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By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941

By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941

By R. W. Brown, J. L. Loper

The process of sand erosion has been harnessed to perform a useful function—the directed perforating of oilfield tubular goods and formation rock. In this process the sand is carried by a liquid medium and the resrrlting slurry is forced through a nozzle at an extren~ely high velocity. Upon impingement against casing or formation, the fast-moving sand particles erode a perforalion in the casing followed by cavity formation in the medium behind the casing. The many factors influencing the rate and extent of this penetration are inherently difficult to establish experimentally. Equations describing submerged jet behavior have been applied to these conditions. The following paper develops the equations for predicting the performance of the perforating jet. INTRODUCTION The cutting power of high-velocity sand has been well known in the petroleum industry for many years. Sand carried by a high-velocity gas stream causes severe erosion. This effect has been the cause of numerous production problems in certain areas. It was logical to expect that this phenomenon would one day be adapted to useful industrial applications. Development of mobile, high-pressure, high-horsepower pumping equipment in the last decade has made this possible. The sand erosion process involves pumping a fluid containing abrasive solids through a set of nozzles at a high differential pressure (2,000 to 4,000 psi). The pressure conversion into kinetic energy imparts high velocity to the sand particles which, upon impact with the formation face or casing wall, erode the material in an organized pattern. This paper attempts to establish the effects of the various parameters and to predict the performance and limitations of the process. The following factors will be considered: nozzle differential pressure, perforation size, sand concentration, nozzle stand-off distance and backpressure. In general, this discussion is presented along theoretical lines and is substantiated by field results and data where reliable field data exists. POWER EQUATIONS The penetration rate of a high-velocity hydraulic jet is proportional to the power or energy of the jet at the point in quesion. The power of the submerged jet will decrease with distance (or penetration) into the cavity created by the jet. As the cavity is extended into the formation, the power of the jet diminishes to a value equal to the threshold cutting power of the particular formation which is defiined as the lowest power level at which the formation will be abraded by the jet. Obviously, when this point is reached, no further cutting of the formation can occur. It is assumed that this power level for a particular formation is a function of the hardness of that formation. The following equation can be written for the hydraulic process of formation abrasion.

By R. W. Jenkins

TRACKLESS equipment is being used by the Coplay Cement Manufacturing Co. to develop a folded limestone deposit economically and safely with inexperienced men. Cost and quality of development stone results in a saving when it is used in- stead of outside sources of limestone. This favorable cost has been attained by following a methods development and training program described in this paper. It is expected that further savings in favor of the mined stone will be made when stopes now being prepared are in production. The present equipment will be used for loading from stope draw points. The limestone is blended with quarried cement rock to serve as raw material for Portland cement, first produced in this country by Coplay Cement Manufacturing Co. from a process developed by its president, David 0. Saylor, in 1873. For many years the cement rock alone or with a small amount of added limestone was used for raw materials. Later as specifications were raised and the richer portions of quarries were depleted, limestone from outside sources was required in increasing amounts. In 1925 D. J. Uhle, the general manager, began to prospect company property for limestone.

Jan 1, 1954

By C. H. Mathewson, A. U. Seybolt

As is well known, many questions affecting the properties and uses of a metal cannot be answered without careful consideration of the state of purity realized in the various operations of preparation, refining, or special treatment that have brought the product to its final state. The occurrellce of an impurity in minute quantity offers no guarantee that its effect will be inconsiderable because dissolved substances often modify the properties of a metal quite out of proportion to their concentration. In such cases the determination of solid solubility must be accepted as a problem of considerable difficulty, requiring the use of especially purified materials and methods not ordinarily used in the metallurgical laboratory. This aspect of the equilibrium between metals and their oxides is especially important and a search for fundamental data reveals little except conflicting opinion even concerning the systems of common occurrence and interest. Rhines and Mathewson1 in 1934 studied the solubility of oxygen in solid copper by annealing to equilibrium in air and gave reasons for the failure of other methods, notably the ordinary procedure of heat-treatment followed by microscopic examination, to yield reliable results. In this paper, a similar study has been made of the solubility of oxygen in cobalt. The simple theory of this method is outlined below. Conditions of Equilibrium between a Metal and Dissolved Oxide at Different Temperatures and Pressures The general conditions of equilibrium in any system are conveniently summarized in a projection of the triple curves of the P, T, X space

