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By L. S. Richardson, N. J. Grant

Iodide-grade titanium, two oxygen alloys, and two aluminum alloys were studied by means of creep-rupture tests from 1000° to 2000°F. From the test information an evaluation was made of, 1) the relative creep-rupture strengths of the u (hexagonal-close-packed) and 0 (body-centered-cubic) forms of titanium and some of its alloys; 2) the effects of solid-solution strengthening by oxygen and aluminum on the u and 0 structures; and 3) the extent and effect of atmospheric oxygen alloying on rupture life in tests above about 1000°F. THE use of titanium alloys at temperatures above 1000° F has been considered unlikely by most investigators because of low creep strength (based on a requirement for room-temperature ductility, formability, and weldability) and low oxidation resistance. The results of this testing program do not entirely uphold this pessimism in terms of strength and oxidation resistance. The observations described below are based entirely on stress-rupture results, although some creep tests were also carried out on these alloys. Three items of primary importance are covered: 1) Stress-rupture data in the form of the Larson-Miller parameter curves for several titanium alloys at temperatures up to 2000°F; 2) The relative strengths of the hexagonal-close-packed a structure and the body-centered-cubic 0 structure; 3) The effects of solid-solution alloying on the creep-rupture properties of titaniu'm at elevated temperatures. Only two investigatons have reported the creep- rupture properties of titanium at temperatures above 1000° F. Lunsford and rant' tested iodide titanium; their values are also utilized in the paper. EXPERIMENTAL PROCEDURE After a few tests had been made in a conventional creep-rupture test machine, it became clear that some sort of atmospheric protection would be necessary for short-time tests conducted at temperatures above 1600°F, or for times greater than 100 hr at 1200°F or above. Several furnace units and test machines were constructed, the most successful of which is shown in Fig. 1. Certain experimental difficulties peculiar to titanium were encountered; for example, the use of molybdenum holders was dictated because titanium forms low melting-point eutectics with conventional high-temperature alloys containing appreciable amounts of iron, nickel, or cobalt. This same difficulty made the use of chrome l-alumel thermocouples in direct contact with a test specimen impossible, above about 1500" F. The high-temperature high-vacuum furnace shown in Fig. 1 was capable of maintaining a vacuum of better than 10"5 mm of mercury at 2000°F (pressure measured in cold part of system) and 5 X lo-' mm at room temperature. Most of the tests eonducted in vacuum were at temperatures

Jan 1, 1960

By John E. Sherborne

Much valuable scientific research has been performed in recent years on the subject of phase behavior of hydrocarbons.l-11 Engineers employed in petroleum production are interesting themselves in this work as well as in methods of applying the fundamental data available to the solution of their various problems. Recently a number of papers have been published in which applications of phase behavior have been made to specific cases pertaining to critical phenomena.l2-16 Little effort, however, has been made in the literature to show the relation between changes occurring in the critical region and the more common phase behavior, therefore it is believed that a presentation of the fundamentals of phase behavior with reference to hydrocarbons is timely. Study of phase behavior is not new. In the metallurgical field, knowledge of heterogeneous equilibria has advanced tremendously, particularly with reference to solid-solid and solid-liquid behavior. Much is known about vapor-liquid equilibria too, but few engineers are familiar with this subject. Definition of Terms In a discussion of this sort, a definition of terms used is most important. Such terms as "pressure," "temperature" and "volume" need little definition other than mention of the units in which they are considered. Pressure is expressed in pounds per square inch absolute. Temperature is usually expressed as degrees Fahrenheit or degrees Rankine. In considering thermodynamic and phase behavior, the use of the absolute, Rankine, scale is desirable. Volume is expressed as specific volume, such as cubic feet per pound. This will be recognized as the reciprocal of the specific weight. In considering systems composed of more than one component, it is sometimes desirable to consider molal

