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By B. H. Sage

VARIATIONS in the composition of the liquid phase of natural reservoirs which are continuous through significant ranges in elevation have been noted by petroleum technologists. In general, there is a greater gas-oil ratio and the gravity of the oil is higher in production from the upper parts of the formation. In the present paper the possible changes in composition with elevation which would result from the attainment of thermodynamic equilibrium in a uniform gravitational field have been evaluated for a naturally occurring hydrocarbon liquid, a binary hydro-carbon liquid phase and a binary hydrocarbon gas. The results indicate a progressive decrease in the mole fraction of the components from methane through the butanes with increasing depth, accompanied by a corresponding increase in the amount of the heavier components making up the system. The magnitude of these variations is perhaps insufficient to explain completely the variations in the properties of the liquid phase that are encountered at various elevations within a particular producing horizon. However, the changes are significant and the treatment presents an example of the application of thermodynamic data to the evaluation of the properties of hydrocarbon fluids under the conditions approaching those encountered in natural reservoirs.

Jan 1, 1938

By John P. Hager, Adolfo R. Zambrano

The thermodynamics properties of the liquid Pb-Ag-Au system have been determined from galvanic cell measurments five pseudobinary systems of fixed XAg/XAu ratio. The galvanic cell employed a molten PbO-SiO2 electrolyte and was operated between 775" and 1030°C. The thermodynamics properties of lead were obtained directly from the experimental data, whereas the excess integral molar properties and the activities of silver and gold were obtained by means of the Gibbs-Duhem equation. The calculated proper -ties of the Ag-Au system agree well with the published properties. The liquidus surface of the Pb-Ag-Au system has been determined at 1200°K. In Parts I' and 11' the galvanic cell Mo,Pb(l)|(PbO-SiO2)(l) SiO2(s) |Pb(alloy)(l), Mo [I] was used to determine the thermodynamics properties of the Pb-Ag and Pb-Au systems, respectively. The use of cell I, in which a molten oxide electrolyte is employed rather than the classical fused-salt electrolyte, was shown to result in more accurate ther-modynamic measurements in that the displacement reaction at the alloy-electrolyte interface (l/Zb)B(alloy) + (I/za)A+Za = (1/Za)A(alloy) + (1/Zb)B+zb [1] was minimized. For the Pb-Ag system, where B = Ag(l), the error in the activity of lead (aPd) re-sulting from Reaction [I] was calculated to be less than 1 pct.l For the Pb-Au system the error in aPb was calculated to be less than 0.5 pct.2 Also, electro-transport measurements on the PbO-SiO2 electro-lyte1,2 established that the conduction was entirely ionic and that lead was present only in the divalent state. In the present study the experimental technique is extended to an investigation of the thermodynamic properties of the liquid Pb-Ag-Au system. Five pseudobinary systems of fixed X Ag/XAu ratio were selected. The experimental results were then combined with the previous measurements on the component binary systems Pb-Ag1 and Pb-AU2 to calculate, by means of the Gibbs-Duhem equation, the molar and partial molar mixing properties for the liquid ternary solutions.

Jan 1, 1970

By C. M. Young

Bituminous coal piled in heaps or bins frequently undergoes a process of spontaneous heating as the result of the absorption of oxygen. It seems probable that the first absorption of oxygen by coal which has not previously been exposed to the air may occur as a condensation or a combination of oxygen in some form which does not result in the production of carbon dioxide, but slow combustion soon begins. The absorption of oxygen is accompanied by an increase of temperature, and this by an increased rapidity of absorption; hence the dangerous condition proceeds from bad to worse, until the kindling point is reached, unless the process is interrupted. A dangerous rise of temperature can be prevented by excluding oxygen, by increasing the bulk of coal in proportion to its surface exposed, or by circulating enough air to dissipate the heat produced. The storage of coal, in practice, varies from almost complete exclusion of oxygen, by storing under water, to such freedom of access as exists when the coal is stored in open piles. Oxygen available for absorption by coal is supplied by the air in the interstices between lumps and by additional air which may enter the pile through circulation. The size of the coal largely affects both of these supplies; for if the fragments are small the spaces between them constitute a small percentage of the total volume, and little oxygen will be available unless the circulation of air brings in a fresh supply, while with large fragments the percentage is relatively large; circulation also is much easier through a pile of coarse lumps. In the case of lump coal, although a large amount of air may be present, the exposed surface is comparatively small and there is little opportunity for the absorption of oxygen to be so rapid as to cause dangerous heating. Attempts have been made to prevent heating by allowing a sufficient circulation of air to carry off the heat generated; obviously this method cannot be applied to fine sizes nor mixed sizes. When storing coal at the University of Illinois, an attempt has been made to use so much fine coal and to pack it so thoroughly as to prevent circulation of air, while also reducing the original air in the pile so as to prevent heating. This method has been fairly successful, but in some

