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By E. A. Steigerwald

E. A. Steigerwald (Thompson Ramo Wooldridge, Inc.1— he authors' results clearly indicate that cracking can be produced by the hydrogen pressure developed during a charging operation. This type of cracking or blistering has also been observed in polycrystalline materials24"28 when the charging conditions are sufficiently severe and is often referred to as irreversible embrittlement since it cannot be removed by a baking treatment. There are additional data, however, which must be considered before a pressure theory can be generally employed to account for all failures which occur as a result of hydrogen. In many cases, hydrogen embrittlement in a tensile test or in delayed failures under static loads is a reversible phenomena which cannot be simply explained on the basis of preexisting cracks generated by the charging operation. It is this aspect of the problem which has prompted many investigators to seek mechanisms other than hydrogen pressure to explain their results.24'n728 Fig. 15 indicates an example where, under specific experimental circumstances, hydrogen embrittlement can occur at liquid nitrogen temperatures. In this case, which has been previously decribed,'' specimens were charged with varying quantities of hydrogen, immediately quenched, and tested in liquid nitrogen (-320°F). A companion set of identical specimens were charged, aged at 300°F to remove the hydrogen, and also tested at -320°F. When the current density was greater than lo-' amp per sq in., embrittlekent occurred in both sets of specimens, indicating that cracking had occurred during charging and the embrittlement, as in the case of Fe-Si single crystals, was irreversible. At current densities between approximately 103 and lo-' amp per sq in, the embrittlement was present only for those specimens which contained hydrogen during the testing sequence. The embrittlement was therefore reversible with respect to the aging and charging operations. Since extensive hydrogen movement would not be expected at -320°F, it is difficult to reconcile these data with a mechanism which requires pressure and pressure dependent growth of preexisting cracks. There are other features of hydrogen embrittlement such as the reversibility of the incubation time for delayed failure with respect to applied stressg0 and the influence of prestraining31 which are also difficult to explain using a pressure model. Any general mechanism of hydrogen embrittlement will have to consider the reversible aspects of the embrittlement data as well as the irreversible portion which has been clearly presented for the Fe-Si crystals and which is consistent with a pressure model. A. S. Tetelman and W. D. Robertson (authors' reply)—he authors agree with Dr. Steigerwald that a general mechanism of hydrogen embrittlement must be applicable in all cases where embrittlement occurs. Dr. Steigerwald's experiments were performed on an iron alloy which has an extremely complex microstructure, and therefore does not lend itself to the direct and detailed observations that can be made in Fe-Si. The change in the characteristics of cracks as a consequence of annealing at 300°F is not really known in detail but it is probable that stress-relaxation (blunting) occurs, dislocations produced near the crack tips will be pinned by carbon atoms, and hydrogen will be lost to the atmosphere. Any, or all of these effects of annealing will alter the ease with which a crack subsequently propagates under applied stress. A quantitative treatment of the problem must take these effects into account. Since diffusional processes are presumably eliminated at -320°F, the general mechanism proposed by Dr. Steigerwald's colleagues cannot be operative at this temperature. A detailed discussion of the general' inapplicability of this mechanism has been presented elsewhere. However, the data presented by Dr. Steigerwald in his discussion can be explained in terms of a pressure model. Crack propagation under internal pressure P and applied stress occurs when where is the total energy expended in creating new surface area and by plastic work at the crack tip. The total crack length increases with increasing current density, since we have shown that it systematically increases with hydrogen concentration and Dr. Steigerwald has shown that hydrogen concentration increases with current density. For large L (high current density) Eq. [I] can be satisfied even if P = 0 and the embrittlement process does not require the presence of hydrogen. Specimens charged at a lower current density will con-

Jan 1, 1963

By V. G. Leak, R. A. Swalin

The dilhsion of silver and trace concentrations of tin in liquid silver has been rrzeasured in the temperature range from about 975° to 1350°C. The difBsion dala. fil lhe following equations: fov self-diffusion of silver The ratio of DSn to DAg is found to be about 1.34. The higher diffusivity of tin is interpreted in terms of the coullombic repulsion which results from the fact that tin dissolved in silver has a valence of +3 relative to silver. THE phenomenon of diffusion has been well-described theoretically for hard-sphere gases and solids and found to be in good agreement with experimental data for certain gases and solids. Liquid-diffusion phenomena have not been well described theoretically and there is generally a lack of good experimental data. In this investigation self-diffusion and solute diffusion in liquid silver were studied. Silver was chosen as a solvent for two main reasons. First, silver is a noble metal and the atoms are considered to have a spherically symmetric charge field; hence the liquid may be considered to be a random array of approximate hard spheres. Mercury, gallium, and other lower-melting metals were eliminated from consideration since it appears possible that in their liquid states there is some residual long-range order and directional bonding. Second, silver behaves as a monovalent solvent and, while cadmium, indium, tin, and antimony all have nearly the same atomic size, they have chemical valences relative to that of silver of +1, +2, + 3, and +4, respectively. Slifkin, Lazarus, and coworkers1-5 investigated the diffusion of these solutes in solid silver and found that their diffusion rates increased with an increase of the excess valence of the solute. In the solid state the diffusion-rate increase was calculated to be due to a change in local modulus of the solvent caused by the excess valence of the solute.1"3 For the present investigation it was planned to determine the effect of valence upon solute diffusion in liquid silver. It was deduced that a coulombic repulsion between solute and solvent might be responsible for larger volume fluctuations in the vicinity of the solute thereby enhancing the diffusion of the solute atoms. Tin was the first solute investigated and was chosen for experimental convenience. If an excess-valence diffusion effect exists in the liquid state, the solute tin with its excess valence of + 3 might show a large enough effect to distinguish it from the self-diffusion of silver in silver. The silver self-diffusion data were obviously required as a base line for comparison. In addition silver self-diffusion was investigated with a view toward examining the data in connection with the Sutherland- Einstein: Coheen-Turnbull,7 and swalin8 theories of diffusion in liquids. I) EXPERIMENTAL TECHNIQUES The diffusion coefficients for tin and silver in liquid silver were determined in separate experiments using the capillary-reservoir method of Anderson and saddingtono but following closely the experimental techniques outlined by Ma and Swa1in. The radioactive alloy bath was prepared by plating either tin-113 or silver-110 m isotope* onto 99.999 *Isotopes obtained from Oak Ridge National Laboratory. pct Ag rods.* The silver and isotope were melted *Silver obtained from Cominco Co. and mixed in a graphite crucible under a purified argon atmosphere, then outgassed for capillary filling. Some of the fused-silica capillaries were filled individually as reported by Ma and Swalin, but most were filled in a different manner. A long piece of capillary tubing was sealed off on one end and held in the system so that the open end was just above the surface of the molten alloy. The system was evacuated, the open end submerged into the alloy, and argon was admitted into the system up to atmospheric pressure. The molten alloy was forced up the capillary several inches where it solidified and was subsequently cut into segments of the proper length for diffusion annealing. The apparatus for diffusion annealing was the same as that used for capillary filling except that a Pt—Pt, 10 pct Rh therinocouple was placed in the solvent bath in order to accurately measure the temperature during the run. A diagram of the dif-

Jan 1, 1964

By J. E. Warren, J. H. Hartsock

Because of the extensive utilization of hydraulic fracturing for the stimulation of low-productivity wells, the two related problems of fracture design and evaluation have become economically significant and, as a consequence, helve motivated this investigation. The producing characteristics of horizontally fractured wells were studied to determine the fracture configuration that should be employed as the basis for the design of the treatment and to develop a method that can be used to establish the degree to which the design objectives have been achieved. The equations which describe the steady-state flow of a single-phase fluid into, and through. a finite-capacity fracture were solved numerically for an idealized reservoir-fracture model. The numerical results were used to obtain an apparent skin effect for each combination of the parameters considered. Based on the computed results, subject to the limitcitions implied by the assumptions that were made, the following general conclusions were drawn. 1. For a radius of drainage at least four times us large as the radius of the fracture, an apparent skin effect that is independent of the radius of drainage can be calculated. 2. The productivity of the hydraulically fractured system, relative to that of the unfructured well, can be determined from the apparent skin effect and can be used to establish design objectives. 3. In the evaluation of a fracture job, it is not Possible to determine both the radius of the fracture and its flow capacity uniquely from the apparent skin effect; an independent determination of one of the quantities is necessary. lNTRODUCTION Although hydraulic fracturing has been employed as a method for stimulating the productivity of literally hundreds of thousands of wells during the past 10 years, it is only in the last few years that improvements in fracture design1-6 and fracturing technique' have combined to increase the probability of obtaining a successful treatment to such an extent that the mechanics of the method may be considered to be standardized. From an economic point of view, however, two related questions must be satisfactorily answered before hydraulic fracturing can be used in the most profitable manner. The two questions are the following. I. For a particular well in a given formation, what are the optimum design specifications for the fracture treatment? 2. Have the design objectives been achieved by the fracture treatment? The significance of these questions has been recoguized, and some attempts to obtain answers have been made. Howard, et al,8 endeavored to determine the optimum treatment, based on maximizing profits, for any given formation; unfortunately, this work was based on a crude method for approximating the productivity of a well. Carter and Tracy9 utilized the same approximation to study the effect of fracturing on the behavior of a well producing by virtue of a solution-gas drive. Electrolytic models were used by van Poollen10 to investigate the variation in productivity due to fracturing; however, only a limited number of results were presented. Later, from the same model results, van Poollen, et al,11 attempted to justify an approximate expression for determining the productivity of a fractured well. It is quite apparent that there is a definite lack of the practical information necessary for specifying the optimum fracture configuration to be considered for design purposes. The only detailed attempt to develop a procedure for evaluating the result of a given fracture treatment appears to be that of van Dam and Horner.12 These authors described a technique for analyzing pressure build-down data, obtained immediately after fracturing, to determine the final fracture volume, the final fracture porosity, the fracture area, the fracture thickness and the in situ fluid loss of the fracturing fluid. While this approach should be useful whenever acceptable pressure measurements are available, it does not yield a value for the flow capacity of the fracture. Since the problems of fracture design and evaluation are inversely related, it should be sufficient to study the effect of the fracture configuration on the performance of a well. The primary objective of this investigation is to evolve a technique for computing the desired solutions. The secondary objective is to analyze these computed results in order to prescribe a method for evaluating fracture treatments. Because this study is exploratory in nature, its scope