Jan 1, 1940

By John E. Sherborne

Much valuable scientific research has been performed in recent years on the subject of phase behavior of hydrocarbons.l-11 Engineers employed in petroleum production are interesting themselves in this work as well as in methods of applying the fundamental data available to the solution of their various problems. Recently a number of papers have been published in which applications of phase behavior have been made to specific cases pertaining to critical phenomena.l2-16 Little effort, however, has been made in the literature to show the relation between changes occurring in the critical region and the more common phase behavior, therefore it is believed that a presentation of the fundamentals of phase behavior with reference to hydrocarbons is timely. Study of phase behavior is not new. In the metallurgical field, knowledge of heterogeneous equilibria has advanced tremendously, particularly with reference to solid-solid and solid-liquid behavior. Much is known about vapor-liquid equilibria too, but few engineers are familiar with this subject. Definition of Terms In a discussion of this sort, a definition of terms used is most important. Such terms as "pressure," "temperature" and "volume" need little definition other than mention of the units in which they are considered. Pressure is expressed in pounds per square inch absolute. Temperature is usually expressed as degrees Fahrenheit or degrees Rankine. In considering thermodynamic and phase behavior, the use of the absolute, Rankine, scale is desirable. Volume is expressed as specific volume, such as cubic feet per pound. This will be recognized as the reciprocal of the specific weight. In considering systems composed of more than one component, it is sometimes desirable to consider molal

Jan 1, 1940

By J. W. Hickman

INTRODUCTION MOST of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.1 In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,2 nickel,2 chromium ,2 Copper2, tungsten,3 molybdenum,3 beryllium ,4 uranium,4 thorium4 titanium5 and zirconium5 while investigations are in progress on tantalum and columbium, The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single, phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally, Examples of solid solutions which may present difficulties are MoO2 and W02, Fe3O4 and FeO-Cr2O3 since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of log10 KR for the several temperatures. [OF°R = -RT In KR 0 and-~75T = logi°KR] [?F°R] and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the values given in Table I to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium' oxide to form

Jan 1, 1948

By G. I. Madden, L. H. Van Vlack

WhEN basic refractories which contain peri-clase, MgO, are used in steel furnaces, they are altered by iron oxide to form magnesiowiistite, (Mg,Fe)O, and an iron-rich magnesioferrite, (Mg,Fe)Fe2O4. Silica, which is usually present, produces a silicate liquid that surrounds the solid phases. The individual crystalline grains of the above two solid phases grow at elevated temperatures. Previous papersL" showed that, if either periclase or magnesiowiistite is present as the only solid phase, its grain size increases in proportion to temperature and in proportion to the square root of time; the growth rate is reduced slightly if the amount of silicate liquid is increased. Similar results have been observed for iron-rich magnesioferrite.3 To determine the effect of the presence of two solid phases on the rate of grain growth, micro-structural studies have been made on samples containing both magnesiowustite and magnesioferrite. The experimental procedure was the same as that followed in the previous studies of this type.'12 Briefly, this included determination of compositions from the available phase relationships4 that would produce the two phases of interest at the firing temperature and using reagent-grade raw materials to prepare mixtures of these compositions. The mixtures were pressed into pellet-size samples and then fired at the desired time and temperature. The samples were water-quenched to preserve the microstructure present at the firing temperature. Standard reflected-light metallographic techniques were used for sample examination and sample analysis. Grain sizes were determined by measuring the mean diameter of a number of randomly selected grains in a two-dimensional microsection. A large cross section of the sample was covered to prevent biased data resulting from such effects as localized differences in the radius of curvature of the crystal grains. Examination indicates that grain growth is restricted when more than one solid phase is present. This is illustrated in Fig. 1 for: (a) magnesiowustite plus a silicate liquid; (b) magnesioferrite plus a silicate liquid; and (c) magnesiowiistite and magnesioferrite plus a silicate liquid. Fig. 2 plots the

Jan 1, 1964

By Harry T. Davis, Jasper L. Stuckley

The object of this paper is to record and interpret field and laboratory observations made by the writers during five years of study of the barite deposits of North Carolina. Deposits of barite are known to occur in three localities in North Carolina (Fig. 1) two of which—the Hot Springs and Kings Mountain —contain material of economic value. The Hot Springs area begins near Bluff, some 6 miles south of Hot Springs, and continues northeast by Stackhouse; a total length of 7 miles. The Kings Mountain deposits lie along a belt that extends from the north end of Crowders Mountain in a southwestward direction, along the east side of this and Kings Mountain, to Kings Creek, South Carolina. The third locality is 3½ miles southeast of Hillsboro, Orange County, a short distance west of the highway leading from Hillsboro to Chapel Hill. It is not known when barite was first discovered in North Carolina, but production from the Hot Springs area began some 50 years ago. The state has never produced large quantities of barite—usually there have been less than three producers—and definite figures are not available, but reasonably reliable estimates indicate a total production of 300,000 tons. From 1901 through 1920 barite mining was on a seemingly prosperous basis and a large tonnage was shipped from the Hot Springs and Kings Mountain areas. With the depression of 1920 the industry began to decline and production practically ceased in 1926. Geology of the Barite Areas In the Hot Springs area barite is found in the Max Patch granite of Archean age and the Snowbird formation of Cambrian age. The Max Patch granite is of two varieties, one gray to whitish and the other red. The gray granite is coarse, at times porphyritic, and composed of quartz, orthoclase and plagioclase feldspar, with a little biotite and muscovite. The red granite is also coarse and differs from the other only in having conspicuous pink and red feldspar. Both varieties have been much metamorphosed and weathered in places, so that they contain secondary