Jan 1, 1918

By Allan T. Gwathmey, J. Bruce Wagner, Kenneth R. Lawless

Between 250°and 550°C in oxygen pressures of 10 to 760 mm Hg, the relative oxide thicknesses formed per unit time on the (100), (111), (110), and (320), decreased in this order. The predominant oxide orientation was (001)Fe3O4 and [110] Fe304 A small amount of a-Fe2O3 which exhibited a fiber pattern was observed in all oxides except those formed at 250°c in low oxygen pressures. IN order to understand the properties and behavior of thin films, particularly their role in oxidation reactions, there is needed more experimental information on their structure, composition, and kinetics of formation on clean surfaces of known geometry. The present study was undertaken to obtain such information for thin oxide films formed on single crystals of a body centered cubic metal, iron. Crystals in the form of spheres were used in order to expose all possible crystal planes to the reactant gases simultaneously. Using this procedure the relative rates of oxidation of all planes could be estimated, and those exhibiting, maximum or minimum oxidation rates could be selected for a more intensive study of composition and expitaxy. Since the three types of information were obtained from the same experiment using a single crystal substrate, any differences between rate, composition, and expitaxy on the several planes may be attributed to the influence of the substrate structure. EXPERIMENTAL The starting material for this study was Armco iron rods, 6 in. long and 3/8 or 1/2 in. in diam. The analysis was reported to be 99.8 pct Fe, with major impurities listed as carbon 0.018 pct, manganese 0.027 pct, phosphorous 0.005 pct, sulfur 0.029 pct, silicon 0.005 pct, and copper 0.11 pct. These rods were cleaned with ether and heated in an atmosphere of moist hydrogen at 950°C for three days. The purpose of this treatment was to decarburize the iron and to provide a consistent, uniform grain size for the growth of single crystals. Crystals in the form of rods, up to 1/2 in. in diam and 2 in. long, were prepared by a method similar to that reported by Leidheiser and Buck.2 Spherical crystals, 3/8 and 1/2 in. in diam and having a handle about 1/4 in. in diam by 112 in. long, were machined from the single-crystal rods. After machining, each crystal was etched in aqueous nitric acid to remove the cold-worked metal at the surface. Before each experiment, the crystal was polished mechanically with metallographic papers through number 4/0, and electropolished in a perchloric acid-acetic anhydride mixture by the method of Jacquet and Rocquet.3 The crystal was washed in running distilled water for at least 5 min. The excess water was blotted with a soft paper tissue, and the crystal was placed in an all-glass reaction vessel (See Fig. 1). The crystal was heated at 550°C in hydrogen for at least 8 hr prior to the oxidation in order to reduce any surface oxides and to help relieve any stresses in the metal. For the structure and composition studies, flat faces were cut parallel to (loo), (111), and (110) planes on the iron crystal spheres. The orientation of these faces was checked by a back-reflection X-ray diffraction technique. The faces were within 2 deg of the desired orientation. The flat faces were treated as described above except that prior to electropolishing they were given an additional polish on metallographic felt saturated with twenty-minute levigated alumina. After the crystal was heated in hydrogen for at least 8 hr, the temperature was adjusted to the desired value, and the hydrogen was evacuated. Commercial oxygen which had been purified by successively passing through tubes containing magnesium perchlorate, Ascarite and magnesium perchlorate was admitted to the desired pressure as measured by a mercury manometer. A resistance-wound furnace surrounded the oxidation chamber, and a temperature controller maintained the temperature within ±3°C. The furnace was provided with a small window for observing the crystal. The changes in thickness of the oxide films were followed by observing the interference colors. The oxidation was allowed to proceed until the desired oxide thickness was attained on a given crystal plane. The experiment was terminated by evacuating the oxidation

