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By D. T. Novick, M. B. Bever, B. Roessler

Ordered and disordered specimens of the alloy CusAu were cold worked and then annealed at 2880, 310°, and 340°C, together with disordered unworked specimens. me resistivity decreased during annealing mainly as a result of ordering; the resistivity measurements suggest that in cold-worked specimens the growth of antiphase domains is impeded. The strength properties increased during annealing at 288 "C; in cold-worked specimens this increase was lo a level above that for cold-worked specimens which had not been annealed. X-ray diffraction showed that after annealing for a few hours at 288ºC, the long-range order increased to a constant value; additional annealing at 288ºC resulted in the growth of antiphase domains in which the degree of order was constant. Changes in peak breadth and particle size confirmed that in cold-worked specimens the major effects of cold work were not eliminated during annealing at 288 "C, although a slight recovery process occurred. When a specimen of the alloy Cu3Au is heated to a temperature below the critical temperature (388ºC), long-range ordering tends to occur in a specimen containing less than the equilibrium amount of order characteristic of that temperature Ideally, a specimen of Cu3Au contains no long-range order if it has been quenched from above the critical temperature. Long-range order is reduced by cold work. If cold-worked specimens are heated, restoration processes such as recovery and recrystallization may occur,

Jan 1, 1963

By R. D. Stover, F. O. Shuck

The variation of binary-diffusion coefficients with composition in the liquid Bi-Sn system at 300°C was measured using the capillary-reservoir technique. The experimental coefficients did not exhibit a simple composition dependence. A number of tests were also made to determine the effect of variation of density with composition on convection within the capillaries. These tests indicate that the density changes arising from composition duferences may give rise to high diffusion coefficients unless care is taken to maintain a stable configuration. In recent years there has been considerable interest in diffusion in liquid metals. However, the bulk of the work done to date has involved measurements of self-diffusion or diffusion of dilute concentrations of "solute" metals. Because there are possible applications to liquid phase processing of metal alloys and since additional data may help to clarify the nature of diffusion in liquid metals, investigations of the concentration variation of diffusion coefficients in binary alloys have been undertaken. Of past studies only two have covered large ranges of binary composition. Niwa et al.' investigated the Pb-Sn, Bi-Pb, and Bi-Sn systems and Grace and Derge2 investigated the Bi-Pb system. Because of the discrepancy between the data of these investigators, it was deemed desirable to check the possibility of convection arising from the variation of density with composition. The capillary-reservoir technique of Anderson and saddington3 was chosen for the present investigation since it has been widely used for measurements involving dilute solute concentrations and it was the technique used by Grace and Derge.2 It was necessary, however, to modify the normal procedure of using a pure metal bath to avoid measurement of integral diffusion coefficients over large concentration ranges. The alloy system chosen for study was the Bi-Sn system for which there are some data available.' EXPERIMENTAL PROCEDURE In order to utilize the capillary-reservoir technique for measurements of diffusion coefficients as a function of composition, it was necessary to modify the normal procedure slightly. This modification consisted of using a reservoir composition which was only slightly different from that in the set of capillaries, in order that the integral coefficients measured might be taken over a small composition range and might thereby be assumed to approximate the differential coefficient at some average composition between that of the capillary and that of the bath. It was found that a composition difference of approximately 0.10 mass fraction provided a satisfactory compromise between a small increment in composition and reasonable accuracy in measuring changes of composition. The alloys were prepared from tin and bismuth of 99.999 pct purity. The materials were first cleaned of surface oxides, then weighed and melted to form a homogeneous alloy in a Pyrex filling apparatus. The capillaries used were of precision bore Pyrex tubing 1.000 *0.005 mm bore. Capillaries of various lengths (from 2.85 to 5.85 cm) were cut and sealed at one end by fusing a 3-mm Pyrex rod to the end. The capillaries were filled by inserting them into the filling chamber, evacuating the chamber, submerging the capillaries, and pressurizing the chamber with argon. Two sets of capillaries were prepared for each run. One set contained an alloy more dense than the bath alloy and one set a less dense alloy. This procedure was followed so that the effect of density difference on the measurement could be determined. After filling one set of capillaries, these were placed open end up in a capillary holder and transferred to the diffusion chamber which consisted of a Pyrex tube inserted into a graphite block. The second set of capillaries was then filled and placed into the diffusion chamber. The reservoir alloy, which had been melted in a separate crucible, then was poured carefully into the diffusion chamber. Sufficient reservoir alloy was used to cover all capillaries to a depth of several centimeters. All of these operations: capillary filling, melting of alloys, and diffusion anneal, were carried out in a fused-salt bath which maintained a temperature of 300"*1°C. All capillaries were permitted to diffuse for approximately 48 hr. At the end of the diffusion period the capillary holder was removed from the bath and