Jan 1, 1935

By A. U. Seybolt, C. H. Mathewson

As is well known, many questions affecting the properties and uses of a metal cannot be answered without careful consideration of the state of purity realized in the various operations of preparation, refining, or special treatment that have brought the product to its final state. The occurrellce of an impurity in minute quantity offers no guarantee that its effect will be inconsiderable because dissolved substances often modify the properties of a metal quite out of proportion to their concentration. In such cases the determination of solid solubility must be accepted as a problem of considerable difficulty, requiring the use of especially purified materials and methods not ordinarily used in the metallurgical laboratory. This aspect of the equilibrium between metals and their oxides is especially important and a search for fundamental data reveals little except conflicting opinion even concerning the systems of common occurrence and interest. Rhines and Mathewson1 in 1934 studied the solubility of oxygen in solid copper by annealing to equilibrium in air and gave reasons for the failure of other methods, notably the ordinary procedure of heat-treatment followed by microscopic examination, to yield reliable results. In this paper, a similar study has been made of the solubility of oxygen in cobalt. The simple theory of this method is outlined below. Conditions of Equilibrium between a Metal and Dissolved Oxide at Different Temperatures and Pressures The general conditions of equilibrium in any system are conveniently summarized in a projection of the triple curves of the P, T, X space

Jan 1, 1935

By E. N. Pennebaker

A PRESENT, a comprehensive account of the geology and ore deposits of the Robinson mining district, in eastern Nevada, is not warranted. Though several years' work has been done, the district is so large that it will be some time before the investigation nears completion. In this paper I purpose merely to discuss methods of study and the application of geologic data to the search for ore. In the first place, the purpose of a geological depart¬ment in a mining organization is to collect and correlate all geologic and engineering data likely to be useful. In an extensive and well developed mining camp this involves a detailed study of the structure and stratigraphy of the district as a whole, as well as careful analysis of the orebodies exposed. The problem then is to find continuations or similar ore environments in other parts of the district in which like phenomena have been active, and to explore these for new orebodies. Experience gained in other similar mining districts is useful but one must always remember that a great many mining districts are unique and that exploration rules and procedure applying to one cannot always be transferred to another of apparently similar character and be made to work. One also has to be careful in moving from one to another part of the same district. The geologist must first examine the region critically to determine its individual characteristics. .

Jan 1, 1932

NEW MEMBERS The following list comprises the names of those persons Who became members during the period July 10, 1918, to Aug. 10, 1918. ARCHER, EUGENE G., assayer and Chem., Granby Cons. Min. Smelt. & Power Co.,Anyox, B. C., Canada. BAKER, ROBERT C Mech. Engr. and Draftsman, Moctezuma Copper Co., Nacozari, Son., Mexico. BARNES, EDWARD A Supt., Fort Wayne Works, General Electric Co., Fort Wayne, Ind. BARNHART, EDWIN Engr. of Tests, Bethlehem Steel Co., Sparrow's Point, Md. BENSLEY, MAURICE D Pres. and Mgr., Frontier Brass Foundry, Inc., Niagara Falls, N. Y. BRADLEY, JOHN C Met., The American Brass Co., Waterbury, Conn. BRAGG, C. T Works Mgr., Michigan Smelt. & Refin. Co., Detroit, Mich. BRYMER, GEORGE W Min. Engr., 922 Union National Bank Bldg., Scranton, Pa. CHIVVIS, NORMAN Met. Engr., More-Jones Brass & Metal Co., 3144 North Broadway, St. Louis, Mo. CRAWFORD, R. D Prof. of Mineralogy & Petrology, Univ. of Colorado, Boulder, Colo.

Jan 9, 1918

By H. W. Hindry

This paper presents the ingredients com-~osing a type of oil-base mud that has been successfully used in drilling oil horizons in California, the effect of ingredient concentrations on physical properties, methods of handling at the well and possible advantages of a waterless drilling fluid with excellent plastering properties. Introduction An oil-base mud is a rotary drilling fluid in which oil has been substituted for water as the principal liquid ingredient. In recent years such a mud has been developed and used successfully for drilling the oil horizons of wells in various Calilornia fields. There are several types of oil-base mud, but only the type that is currently used to any appreciable extent will be considered at this time. The oil-base drilling-mud compositions used by Shell Oil Company, Incorporated have been covered by several patent applications on which patents are expected to issue at an early date. The purpose of this paper is to present data on the fundamental design of the mud; the ingredients used and their specifications; the effect of ingredient concentration on physical properties; the selection of the proper mud; the facilities needed for handling the mud; and a general discussion on drilling with oil-base mud. In view of the early stage of development of oil-base mud, the great number of vari- ables, and the almost unlimited possible combinations of these. variables, which in turn require extensive laboratory study, there are certain irregularities and omis. sions in the data presented here. However, it is believed that sufficient data are at hand to permit a fairly complete analysis of the characteristics of oil-base muds. In view of the excellent plastering properties of oil-base mud when properly proportioned, its use should: (I) minimize the possibility of impairing the natural flow potentialities of the producing horizon such as that resulting from infiltration of water from water-base muds; (2) permit smaller clearances for setting liners, since the mud sheath has no appreciable thickness; (3) eliminate the possibility of clogging the perforations of the liner with thick mud sheath; (4) facilitate the removal of the mud sheath from the walls of the hole, for its mud sheath has no appreciable strength; (5) assist in drilling through formations, such as "heaving shale," where water wetting appears to be a source of difficulty. (6) permit cores to be obtained without contamination from drilling water. Fundamental Design of an Oil-base Mud In the design of any rotary drilling mud it is necessary to select materials that will fulfill the following requirements: (I) act as the liquid medium and regulate the viscosity; (2) impart initial and final plastering properties; (3) give gel strength and structure in order to prevent settling; (4) serve as a weighting material. The