Jan 1, 1962

By Frederick N. Rhines

BECAUSE of the nature of the environments in which metals are handled, it is natural that gases should be suspected of intruding into metallurgical operations, there to produce effects both beneficial and detrimental. The problem of tracing and controlling such effects is often made difficult by the complexity of the conditions surrounding 'their occurrence, even though the fundamental mechanisms involved may be simple and of familiar type. Many gas-metal reactions are known to be implemented by processes of diffusion. These form a homogeneous group of phenomena which become more readily understandable when viewed together, in that the knowledge gained from one serves to interpret the next. It is the purpose of the present paper to present, by means of examples drawn from practice, a brief survey, of the ways in which gas-metal diffusion serves and obstructs the purposes of the metal-fabricating industries. The selection of the cases described was made by consulting more than thirty-six practicing experts whose combined experience provided an extensive coverage of the field and who were in a position to supply examples of occurrences of present day interest. The response was generous and it is regrettable that space permits the description of only a limited number of typical examples with but brief mention of parallel cases. THE NATURE OF GAS-METAL DIFFUSION The term "gas-metal diffusion," although commonly used, is ambiguous in so far as it implies that a definite group of substances may be identified as gases and may be expected to behave in a manner distinct from other substances in association with metals. "Gases" such as oxygen and hydrogen when diffusing through a liquid or solid metal are properly components of the liquid or solid solution; they behave as alloying elements and are not to be distinguished in their diffusion characteristics from other elements, except that each has an individual rate of diffusion. On the other hand, a number of metals in certain temperature ranges are volatile to the extent that they may appear in the form of vapor in metallurgical operations. For the sake of greater definiteness, therefore, it will be convenient to- regard as "gas-metal diffusion" any process in which the result depends upon one or more of the diffusing elements appearing, at some stage, in the gaseous state, or as a compound gas. No element, gaseous or otherwise, can diffuse through a liquid or solid metal unless it is at least slightly soluble in that metal. The elements of low atomic number

Jan 1, 1944

By Henry Rawdon

THE structure of wrought iron as usually described by metallographists and workers in metal in general is that of a fairly pure iron. Impurities, if present, are usually considered as being in solid solution in the crystals of the ferrite matrix or as forming part of the ever present "slag streaks." Attention is herein directed to one type of these dissolved impurities; to the detection of such impurities, particularly in low-grade irons, and to their possible influence on the physical properties of the metal. The attention of the Bureau of Standards was first directed to wrought iron of the peculiar and unusual characteristics to be described later, in material which had failed in service and was submitted for test. The examination was extended to other grades of wrought iron, to see whether such features are of common occurrence in this class of material. MICROSTRUCTURE OF WROUGHT IRON Usual Structure The general microstructure of wrought iron is so well known that a detailed description of it here is needless. There is shown in Fig. 2 the structure of a sample of Swedish iron which illustrates well the matrix of ferrite crystals in which are embedded the slag threads so characteristic of the puddling process and the subsequent working of the material. The usual commercial product contains varying amounts of the impurities commonly associated with iron and steel, i.e., manganese, phosphorus, silicon, and sulphur together with small amounts of carbon. Of these, the larger part of the phosphorus and some of the silicon present are held in solid solution in the ferrite while most of the remaining impurities, other than carbon, exist in the inclosures of slag. Aside from the discontinuities introduced by the slag streaks the ferrite matrix has the microstructure and appearance of a pure metal. No definite orientation of the various crystals or grains is apparent; deep etching of the specimens reveals no intracrystalline features (i.e., within the grains) other than those noted in "pure" metals in general (etching pits).

Jan 9, 1917

By David M. Parkes

This paper outlines the achievements to date at the British Columbia mine of Kaiser Resources Ltd. Almost one million raw short tons (855,000 metric tonnes) are now produced per year from a single monitor operation working 15 short shifts per week. Progress has been made in reducing the angle at which coal will flow in flumes by modifying the shape and the plastic linings. Improvements have been made in transporting coal from heading machines, and in the design of the present and future coal: water circuits. The development of hydraulic mining is still young and many improvements are being made.