Jan 1, 1969

By L. W. Holm

Laboratory flooding experiments on linear flow systerns indicated that high oil displacement, approaching that obtained from completely miscible solvents, can be attained by injecting a small slug of carbon dioxide into a reservoir and driving it with plain or carbonated water. Data are presented in this paper which show the results of laboratory work designed to evaluate this oil recovery process, particularly at reservoir temperatures above 100°F and in the pressure range of 600 to 2,600 psi. Under these conditions CO2 exists as a dense single-phase fluid. It was found that a bank, rich in light hydrocarbons, was formed at the leading edge of the CO? slug during floods on long cores. Formation of this bank is probably due to a selective extraction by the C02 and, it is believed, partially accounts for the attractively high oil recoveries. In crddition to the efficient displacernerlt of oil from the pores of the rock by this process, the favorable rnobility ratio related to a C0 2-water flood also contributes to high oil recovery. A further advantage of this process is noted on limestone and dolomite rock, in that the CO1 reacts with the porous medium increasing its permeability. Flooding experiments were conducted on sandstone and vugular dolomite models. The results of this experimental work show the effect on oil recovery of type of porous medium, pore geometry, flooding length, and flooding pressure. The porosity of the cores and rilodels varied from 16 to 21 per cent and their pern~eabilities ranged from 100 to 200 md. A reconstituted West Texas reservoir oil, a West Texas stock tank oil, an East Texas stock tank oil and Soltrol were used to represent reservoir oils in this study. Oil recoveries ranging from 60 to 80 per cent of the original oil in place in these cores were obtained by CO2,-carbonated water floods at pressures between 900 and 1,800 psi, compared with conventional solution gas drive and water-flood recoveries of 30 to 45 per cent on the same cores. Oil recoveries greater than 80 per cent resulted frorn f1oods at pressures above about 1.800 psi. There high recoveries were noted from both the sandstone and the irregular Porosity carbonate cores. In all floods, additional oil was recovered by a solutiorr gas drive resulting from blowdown following the flood. Oil recoveries of 6 to 15 per cent of the original oil in place were obtained during this blowdown period. This additional recovery was found to be a function of oil remaining after the flood, decreasing with decreasing oil saturation. It was also noted that highest oil recoveries by blowdown were obtained when carborlated water rather than plain water followed the CO, slug. INTRODUCTION Miscible phase or solvent flooding processes, which are designed to increase oil recovery -from petroleum reservoirs, involve the injection of small quantities of a petroleum solvent into the reservoir, followed by an inexpensive scavenging fluid which is miscible with the solvent. Essentially complete displacement of oil from the pores of reservoir rock has been obtained by this technique. CO,, although not completely miscible with most reservoir oils at moderate pressures, is highly soluble in these oils at pressures above about 700 psi; there is appreciable swelling and reduction in the viscosity of oil when CO, is dissolved in it. Therefore, CO, could be expected to perform similarly to other oil solvents as a displacing agent. CO, is also highly soluble in water at elevated pressures, so water should be a satisfactory material to drive a slug of CO, through an oil-bearing reservoir. A favorable mobility ratio would be obtained through the reduction in viscosity of the oil and the use of water as a final displacing agent. A number of investigations of the use of CO, to improve oil recovery have been reported in the literature.2,3,4,5,6 These studies, however, have been conducted on uniform porosity sandstone at relatively low temperatures and pressures. The behavior of CO1 as a flooding agent at temperatures above its critical temperature could not be predicted adequately from these studies, particularly for the case of non-homogeneous rock. The purpose of this work was to evaluate the oil recovery efficiency of a process involving the injection of a CO2 slug followed by carbonated water, at reservoir temperatures above 100°F and in the pressure range of 600 to 2,600 psi, and to compare this process with conventional water flooding. The investigations were primarily designed to provide information on the efficiency of the process in irregular porosity carbonate rock. The effects of flooding path length, the presence of free gas, the type of oil to be recovered, and the amount of solvent required were also determined. The essential results of static phase behavior studies and experimen-