Jan 1, 1941

By H. W. Hindry

This paper presents the ingredients com-~osing a type of oil-base mud that has been successfully used in drilling oil horizons in California, the effect of ingredient concentrations on physical properties, methods of handling at the well and possible advantages of a waterless drilling fluid with excellent plastering properties. Introduction An oil-base mud is a rotary drilling fluid in which oil has been substituted for water as the principal liquid ingredient. In recent years such a mud has been developed and used successfully for drilling the oil horizons of wells in various Calilornia fields. There are several types of oil-base mud, but only the type that is currently used to any appreciable extent will be considered at this time. The oil-base drilling-mud compositions used by Shell Oil Company, Incorporated have been covered by several patent applications on which patents are expected to issue at an early date. The purpose of this paper is to present data on the fundamental design of the mud; the ingredients used and their specifications; the effect of ingredient concentration on physical properties; the selection of the proper mud; the facilities needed for handling the mud; and a general discussion on drilling with oil-base mud. In view of the early stage of development of oil-base mud, the great number of vari- ables, and the almost unlimited possible combinations of these. variables, which in turn require extensive laboratory study, there are certain irregularities and omis. sions in the data presented here. However, it is believed that sufficient data are at hand to permit a fairly complete analysis of the characteristics of oil-base muds. In view of the excellent plastering properties of oil-base mud when properly proportioned, its use should: (I) minimize the possibility of impairing the natural flow potentialities of the producing horizon such as that resulting from infiltration of water from water-base muds; (2) permit smaller clearances for setting liners, since the mud sheath has no appreciable thickness; (3) eliminate the possibility of clogging the perforations of the liner with thick mud sheath; (4) facilitate the removal of the mud sheath from the walls of the hole, for its mud sheath has no appreciable strength; (5) assist in drilling through formations, such as "heaving shale," where water wetting appears to be a source of difficulty. (6) permit cores to be obtained without contamination from drilling water. Fundamental Design of an Oil-base Mud In the design of any rotary drilling mud it is necessary to select materials that will fulfill the following requirements: (I) act as the liquid medium and regulate the viscosity; (2) impart initial and final plastering properties; (3) give gel strength and structure in order to prevent settling; (4) serve as a weighting material. The

Jan 1, 1941

By Herbert H. Kellogg

C. M. Decroly (University of Brussels, Belgium) — The importance of the fluorides in the process metallurgy of special metals has already been accepted and it will probably increase in the future. Free energy diagrams as such established by Professor Kellogg are therefore very useful. It is interesting to note that the absolute value of the standard free energy of formation of HF increases with temperature, whereas for almost all the other fluorides it decreases; consequently it should be theoretically possible to reduce all the fluorides of the metals which, at low temperature, have a greater affinity for fluorine than hydrogen by this last element, provided a sufficiently high temperature is used in order to have a good efficiency. However, with regard to the reduction of UFe by hydrogen, I doubt that it will be possible to obtain directly the metal at comparatively low temperatures. There are other uranium fluorides which are more stable than UF6 and it is very likely that such fluorides will be obtained first. For example, in considering the reaction: UF6gas + H2gas + UF1so1id + 2 HFgas it is found, using the thermodynamic data of Brewer et al, that ?H298 = —66 kcal and ?G°298, = —65.2 kcal. As a result, the reduction of UF6 to UF4solld should proceed spontaneously even at ordinary temperature. On the other hand, the standard free energy of formation of UF4solid at 298°K is AG°298 = -209 kcal per mol of F2. The reduction of UF4 by hydrogen will be practically difficult and, as it is known, the only practical way of reducing this compound is to use alkaline-earth metals such as calcium or magnesium. I should like to point out, further, that the fluorination of many metal oxides can be carried out very easily by using the ammonium difluoride method of preparation, which renders the use of fluoride gas unnecessary. The first compound formed is generally a double fluoride of the metal and ammonium. This compound can be decomposed by heating either in a vacuum or in an inert atmosphere, ammonium fluoride being volatilized leaving the metal fluoride in a very pure state. H. H. Kellogg (author's reply)—Professor Decroly is quite right in pointing out that the formation of lower halides of uranium may complicate the reduction of UF6 by H2. I was unable to find his reference to the free energy of formation of UF4 in the compilation of Brewer.13 however. The value of AG°298, = —209 kcal for formation of ½ UFa seems rather high, and I hope the source of this value may be made clear.