Jan 1, 1976

By Jesse E. Wyrick

Gases and vapors are being safely stored in caverns constructed in salt formations. The storage of gas is cost competitive with other methods of gas storage and offers many advantages. Storage can be designed for high gas recovery rates and many operating caverns allow gas recovery rates in excess of 300 million cubic feet per day. Fenix & Scisson has constructed or consulted on many of these storage projects and presents some case histories beginning with the conversion of a bedded salt cavern to gas storage in 1961. Discussion includes basic considerations for storage construction, confirmation, and operation.

Jan 1, 1985

By Albert H. Chester

During the summer of 1875 I visited some of the iron mines of Houghton County, Mich., and was quite interested to observe the progress made there within a few years. Working in open pits is gradually giving place to underground work in most of the mines where this system is practicable. In some cases, as in the Lake Superior Mine, the body of ore is so irregular, and the deposit so liable at any time to be pinched out, or nearly so, that it. has been found impractical, if not impossible, to lay out any plan for systematic underground work. But in many other mines the deposit is so regular in character, that the work can be laid out in shafts at regular intervals, and a series of 60 feet levels. The Michigammi Mine, opened in 1872, and first worked in 1873, is arranged on this plan, though some quarrying is still done. But the men are being put at overhead stoping as fast as it can be got ready for them, and before long it will all be worked in this way. The New York Mine is undergoing a similar change to the pillar system, and several others have either been changed, or it is about to be done. My principal object in visiting this region was to obtain samples from some of the important mines, so as to be able to answer the question: "What is the average percentage of iron in the Lake Superior ores?" Most iron furnaces work on mixtures of ore, so that it is impossible to tell, from their records, just the percentage in each one.

By John J. Reed

Great strides have been made during the past few years in the field of rock mechanics, and steps have been taken to implement our newly acquired knowledge to advance the mining industry and improve the lot of the miner. This article is a summary of the latest progress in those areas of rock mechanics indicated by the subtitles. Let's look at these new tools for mining men. GROUND STABILITY DETERMINATIONS Much valuable information in the field of rock mechanics can be obtained by relatively simple, inexpensive measurements and observations, and this kind of investigation can be classed under the general heading of "Ground Stability Determinations." The instrumentation involved in this type of work is relatively simple and inexpensive, and its operation is not difficult to understand.1,2 Precise deformation measurements accurate to a few thousandths of an inch are very helpful in detecting stope convergence, pillar compression, floor heave, etc. Such measurements recorded over a period of weeks and months will detect and forwarn against failure of the overall mine structure long before any other visual evidence can be observed. Such advance warning then permits the introduction of sufficient artificial support in time to do some good. Instead of precise measurements which must be made with a special instrument, sensitive warning lights can be used which will flash red upon sensing movements as small as .002 or .003 in. These devices are well received by miners, and very practical under noisy conditions. High precision is important tit this area, but in large openings, engineer's tapes plus machinists scales reading to .01 in. may be sufficient. Uniform tensioning of the tape is of course essential. Long term, precise measurements have shown repeatedly that opening convergence lends to be slow and uniform except when accelerated to sudden large displacements by blasting, rock bursts or other sudden large scale failures. It is interesting to note that measurements in South Africa in very deep mines have shown 40% of the closure was footwall rise, and only 60% was hanging-wall sag.

Jan 4, 1962

By Porter W. Shimer

The solution used in the following method for phosphorns-determination is the filtrate obtained in the nitric and sulphuric acid method for the determination of silicon (Transactions, vii., 346). This filtrate, being easily and quickly obtained, and always quite free from silica, is a desirable one for phosphorus-precipitation. IN order, however, to get all the phosphorus in a precipitable form the solution must be made under conditions more strongly oxidizing than simple solution in boiling nitric acid. In a solution thus

Jan 1, 1889

By Robert L. Zerga

Mining equipment and systems have been incorporated into the San Manuel mine to meet the requirements of ore development and extraction. A general discussion of the existing equipment as it relates to the specific methods is presented. A comparison is made between original and present equipment, and future equipment needs. The problems, successes and failures of mining equipment adaptation for the San Manuel mining system are highlighted.