Jan 1, 1935

By Harry T. Davis, Jasper L. Stuckley

The object of this paper is to record and interpret field and laboratory observations made by the writers during five years of study of the barite deposits of North Carolina. Deposits of barite are known to occur in three localities in North Carolina (Fig. 1) two of which—the Hot Springs and Kings Mountain —contain material of economic value. The Hot Springs area begins near Bluff, some 6 miles south of Hot Springs, and continues northeast by Stackhouse; a total length of 7 miles. The Kings Mountain deposits lie along a belt that extends from the north end of Crowders Mountain in a southwestward direction, along the east side of this and Kings Mountain, to Kings Creek, South Carolina. The third locality is 3½ miles southeast of Hillsboro, Orange County, a short distance west of the highway leading from Hillsboro to Chapel Hill. It is not known when barite was first discovered in North Carolina, but production from the Hot Springs area began some 50 years ago. The state has never produced large quantities of barite—usually there have been less than three producers—and definite figures are not available, but reasonably reliable estimates indicate a total production of 300,000 tons. From 1901 through 1920 barite mining was on a seemingly prosperous basis and a large tonnage was shipped from the Hot Springs and Kings Mountain areas. With the depression of 1920 the industry began to decline and production practically ceased in 1926. Geology of the Barite Areas In the Hot Springs area barite is found in the Max Patch granite of Archean age and the Snowbird formation of Cambrian age. The Max Patch granite is of two varieties, one gray to whitish and the other red. The gray granite is coarse, at times porphyritic, and composed of quartz, orthoclase and plagioclase feldspar, with a little biotite and muscovite. The red granite is also coarse and differs from the other only in having conspicuous pink and red feldspar. Both varieties have been much metamorphosed and weathered in places, so that they contain secondary

Jan 1, 1935

By J. R. Kyte, R. L. Dalton, V. O. Naumann, R. L. Ridings, R. W. Greene

This paper presents a one-dimensional numerical method for calculating dissolved-gas-drive behavior for a single well or a linear reservoir. Pressure and saturation distributions can be calculated, including the effects of capillary and gravity forces. The analysis has been programmed for solution on the IBM 7090 digital computer. A comparison of experimental and calculated behavior for two linear models demonstrates that the method is suitable for calculating dissolved-gas-drive behavior under reservoir conditions of flow. Dissolved-gas-drive tests were run, at different production rates and with oils of different viscosities, on short (6.ft) and long (173ft) flow models. For tests approximating reservoir pressure gradients and flow rates, there was excellent agreement between experimental and calculated results. A series of calculations of well behavior for thin, horizontal, homogeneous, dissolved-gas-drive reservoirs shows that ultimate recovery is independent of production rate or well spacing in such cases. These calculations also show that Muskat's method and similar material-balance analyses are not applicable under some conditions particularly for high pressure drawdowns. INTRODUCTION The problem of calculating dissolved-gas-drive reservoir performance has received a great deal of attention throughout the oil-producing indusfry for many years. Really significant advances, however, have been made only in recent years. The rapid evolution of high-speed computing equipment and techniques has opened up new approaches to the problem and led to realistic, quantitative analyses free of many of the assumptions and limitations of earlier methods. The one-dimensional numerical method described in this paper includes the effects of both gravity and capillary forces. A number of test calculations, based on different rates, spacings, and rock and fluid properties, have shown that the method is adequate for systems that can be reasonably represented by a one-dimensional model (linear or radial) and in which fluid segregation perpendicular to the direction of flow is not important. Along with the development of mathematical methods, an experimental program was conducted and the data were used to test the validity of the theoretical basis of the mathematical method. Linear models were used and all experiments were run using 1,000-psig bubble-point oils. The use of long, high-pressure models enabled us to more closely approach reservoir gradients and flow rates. MATHEMATICAL FORMULATION DIFFERENTIAL EQUATIONS The differential equations describing dissolved-gas-drive behavior in one dimension dare summarized here. They include Darcy's law for flow of oil and gas (Eqs. 1 and 2) and the equations for conservation of mass for oil and gas (Eqs. 3 and 4). The oil and gas pressures are related by capillary pressure (Eq. 51.