Jan 1, 1952

By R. B. Mears, E. H. Dix, R. H. Brown

In the Institute of Metals Division Lecture of 1940, E. H. Dix, J~.(I)~ discussed the acceleration of the rate of corrosion by high constant stresses. Experimental data obtained on this subject at the Aluminum Research Laboratories and a theory compatible with these facts were included in that lecture. The present paper contains data and ideas subsequently developed at the Aluminum Research Laboratories. Dix pointed out that in order for acceleration of corrosion by constant stress to occur: (1) There must exist in the alloy a susceptibility to selective corrosion along more or less continuous paths, as for in- stance at grain boundaries, and (2) There must exist a condition of high stress acting in a direction tending to pull the metal apart along these continuous paths. Acceleration of corrosion rate by stress is not confined to any one alloy system. Table I lists some of the metals and alloys and some of the corroding environments in which acceleration of corrosion by stress was sufficient to cause cracking (stress- corrosion cracking). It will be noted that the variety of alloys in which stress-corrosion cracking has occurred is rather large. Also, it will be observed that

Jan 1, 1945

By E. M. Norris

DURING the winter and spring of 1917, an unprecedented number of underground fires occurred in the Butte district. With one exception, these fires were caused by the failure of electrical equipment, and called attention to the increased fire hazard in underground mining operations occasioned by the extensive use of electricity. Five local conditions that contributed toward a heavy fire risk were (1) The heavy continuous timbering necessary for mine supports; (2) the strong ventilating pressures in the shafts and main airways; (3) the subsidence and faulting movements in the country rock, which ruptured cables and displaced trolley and lighting wires; (4) the strongly acid mine waters, which quickly developed any weak points in the electrical insulation;(5) oxidation in old stopes containing large amounts of timber. In the summer of 1917, a comprehensive plan of fire prevention was begun by the Anaconda Copper Mining Co., which involved a thorough and intensive development of the preventive measures then in use. These were as follows: Fireproofing, remodeling and strengthening electrical insulations, extension of underground water system, control of ventilation, maintaining efficiency of fire-fighting crews, and reorganization of fire patrol.

Jan 2, 1922

By J. Weertman

High-temperature creep experiments were carried out on indium, lead, and on binary substitutional alloys of In-Pb, In-Sn, In-TI, In-Cd, In-Hg, Pb-Bi, Pb-Sn, Pb-In, and Pb-Cd. The stress at which the power law creep equution breaks down was found to be much smaller for indium and lead than for metals with larger elastic moduli. The exponent over the stress in the power law creep equation was found to decrease upon alloying from values close to 4.5 to values near 3. THIS paper describes a set of high-temperature creep experiments made on high-purity lead and indium and on lead-rich and indium-rich single-phase binary alloys of various metals. These ex- periments were carried out to check two predictions of some creep equations derived by us"2 from a dislocation creep model due essentially to Mott. This model is shown in Fig. 1. Here dislocation loops are emitted from sources, not shown, situated on different slip planes. As the loops expand they come into each others' stress fields and are stopped. However, at high temperatures, as Mott has pointed out.