By C. S. Finney, John Mitchell

The growing popularity in the United States of the vertical-flue even was emphasized when in 1905 the United States Steel Corp. chose the Koppers oven as the type which best suited their requirements. Heinrich Koppers was born on November 23. 1872. at a small farm in Walbeck near Geldern on the lower Rhine. When young Koppers was eight years old, however the family moved away from the farm to the industrial city of Bochum in the Ruhr. Here Koppers attended public school and subsequently served an apprenticeship to a tinsmith before taking a job as a lathe operator with a local steel company. He had ambitions to be much more than a machinist, however, and used his week-ends and evenings to improve his theoretical background by taking courses at a vocational-training school in Bochum. After winning the highest honor the school could bestow (the silver Staats-medaille), Koppers went on to continue his education at the Rheinisch-Westfalische Hüttenschule in Duisberg. One of his teachers there, Fritz Wüst who later became a professor at the Technische Hochschule at Aachen, recognizing Koppers' unusual abilities, predicted for him a great future. In 1894 Heinrich Koppers joined the firm of Dr. C. Otto and Co. in Dahlhausen, and in 1899 while superintendent of the Mathias Stinnes mine he built his first battery of ovens for Hugo Stinnes, the German industrialist. Two years later he started his own organization, and in 1902 he made Essen his headquarters. It was to Essen that a group of engineers from the United States Steel Corp. went in 1906 with an invitation to Koppers to design and supervise the construction of four batteries of ovens at the Joliet works of the Illinois Steel Co. Each battery was to consist of 70 ovens. Arriving in the United States in 1907, Koppers established a branch of his firm in Joliet, and construction began. The first battery was fired on July 27, 1908. Rugged and simple, these ovens incorporated basic design features which were to make the Koppers oven and its future modifications the choice of a very large segment of the by-product coking industry of America. The 280 ovens at Joliet were 35 ft long, 8 ¾ ft in height, and tapered from 21 to 17 in. The total daily capacity of the four batteries was 2240 tons of coke. The ovens were of the new cross-regenerative type; that is, instead of longitudinal regenerators serving an entire battery, as in the older Koppers ovens, cross regenerators for each separate oven were employed. Fuel gas was supplied from the side of the battery through ducts in the brickwork known as gun flues, which reached to the center of the battery under the vertical heating-flues. Removable, ceramic gas-nozzles fitted at the top of each gun flue helped to insure good control over the distribution of the fuel gas, and uniform heating conditions were also promoted by regulating the air supply to, and the suction in, each heating flue. A different refractory w& used for each battery. One was built of American silica brick, one of American quartzite, and two of imported German quartzite. The installation at Joliet proved to be very successful, and in 1911, 490 additional' Koppers ovens were built for the Illinois Steel Co. at the great new steelworks at Gary, Ind. By 1912 the H. Koppers Co. had established its headquarters in Chicago and was rapidly extending its business to include construction for such iron and steel companies as the Woodward Iron Co. at Woodward, Ma. (80 ovens in 1912); the Tennessee Coal, Iron and Rail- road Co. at Fairfield, Ala. (280 ovens in 1912); the Inland Steel Co. at Indiana Harbor, Ind. (86 ovens during 1913 and 1914) ; and the Republic Iron and Steel Co. at Youngstown, Ohio (68 ovens in 1913). In 1914 a group of men in Pittsburgh bought a major shareholding in the H. Koppers Co., and moved the headquarters of the organization from Chicago to their own city. Under its new management the company was highly successful in obtaining a large share of the contracts for by-product installations built during World War I. In 1917 the remaining German interests in the company were

Jan 1, 1961

By Appendix by A. S. Goldoni, R. E. Tate, E. M. Cramer

The diffision coefficient for self-diffision of plutonium in the temperature range 350" to 440°C has been measured by using puZ3 as the tracer isotope. Autoradiopaphic techniques were used to inzlestigate the possibility of grain boundary diffusion, hut only evidence for volume diffusion was found. The least-squares fit of the data gives the .following equation for the diffision coefficient: The computer least-squares technique for fitting the nonlinear equations is outlined. DETERMINATION of the self-diffusion coefficient of the fcc 6 phase of plutonium is in principle a straightforward experimental task. However, the chemical reactivity, the intense @ activity, and the toxicity of plutonium put limitations on the experimental techniques. The technique selected included roll bonding for preparation of the diffusion couples and pulse-height analysis of the @-particle activity to determine the distribution of the PU tracer in the diffusion couples. EXPERIMENTAL PROCEDURE Couple Preparation. Cylinders about 0.5 in. in diam were cast from two special stocks of plutonium, one of which had been enriched in puZ3', as shown in the isotopic analyses listed in Table I. For each roll-bonded composite sheet, a cylinder 0.437 in. in diam and 0.190 in. thick was turned from each kind of plutonium on a lathe in a 98 pct He atmosphere. The two freshly machined cylinders were positioned face to face in a tube of commercially pure aluminum which had been sealed at one end by welding and the assembly was evacuated on a vacuum manifold overnight. The elapsed time between machining the faces of the plutonium cylinders and evacuating the loaded tube was about 15 min. After overnight evacuation of the assembly the indicated vacuum was 1 X 10"5 torr or better. The aluminum tube was then warmed and pinched off with a cold-welding tool. The pinched-off weld was also fusion-welded as an additional precaution against leakage of air into the evacuated assembly. The assembly was immediately heated for 30 min in a 250°C furnace and reduced in thickness by being passed through a rolling mill with rolls heated to 200°C. The rolling schedule (four passes of 100 mils each with a 10-min reheat after two passes) reduced the thickness of the assembly to 100 mils. The rolled assembly was allowed to cool normally in air. The rolled assembly was sheared at the edges and the aluminum peeled from the composite plutonium sheet. The elliptical sheet was about 0.060 in. thick and usually three 0.383-in.-diam disks could be punched from its central portion. The sheet was heated on a hot plate to the ductile low 0 range (140°C as measured by temperature-indicating pellets) before each disk was quickly punched. The quality of the bond in the disks was evaluated by metallographic examination of the scrap sheet adjoining the hole left by the punch. Only well-bonded specimens without oxide in the interface (as indicated by metallography) were considered satisfactory for further use. More than half of the specimens so examined contained sufficient oxide in the interface to be rejected. Diffusion Anneal. Each disk to be diffusion-annealed was wrapped in 1-mil-thick tantalum foil and sealed within a Pyrex capsule evacuated to 1 x 10~5 torr or better. This capsule was then sealed within another Pyrex capsule at a similar pressure. The diffusion anneals were carried out at temperatures between 350" and 440°C in Marshall furnaces adjusted to have a temperature gradient of not more than *1/2"C over a 5-in. length. This gradient was then further smoothed by using a nickel tube as a liner in the furnace. The liner was divided into three longitudinal cavities by a septum of nickel sheet to which two calibrated Chromel-Alumel thermocouples were attached. One thermocouple was used for controlling the furnace temperature by means of a Brown Pyrovane controller equipped with a Capaciline anticipation circuit; the second thermocouple was monitored twice daily with a Leeds and Northrup K-2 precision potentiometer.

