not arise within one single parent grain and, furthermore, orientations of grains in the group

Jan 1, 1944

By C. G. Dunn

Many investigations have been made concerning the nature of plastic deformation and recrystallization of metals either in the form of polycrystalline materials or in the form of single crystals. However, similar work on strip materials composed of large grains as thick as the strip and having a high degree of preferred crystal oricntation has not been carried out extensively. Such materials are ideal not only for studying changes in single crystals under conditions where neighboring grains exert their influences but also for obtaining the complete change in orientation of a grain or group of grains during the course of plastic deformation and subsequent recrystallization. It is well known that first-order twins in the form of Neumann bands may be produced during the plastic deformation of ferrite crystals, particularly silicon ferrite crystals.l--3 Furthermore, it is believed that high-stress regions exist in the vicinity of these bands4. and it has been said that these banded regions would be active in recrystallization processes.5 Evidence to that effect in silicon ferrite had already been presented with photomicrographs showing recrystallization among Neumann bands during the early stages of recrystallizati~n.5,6 Similar evidence has been published for nonferrous metals5 Merging of fine parallel deformation bands during annealing to form twin bands of ordinary appearance in alpha brass has been offered not only as evidence of an active role being played by mechanical twins but also as evidence that such twins cxisted prior to recrystalli~ation.5 Proof that such new structures are actually first-order twins, or even twins at all, must be considered inadequate except for those cases where X-ray or optical data have been obtained to confirm the necessary oricntation relationship.7,8 A. B. Greninger has obtained excellent iliustrations of annealing twins in alpha iron.9 Since his material was previously deformed by sharp hammering, a process that generally induces Neumann bands, the existence of twins following annealing might suggest that they grew from mechanical twins. In connection with transformation twins in alpha iron, Greninger reported that grains containing three twin orientations occurred rarely and none occurred with three sets of well-developed bands.9 The work at the Pittsfield Works Laboratory on silicon ferrite in the form of large-grained strip steel deformed a small amount and annealed to partially recrystallize the grains indicates that the deformation and recrystallization processes that lead to annealing twins involvc more complex processes than the formation of Neumann bands and the growth of such bands. Some groups of annealing twins are obtained which contain not only three well-developed twin structures, but also contain more than one order of twins. It is also shown, in one case, that an interrelated group of twins did not arise within one single parent grain and, furthermore, orientations of grains in the group

Jan 1, 1944

By M. W. Burkart, B. Lustman

Uranium-base alloys exposed to high temperature water fail either by uniform oxidation or by sudden cracking and disintegration of the metal. The disintegration results from the oxidation of a second phase which is precipitated during the corrosion process. The precipitate has been identified as a metastable hydride of uranium. URANIUM-BASE alloys consisting of the body-centered-cubic ? phase are susceptible to two different modes of corrosion failure when exposed to high temperature water. In the first process, a smooth oxide film is formed on the metal surface which continually flakes off during exposure and results in a uniform weight loss of the specimen. The oxide is present as a thin, adherent layer whose thickness remains approximately constant. As the metal oxidizes during corrosion, a nonadherent layer is built up on this film and continually sloughs off. Coincident with the uniform corrosion just mentioned, another process occurs which eventually leads to failure of the metal by cracking and general disintegration. The failure takes place during a relatively short time compared to the total exposure. To distinguish this type of failure from the uniform corrosion, the cracking or disintegration of the metal will be referred to as discontinuous failure. For the ? phase uranium alloys it is discontinuous failure rather than uniform corrosion that limits the useful corrosion life of the alloy. This paper will be concerned primarily with the mechanism of discontinuous failure. Physical Changes During Corrosion—The alloys used in this investigation were ? phase uranium alloys containing 7 to 12 wt pet Mo or Cb. The preparation of the alloys, the method of corrosion testing, and the actual corrosion results are presented in another paper.&apos; The ? quenching treatment consists of annealing the alloy for 24 hr at 900°C in a sealed Vycor glass tube filled with helium and then water quenching to room temperature without breaking the tube. The corrosion behavior typical of a ? phase uranium alloy is shown in Fig. 1. This specimen was a U-12 wt pet Mo alloy tested in pressurized, degassed water at 650°F. The corrosion rate was practically constant at 0.28 mg per sq cm per hr or increased slightly until about 15 to 20 days of exposure, when the onset of discontinuous failure occurred in this particular sample, and the specimen soon began to crack and disintegrate. The simultaneous increase in the observed corrosion rate is a result of the increased area of exposure due to cracking of the specimen. The microstructure of a specimen that failed by cracking is shown in Fig. 2. The presence of a plate-like precipitate can readily be seen. Metallographic examination of corrosion specimens reveals that the onset of discontinuous failure is always preceded by the formation of a plate-like second phase in the ? uranium matrix. Hydrogen analyses of specimens periodically withdrawn from corrosion test reveal that the hydrogen content of the alloy increases on exposure to the high temperature water, as shown in Fig. 3. The hydrogen is available as a corrosion product resulting from the formation of UO2 by the reaction of the alloy with water. Specimens analyzed just prior to discontinuous failure contained as much as 1200 ppm H, whereas the plate-like phase appears to precipitate out at a hydrogen concentration of between 10 and 25 ppm. The observed increase in hydrogen content prior to and during the formation of the plate-like precipitate suggests that this constituent may be a hydride of uranium. Additional evidence linking the identity of this phase to a hydride is that it can be removed by vacuum annealing at temperatures of 100°C and above. Decomposition products of the ? phase would certainly not dissolve at such temperatures, nor could other likely products of corrosion, such as oxides, be dissipated at any of the test temperatures. The precipitation and growth of the second phase during corrosion is accompanied by an increase in hardness of the specimen. The hardness increase results from the dispersion of the harder precipitated

Jan 1, 1959

By Walter G. Perkins

As this particular product holds a place by itself, it seems desirable to give a paper dealing especially with it as a corollary to my paper entitled " The Litharge Process of Assaying Copper-Bearing Ores and Products, and the Method of Calculating Charges."* The process is first to convert the metallic copper into matte by the addition of sulphur, allowing the two elements to combine at the bottom of the crucible when heat is applied. The

Jan 1, 1903