Jan 1, 1961

By R. L. Moment

The anisotropic elastic behavior of rolled beryllium sheet has been measured, using a pulse echo technique, and compared with X-ray diffraction data. Calculated elastic stiffness constants compared favorably with published values for beryllium single crystals which were attributed to the strong (0002) rolling plane texture. Variations of Young's modulus in the yolling plane could be associated with the velative distribution of (0002) planes out of their ideal position in the rollitzg pkule. WHEN a metal is subjected to cold working such as drawing, forming, or rolling, a crystallographic texture develops which can significantly alter its physical properties. One method for detecting this texture is X-ray diffraction, but Alers and Liu' have recently pointed out how the prediction of anisotropic physical properties from pole figures alone is not always accurate due to differences in interpretation. Variations in Young's modulus with orientation or, more completely, the values of the effective elastic constants of the worked metal, also serve to indicate the presence of a texture. In fact, as Alers and Liu' pointed out, calculated variations in Young's modulus for assumed orientations, when compared with experimental data, can be used to eliminate some of the uncertainty in interpretation of X-ray pole figures. Thus, elasticity measurements can serve not only to clarify any unusual elastic behavior of worked metal, but also to detect and in part determine the nature of its texture. X-ray determination of the texture of rolled beryllium has been reported by Smigelskas and Barrett,2 who found a strong texture of (0002) in the rolling plane with (1070) planes normal to the rolling direction. In the case of metal rolled at room temperature, they reported that [1010] directions also appeared at positions 60 and 120 deg from the rolling direction in the rolling plane, while in more recent work Keeler3 found these directions were also tilted towards the rolling plane. The texture for beryllium rolled at 80O0C, however, only showed (1010) planes normal to the rolling direction and the spread of (0002) planes out of the rolling plane was less. In looking for elastic anisotropy one might consider unidirectional rolling of a metal as introducing an or-thorhombic symmetry through reorientation of the grains, since the three deformations, compression, extension in the rolling direction, and extension in the cross direction, are orthogonal to each other and unequal in magnitude. Thus the rolled sheet could be treated like an orthorhombic single crystal and the nine stiffness constants of the elasticity tensor used to calculate the anisotropy of Young's modulus, the shear modulus and Poisson's ratio. In this case we could write: which is symmetric about its diagonal. Borik and Alers4 have recently used this approach on rolled die steel with very good results. They found, however, that instead of displaying orthorhombic elastic symmetry their specimens could be considered tetragonal in which case Cr1 = c22, c13 = Ca, and c44 =cjj. This conclusion was made solely on the basis of the measured tensor elements, and serves to point out the advantage of this method for studying the anisotropy of rolled metals. Their calculated values for Young's modulus as a function of angle in the rolling plane also checked very well with direct measurements made on different specimens using the resonance technique. In the present study, cross-rolled beryllium was used which had been unidirectionally rolled about 11 pct for the final reduction. This imparted a slight anisotropy in the rolling plane which was detected both by X-ray techniques and elasticity measurements. For purposes of discussion in this paper, the rolling direction is that direction in which the most reduction passes were made and cross direction is the normal to the rolling direction in the rolling plane. It was also decided to consider the rolled sheet as displaying orthorhombic symmetry for the purpose of obtaining elasticity samples with the direction defined as in Table I. Any change in the final symmetry attributed to the sheet would then be made on the basis of the measured elastic stiffnesses. The final data would then be compared with that expected from the X-ray study and that reported for beryllium single crystals. EXPERIMENTAL PROCEDURE Rolling Schedule. The samples used in this study were taken from a large sheet which, because of its size, had to be unidirectionally rolled for the final reduction. The resulting texture was that of cross-rolled metal with a slight unidirectional texture superimposed. A cast beryllium ingot, 9.500 in. sq by 3.325 in. thick, was cross-rolled to 81 pct reduction followed by unidirectional rolling for an additional 11 pct to give a total reduction of 92 pct. The thickness of the final sheet ranged from 0.265 to 0.280 in. Reduction up to 67 pct was done at 980°C and the final 25 pct at 870°C. Analysis for metallic impurities showed aluminum 0.06 pct, iron 0.19 pct, and silicon 0.11 pct, giving a beryllium purity of 99.64 pct.