Jan 1, 1964

By Paul M. Tyler

YEAR after year, the kaolin industry of the United States has been setting new production records and making better products. High-grade paper, pottery, and rubber clays are produced in this country mostly in the South. Georgia alone contributes over 70 pct and South Carolina almost 20 pct of the total domestic output. Residual kaolin is mined in North Carolina, highly plastic but naturally sandy Tertiary (Eocene) potting clays are worked in north central Florida, and good white clays are produced in several other states, but the main sources of kaolin or china clay have been numerous deposits in the Tuscaloosa (Upper Cretaceous) formation. This formation of generally sandy sediments is called the Middendorf member in older geologic reports and corresponds in age with some of the New Jersey clays. As shown in fig. 1, it crops out almost continuously in a generally southwesterly direction across South Carolina and Georgia and into Alabama. Clay is mined from this formation in all three states but the principal producing centers lie within about 10 miles of a straight line drawn between Aiken, S. C., and a point about 10 miles south of Macon, Ga. The white kaolins of the South were recognized and used prior to the Civil War but suitable treatment processes were not introduced until World War I when imports, chiefly from England, were curtailed. Although imports of high-grade clays were resumed after 1918, the domestic industry managed to treble its prewar production record during the early 1920's and has continued to grow. Whereas the 1909 to 1913 average total production in the United States was only 132,104 short tons valued at $705,352 f.O.b. mines, the output in 1948 was 1,-568,848 tons worth $19,756,738. Paradoxically, it seems in retrospect that the early failure of the American industry to meet foreign competition was due to the superior quality of our sedimentary clays in their natural state. Kaolin, of course, is the principal decomposition product of feldspars which originate in acidic igneous rocks such as granite, aplite, alaskite, granodiorite, quartz porphyry, etc. English china clays occur in residual deposits and before they can be marketed they have to be treated to remove accompanying quartz, mica, and other impurities. Notwithstanding the relatively crude methods employed, the final product is a beneficiated clay which is subject to a certain amount of technical control as to quality and uniformity. Although the naturally concentrated deposits in Georgia and South Carolina contain some of the finest crude white kaolin in the world, even it can be made better by suitable treatment. In recent years well over half of the high-grade china clay produced in the United States has been used in making paper. Some qualities of paper clays are still produced by the dry process, or air flotation, but the paper industry's specifications have grown so exacting that wet processing was adopted and more refined methods had to be perfected. Notwithstanding notable advances in clay-preparation technology during the past decade, or possibly because these advances have implemented and encouraged technologic changes in consuming industries, demand has grown for products of higher uniform quality than can be obtained from even the best natural deposits without rigidly controlled fractionation. Largely as a result of the wide adoption of machine coating for paper, the clay industry has been obliged not merely to eliminate virtually all mineral impurities but also to segregate the clay substance itself into narrow particle-size ranges. By extraordinary coordination of sales effort and production technology, several Georgia companies manage to market a wide variety of specialized joint products but the commercial success of many producers depends upon their mining only the best parts of their deposits and then skimming the cream of this almost pure clay in order to obtain a maximum yield of kaolinite finer than about 2 microns in maximum particle size and possessing low viscosity as well as the more familiar attributes of suitable color and brightness, or reflectance. To the casual visitor from another mineral industry, the kaolin mines and plants may appear to be

Jan 1, 1951

By Paul M. Tyler

YEAR after year, the kaolin industry of the United States has been setting new production records and making better products. High-grade paper, pottery, and rubber clays are produced in this country mostly in the South. Georgia alone contributes over 70 pct and South Carolina almost 20 pct of the total domestic output. Residual kaolin is mined in North Carolina, highly plastic but naturally sandy Tertiary (Eocene) potting clays are worked in north central Florida, and good white clays are produced in several other states, but the main sources of kaolin or china clay have been numerous deposits in the Tuscaloosa (Upper Cretaceous) formation. This formation of generally sandy sediments is called the Middendorf member in older geologic reports and corresponds in age with some of the New Jersey clays. As shown in fig. 1, it crops out almost continuously in a generally southwesterly direction across South Carolina and Georgia and into Alabama. Clay is mined from this formation in all three states but the principal producing centers lie within about 10 miles of a straight line drawn between Aiken, S. C., and a point about 10 miles south of Macon, Ga. The white kaolins of the South were recognized and used prior to the Civil War but suitable treatment processes were not introduced until World War I when imports, chiefly from England, were curtailed. Although imports of high-grade clays were resumed after 1918, the domestic industry managed to treble its prewar production record during the early 1920's and has continued to grow. Whereas the 1909 to 1913 average total production in the United States was only 132,104 short tons valued at $705,352 f.O.b. mines, the output in 1948 was 1,-568,848 tons worth $19,756,738. Paradoxically, it seems in retrospect that the early failure of the American industry to meet foreign competition was due to the superior quality of our sedimentary clays in their natural state. Kaolin, of course, is the principal decomposition product of feldspars which originate in acidic igneous rocks such as granite, aplite, alaskite, granodiorite, quartz porphyry, etc. English china clays occur in residual deposits and before they can be marketed they have to be treated to remove accompanying quartz, mica, and other impurities. Notwithstanding the relatively crude methods employed, the final product is a beneficiated clay which is subject to a certain amount of technical control as to quality and uniformity. Although the naturally concentrated deposits in Georgia and South Carolina contain some of the finest crude white kaolin in the world, even it can be made better by suitable treatment. In recent years well over half of the high-grade china clay produced in the United States has been used in making paper. Some qualities of paper clays are still produced by the dry process, or air flotation, but the paper industry's specifications have grown so exacting that wet processing was adopted and more refined methods had to be perfected. Notwithstanding notable advances in clay-preparation technology during the past decade, or possibly because these advances have implemented and encouraged technologic changes in consuming industries, demand has grown for products of higher uniform quality than can be obtained from even the best natural deposits without rigidly controlled fractionation. Largely as a result of the wide adoption of machine coating for paper, the clay industry has been obliged not merely to eliminate virtually all mineral impurities but also to segregate the clay substance itself into narrow particle-size ranges. By extraordinary coordination of sales effort and production technology, several Georgia companies manage to market a wide variety of specialized joint products but the commercial success of many producers depends upon their mining only the best parts of their deposits and then skimming the cream of this almost pure clay in order to obtain a maximum yield of kaolinite finer than about 2 microns in maximum particle size and possessing low viscosity as well as the more familiar attributes of suitable color and brightness, or reflectance. To the casual visitor from another mineral industry, the kaolin mines and plants may appear to be

Jan 1, 1951

By Joseph Lindmayer, Karl M. Busen

If silicon is in contact with silicon oxide, a heterojunction is formed which induces an inversion layer ("channel"). Influences of impurities and structural parameters on the channel are discussed. There seems to be no relation between surface damage in silicon and the channel. Phosphorz~s doping of the silicon oxide has no pronounced effect on the channel. Channels which were well above the range predicted by the heterojunction model were related to the action of H* at the silicon/silicon oxide interface. Channels which were well below tlze range predicted by the heterojunc-tion model were related to a transition region in the oxide adjacent to the interface. In support of the assumed transition region and the H+ are the ex-periments described on the paper. Furthermore, the concept of metastable OH groups in silzca, known from other publications, has been used to explain certain channel characteristics by the formation and the accommodation of hydrogen in the silicon oxide. THE electrical characteristics of a semiconductor device in many cases are influenced by the conditions of its surface. Because these conditions often are changing with temperature, time, ambient, or other parameters, numerous attempts have been undertaken to stabilize them by suitable processes. Several years ago Atallal studied the silicon/silicon dioxide interface and since then increasing attention has been given to the silicon dioxide as a means to stabilize silicon surfaces. This led to the evolution of the planar silicon devices where oxide layers are used to protect places at which the junctions are intersecting the surface. The formation of the oxide layers on silicon can be carried out by a variety of processes: high-temperature thermal oxidation (exposing the silicon surface to oxidizing agents such as 02, HzO, COz), evaporation of SiOz, or anodic oxidation of silicon. Originally the oxides were considered able to "passivate" the silicon surface and it was understood that they 1) protected the surface against any influence from the ambient and 2) stabilized surface conditions which were necessary for proper device performance. It soon was realized that the second quality was not always obtainable: Atalla and Tannenbaum showed that, in the process of forming a layer on doped silicon by thermal oxida- tion, electrically active impurities in the silicon near the interface are redistributed, thus giving rise eventually to the formation of unwanted charge distributions. The degradation of planar junctions during reoxidation of silicon was observed by Barson et a. Surface studies with silicon planar junction structures indicated that the breakdown voltage depended on the kind of procedure which was applied during or after oxidation.*" Yamin and worthinge report on charge storage and dielectric properties of SiOz films at elevated temperatures. Another influential parameter on the silicon surface is discussed by Lindmayer and usen,' namely the appearance of a surface potential on silicon as a consequence of the heterojunction formed by the silicon/silicon oxide interface. In the present paper the influence of impurities and structural parameters in silicon oxide in connection with the heterojunction is a particular object of our investigations. I) EXPERIMENTAL The material used was 10 ohm-cm p-type silicon slices with either damaged surfaces (mechanically lapped or polished) or damage-free surfaces (chemically polished). The majority of the slices were oxidized for 1 hr and 20 min at 1250°C in a steam + oxygen atmosphere generated by passing O2 through HzO at 90°C (wet oxygen). This led to oxide layers of about 9000 A. On some slices oxide layers were grown in pure oxygen (dry oxygen). By a photoresist process a set of 20 by 200 mil windows was then etched out from the oxide layer. The pattern of the windows is shown in Fig. 1. In a subsequent process n-type pockets with surface concentrations between 2 x 10" and 5 x 10" cm"3 were formed by phosphorus diffusion. This allowed ohmic contacts between the silicon surface and tungsten probes which for electrical measurements were placed into two adjoining windows and