By R. C. Hall

The magnetic anisotropy and magnetostriction of single crystals of alloys between 25 and 59 wt pct Co in Fe have been determined in the disordered and ordered states. The magrzetostriction is large and positive for all alloys in both states of order (up to 150 x 10-6 for A,, and 40 x 10-6 for 111). The magnetic anisotropy becomes zero rzear 41 pct Co for the disordered state. Ordering shifts the zero-anisotropy composition to about 50 pct Co. COBALT-iron alloys have for many years been of interest as magnetic materials because they have unusually high magnetic saturation values.' This interest was increased recently by the development of Supermendur.' Supermendur is an alloy of 49 pct Co-49 pct Fe-2 pct V* which was found by suitable purification and heat treatments, including a magnetic anneal, to possess excellent magnetic properties. These included a square hysteresis loop with a low coercive force and a high magnetization, and a low total loss. Two factors which are important in determining the magnetic hysteresis properties are the basic magnetic properties of magnetostriction and anisotropy. Alloys having zero anisotropy and zero magnetostriction show improved hysteresis properties.3 Since very meager data4-' are available in the literature on the single-crystal anisotropy and magnetostriction of the cobalt-iron alloys, the present program was undertaken to determine these two properties in the disordered and ordered states. EXPERIMENTAL TECHNIQUES Ingots of the cobalt-iron alloys containing from 25 pct to 59 pct Co in iron were vacuum melted from electrolytic iron and cobalt of 99.9 pct purity. The ingots were cooled at a rate of about 1°C per hr through the transformation temperature (950" to 980°C dependent on the alloy content) for the growth of large grains. From these grains, single-crystal disks were fabricated with either the (110) or (100) plane parallel to the faces of the disk. The crystals were given two heat treatments to produce either the ordered state (cooling rate of 20°C per hr from 850 "C) or the disordered state (water quench from 850 °C). Since the iron-cobalt alloys order very rapidly, the water quench may not have produced complete disorder in all cases. Due to the method of growth, the crystals were not perfect. Most of the samples had low-angle boundaries and a few had some small included grains. These imperfections could and probably did affect the accuracy of both the magnetic anisotropy and magnetostriction measurements. Much of the scatter in the data may be attributed to the crystal imperfections. The methods of determining the spontaneous saturation magnetostriction and the anisotropy have been previously described.419110 MAGNETOSTRICTION The magnetostriction in the [loo] and [Ill] directions (hO0 and ?111 respectively) is illustrated in Fig. 1 for the disordered state. Both ?100 and ?111i became large positive values as cobalt was added to iron. The state of order did not have a large effect on the magnetostriction. The effect of order did not appear too consistent in these data. Tentative curves are shown in Fig. 1 for the ordered magnetostriction near the FeCo composition; here ?100 appeared to be lowered and ?111 raised as the degree of order was increased. These results agree qualitatively with the

Jan 1, 1961

By Masayuje Otagawa

The mining methods adopted in Japanese mines are less known to the mining world than those of other countries, owing to the geographical remoteness, but they present many features of interest to mining engineers. The Ashio copper mine is at the town of Ashio, in Tochigiken, about 109 mi. (175 km.) from Tokyo by the Imperial Government railroad. The area of the concession owned by the Furukawa Mining Co. is 5000 acres (5023 ha.). The mine was formerly divided into three, viz. Hon-ean, Kotaki, and Tsudo, which are distant 3 mi. (4.8 km.) from each other as shown in Fig. 1. However, in 1914, when the writer was general manager, the three mining plants were amalgamated into one with the result of simplifying the working projects and increasing the operating efficiency. The mine was visited by the Institute party in November, 1911, when K. Inouye was the general manager. Shortly afterward, the writer was appointed manager, and, in 1915, he was succeeded by Dr. K. Asano. At the end of 1917, K. Kibe became general manager and, after two years, was succeeded by the present manager, I. Sugimoto. For some time Dr. J. Kojima was acting general manager. It is necdless to say that the gentlemen mentioned are all members of the Institute, as is also Baron T. Furukawa, president of the company. Since the discovery of the enormous masses, called "kajika" or "bullhead" deposits, which the writer has described elsewhere,' the mining methods have been varied to meet the different conditions presented by these deposits. The Ashio Ore The country rock of this mine consists of the middle Chichibian slate and quartzite into which has been intruded a post-Tertiary plagio-liparite neck more than 2 mi. in diameter, in the shape of an inverted cone which narrows downward to a relatively small diameter in depth.