Jan 1, 1968

By E. A. Gulbransen, K. F. Andrew

The gas-metal reactions of zirconium are very interesting. The metal is extremely stable at room temperature to reactions with the several gases present in air and the metal will stay bright indefinitely. However, at temperatures of several hundred degrees higher the metal reacts readily with oxygen, nitrogen and hydrogen. This behavior, in addition to the fact that zirconium is one of the higher melting point metals which might have high temperature applications under the proper conditions, resulted in the work reported in this communication. There are several factors which indicate that zirconium might have good oxidation resistance at elevated temperatures. These are: (1) the high melting point of approximately 1860°C, (2) the high melting point of the oxide of approximately 2675°C, (3) the high degree of thermodynamic stability of the oxide to chemical reaction and the low decomposition pressure of the oxide and (4) the possible formation of a continuous oxide film since the volume ratio of oxide to metal is greater than unity. The unfavorable factors are: (1) the metal reacts to form nitrides, hydrides and carbides, (2) the oxide is soluble at elevated temperatures in the metal and (3) the oxide ZrO2 undergoes crystal structure transformations at high temperature. The oxidation resistance of this metal is not only a question of the rate of film formation but is complicated by the fact that the oxide and other reaction products dissolve in the metal which in turn will affect the physical and mechanical properties of the metal. The protection of the metal to nitride formation must be considered separately from the oxide problem. One unfavorable factor is that the volume ratio of the nitride to the metal is about unity. This indicates that a discontinuous film might be formed. This paper will present measurements on the rates of reaction of the metal with O2, H2 and N2 over a wide temperature and pressure range. The reaction in high vacuum and the stability of the several compounds formed will be presented. The results are correlated with fundamental rate theory and with the physical and chemical structure of the metal and film. Literature Although many papers have been published on the chemical reactions of zirconium with various gases, comparatively few are concerned with the protective nature of the metal and its reactions at normal pressures. The studies in the pressure range below 0.01 mm of Hg gas pressure are largely of interest in the nature of the adsorption of gases by hot filaments in high vacuum apparatus. The reactions of zirconium in this pressure range have been reviewed by Fast8 and by RaynOr.27 In spite of certain differences of opinion as to the maximum adsorption temperatures for various gases, the low pressure range is qualitatively understood. Some of these papers will be mentioned briefly here. 1. LOW PRESSURE Ehrke and Slack' find that oxygen reacts above 885°C and hydrogen above 760°C. Nitrogen does not react up to a temperature of 1527°C. Fast9 on the other hand observes that oxygen is absorbed above 700°C and nitrogen at temperatures exceeding 1000°C. Hydrogen is absorbed from 300" to 400°C and liberated between 500" and 800°C. It is readsorbed at 862°C and released above 862°C. Hukagawa and Nambo22 find a rather complicated picture for the absorption of oxygen. A rapid initial absorption is found between 180" to 230°C. Further oxygen is not taken up until a temperature of 450°C is reached. The optimum temperature for complete absorption is 650" to 700°C. Nitrogen is found to be completely adsorbed at 600°C. However some of the gas is evolved at higher temperatures. Their data on the absorption of hydrogen indicate some of the gas is removed at 550°C. Guldner and Wooten17 in a study of the low pressure reactions of zirconium with various gases observed that the reaction with oxygen occurs at temperatures above 400°C and that the oxide is formed. The reactions with carbon monoxide and carbon dioxide occur rapidly at temperatures of about 800°C with the oxide and carbide being formed. Zirconium reacts at temperatures of 400°C slowly and at 800°C rapidly to form the nitride and with hydrogen and water at 300°C to form the hydride and a mixture of the oxide and hydride respectively. 2. NORMAL PRESSURE DeBoer and Fast3 in a study of the electrolysis of oxygen in zirconium find that the metal absorbs up to 40 at. pct of oxygen without forming a new phase. The solubility of nitrogen in the lattice has been studied by de Boer and Fast4 and Fast10 and is found to be considerable. At higher temperatures the oxide dissolves in the lattice at an appreciable rate according to Fast10 and the zirconium surface becomes active. De Boer and Fast4 and Hägg18 have studied the solubility of hydrogen and find that at room temperature the solubility corresponds to ZrH1.95 Desorption occurs on lowering the pressure. Hydrogen is stated to be more soluble in the ß-form and the