Jan 1, 1965

By Shozo Saito, P. A. Beck

Mettrllographic and X-ray diffraction study of Cb-Co alloys in the Composition range of 7 to 33 nt. pct Cb, after annealing at 1175 °', showed that near 25 al. pct Cb on MgNi,-lype hexagonal Laves Phaseexists in a narrow composition range, and that an MgCl- type cubic Laves Phase occurs between approximately 27 and 32.6 ut. pd Cb. Lattice parameter and density measures indicated that, in both phases. the deviations from proper Loves sloichimetry result from the substitution of cobalt atoms for some 0f the columbium atoms. Tlle same phases occurant 1000'C, together with an additional phase of unknown structure, which appears between the hexagonal Laves phase and the cobalt-bose terminal solid solutions KOSTER and Schmid' identified a phase corresponding to the composition VCo,, and more recently the crystal structure of this phase has been determined.' In the Ta-Co system Korchynsky and Fountain recently found two intermediate phases at the composition Taco,, one of them metastable. In contrast to the V-Co and the Ta-Co systems, in the Cb-Co system no intermediate phase has been found4 at the composition CbCo,. The present investigation was undertaken in order to reexamine the question of the existence of such a phase. EXPERIMENTAL PROCEDURE Twelve alloys were prepared by arc-melting in a water-cooled copper crucible under helium atmosphere. Electrolytic cobalt and 99.9 pct pure colum-bium powder have been used as starting materials. It was found that melting losses can be reduced by compressing the colunlbium powder in the form of thin pellets before melting. For the alloys used the melting losses were not higher than 1 pct. The intended compositions of all alloys and the chemical analyses of three of them are given in Table I. Specimens from all alloys were annealed in evac- uated fused silica tubes at 1175°C for 3 days and quenched in cold water. A second set of specimens of most alloys was annealed at 1000°C for 7 days and then quenched in cold water. The annealed and quenched specimens were examined metallographically, using the following etchant: 60 pct glycerine +20 pct H,NO, + 10 pct HF + 10 pct water. Powder specimens for X-ray diffraction were prepared by crushing annealed solid specimens in a mortar. Alloys containing 27.3, 28, 29.7, and 32.6 at. pct Cb annealed at either 1175" or 1000°C were very brittle and it was found unnecessary to reanneal the powders. However, alloys containing 24.8 at. pct Cb, or less, especially those annealed at 1000°C, were much less brittle and re-annealing was required to remove the strains present in the crushed powders. In each case reannealing was done at the same temperature at which the corresponding solid specimens were annealed and it, too, was followed by quenching in cold water. In many instances X-ray diffraction patterns were also taken of the polished and etched solid specimens and compared with the corresponding X-ray diffraction patterns obtained with powders. The X-ray diffraction patterns were taken with an asymmetrical focusing camera, using CrK radiation. For precision lattice parameter measurements some X-ray diffraction patterns were taken with a symmetrical focusing camera, again using CrK radiation. EXPERIMENTAL RESULTS A microscopic examination of the alloys annealed at 1175°C revealed that the alloy containing 25.5 at. pct Cb was composed of a single phase, but that the 24.8 at. pct Cb alloy did contain a small amount of a second phase, identified by means of X-ray diffraction as having a fcc structure, undoubtedly the terminal solid solution based on cobalt. Apart from the few very weak lines corresponding to this minor phase, the X-ray diffraction patterns of these alloys could be well interpreted in terms of a MgNi,-type hexagonal Laves phase structure. The indexing of the X-ray diffraction pattern, Table 11, yas based on the lattice parameter values a, = 4.740A and c,

Jan 1, 1961

By C. Law McCabe, R. G. Hudson

The Knudsen cell has been employed to determine the free energy of formation of Mn7Cs in the temperature range 800" to 950°C. A value of 66,440 cal was found for hH°o for a-manganese. Measurements of the pressure of manganese over a mixed carbide, (Fe,Mn),C, points to a power relationship between aun7cs and N.4,. RECENTLY Kuo and Perssonl have reported that the carbide of manganese which is in equilibrium with graphite at temperatures up to 1100° C is Mn7Ca. There are no published data on the thermo-dynamic properties of this compound. In order to determine the stability of Mn7Ca, it appeared that, by obtaining the pressure of manganese above 8-manganese and also above Mn,C, in equilibrium with graphite, the free energy of formation of Mn7Ca from 8-manganese and graphite could be obtained. In addition, the vapor pressure of manganese, reported by Kelley From data of Bauer and Brunner,' is subject to some uncertainty and further determinations of the vapor pressure of manganese seemed warranted. In this investigation of the pressure of manganese vapor above pure manganese and also above the carbide of manganese in equilibrium with graphite the apparatus used is the Knudsen orifice cell. The same apparatus, experimental procedure, and method of calculating the pressure was used in this investigation as in one previously reported.~ Care was taken to insure that the cells were at constant weight before using them in a run. The manganese charged in the cell was CP grade powder, carbon free, obtained from the Fisher Scientific Co. A spectroscopic analysis of the manganese after appreciable amounts of it had vaporized from the Knudsen cell showed that no element was present in sufficient quantities to contribute to a weighable weight loss or to decrease the vapor pressure of manganese to any appreciable extent. The spectro-graphic analysis was 0.002 pct Cu, 0.05 pct Fe, 0.002 pct Pb, and 0.002 pct Ni. 8-manganesea is the allo-tropic form of manganese which was present in the cell at temperatures used in this investigation. The manganese carbide, Mn,Ca, was made in the following way: In a closed graphite cell manganese powder was added to graphite powder, which was made from graphite rods for spectrographic use. The manganese powder was the same as that described previously; 5 pct excess graphite was added over that required for the formation of Mn7C,. The mixture was heated in a closed graphite cell for approximately 20 hr at 1350°K under vacuum. X-ray analysis revealed that there was no manganese present after this treatment, but that the lines due to Mn,C, were present. In order to prove that there was no volatile carbide of manganese which was effusing out of the cell, the following experiment was performed: A graphite effusion cell containing graphite power, in excess of that to form Mn,C, of a desired amount, was brought to constant weight on heating at 1228°K. The required amount of manganese was accurately weighed and then added to the graphite effusion cell. The cell was placed in a vacuum at 1228°K for one week, which was the time calculated for the manganese to have effused completely, assuming instantaneous formation of Mn,C8. The cell was then weighed again. This experiment was carried out on two different occasions and both times the weight loss of the cell came within 1 pct of the weight of manganese originally charged minus the weight of manganese left in the cell, as determined by chemical analysis. These data are summarized in Table I. This agreement is considered to be within experimental error and is taken as proof that no carbide of manganese is volatile in this temperature range. It was established, by X-ray analysis, that Mn,C, formed before appreciable amounts of manganese vaporized from the metal powder which was charged. The identification of the carbide of manganese which was present in the Knudsen cell in equilibrium with graphite and manganese vapor was carried out by Kehsin Kuo at the University of Uppsala. He established that the authors' sample, which was submitted to him for analysis, contained the phase