Jan 1, 1981

By Murray F. Hawkins, W. J. Ainsworth

In all types of subsurface pressure gauges the extension which occurs in the pressure-sensitive element is a function of the difference between the external (well or calibration) pressure and the internal pressure within the gauge, rather than a function of the external pressure only. The internal pressure is near atmospheric and depends upon (a) the quantity of air sealed within the gauge at the time of calibration or measurement, (b) the quantity of moisture (liquid water), if any, sealed within the gauge, and (c) the temperature at which the calibration or well measurement is made. Part of this correction for the change of internal pressure with temperature is taken care of by the customary temperature coefficient of the gauge. However, part of it is not, and while this portion may be only a few psi, it is nevertheless predictable or preventable, and should be considered in precision measurements. ERROR NO. 1 If air is sealed in the gauge at the same temperature and pressure for both the calibration and the well measurements, the usual temperature correction will take care of any difference between calibration and well measurement temperatures. However, if air is sealed within the gauge at temperature T1 and pressure P1 at calibration but at temperature T2 and pressure P2 for a well measurement, because different amounts of air are sealed within the gauge in each case, the internal pressure at. or corrected to, calibration temperature Tr will he different by where all temperatures and pressures are absolute. The calibration temperature is used, and not the well measurement temperature, because the usual temperature correction reduces the well measurements to calibration temperature. The correction term as calculated by the above equation is separate from. and in addition to, the usual temperature correction. Example: T, = 540°R, sealing temperature at calibration P, = 14.7 psia, sealing pressure at calibration T2 = 460°R, sealing temperature at well P2 = 14.7 psia, sealing pressure at well Tr = 660°R, calibration temperature AP = 660 [14.7/460 — 14.7/540] = 3.1 psi While this error is small even under these somewhat maximal conditions, it nevertheless represents a practical situation which did occur, and which as a matter of fact gave rise to this note. Where AP is positive, as above, the correction is added to the measured pressure; where negative, subtracted from the measured pressure. This correction should also be considered in successive calibration runs where the gauge, for example, may be warm from a previous calibration at an elevated temperature. ERROR NO. 2 Where a small quantity of moisture (liquid water) is sealed within the gauge at atmospheric conditions, the increased vapor pressure of the water at higher well or calibration temperatures will cause an increase in internal pressure. This moisture will come presumably from condensation within the gauge following temperature changes, from moisture on the operator's hands, and from atmospheric moisture (rain, mist, fog, etc.). Calculation shows that approximately 0.2 cc of water (three to four drops) is sufficient to saturate the air within an Amerada RPG-3 Gauge at 160°F, at which temperature the vapor pressure of water is about 5 psia. As the vaporization occurs in a sealed volume, the increase in internal pressure will be in excess of this 5 psi. At higher temperatures the pressures will be higher; however more water will be required to saturate the air within the gauge. Some experimental work was carried out with an Amerada RPG-3 Gauge at 200°F fitted with a 1,000 psi element, both with a dry recording chamber and with a small amount of water added. The results directly proved the existence of the error due to the presence of moisture, and, it is felt, indirectly, due to the differences in sealing temperatures and pressures, as both effects may be ascribed simply to an increase in the moles of gas within the recording chamber. SUMMARY In precision measurements the error introduced by sealing the gauge during a well test at a different temperature and pressure from that of calibration may be corrected for by using the equation presented, or it may be prevented by taking care always to seal the gauge at near calibration conditions. The error introduced by sealing moisture in the gauge may be prevented by taking care to keep moisture out of the gauge, or by removing the moisture by either warming or evacuating the gauge. Both of these errors are independent of the range of pressure measurement and the type of gauge, and are in addition to the usual temperature correction. ACKNOWLEDGMENT Appreciation is expressed to W. B. Kendall, Geophysical Research Corp., Tulsa, Okla., who pointed out the error from differences in sealing temperatures during some winter work in Canada. ***