Jan 1, 1923

By Masayuje Otagawa

The mining methods adopted in Japanese mines are less known to the mining world than those of other countries, owing to the geographical remoteness, but they present many features of interest to mining engineers. The Ashio copper mine is at the town of Ashio, in Tochigiken, about 109 mi. (175 km.) from Tokyo by the Imperial Government railroad. The area of the concession owned by the Furukawa Mining Co. is 5000 acres (5023 ha.). The mine was formerly divided into three, viz. Hon-ean, Kotaki, and Tsudo, which are distant 3 mi. (4.8 km.) from each other as shown in Fig. 1. However, in 1914, when the writer was general manager, the three mining plants were amalgamated into one with the result of simplifying the working projects and increasing the operating efficiency. The mine was visited by the Institute party in November, 1911, when K. Inouye was the general manager. Shortly afterward, the writer was appointed manager, and, in 1915, he was succeeded by Dr. K. Asano. At the end of 1917, K. Kibe became general manager and, after two years, was succeeded by the present manager, I. Sugimoto. For some time Dr. J. Kojima was acting general manager. It is necdless to say that the gentlemen mentioned are all members of the Institute, as is also Baron T. Furukawa, president of the company. Since the discovery of the enormous masses, called "kajika" or "bullhead" deposits, which the writer has described elsewhere,' the mining methods have been varied to meet the different conditions presented by these deposits. The Ashio Ore The country rock of this mine consists of the middle Chichibian slate and quartzite into which has been intruded a post-Tertiary plagio-liparite neck more than 2 mi. in diameter, in the shape of an inverted cone which narrows downward to a relatively small diameter in depth.

Jan 1, 1923

By Fred C. Bond

The process of comminution by grinding is properly classified as an art, rather than as a science. Like most other operations concerned in ore dressing, or in the treatment of nonmetallic minerals, the mathematical relationships of rock breaking are still obscure, and much disputed. If some basic formula exists, comparable for instance to E = RI in electricity, it has not yet been placed in common use. The absence of such a comprehensive mathematical background undoubtedly is the cause of many inefficient designs and installations, as well as of much poorly oriented experimental work. On the other hand, the mathematical immaturity of the process constitutes an opportunity for a real contribution on the part of those who enjoy mental pioneering. Some of the statements made in any such exploratory work may be little more than opinions, and it is to be expected that some will later be proved untrue; but such an evolutionary development is necessary if we are ever to arrive at the fundamental laws, the discovery of which can change the empirical art into a mathematically exact science. The most significant principle of comminution that we possess is probably Rittinger's law, which states that the work done in crushing or grinding is proportional to the area of the new surface produced. There is an alternative theory, known as Kick's law, which formerly was preferred to Rittinger's but which now is rather discredited. According to Kick, the work done in comminution is proportional to the volume, or weight, of the pieces broken, or to the cube of their diameters, while according to Rittinger it is proportional to the square of the diameters. Careful determinations of size distribution below the limit of sieve sizes1 indicate strongly that under ordinary grinding conditions the amount of new surface area produced is directly proportional to the net power input. Changes in the size ratio between the balls and the particles cause important differences in the proportion of the product that passes a given mesh size, but do not affect the total amount of new surface area; they merely change the distribution of the surface among mesh sizes. The principle of constant surface area is the logical result of Rittinger's law, and it may well have an important bearing on the comminution theories of the future. Formula for Ball Wear Grinding tests have been made in the Allis-Chalmers laboratory for more than 9 years, using a standard charge of mixed balls of different sizes; and a continuous record has been kept of the rates of wear of each size. These results have been combined and plotted in various ways in order to discover the relationship that exists