Jan 1, 1958

By P. J. Spencer, J. N. Pratt

The vapor pressure of manganese over liquid Mn-Sn alloys has been determined by a high-temperature torsion-effusion technique. Alloys containing from 8 to 100 at. pct Mn were investigated in the temperature range jrom 1280" to 1580" and the measured pressure values were used to calculate the partial and integral thermodynamic properties of the liquid alloys. The activities show small negative departures from ideality while the integral heats and excess entropies of mixing are asymmetric inform, changing from positive to negative with increasing manganese content. The possible contribution of various factors to the observed thermodynamic properties is discussed. COMPARATIVELY few thermodynamic data are available for manganese alloy systems.' Therefore, as part of a continuing program of studies of the thermodynamic properties of transition metal alloys, measurements have been made on various binary alloys involving this element. In recent publications,2~3 investigations of liquid Mn-Cu alloys and of the Mn-Au system in both solid and liquid states have been reported. For the first-mentioned system the work suggested that magnetic interactions may be responsible for the observed form of the thermodynamic properties, while in the second the influence of the electrochemical factor appears to be dominant. The present paper describes a similar study of liquid Mn-Sn alloys. Again the thermodynamic properties have been obtained from vapor pressure measurements made by use of a high-temperature torsion-effusion technique.4 A detailed description of the apparatus and of the experimental procedures used in alloy preparation and pressure measurement may be found elsewhere.2'4 EXPERIMENTAL RESULTS Sixteen alloys, ranging in composition from 8 to 100 at. pct Mn, were prepared from spectroscopically standardized manganese of 99.99 pct purity and tin of 99.999 pct purity, both supplied by Johnson-Matthey and Co., Ltd. One-gram samples of the alloys were obtained by carefully weighing appropriate amounts of the pure components into an effusion cell; this was then suspended in the apparatus and the metals melted together in situ by heating under vacuum to approximately 1550°K. After allowing sufficient time for a homogeneous liquid alloy to be formed, vapor pressure measurements were commenced. These were determined as rapidly as possible at a series of steady temperatures within the range of interest. The duration of experimental runs on individual samples was kept sufficiently short to ensure insignificant varia- tion of alloy composition during investigation. After completing pressure measurements, the alloys were rapidly cooled and their compositions checked by weighing or chemical analysis. All experiments were conducted using effusion cells machined entirely from boron nitride. Measurements were made using a variety of cells with orifice areas ranging from 0.0032 to 0.0075 sq cm and lengths of the order of 0.04 cm; the usual effusion correction factors for orifice geometry and molecular distribution were calculated using Freeman and Searcy's equation5 and had values between 0.6 and 0.75 for the orifices employed here. The vapor pressures of manganese over the alloys were measured at approximately 20°K intervals in the temperature range 1280" to 1580°K. In view of the close approximation of the measured pressures to Clausius-Clapeyron behavior in the experimental temperature range, the data for each alloy have been expressed by equations of the form: logp(atm) =-A/T + B A least-squares computer treatment was applied to the vapor pressure values in order to obtain the coefficients A and B with their associated error. The resulting equations are listed in Table I, together with the equation for pure solid manganese obtained from a previous study.4 To minimize the effect of possible apparatus calibration errors, the activities and partial free energies of manganese in the alloys were calculated by initial reference to the latter equation, obtained from identical torsion-effusion measurements. The immediately resulting thermodynamic quantities, based on a solid manganese reference state, were then converted to refer to the more appropriate supercooled pure liquid manganese standard; tabulated values of the free energies of solid and liquid manganese from Hultgren et al.' were used for this purpose. Partial entropies of solution of manganese were calculated from the temperature coefficients of the free energies and partial heats from the Gibbs-Helmholtz relationship.

Jan 1, 1969

By J. L. Bray, S. T. Ross

The paper provides electrometallurgical data on the problem of germanium removal from zinc sulphate solutions. Germanium traces have caused much concern to the zinc refiner. Confirmatory evidence of interaction between germanium and cadmium is presented. Statistical analysis of data expands its significance and enhances its value. Further research is outlined. THE literature contains many references to the effects of trace amounts of germanium in the production of electrolytic zinc. One of the authors had experience with this troublesome element as early as 1917 at Trail, B. C. In 1929, Tainton and Clayton' reported that concentrations of as little as one part per million of germanium were sufficient to cause serious losses in current efficiency. Liddell2 reported that trace amounts of germanium cause marked lowering of the hydrogen overvoltage of electrolytic zinc cells, so that commercial production was impaired. Bray3 recorded the history of germanium in relation to electrolytic zinc production, noting that concentrations below 10 ppm have been found to yield low current efficiencies and copious hydrogen evolution. Koehler' stated that germanium "when present to the extent of a small fraction of one part per million per liter, causes serious evolution of hydrogen with a corresponding reduction in current efficiency." Recently, however, S. W. Ross" reported, from Risdon, Tasmania, that "in the course of leaching . .. dissolved traces of germanium... if not removed almost completely ... increase the reversion of cadmium during the filtration of the copper-cadmium precipitate and reduce the current efficiency during subsequent analysis." The copper-cadmium precipitate referred to is the residue from the zinc-dusting purification of zinc sulphate leach solutions. In the face of such conflicting testimony and with the increasing industrial importance of pure germanium and zinc it was decided to investigate the relationship between cadmium and germanium. Furthermore, other work by the authors showed certain discrepancies to exist in the theories of Tainton, et al. In the laboratory, without marked efficiency decreases, the authors have deposited zinc successfully from solutions containing as high as 1 g per liter of germanium. This could be done only when there was no cadmium present. Preliminary investigations of the suspected rela- tionships were carried out by means of emission spectrographic analysis using a beryllium internal standard. Several solutions containing 100 g per liter of zinc, as zinc sulphate, and 1 g per liter of cadmium, as cadmium chloride, were prepared. These concentrations were on the order of those obtained during a commercial low-acid leaching process. Varying concentrations of germanium were added to these solutions so that the range of 0.0000 to 0.5000 g per liter of germanium was covered. A 250 ml sample of each solution was agitated with 2.5 g of zinc dust for 30 min, filtered, and the filtrates were examined spectroscopically. Qualitative evidences of cadmium traces were found in those filtrates which originally contained above 10 ppm of germanium. Reliability of the analytical method did not permit quantitative investigations since cad-Table I. Current Efficiencies Obtained at 0.0000 and 1.5000 G per Liter Cadmium Concentrations Ge Concentrastion,* Cd Concentration,* EtBclenoy, G per Liter G per Llter Pot 0.0000 0.0000 84.270 0.0010 0.0000 94.849 0.0050 0.0000 92.649 0.0075 0.0000 94.039 0.0100 0.0000 96.084 0.0000 1.5000 93.460 0.0010 1.5000 95.158 0.0050 1.5000 92.148 0.0075 1.5000 91.260 0.0100 1.5000 84.546 • Cd and Ge concentrations shown are those existing before zinc-dust purification. mium determination in the concentrations present in zinc-dusted solutions lacks sufficient sensitivity for reproducible results. As a consequence of the inability of the investigators to obtain acceptable results through direct quantitative analysis, an indirect approach was devised. This indirect method involved a study of the current efficiency, in a model zinc cell, as a function of the concentrations of cadmium and germanium. Variables such as cell temperature, voltage, current density, anode spacing, relative electrode area, degree of agitation, cathode preparation technique, time, acid concentration, and solution volume were held constant. Fig. 1 shows the cell used. The current was fur-

Jan 1, 1952

By John Tabor, R. B. Spivey

INTRODUCTION Shafts have been sunk in a number of ways. By and large, however, most have been sunk by drill, blast, muck, and slip form methods. Most methods have provided satisfactory means of completion. The major drawbacks to the conventional methods have been: (1) un- reliable cost estimates for completion; (2) unreliable rates of progress; and (3) unreliable integrity of the shaft lining. Recently , engineering design studies have been done that strongly indicate, that, by the use of existing proven technology, shafts can be completed faster, more cheaply, safer, and with a better lining that has been possible using conventional methods. THE METHOD The alternate method utilizes the techniques of big hole drilling, shield excavator tunnelling, and pre-cast concrete lining. Big Hole Drilling - Drilled shafts have been completed for several years and I don't intend to address the technology, only to point out the use of drilled shafts is an alternate method of shaft sinking. Ideally, in a multi-shaft mine, the first shaft would be blind bored and cased to a size, whereby it can handle the muck from the excavation of subsequent shafts. It should be an 8' to 10' completed diameter. The cost of such a shaft in sedimentary formations compares favorably with a conventional shaft. However, it is much faster. For additional shafts, the role of the drill is to complete small holes (3' to 4') to the desired horizon. This is merely a hole to allow slashing to a larger size with easier muck removal from an underground drift connected to the previously drilled shaft. The smaller holes, just as the larger one, should be cased and grouted into place so as to assure a smooth open hole. SHIELD EXCAVATOR Theory and History - Tunnelling Shields have been in common use for several decades, and steam powered shields were used in England over 100 years ago. The purpose of the shield is to provide temporary ground support, protect personnel during operation, and to house the excavating equipment. The excavating equipment approach has varied from attempts at a continuous or semi-continuous boring machine, the tunnel mole, to a mechanical or hydraulic digging arm. The shield may or may not be an active digging element. If not active, the boring tool or cutter is advanced ahead of the shield to full diameter and then the shield is moved up to the cutter, or the shield advances along with the cutter. If active, the cutter opens a conical free face, and the shield is either jacked forward so that the leading edge spalls rock to the free face or poling plates are thrust forward to spall to the free face. In either approach, various methods of muck removal are incorporated into the shield. These may be gathering arms, conveyors, or with moles, hydraulic transport, where the cuttings are sufficiently fine. The efficiency of the muck removal system is critical as excavation is rapid and the system could easily become muck-bound. Application to Shaft Sinking- Technically, the use of a shield to sink vertical shafts is no different than a tunnelling operation. It is, in fact, less complex in most respects. Muck and water removal are difficult in a blind-driven shaft. However, where an underground opening is available for handling muck and water, rapid shield sinking is possible, using a pilot hole for muck and water to fall through and be removed from below. The Tabor Mining Shield is basically a caisson approach, whereby, the ground is only seen at the face or bottom. It does have hydraulic jacks to force it downward and has segmented cutting edges which allows forepoling ahead of the shield. The hydraulic excavator allows mining in the center of the face around the previously drilled hole with the forepoling segments slabbing to this free face. First, the drilled hole is cased and grouted. The machine is a tube with an excavator. The work cycle is as follows: (1) The casing and grout are cut at predetermined intervals by shaped charges. (2) The casing is crushed by the excavator, removed from the hole and hoisted to the surface. (3) The excavator then rips out a face around the hole by digging the formation in tension and breaking the pieces