Jan 1, 1950

By B. C. Wonsiewicz, W. W. Wilkening

Following a procedure proposed by Wheeler and Ireland, Plane stress yield loci were constructed from Knoob hardness numbers. Basically, six differently oriented hardness measurements were made on three orthogml surfaces through pure poly crystalline magnesium sheet, a magnesium single crystal, and sheet of the magnesium alloys: Mg + 0.5 pct Th, Mg + 4 pct Li, AZ31B, and EKOO. Hardness loci were found to be in poor agreement at small strains (E < 0.05) with loci established by a more rigorous technique. At larger strains (E - 0.10) the agreement is fair, but at this stage in deformation the conventional locus has lost much of the asymmetry that characterizes these anisotropic materials. Two effects which will lead to distortions in the Khn locus are discussed with reference to the geometry of plastic flow during a hardness test. DETERMINING a material&apos;s resistance to multiaxial loading is of interest not only from a structural design viewpoint but also from that of deformation processing. Unfortunately, the determination of the yield locus, although simple in principle, involves tedious procedures if the results are to be at all rigorous.&apos; The idea, first proposed by Wheeler and 1reland2 of determining the yield locus by means of six Knoop hardness impressions along the principal directions in a material has obvious appeal. It is simple, quick, and should be applicable to very thin sheets. If such a technique could be demonstrated to produce consistently reliable results, it would be of interest to both researcher and designer. Lee, Jabara, and ackofen have compared the yield locus determined by Knoop hardness measurements (the Khn locus) to a locus determined by more rigorous techniques. They found good agreement for two titanium alloys at a plastic strain of about 1 pct. The purpose of this paper is to investigate if the Khn locus construction is a reasonable approximation to the locus of a highly anisotropic material. Examples of such materials are magnesium and magnesium alloys which have severely distorted yield loci which in turn reflect markedly dfferent yield strength in different directions.&apos; In pure magnesium, for example, the yield stress in tension along the transverse direction may be four times the yield stress in compression in the same direction and twice the tensile yield stress in the rolling direction. Predicting such large differences ought to serve as a severe test of the Khn locus construction. EXPERIMENTAL PROCEDURES Samples of rolled sheet, 0.250 in. (6.35 mm) thick, of pure magnesium and four magnesium alloys (Mg experimental materials. The pure magnesium together with the lithium and thorium alloys were those used in the study of Kelley and Hosford. The grain size was ASTM number 4 for the pure magnesium and number 6 for the alloys. HARDNESS TESTING The materials were sectioned along the rolling and transverse planes, mounted in a quick setting resin, and mechanically polished. Most of the hardness tests were performed on a surface prepared by electro-polishing (30 pct nitric acid in methanol at 0°C and 20 v) with the exception of the AZ31B and EK00 alloys which were made directly on a metallographically polished surface. However, subsequent hardness tests on the same sample after heavily electropolishing, revealed essentially the same hardness as before. At least twenty Knoop hardness impressions under a 100-g load were made in each of the six orientations shown in Fig. 1. The average hardness number and standard deviation were then calculated for each orientation. CONVENTIONAL LOCUS CONSTRUCTION Yield loci were constructed using a technique described in detail by Lee and ackofen,&apos; in which the flow stress (stress at a given plastic strain) fixes the coordinates of a point on the locus and measurements of the strain ratio serve to establish the slope of the locus at that point. The loading paths which correspond to uniaxial tension or compression tests establish the four intercepts of the locus with the coordinate axes plus one point on the balanced biaxial tension line Tensile testing was performed along the rolling and transverse (r, t) directions. Samples had a uniform rectangular gage length 1 by 4 by 4 in. (25.4 by 6.35 by 6.35 mm) and were deformed at a strain rate of 3.33 x 104 sec-&apos;. The tests were interrupted periodically to unload the sample and measure the plastic strains by means of X-Y post yield strain gages. Compression tests in the rolling, transverse, and through-thickness (r, f, z) directions were performed on 1/4 in. (6.35 mm) cubes at an initial strain rate of 8.33 x sec-&apos;. Lubrication was provided by 0.002 in. (51 pm) Teflon sheet which was renewed after unloading for micrometer measurements used to calculate the strains.

Jan 1, 1970

By R. W. Fenn, H. A. Lepper, W. R. Hibbard

THIS paper reports the results of static tension and torsion tests made on single crystals of alpha brass for the purpose of determining its elastic coefficients. 70-30 alpha brass was chosen because it has been used extensively in the study of the plastic deformation and because it has the following desirable characteristics: (1) face-centered cubic structure, (2) marked elastic anistropy, (3) low elastic modulus. In 1928 Masima and Sachs&apos; using static methods reported the following values for the elastic coefficients of 72-28 pct alpha brass: S11 = 19.4 X 10-13&apos; cm2 per dyne S12 = —8.35 X 10"&apos; cm2 per dyne S44 = 13.9 X 10-13= cm2 per dyne These values were obtained from the measurements shown in fig. 1. The experimental points for both tension and torsion lie consistently below the lines drawn to represent them. Fig. 2 shows the stress-strain curves for their specimens. Only a few points in the elastic range of these curves were available to obtain their values for Young&apos;s modulus. Therefore, it was considered that a re-evaluation of these data was desirable. In addition a variation of from 1.13 to 1.485 kg per mm2 was found in the values of the critical resolved shear stress for 70-30 alpha brass reported by Burghoff,² Treuting and Brick: Martin,4 Maddin, Mathewson and Hibbard5,6 and von Goler and Sachs.&apos; Therefore, it was desired to evaluate the conclusion of Boas and Schmid8 that a constant resolved shear stress and not a constant elastic shear initiates plastic deformation. Theoretical Considerations*: The elastic deformation of cubic crystals may be defined by three elastic coefficients (S11, S12, S44,) or three elastic parameters (C,,, C,, C,,). These coefficients or parameters are sufficient to define the stress and strain relations for cubic crystals in the generalized form of Hooke&apos;s law referred to Cartesian coordinates. Elastic parameters and coefficients in the cubic system are related by the expressions: C11 —S11+S12/(S11-S12)(S11+2 S12) C12=-S12/(S11-S12)(S11+ 2 S12) (S11 — S12) (S11 + 2 S12) [2] C44 =1/S44 PI It is possible to determine all the elastic coefficients for a cubic metal by measuring two of the three elastic constants: Young&apos;s modulus (E), torsion modulus (G), or compressibility (S). The following relations exist between crystallographic orientation and E, G and S for cylindrical crystals of the cubic system: 1/E = S11 — 2 [(S11 - S12) — Su] (?1² ?2² + ?2²?83 + ?3² ?1²) [4]