Jan 1, 1943

By Fred C. Bond

The process of comminution by grinding is properly classified as an art, rather than as a science. Like most other operations concerned in ore dressing, or in the treatment of nonmetallic minerals, the mathematical relationships of rock breaking are still obscure, and much disputed. If some basic formula exists, comparable for instance to E = RI in electricity, it has not yet been placed in common use. The absence of such a comprehensive mathematical background undoubtedly is the cause of many inefficient designs and installations, as well as of much poorly oriented experimental work. On the other hand, the mathematical immaturity of the process constitutes an opportunity for a real contribution on the part of those who enjoy mental pioneering. Some of the statements made in any such exploratory work may be little more than opinions, and it is to be expected that some will later be proved untrue; but such an evolutionary development is necessary if we are ever to arrive at the fundamental laws, the discovery of which can change the empirical art into a mathematically exact science. The most significant principle of comminution that we possess is probably Rittinger's law, which states that the work done in crushing or grinding is proportional to the area of the new surface produced. There is an alternative theory, known as Kick's law, which formerly was preferred to Rittinger's but which now is rather discredited. According to Kick, the work done in comminution is proportional to the volume, or weight, of the pieces broken, or to the cube of their diameters, while according to Rittinger it is proportional to the square of the diameters. Careful determinations of size distribution below the limit of sieve sizes1 indicate strongly that under ordinary grinding conditions the amount of new surface area produced is directly proportional to the net power input. Changes in the size ratio between the balls and the particles cause important differences in the proportion of the product that passes a given mesh size, but do not affect the total amount of new surface area; they merely change the distribution of the surface among mesh sizes. The principle of constant surface area is the logical result of Rittinger's law, and it may well have an important bearing on the comminution theories of the future. Formula for Ball Wear Grinding tests have been made in the Allis-Chalmers laboratory for more than 9 years, using a standard charge of mixed balls of different sizes; and a continuous record has been kept of the rates of wear of each size. These results have been combined and plotted in various ways in order to discover the relationship that exists

Jan 1, 1943

By S. Skowronski

OvErpolEd copper, as commonly defined,- is copper which has been excessively reduced during the poling period of the refining process. Owing to its porosity, such coppcr is unfit for commercial purposes. The cause of this phenomenon is undoubtedly the lack of oxides in the copper, yet this does not completely explain it. Refined copper of the same "pitch" and "set" varies considerably in oxygen contents, and analyses of overpoled bars also show similar wide differences; moreover, it is possible to melt copper in 'crucibles so as to obtain bars that are practically free from oxygen although they show a "tough pitch" and "level set" surface. Frederick Johnson advances the following theory: The regulation of the quantity of oxygen in copper is the keynote of all copper refining. It is the presence of a well defined proportion of oxygen in the form of cuprous oxide, forming a copper-cuprous oxide eutectic, which enablcs copper to be cast free from blowholes. It seems that when oxygen is present, other gases are less soluble in molten copper; when oxygen is absent, or is present in insufficient quantity, the copper dissolves other gases, such as hydrogen and carbon monoxide, which are insoluble in the copper when solid, and, being rejected during the process of solidification, causes internal porosity and external ridges and excrescences.1 The "level set" of wire bars, etc., is entirely the result of a compromise between the occluded gases and cuprous oxide. With excess of the former the metal would be "overpitch" and spongy, while an excess of the latter would result in the metal being "underpitch" and brittle.2 The result of the absorption and subsequent expulsion of reducing gases, carbon monoxide and hydrogen,' and the effect of this action on the overpoling of copper are in dispute; the literature on the subject is full of contradictory statements and will continue to be so until better analytical methods have been developed. Sulfur, however, is tangible. The refiner can see it in his button sample and consequently attributes to it any trouble that may happen during the melting of the copper.