Jan 1, 1982

By G. Britsianes, T. L. Joseph

THE reduction of a lump of iron ore is a complicated sequence of up to three reactions proceeding simultaneously in a gas-solid system. As the ore moves down the blast furnace into zones of higher temperature and higher reducing power, it is successively reduced through the three oxides of iron into metallic iron. The reduction process involves much more than chemical problems. Physical factors add to the complexity of the overall process. Under optimum conditions, reduction of the ore is completed at a level about one-half way down the blast furnace stock column. At this point, the ore undergoing reduction has attained a temperature of about 1000°C and has been in the furnace for about 6 hr. On the practical side, the behavior of the ore during smelting has been of great interest to operators. Unsatisfactory blast furnace operation on burdens containing magnetite ore or badly slagged sinter has often been attributed to poor re-ducibility. The question of reducibility has also been raised in formulating quality standards for agglomerates such as nodules, briquettes, and pellets. In the present investigation, the solid phases formed during reduction were studied as a step toward a better understanding of the overall process. Equilibrium Studies The iron-oxygen equilibrium diagram shown in Fig. 1 reveal; a number of facts pertinent to the gaseous reduction of iron ores. This diagram is from the work of Darken and Gurryl, 2 and represents a correlation of the best available data. Four solid phases may exist during the complete reduction of hematite to metallic iron. These are hematite (Fe2O3), magnetite (Fe3O4), wustite (FeO), and iron (Fe). The wustite phase is a solid solution which is not stable below 570°C. At this temperature the solid solution undergoes a eutectoid-type of decomposition into the phases, magnetite and iron. Thus above 570°C, the diagram dictates that a hematitic ore should pass through a four-phase sequence on reduction to metallic iron. Below 570°C, only hematite, magnetite, and iron should appear. Information on the iron-oxygen system has been derived largely from CO and H2 reduction equilibria. The Fe-C-0 relationships have been studied extensively by R. Schenck and his coworkers and well summarized by H. Schenck.3 More recent studies have been made by Darken and Gurry.1, 2 Data from these sources have been combined and plotted in Fig. 2. With respect to the Fe-H-O system, the works of Emmett and Schultz4 seem the most reliable, and these data have also been included in Fig. 2. Certain physical properties of the solid phases of the iron-oxygen system are summarized in Table I. The crystallographic information is of special interest as much of the present work has been concerned with the X-ray analysis of the products of reduction. Reduction with Hydrogen The reduction of ore with hydrogen is the net result of two or more gas-solid reactions. Above 570°C, the reaction sequence may be represented by stoichiometric stages as follows: 3Fe203+ H2e2Fe,O, + H20 [1] 2Fe3O, + 2H2 6FeOw + 2H2O [2] 6FeOw + 6H3 ^ 6Fe + 6H=O [3] Fe2O3 + 3H2 ^ 2Fe + 3H,O. [4] These reduction reactions follow the general form: A (solid) + B (gas) e C (solid) + D (gas). This type of gas-solid reaction has been investigated by Langmuirl' who has shown that such reactions can occur only at the boundary between the two solid phases. Furthermore, a nucleus of the second phase must initiate the reaction. Once such an interface exists, the reaction proceeds through a layer of the solid reaction product (C). The specific mechanisms involved will depend a great deal on the properties and condition of this particular layer. A number of heterogeneous reactions such as the dehydration of single crystals of copper penta-hydrate and the calcination of limestone follow this type of process. It should be noted that the inter-facial type of reaction also occurs even in dense polycrystalline material which simulates a mono-crystalline behavior.

Jan 1, 1954

By R. J. Wasilewski

Electrical resistivity variation with temperature was measured on a series of alloys containting up to 33 at. pct of oxygen over the range 77° to1500°K. The resistivity behavior is highly anomalous and itzconsistent with simple metallic conduction. Both composition and temperature-depended resistivity singularities were observed. A few experiments carried out on Ti-N and Zr-O alloys indicate the presence of similar anomalies. These observations, together with the published data on effects of substi-tutional alloying on the resistiuity of titanium, suggest that the anomalies are inhevent in the electron structure of this group oj metals. The existence of two-band conduction, and a significant shift of bands relative to each other with temperature and/or the electron concentration are suggested. CONSIDERABLE advances have been made in recent years in the alloy theory of simple metals. Very little, however, is known about the bonding in transition metals and their alloys.&apos; Titanium, with its relatively few electrons, may be expected to show simpler alloying behavior than the more complex transition elements. Its alloys with the interstitial elements appear particularly attractive in an investigation of bonding characteristics because of a) the simple nature of the solute elements, b) the remarkable similarity between the equiatomic structures Tic, TiN, and TiO, and c) the extensive solid solubility ranges of oxygen and nitrogen in a titanium reported.2,3 The Ti-O system was chosen for the most extensive investigation because of the relative ease of preparation of suitable specimens. Since the main object of the work was to obtain data on the bonding and its changes on alloying, electron-sensitive properties were primarily investigated. The present work describes the investigation on the electrical resistivity-temperature-oxygen content relationships. A few experiments were also carried out at selected compositions in the Ti-N and Zr-O systems. EXPERIMENTAL Materials and Method. Polycrystalline specimens were prepared in the form of hairpin strips some 50 by 5 by 0.15 to 0.50 mm by direct metal-gas reaction. This was carried out by controlled oxidation followed by a homogenizing anneal at a higher temperature. All the test specimens were fully homogenized as judged from the uniform microstructure and microhardness. To avoid preferred orientation, each strip specimen was annealed in the ß range prior to the oxidation, this procedure assuring random orientation in the strip;4 hence any texture resulting from the oxidation reaction itself affected all the specimens to a similar extent. Titanium used was of high purity (66 DPN, 10 Kg load; major impurities 0,-43G ppm, N,-70 ppm, C-25 ppm, Fe-14G ppm). The solute content of the alloys was determined by weighing, after the reaction with a known amount of oxygen. The specimens in which the discrepancy between the volumetric and gravimetric measurements exceeded 2 pct (or 0.2 mg for the low oxygen alloys) were rejected. The mean between the two measurements was then taken as the oxygen content of the alloy. Check analyses showed no measurable nitrogen contamination. All oxygen contents are given in atomic percent. Zr-O alloys were prepared in identical manner from hafnium-free crystal bar metal, cold-rolled to strip 0.25 mm thick. Ti-N alloys required very long reaction times at the maximum temperature available (1250°C). In order, therefore, to detect possible oxygen contamination, duplicate specimens were reacted in every experimental run, and one of these was analyzed both for oxygen (vacuum fusion) and for nitrogen (Kjeldahl). Only the specimens in which the check analysis showed < 1000 ppm O were then used for resistivity investigation. Since only relatively high nitrogen alloys (7.1 at. pct; i.e., 2 wt pct N,) were investigated, this oxygen contamination was considered permissible. Dc resistance was measured by the four-probe method as previously described.= The temperature was determined with a calibrated thermocouple placed in the center of the specimen hairpin. The errors in the specimen resistance values thus obtained were estimated at 1 pct due almost exclusively to the finite thickness of the potential wires and the consequent uncertainty as regards the true resistance length of the specimen. For the calculation of the specific resistance, however, no dimensional measurements could be carried out on most of the