Jan 1, 1956

By Charles Catlett

THE rapid development of the Portland-cement industry implies that the country is being very carefully searched for material suitable for its manufacture. Such material can be found at a great many places ; but deposits thoroughly satisfactory in chemical composition, and at the same time meeting all the other requirements connected with the economic production and profitable marketing of the product, are exceedingly few, if I may judge from the investigations which I have had to make in a number of States. The raw mixture which by its clinking and grinding forms Portland cement contains approximately 75 per cent. of carbonate of lime. This is found in nature as limestone or marl. The natural rock commonly carries either more than the required percentage of carbonate of lime (in which case it has to be reduced by suitable admixture of clayey ingredients) or less-in which case purer lime carbonate has to be added. The controlling ingredient, therefore, is carbonate of lime, or limestone of the right composition. Among the most serious difficulties is that of finding limestones low enough in magnesia to meet the exacting requirements of certain specifications. All engineers recognize that there is a limit beyond which it is not safe to let the magnesia go; but within that limit there is considerable difference of opinion. Until that difference is finally settled, no one would be willing to invest the large sum of money necessary for a Portland-cement plant, if it were not certain that the usual requirements in this particular could be satisfied. The usual limit in well-established specifications is 5 per cent. of magnesium oxide in the finished cement, but many specifications limit the amount to 3 per cent. These figures

Jan 9, 1907

By A. Phillips, H. J. Fisher

The influence of temperature and composition on the viscosity of high-purity liquid metals and alloys of the Pb-Sn and Sb-Cd systems was investigated by the logarithmic-decrement method. The variation of viscosity with temperature above the liquidus followed the equation: n = AeE/RT No large increase in viscosity was found just before normal freezing of any of the metals or alloys investigated. Certain alloys, supercooled below their stable liquidus, however, did show a marked increase in viscosity. Experimental activation energies for viscosity were determined for the metals investigated. Liquid-metal density values were obtained by a modified Joeger's method. IK an investigation of the properties of molten metals, the study of viscosity as a suitable means for studying the physical nature of the metallic liquid state has been utilized. Although interest in the relationship of the liquid to the solid-metal state holds promise of broadening the knowledge of metals in general, much information that is available regarding the influence of temperature and composition on viscosity, especially near the freezing point, is still controversial. The purpose of this paper is to present the results of recent work on this subject. Although interest in factors influencing the fluid behavior of metals and alloys has arisen from theoretical as well as applied studies of liquid-metal properties, the development of a comprehensive theory of the mechanism of viscosity has been handicapped because so little is known about the liquid state. Several theories of viscosity have been proposed and among the more recent are those of Andrade,1 Bernal,2 Frenkel,3 Eyring,4 and Gutmann and Simmons.5 Athough these contributions have helped to establish a basis of approach for studying the nature of viscosity, the fundamental aspects of the variation of viscosity with alloy composition have, in general, been neglected. Experimental Metals and Alloys Investigated: The Pb-Sn and Sb-Cd alloy systems were selected for investigation because they form constitutional features of theo-

Jan 1, 1955

By D. E. Pickett, E. G. Joe

In accordance with good industrial practice, Canadian metallic-ore concentration plants have always recycled a high proportion of process water to save reagents, save power, conserve water resources, and to protect the community water supplies, to give only a few reasons. In the last few years there has been awakened public concern for the environment and, consequently, government regulations have been added as additional reasons. Present recycling practices are summarized as a basis for improved plant design and operating procedures and for further research. In addition, an attempt is made to determine why plants do not recycle water in certain situations. Although not all Canadian mills are covered, the many examples given indicate the problems and the effort being made to solve them. Wherever available, the chemical quality of the water and the process requirements are indicated as well as the other parameters affecting water recycling at each operation.

Jan 1, 1975

By William F. Campbell

One of the deepest coal operations today is the Springhill No. 2 mine of Cumberland Railway & Coal Co., subsidiary of Dominion Coal Co. Ltd. Mining is now conducted at a slope distance of 14,000 ft, with 4400 vertical ft of cover. The record of Springhill No. 2 can be said to contain the history of bumps in the Province of Nova Scotia. The Springhill coal field forms part of the Cumberland field of Carboniferous age. There are seven mineable fields in the area, numbered in the order they were discovered. Mining has been carried on in all but the No. 4 and 5 seams, but present operations are confined to the No. 2. Fig. 1 shows a vertical section through the seams.