Jan 1, 1919

Jan 1, 1936

Jan 1, 1936

By D. B. Robinson, C. A. Macrygeorgos, G. W. Govier

Experimental data have been obtained on the volurrletric behavior of ternary mixtures of methane, hydrogen sulfide and carbon dioxide at temperalures of 40°, 100" and 160°F up to pressures of 3,000 psia. The results indicate that the compressibility factors for this system do not agree with compressibility factors for sweet natural gases at the same pseudo-reduced conditions. The deviation increases as the temperature and methane content decrease. Discrepancies of up to 35 per cent were observed. A careful analysis has been made of the existing pUrblished data on compressibility factors for binary systems containing light hydrocnrbons and hydrogen sulfide or carbon dioxide. It has been found that the deviation of actual from predicted compressibility factors for methane-acid gas mixtures is a function of the methane content and the pseudo-critical properties,.v of the mixture. The ratio between actual compressibility factors for methane-acid gas mixtures and compressibility factors for sweet natrlral gases at the same pseudo-reduced conditions has been currelated over a range of pP,, from 0 to at least 7 arid a range of pT, from about 1.15 to at 1east 2 0 with an error not exceeding 3 per cent and over most of the range within I per cent. The validity of the correlation for mixtures containing appreciable hearvier hydrocorbons has not been fully established, but it is shown to be preferable than the use of a corretation based only on hydrocarbons. INTRODUCTION Although a relatively accurate method for predicting compressibility factors of pure materials is provided by charts based on reduced properties and the assumption that the compressibility factor is a unique function of T P and z the determination of the correct values of compressibility factors for gas mixtures is somewhat difficult. Two general methods of dealing with gaseous mixtures have been proposed. The first assumes a direct or modified additivity of certain properties of the mixture in terms of the properties of the individual components. Examples of this method are based on the familiar laws of Dalton and Amagat. The second method averages the constants of an equation of state applicable to the pure components. Both of these methods are of limited value in engineering calculations because the first usually provides reliable answers only over narrow ranges of pressure and temperature and the second is cumbersome to handle. In petroleum engineering practice accurate estimations of the volumetric behavior of natural gases arc frequently required. To fulfill this need, several generalized compressibility charts have been developed.' ' Of these, the one prepared by Standing, el al is widely used at present. In the construction of charts of this type a third method for dealing with mixtures has been followed. It is based on correlation of pseudo-critical properties as outlined by Kay and calculated from the critical properties of the individual components in a mixture. Although these charts provide relatively accurate information on the compressibility of dry or wet sweet natural gases, they are less reliable when used for gases containing high concentrations of hydrogen sulfide or carbon dioxide or both. Thus, an experimental program, although time consuming, is the best means now available for the determination of the volumetric behavior of sour or acid gas mixtures. An increased interest in the behavior of these gas mixtures, particularly in connection with some of the fields in Western Canada where the acid gas concentration of the reservoirs may be as high as 55 per cent and where hydrogen sulfide alone may be as high as 36 per cent, provided the incentive for this study. It was the purpose of the investigation to determine the volumetric behavior of selected mixtures of methane, hydrogen sulfide and carbon dioxide over a range of temperature from 40" to 160°F and at pressures up to 3,000 psi. EXPERIMENTAL METHOD The apparatus used in this investigation was basically the same as that described by Lorenzo.'" The amount of each pure component used in preparing the gas mixtures was measured over mercury in a glass-windowed pressure vessel. The pure components were then transferred individually in the desired amounts to a second glass-windowed pressure vessel where the volumetric behavior of the mixture was determined. Volume was varied by mercury injection or withdrawal. The capacity of the cell was about 125 cc. Temperatures in the cells were measured with copper-constantan thermocouples and a Leeds Northrup semi-

By J. H. Scaff, W. G. Pfann

The effects of impurities on the electrical properties of silicon are discussed in a companion paper by Messrs. Scaff, Theuerer, and Schumacher.' It was shown that an ingot of silicon which contained boron and phosphorus in certain concentrations consisted partly of p-silicon and partly of n-silicon2 and that the common boundary between these regions was the source of a photo-voltage. These features were ascribed to the segregation of boron and phosphorus during solidification of the ingot. Because of different rates of segregation the first portion of the ingot to freeze contained a molar excess of boron over phosphorus and hence was p-silicon. The last-solidified region contained a molar excess of phosphorus and was n-silicon. This paper is concerned with the microscopic examination of such ingots. The microstructures are rather unusual in certain respects and their study has helped to show how the segregation of minor elements modifies the electrical properties of silicon. The microstructures of ingots prepared from two lots of silicon, designated 1 and 2, will be described. These lots were obtained from the Electro Metallurgical Co. Both contain 99.8+ pct silicon, but they differ in impurity analysis. For each lot will be shown the microstruc-ture of a slowly cooled ingot, for which the time of solidification is 6 min., and that of a rapidly cooled ingot, for which the time of solidification is 2 min. The ingots were prepared from 45 g charges of silicon. When an alloy freezes a cored structure is generally produced because of insufficient diffusion to remove concentration differences established during freezing. As a result of coring the first portion of a crystal to freeze is usually poorer in solute than equilibrium requires, while the last material to solidify is richer. In a columnar grain, growth is principally unidirectional and coring can produce a concentration gradient along the entire grain. By carrying the picture of the coring process from a single grain to an entire ingot in which columnar grains are aligned more or less radially, one can easily see that a composition gradient could be established between the outside and center of the ingot. This, to a considerable extent, occurs during the solidification of a slowly cooled ingot of silicon. Slowly Cooled Ingot In slowly cooled ingots of both lots of silicon, columnar grains which are approximately radial in direction and longest at the top of the ingot enclose a region in which the shapes and align- ment of the grains are considerably less regular. The central region is last to solidify and contains cavities and inclusions. The sketch of Fig 1 illustrates some of these features, as well as others which will be described below. If a polished section of an ingot is etched in a mixture of 2 parts of 20 pct HF and 98 parts of HNO3 the p-n barrier becomes visible. The overall shape of the barrier in a slowly-cooled ingot is roughly oval, as may be seen in Fig 1. The proportion of n-silicon, that is, the region enclosed by the barrier, is considerably greater in ingots of lot 1 than in those of lot 2. A sample about 34 x 1/8 X 1/8 in. was cut from a slowly cooled ingot of lot 1 with its long direction extending from the top of the ingot to the porous region. Thus its upper half was psilicon, its lower half n-silicon. A longitudinal face was polished and etched in the acid mixture. The areas of interest are identified in Fig 2. A band of parallel markings extends across the sample in the columnar region. These striae are roughly parallel to the upper surface of the ingot and cross grain boundaries with only slight deviations. They are quite distinct in the n-silicon,