Jan 1, 1962

By R. Al-Hussainy, P. B. Crawford, H. J. Ramey

The effect of variations of pressure-dependent viscosity and gas law deviation factor on the flow of real gases through porous media has been considered. A rigorous gas flow equation was developed which is a second order, non-linear partial differential equation with variable coeficients. This equation was reduced by a change of variable to a form similar to the diffusivity equation, but with potential-dependent diffusivity. The change of variable can be used as a new pseudo-pressure for gas flow which replaces pressure or pressure-squared as currently applied to gas flow. Substitution of the real gas pseudo-pressure has a nrtmber of important consequences. First, second degree pressure gradient terms which have commonly been neglected under the assumption that the pressure gradient is small everywhere in the flow system, are rigorously handled. Omission of second degree terms leads to verious errors in estimated pressure distributions for tight formations. Second, flow equations in terms of the real gas pseudo-pressure do not contain viscosity or gas law deviation factors, and thus avoid the need for selection of an average pressure to evaluate physical properties. Third, the real gas pseudo-pressure can be determined numerically in term of pseudo-reduced pressures and temperatures from existing physical property correlations to provide generally useful information. The real gas pseudo-pressure was determined by numerical integration and is presented in both tabular and graphical form in this paper. Finally, production of real gas can be correlated in terms of the real gas pseudo-pressure and shown to be similar to liquid flow as described by diffusivity equation solutions. Applications of the real gas pseudo-pressnre to radial flow systems under transient, steady-state or approximate pseudo-steady-state injection or production have been considered. Superposition of the linearized real gas flow solutions to generate variable rate performance was investigated and found satisfactory. This provides justification for pressure build-up testing. It is believed that the concept of the real gas pseudo-pressure will lead to improved interpretation of results of current gas well testing procedures, both steady and unsteady-state in nature, and improved forecasting of gas production. INTRODUCTION In recent years a considerable effort has been directed to the theory of isothermal flow of gases through porous media. The present state of knowledge is far from being fully developed. The difficulty lies in the non-linearity of partial differential equations which describe both real and ideal gas flow. Solutions which are available are approximate analytical solutions, graphical solutions, analogue solutions and numerical solutions. The earliest attempt to solve this problem involved the method of successions of steady states proposed by Muskat.&apos; Approximate analytical solutions&apos; were obtained by linearizing the flow equation for ideal gas to yield a diffusivity-type equation. Such solutions, though widely used and easy to apply to engineering problems, are of limited value bemuse of idealized assumptions and restrictions imposed upon the flow equation. The validity of linearized equations and the conditions under which their solutions apply have not been fully discussed in the literature. Approximate solutions are those of Heatherington et al.. MacRobertsl and Janicek and Katz.&apos; A graphical solution of the linearized equation was given by Cornell and Katz. Also, by using the mean value of the time derivative in the flow equation, Rowan and Clegg&apos; gave several simple approximate solutions. All the solutions were obtained assuming small pressure gradients and constant gas properties. Variation of gas properties with pressure has been neglected because of analytic difficulties. even in approximate analytic solutions. Green and Wilts8 used an electrical network for simulating one-dimensional flow of an ideal gas. Numerical methods using finite difference equations and digital computing techniques have been used extensively for solving both ideal and real gas equations. Aronofsky and Jenkins"I " and Bruce et al.11 gave numerical solutions for linear and radial gas flow. Douglas et al." gave a solution for a square drainage area. Aronofsky 13 included the effect of slippage on ideal gas flow. The most important contribution to the theory of flow of ideal gases through porous media was the conclusion reached by Aronofsky and Jenkins" that solutions for the liquid flow case&apos;" could be used to generate approximate solutions for constant rate production of ideal gases. An equation describing the flow of real gases has been solved for special cases by a number of investigators using numerical methods. Aronofsky and Ferris 10 onsidered linear flow, while Aronofsky and Porter 17 considered radial gas flow. Gas properties were permitted to vary as linear functions of pressure. Recently, CarteP 18 proposed an empirical correlation by which gas well behavior can be estimated from solutions of the diffusivity equation using instantaneour values of pressure-dependent gas

Jan 1, 1967

By E. W. Johnson, M. L. Hill

Cold working of iron-carbon alloys was found to increase greatly the hydrogen solubility and to decrease the diffusivity at temperatures up to 400° C. These effects are increasing functions of both the carbon content and the degree of deformation. The hydrogen behavior is consistent with the idea that cotd working creates "traps", which are concluded to be microcracks in which the hydrogen is chemisorbed. Hydrogen embrittlement is explained by the Petch theory of metal crack surface energy loss due to hydrogen adsorption. HYDROGEN embrittlement of steel has been studied for many years and has been the subject of an extensive literature, but the mechanism of the effect has not been completely understood. The embrittlement is unusual in that the ductility loss is not accompanied by an increase of the yield strength, being primarily a decrease of the fracture strength alone. The loss of fracture strength is usually most severe in the temperature range between 0°and 100°C. Here the solubility of hydrogen in the iron lattice at ordinary H2 pressures is extremely low while the diffusivity is still quite high. From the relationships between the ductility and the hydrogen content, test temperature and strain rate, it is apparent that the hydrogen atoms causing the ductility loss difbse to and concentrate in small regions of the metal which are especially susceptible to the initiation and propagation of fracture. This hydrogen segregation apparently occurs after plastic straining has begun. Below 0°C the ductility loss persists only at low strain rates in confirmation of the view that the embrittlement is diffusion .controlled. The tendency of the embrittlement to disappear above 100°C can be explained by the increasing lattice solubility of hydrogen with rising temperature. A common view of hydrogen embrittlement of steel is that the hydrogen initially dissolved in the metal lattice diffuses to structural discontinuities and there precipitates as H2 gas at very high pressures which assist the external stress in causing premature failure.1,2 The idea of a high H2 pressure in equilibrium with ordinary amounts of hydrogen in steel at room temperature is due to observations of hydrogen behavior in fully annealed material, for which the Sieverts&apos; law constant relating solute concentration to H2 pressure is extremely small. Hydrogen-embrittled steel, however, is always plastically deformed to some extent, and therefore it is important that hydrogen embrittlement be explained primarily in terms of hydrogen behavior in plastically deformed material. Such an explanation is attempted in this paper. Previous studies of hydrogen in cold-worked steel have shown that both the solubility and the diffusion rate are significantly chaned when the steel is cold worked. Darken and Smith discovered that the amount of hydrogen absorbed from acid by cold-rolled steel at 35°C is many times greater than that absorbed by hot-rolled steel. They found also that the hydrogen permeability of the steel is unaffected by cold working. Keeler and Davis4 confirmed the high apparent solubility of hydrogen in cold-worked iron-carbon alloys at temperatures up to and even beyond the recrystallization temperature. They also found that this solubility increase accompanying cold work is a sensitive function of the carbon content, being absent when no carbon is present. The present experimental study was undertaken primarily to obtain an improved understanding of the behavior of hydrogen in cold-worked steel. Data were obtained on the effects of temperature, H, pressure, carbon content, and degree of cold work on the hydrogen solubility and diffusivity in iron-carbon alloys. These data have been helpful in elucidating the nature of the cold-worked steel structure as well as in providing information on the mechanism of hydrogen embrittlement of steel. EXPERIMENTAL Cylindrical specimens for hydrogen absorption and diffusion rate measurements were prepared from three iron-carbon binary alloys and a commercial SAE 1010 steel. The iron-carbon alloys were prepared by vacuum melting electrolytic iron with graphite in a magnesia crucible. The alloys were cast in vacuum as 2 1/2-in. sq ingots weighing about 20 lb each. The ingots were hot rolled (above 1900°F) to 5/8-in.-diam round bars and then cooled in air to room temperature. The resulting metallographic structure consisted of islands of fine pearlite surrounded by free ferrite. Chemical analyses of the materials are given in Table I. The 5/8-in. diam bars were turned to diameters such that cold reduction to the desired final specimen diameters would result in either 30 or 60 pct reduction in area (RA). The machined bars were then cold worked by swaging at room temperature

Jan 1, 1960

By Charles L. Mantell, James E. Hoffmann

Mechanical inclusion, electrophoretic deposition, and adsorption were studied as mechanisms for code-position of aluminas present in copper-plating electrolytes as an insoluble disperse phase. Mechanical inclusion was not a significant factor. That codeposi-tzon of aluminas by an electrophoretic mechanism was unlikely was substantiated by measurements of the potential of the aluminas. The alumina content of the deposits was studied as a function of the pH of the bath. These tests in conjunction with sedimentation studies demonstrated the absence of an isoelectric point for the alutninas over the pH range examined. Thiourea in the electrolyte (a substance known to be adsorbed on a copper cathode during electrodeposition) affected the amount of alumina in the electrodeposit. However, no adsorption of thiourea on aluminas in aqueous dispersions was detected. If it were possible to produce a dispersion-hardened alloy of copper and alumina by electrodeposition, an alloy possessing both strength and high conductivity at elevated temperatures might be anticipated. Investigation of the mechanism of codeposition of aluminas with copper was undertaken with the hope that knowledge of the mechanism would aid in the development of such an alloy. The word "codeposit" here does not necessarily imply an electrolytic phenomenon but rather that the materials codepositing, the various aluminas, are transported to and embedded in the electrodeposited copper by some means. Mechanical inclusion in electrodeposition implies a mechanism of codeposition which is wholly mechanical in nature; the only forces acting on a particle are gravity and contact forces. Such a particle is presumed to be electrically inert and incapable of any electrical interaction with electrodes in an electrolytic plating bath. Processes for matrices containing a codeposited phase by electrodeposition from a bath containing a disperse insoluble phase frequently state that code-position is caused by mechanical inclusion.10,2,12 If settling, i.e., gravity, be the controlling mechanism for codeposition of aluminas, then assumptions may be made that 1) the content of alumina in the electrodeposit should be enhanced by increasing the particle size, 2) the geometry of the system, that is, the disposition of the cathode surfaces relative to the di- rection of the falling particles, should affect the alumina content of the electrodeposit, 3) in geometrically identical systems the chemical composition of the electrolyte employed should exercise no effect on the alumina content of the deposit, that is, the alumina content should be the same in all cathode deposits irrespective of bath composition. A bent cathode19 evaluates the clarity of filter effluent in electroplating baths by comparing the roughness of the deposit on the vertical surface with that on the horizontal surface. Two difficulties are inherent in this technique: 1) the current density on the horizontal portion of the cathode would be substantially greater than that on the vertical surface; 2) should the deposit obtained be rough, projections on the vertical face could act as horizontal planes and vitiate the relationship between the vertical and horizontal surfaces. Bath composition should have no substantial effect on the alumina content of the deposit. Two different electrolytic baths were employed. They possessed variant specific conductances and substantially different pH ranges. The experimental tanks were rectangular Pyrex battery jars 6 in. wide by 3 1/4 in. long by 9 3/4 in. deep. The cathodes were stainless steel 316 sheet of 0.030 in. thickness, cut to 7.5 by 1.75 in. and bent at right angles to form an L-shaped cathode whose horizontal surfaces measured 1.75 by 3.0 in. All edges and vertical surfaces were masked with Scotch Elec-troplaters Tape No. 470. The anodes were electrolytic cathode copper 9 in. high by 2.25 in. wide by 0.5 in. thick. To eliminate inordinately high current densities on the projecting edge of the cathode, the anode was masked 1 in. above and below the projected line of intersection of the cathode with the anode. The exposed area of the anode was equal to that of the cathode, providing both with equal average current densities. The agitator in the cell was of Pyrex glass and positioned so its center line was equidistant from cathode and anode, and a plane passed horizontally through the center of the blade would be located equidistant from the bottom of the cathode and the bottom of the deposition tank. The assembled apparatus is depicted in Fig. 1. Hatched areas on anode and cathode represent the area of the electrodes wrapped with electroplaters tape. MATERIALS The chemicals were copper sulfate—CuSO4 • 5H2O— technical powder (Fisher Scientific Co.). Spectro-graphic analysis showed substantial freedom from antimony, arsenic, and iron. Traces of nickel were present.