Jan 9, 1958

By J. M. Woodall

GuAs crystals which have been grown in quartz boats by the horizontal Bridgman method in the pvesence of Ga20 vapov have beetz found to have carrier and donor distributions which do not correspound to those expected from simple dopant seg-vegation during directional freezing; Instead, the carrier distribution is determined by the heat-trentnzent history of the crystal, while the donor distribution, zohiclz is principally due to silicon, is fixed by the pozuth rate, the geo)tlet.ry of the crystal growth vessel, and tlze initial Ga20 pressure. WHEN semiconducting materials are made into doped crystals by the normal freezing method,&apos; they usually exhibit doping variations along the growth axis. If a) there is no dopant diffusion in the solid, b) the dopant is distributed uniformly in the melt, and c) the distribution coefficient, k, does not vary with composition, then the doping variation along the growth axis is represented by the equation: where C is the doping level in the solid at a point where a fraction g of the original liquid has frozen, and Co is the mean concentration. When the dopant is either a singly ionized shallow donor or shallow acceptor, C also represents the carrier concentration. Even though this equation accurately describes the dcping profiles of a large number of normal freeze systems, there are several special systems for which Eq. [I] does not apply. One such system is the horizontal Bridgman method for preparing oxygen-grown GaAs crystals using quartz vessels. Several workers2"* have shown that GaAs crystals grown by the horizontal Bridglnan method using quartz vessels are generally contaminated with silicon in concentrations in excess of 5 < 10lG atoms per cu cm. This contamination is ascribed to a reaction: occurring at the walls of the crystal-growth vessel which liberates silicon into the melt and Ga2O vapor. It has been shown4 that this reaction, and, hence, the silicon contamination, can be suppressed by the addition of oxygen to the crystal-growth apparatus. It is the purpose of this paper to describe a special apparatus capable of yielding single crystals of GaAs grown in the presence of oxygen and to describe both the kinetics of silicon suppression in this system and the relationship between the carrier concentration profile and the silicon concentration profile. EXPERIMENTAL-CRYSTAL GROWTH A schematic diagram of the apparatus used in the oxygen addition experiments is shown in Fig. 1. The most important features of this apparatus are: a) the use of a sand blasted quartz boat, h) a quartz rod of length 1, with a hole of cross section A, that is placed near the boat to limit the free space volume V, over the melt during the growth, and c) the temperature gradient at and near the solid-liquid interface. Sand blasting the boat is necessary to prevent wetting of the melt. The quartz rod retards the diffusion of the GazO vapor away from the melt to the colder portions of the ampoule. A crystal is prepared by first loading a 5.5-in. boat, which has been cleaned in aqua regia, with 40 g of 99.9999 pct Ga along with 1 to 8 mg of Ga203 powder. GazO3 is a convenient source of oxygen since it reacts with gallium at the melt temperature to form Ga20 vapor, the species which apparently controls the suppression of silicon contamination. The loaded boat, the quartz rod, and the 99.9999 pct As are placed in the ampoule as shown in Fig. 1. Generally, GaAs seeds were not used since most of the unseeded growths resulted in monocrys-tals. The ampoule is evacuated to 10-5 Torr and sealed off. The GaAs melt is synthesized by placing the ampoule into a two-zone horizontal Bridgman furnace. The two zones are separated by several sandwiched layers of -in. Fibre-Fax board drilled with holes slightly larger than the OD of the ampoule. This causes a very large temperature gradient between the two zones, which is necessary for single-crystal growth. The two-zone furnace is mounted on a stand fitted with a roller bearing which allows uniform motion of the furnace in a horizontal direction. A uniform velocity of the stand is achieved by the use of a windlass device which winds up a wire attached to the stand. Movement of the solid-liquid interface is accomplished by fixing the position of the ampoule and moving the stand. Growth rates investigated in this experiment were between 0.4 and 1.2 in. per hr. The composition of the melt is fixed by maintaining an arsenic reservoir at 618°C. The stand is moved away