Jan 1, 1951

By W. H. Geis

The following pages summarize the causes that led to the suggestion of unit operation of the paloma field, the organization of com-mittees, preparation of the Paloma Operators Agreement and the reasons for rejection of the plan. Introduction Long ago an Austrian physicist observed that under certain conditions the condensation of a liquid from gaseous mixtures resulted from pressure reduction. Some 50 years later he would have known that his research was not in vain. He would have seen a group of serious operators and engineers seeking to apply that principle to a conservation . program for unitized production in the Paloma gas field—but he would also have been saddened to see that forces unsympathetic to the application of science in oil production, with little or no appreciation of modern methods and the advantages of cooperation, so far have prevented the adoption of that program. Soon after the Paloma field was discovered it was realized that all the hydrocarbons in the reservoir existed in the gaseous phase. This condition was confirmed over a large area. Therefore, if the field was to be properly exploited with the greatest ultimate recovery of condensate, the hydrocarbons in the reservoir must be produced in the single or gas phase. They must be cautiously extracted with the least possible reduction of the natural pressure. If this could be accomplished, or if artificial pressure control were utilized, the condensation and underground loss of the valuable distillate would be preventable—otherwise it would not be. Wholehearted cooperation of all oper-ators was required in order to accomplish the conservation purposes of the program. To this end the production engineers of the several companies concerned lent their time and talents. They fully investigated the physical relationships of the products within the complicated gaseous mixture, prepared extensive reports on the subject and drew up a reasonably efficient plan of operations, which now is commonly called the "Paloma Unit Plan" but actually was entitled "The Paloma Operators Agreement." All of the engineers were not in perfect agreement on all the features of the plan, or even on all the engineering principles. However, it is safe to say that on all the important or essential factors there was a unanimity of opinion, particularly as to the objectives. These were fairly simple and reduce to one controlling item, "pressure control" by cycling or recycling. Organization The principal operators initiated the program by calling a meeting of all the lessees in the area, at which an organization was perfected, known as the "Paloma Operators Committee." Various subcommittees were appointed to expedite the work, including an "Engineering Committee." These func-tioned in a businesslike manner, frequently reported to the superior committee and

Jan 1, 1942

By W. H. Geis

The following pages summarize the causes that led to the suggestion of unit operation of the paloma field, the organization of com-mittees, preparation of the Paloma Operators Agreement and the reasons for rejection of the plan. Introduction Long ago an Austrian physicist observed that under certain conditions the condensation of a liquid from gaseous mixtures resulted from pressure reduction. Some 50 years later he would have known that his research was not in vain. He would have seen a group of serious operators and engineers seeking to apply that principle to a conservation . program for unitized production in the Paloma gas field—but he would also have been saddened to see that forces unsympathetic to the application of science in oil production, with little or no appreciation of modern methods and the advantages of cooperation, so far have prevented the adoption of that program. Soon after the Paloma field was discovered it was realized that all the hydrocarbons in the reservoir existed in the gaseous phase. This condition was confirmed over a large area. Therefore, if the field was to be properly exploited with the greatest ultimate recovery of condensate, the hydrocarbons in the reservoir must be produced in the single or gas phase. They must be cautiously extracted with the least possible reduction of the natural pressure. If this could be accomplished, or if artificial pressure control were utilized, the condensation and underground loss of the valuable distillate would be preventable—otherwise it would not be. Wholehearted cooperation of all oper-ators was required in order to accomplish the conservation purposes of the program. To this end the production engineers of the several companies concerned lent their time and talents. They fully investigated the physical relationships of the products within the complicated gaseous mixture, prepared extensive reports on the subject and drew up a reasonably efficient plan of operations, which now is commonly called the "Paloma Unit Plan" but actually was entitled "The Paloma Operators Agreement." All of the engineers were not in perfect agreement on all the features of the plan, or even on all the engineering principles. However, it is safe to say that on all the important or essential factors there was a unanimity of opinion, particularly as to the objectives. These were fairly simple and reduce to one controlling item, "pressure control" by cycling or recycling. Organization The principal operators initiated the program by calling a meeting of all the lessees in the area, at which an organization was perfected, known as the "Paloma Operators Committee." Various subcommittees were appointed to expedite the work, including an "Engineering Committee." These func-tioned in a businesslike manner, frequently reported to the superior committee and

Jan 1, 1942