Jan 1, 1950

By F. Kurata, P. C. Davis, T. L. Gore

An experimental method and apparatus for the study of the low-temperature phase and volumetric behavior of volatile mixtures are described. The phase diagrams, including the critical points, and the volumetric behavior of a natural gas and a mixture of the natural gas with methane at temperatures from -40°F to -200°F and pressures to 1.200 11si are givrn. INTRODUCTION Knowledge of the phase and volumetric behavior of mixtures of the light hydrocarbons at low temperatures is becoming increasingly important as interest in low-temperature separation processes increases. Distillation at low-lemperatures has been used for some time to recover ethane and ethylene from natural gas and refinery gas for petrochemical uses. Removal of excess nitrogen from natural gas by distillation has been proposed as a means of increasing the capacity of gas transmission lines and of improving the marketability of the gas.1,2 Evaluation of the latter process has been hampered, however, by the scarcity of data from which the phase behavior of natural gases at low temperatures might be predicted. While existing correlations of vaporization equilibrium constants may be used to predict the behavior of such mixtures at lower pressures, high-pressure computations often require knowledge of the location of the critical point of the system involved. Although correlations have been developed for the prediction of the critical temperature and pressure of certain types of hydrocar-bon systems, they do not apply to very volatile systems such as nitrogen-bear-ing natural gases. This paper describes the initial stages of an investigation of the low-temperature behavior of a numher of natural gases and other gases of commercial interest. The experimental method and apparatus are described. and the phase and volumetric behavior of a natural gas and a mixture of the natural gas with methane are presented. PREVIOUS WORK The published low-temperature vapor-liquid equilibrium data for hydrocarbons and mixtures of hydrocarbons with nitrogen and helium are listed in Table I. Most of these data are for binary systems, and the data of Stutz-man and Brown" at 100 psi are the only data on a natural gas. The data of Bloomer and Parent3 on the methafie-nitrogen system, which have been phblished since this study was completed, are a valuable addition to the knowledge in this field. Prior to the publication of these data the only published critical point data on systems having critical temperatures below the ice point were those of Ruhemann.1 on the methane-

Jan 1, 1952

By David H. Browne, John F. Thompson

The literature dealing with the physical constants of nickel is so fragmentary and unrelated that a synopsis presents unusual difficulties. It is only within the last few years that investigators have understood the importance of placing on record not only the determinations they have made but also the composition, physical treatment, and past history of the material investigated. For this reason much of the earlier literature is valueless. Determinations have been made of the same physical constants on samples differing widely in origin, composition, and treatment, and the results differ widely among themselves. In the first place nickel is almost as flexible a term as steel. Its physical properties are widely influenced by its composition and treatment. It absorbs large quantities of gases and is exceedingly difficult to prepare in a state of chemical purity comparable to gold, silver, or copper. It is vitally affected by thermal and mechanical treatment. Hence in the following pages the recorded literature, where quoted, must be accepted with a certain reserve and used, as far as possible, as a check on later observations, in which these important factors are noted. In every case where new determinations are given, an attempt has been made to record all available information concerning the composition and treatment of the material used so that the data may serve as stepping-stones toward a wider knowledge of the properties of the metal. As this synopsis is an attempt by men of metallurgical training to do what should long before have been done by physicists, it is to be expected that certain errors may have crept in. Any corrections or suggestions

Jan 1, 1921