Jan 1, 1968

By C. S. Barrett, P. Coheur

ANNEALING twins are common in the microstructure of copper that has been rolled and recrystallized. In such samples it follows that a twin relationship should exist between components of the recrystallization texture,1 and several examples of this have been reported. For example, twin relationships have been found in recrystallized electrolytic copper sheet, as indicated in Fig. I, from a paper by Coheur and Lejeune.2 In this pole figure the cube texture (100) [001] is indicated by the hollow squares in the lower half of the figure (the pole figure for 200 reflections) and in the upper, (111), part of the figure. The texture contains, in addition to this orientation, the first-order twins of it, shown in the figure by the filled triangles. This orientation relation has been suggested by others also, under certain annealing conditions,3,4 although pole figures have not been published to confirm it. Some orientations in recrystallized sheets are identical with their twins, because of the symmetry elements of the texture this is true, for example, with the (113) [211] texture so commonly reported for brass-hence it appears impossible in such samples to decide whether the twin relationships result from twinning or merely from the symmetry of the deformation process. The present investigation of a commercial copper strip seems to yield an example in which annealing twins account unambiguously for the principal orientations present. It proves to be a case, also, for which the recrystallization texture cannot be viewed as derived from the deformation texture by a first or second-order twinning mechanism . MATERIALS AND METHODS The samples investigated were of secondary copper (melted in Belgium) to which 0.19 per cent iron had been added to raise the recrystallization temperature. How much the orientation characteristics of this metal can be ascribed to the iron content and how much to other impurities or to melting and pouring practice has not been investigated.* The rolling was done in one direction only, on a mill with rolls of about 20-cm diameter. A strip 10 cm wide was reduced from 5 mm thickness to 0.05 mm by several cold passes at commercial speeds. The samples cut from this 99 per cent reduced strip were X-rayed throughout their entire thickness. A pole figure made soon after rolling and annealing was identical, within experimental error, with one that was made when a two-year interval occurred between rolling and annealing. X-ray patterns were made on a cameral that traversed

Jan 1, 1946

By M. Metzger, T. A. Read

The strengthening effects of hydroxide and synthetic plastic films in the creep of cadmium crystals were studied. The results were broadly consistent with the naive mechanical model. The dislocation-film reactions and the significance of the macroscopic stresses associated with certain films are discussed in the paper. ALTHOUGH a number of studies have been made of the strengthening of metal single crystals produced by surface films usually less than Ir in thickness, the mechanisms underlying this phenomenon are still not well established. Roscoe&apos; first noted the critical shear stress and the stress-strain curve of cadmium-crystal wires to be raised markedly by the presence of oxide films. Subsequent investigators2-&apos; have confirmed the effect for several metals and films including a number of plated poly-crystalline metal films. Harper and Cottrel1" with a thin film on zinc presumed to have formed as a result of etching and washing treatments) did not detect a strengthening at a rate of extension of 10 &apos; sec-&apos; although at lo-&apos; sec-&apos; the film raised the flow stress by 7 pct at 0.0005 extension and by 22 pct at 0.01. The marked strengthening at moderate strains thus appeared to be the result of a dynamical effect dependent on the rate and amount of plastic flow. Other observations&apos;. " are consistent with this view. The large effects of films on the tensile creep rate of single crystals were demonstrated when the observation of Andrade and Randall," that the creep rate of cadmium crystals increased on immersion in aaueous solutions of certain cadmium salts. was shown&apos; * to hold only when a film was present initially and was explained by the attack of the solution on the film and the removal of its strengthening effect. Changes in the creep rate interpretable in terms of the removal or formation of various films have been observed by other investigators.3,8,10,31 Certain other experiments have been reported in which surface films or liquid environments have affected the plastic behavior of metals, but these are not within the scope of the present work which deals with the effect of solid films on single-crystal slip. Possible Mechanisms—The film does not significantly reduce the load on the crystal in the elastic range (the elastic moduli of film and crystal are not too greatly different and the area of the film is so small that its share of the load is negligible) so that the initial operation of internal Frank-Read sources is not affected. However, as Fisher" has pointed out, a source terminating on the crystal surface requires only half the critical stress for activation as an internal source of the same length and a relatively strong film (even a very thin one) would pin the free ends of the surface sources so that, if surface sources are responsible for plastic flow in a clean crystal. such a film would increase by roughly a factor of 2 the stress necessary for generation of dislocation loops at a given rate. The other general possibility is that the film resists the passage to the crystal surface of internally generated dislocations. If the film is adherent and if the specimen is to exhibit slip of the same general character as a film-free specimen, the film must deform or fail in shear at the active slip planes. The naive mechanical model, where shear-stress relaxation across the active slip plane in the metal transfers load to the film until it deforms and slip can

Jan 1, 1959