Jan 1, 1967

By P. K. Koh, H. A. Lewis, H. F. Graff

New data on the distribution of silicon between slag and carbon-saturated iron at 1600Oand 1700OC are presented which, in combination with previously published data, permit the determination of silica activities over a broad range of compositions in the CaO-Al2O3-SiO2 system. The distribution of silicon between graphite-saturated Fe-Si-C alloys and blast furnace-type slags in equilibrium with CO has been described in previous publications.1"3 In this past work the silica-silicon relation was established at temperatures of 1425" to 1&apos;700°C for slags containing up to 20 pct A12O3. This paper presents the results of additional studies at 1600" and 1700° C which extend the silicon distribution data at these temperatures for CaO-A12O3-SiO, slags over a range from zero pct Al2O3 to saturation with Al2O3, or CaO.2Al2O3. The upper limit of SiO2 is set by the occurrence of Sic as a stable phase when the metal contains 23.0 or 23.7 pct Si at 1600" or 1700°C, respectively. The activity of silica over the expanded range is determined directly from the distribution data.3 Recently4-7 other investigators have studied the activities of SiO, and CaO, principally in the binary system, using different methods and obtaining somewhat different results. EXPERIMENTAL STUDY The experimental apparatus and procedure have been fully described in previous publications.1, 3 Six new series of experimental heats have been made, four at 1600° and two at 1700°C. Master slags of several fixed CaO/Al203 ratios were pre-melted in graphite crucibles, and these were used with additions of silica to prepare the initial slag for each experiment. Slag and metal were stirred at 100 rpm and CO was passed through the furnace at 150 cc per min. The initial sample was taken 1 hr after addition of slag at 1600°C or 1/2 hr after addition at 1700°C. The run was normally continued for 8 hr at 1600°C or 7 hr at 1700°C, and the final sample was taken at the end of this period. Changes in Si and SiO2 content indicate the direction of approach to equilibrium, and in a series of runs where the approach is from both sides this permits approximate location of the equilibrium line. Fig. 1 shows the results of such a series of 15 runs at 1600°C for slags of CaO/Al,O3 = 1.50 by weight. Figs. 2 and 3 record other series at 1600°C and Fig. 5 a series at 1700°C with fixed CaO/Al0 ratios. The results of the experiments at 162003°C have been reported in part in a preliminary note.3 In the experiments recorded in Figs. 4 and 6, the slags were saturated with A12O3 (or with CaO.2A12O3 within its field of stability) by suspending a pure alumina tube in the melt during the course of the run. The final slag analyses were used to establish the liquidus boundaries8 in the stability fields of CaO.2Al2O3 and of Al20,. ACTIVITY OF SILICA The free-energy change in the reaction has been calculated by Fulton and chipman2 from recent and trustworthy data including heats of formation, entropies, and heat capacities. The more recent determination by Olette of the high-temperature enthalpy of liquid silicon is in satisfactory agreement with the values used and therefore requires no revision of the result which is expressed in the equation: SiO2 (crist) + 2C (graph) = Si + 2CO(g.) [1] &F° = + 161,500 - 87.4T The standard state for silica is taken as pure cristobalite and that of Si as the pure liquid metal. Since the melts were made under 1 atm of CO and were graphite-saturated, the equilibrium constant for Eq. [I] reduces to K1 = asi /asio2. The value of this constant is 1.77 at 1600°C and 16.2 at 1700°C. Through K1, the activity of silica in the slag is directly related to the activity of silicon in the equilibrium metal.

Jan 1, 1960

By R. C. Gould, A. M. Skov, L. F. Elkins

Comparison of long term decline in oil production during cyclic waterflooding or pressure pulsing of part of the Driver Unit with steady injection-imbibition flooding in the Tex Harvey area led to large expansion of flood in the Driver Unit on the steady injection basis. While the flood has been successful, the major problem has been attainment of satisfactory oil production rates in most of the wells. Large volume fracture treatments of low capacity wells were unsuccessful in achieving sustained increases in production. A two-section area in the Driver Unit has already recovered 620 bbl of oil per acre by waterflood but other areas have not performed so well. Sun Andres water containing 300 to 500 ppm H,S is sweetened to 0.5 to 1 ppm H,S by extraction with oxygen-free flue gas. This prevents contamination of gas produced in the area and apparently it has reduced corrosion in minimum investment, thin-wall, cement-lined water dktribution systems. Cement-lined tubing in injection wells has mitigated corrosion as effectively as thick polyvinyl chloride films have, and at less cost. Introduction As reported in the literature the Spraberry field of West Texas has presented unusual problems for both primary production and waterflood ing. Earlier information from the Spraberry Driver Unit included conception and evaluation of cyclic waterflooding or pressure pulsing in a nine-section pilot test as an aid to extraction of oil from the tight matrix rock and as a boost to normal capillary imbibition forces An additional 5 years&apos; operation in that area, and performance of expanded steady injection water-flood, now covering a total of 68 sq miles, are reported herein. In addition, since the Driver Unit is one of the largest waterfloods in areal extent in the U. S., many operating experiences are presented for the benefit of engineers concerned with operation of other Spraberry floods or with other waterfloods where this reservoir technology and/or water handling technology may be adaptable in part. These include: (1) attempts to improve producing well capacity through large volume fracture treatments, (2) long-term performance of water treating plants utilizing oxygen-free flue gas to extract H,S from sour San Andres water, (3) performance of thin-wall cement-lined pipe in water distribution systems including comparison between those sections carrying raw San Andres water and those carrying treated water, and (4) comparison of performance of various lining materials and subsurface equipment in water supply and water injection wells. These experiences are reported without regard to whether results are good, bad or indifferent. Since the operations reported are limited to the techniques, materials, and equipment actually used in the Driver Unit, no comparison is possible with results of other approaches used in other Spraberry floods or in waterfloods generally under different conditions. However, an attempt is made to quantify these experiences as much as possible in the space available to permit other engineers to select those parts applicable to eheir problems. Background The Spraberry, discovered in Feb., 1949, is a 1,000-ft section of sandstones, shales and limestones with two main oil productive members—a 10- to 15-ft sand near the top and a 10- to 15-ft sand near the base, having permeabilities of 1 md or less and porosities of 8 to 15 percent. Extensive interconnected vertical fractures permitted recovery of oil on 160-acre spacing from this fractional-millidarcy sandstone, but they made capillary end effects dominant. Primary recovery by solution gas drive is less than 10 percent of oil in place, with most wells declining to oil production of a few barrels per day when reservoir pressures are still in the range of 400 to 1,000 psi. Partial closing of the fractures with declining reservoir pressure is believed to be the cause of such low production rates at these relatively high reservoir pressures. In 1952 Brownscombe and Dyes proposed that displacement of oil by capillary imbibition of water from the fractures into the matrix rock might significantly increase oil recovery from the Spraberry, overcoming otherwise serious channelling of water through the fractures." A pilot test conducted by the Atlantic Refining Co. during 1952 through 1955 indicated technical feasibility of the process; but low oil production rates averaging I5 to 20 bbl/well/D failed to create significant interest in large-scale waterflooding at that time." Humble Oil & Refining Co. conducted a highly successful 80-acre pilot test during 1955 through 1958 with

Jan 1, 1969