By Maurice Cook

A procedure of obtaining specimens of lead, tin, and cadmium with a moderately equiaxed structure and a smooth surface suitable for etching without grinding and polishing is described; the advantages of general oblique illumination (as opposed to vertical illumination) in the photomicrography of pure metals .are stated. Using these methods, a statistical study of the changes brought about in deformed lead, on annealing, has been made. The common mode of structural change was found to be recrystallization. Cases of growth of one original grain into another were rare; but if a totally recrystallized specimen was annealed above 200° C., a few large grains appeared and spread over the whole area, except for a certain number of small grains which remain unabsorbed. The temperature needed to produce structural change in lead was found to be lower, the greater the degree of deformation. With tin, an extension of 28 per cent. caused practically no recrystallization at ordinary temperatures, but recrystallization occurred if the specimen was heated to 100° C. In cadmium at low temperatures, the grain size decreased in marked manner as the deformation increased; but at high annealing temperatures, the grain size was comparatively independent of the degree of deformation. THE structural changes in metals brought about by annealing following a deformation at a low temperature has been the subject of many investigations. No less than eleven metals and alloys have been studied in some detail; namely, aluminum,1 tungsten,2 iron,3 copper,4 gold,5

Jan 11, 1924

By Franklin H. Wilson

COPPER base alloys containing various amounts of aluminum and silicon are of considerable commercial interest. In particular the alloy containing 7 pct aluminum and 2 pct silicon shows an attractive combination of high strength with excellent machinability. Since there is no evidence in the literature that this ternary system has been studied since the recognition by Smith1 and Anderson2 in 1939 of the kappa phase of the binary copper-silicon system, the determination of the equilibrium phase relationships in the copper corner of the ternary diagram has been undertaken to provide a fundamental basis for understanding the behavior of these alloys. Phase boundaries have been determined by the micrographic examination of quenched samples while points on the liquidus surface have been obtained by thermal analysis. The results, of sufficient precision to serve their major purpose of providing a guide for the control of the manufacture of alloys in the region covered, are presented in a series of both isothermal and vertical sections of the diagram. ALLOYS STUDIED For a rough survey of the copper corner of this ternary system the compositions listed in Table I (Series A) were employed. The results of examinations of these alloys indicated that the compositions listed in Table 2 (Series B) would further clarify regions of greater complexity. All alloys were prepared as 1200 g heats, the copper being melted under charcoal, and then first silicon and then aluminum were added. An [ ] excess of 0.05 pct silicon was allowed to cover deoxidation losses. Two small bars 5/8 by 1 ¼ by 1 ¼ in. were cast using Durville type casting equipment. Analyses were made on all alloys using material which was hot-rolled at 800 or 850°C and annealed 17 hr at 650°C. All analyses were found to be within 0.05 pct of the nominal composition. Since the precision of analysis is not much better than this, the points of both isothermal sections and vertical sections at fixed aluminum and silicon contents have been plotted at the compositions indicated by the nominal composition.

Jan 1, 1948

By George A. Connell

BORAX, a sodium borate and the principal sodium salt of boric acid, has been surrounded with romance and with a certain amount of mystery. Its early history is not entirely known but it has been contended that Marco Polo in his travels in the Orient introduced this material to the West during the Middle Ages. Without doubt its first source was from Central or Eastern Asia and perhaps from Tibet. The well-known fluxing properties of borax probably introduced its earliest use that of a soldering flux in the manufacture of jewelry. This use, as well as the remote location of most borate deposits, added greatly to the romance associated with the thought of borax. COMPOSITION The common element in all borates is boron but this element has never been discovered as such in any deposit, because of its great affinity for oxygen. Incidentally, this makes its manufacture extremely difficult and expensive. Elemental boron undoubtedly has many properties that make it quite valuable but the extreme cost involved in producing it from its oxidized form prevents its general use or manufacture. The common element in all borates is boron but this element has never been discovered as such in any deposit, because of its great affinity for oxygen. Incidentally, this makes its manufacture extremely difficult and expensive. Elemental boron undoubtedly has many properties that make it quite valuable but the extreme cost involved in producing it from its oxidized form prevents its general use or manufacture. The common element in all borates is boron but this element has never been discovered as such in any deposit, because of its great affinity for oxygen. Incidentally, this makes its manufacture extremely difficult and expensive. Elemental boron undoubtedly has many properties that make it quite valuable but the extreme cost involved in producing it from its oxidized form prevents its general use or manufacture of disodium tetraborate (Na2B4O7.10H2O), and, further, can be considered as the acid salt of monosodium metaborate. However, the term "acid salt" might imply that borax gives an acid reaction in solution, which is not true, since solutions of borax are decidedly alkaline, giving a pH of 9.2. Boric acid, also known as boracic acid, has the chemical formula H3BO3; it occurs in nature as the mineral sassolite. Sassolite has been

Jan 1, 1949

By J. Ellzey Hayden

THE Cliffs Shaft mine of the Cleveland Cliffs Iron Co., located in the city of Ishpeming, Mich., is the largest producer of hard hematite ore on the Marquette iron range. The two shafts, A and B, lying 820 ft. (250 m.) apart on the east-west trend of the ore formation, were sunk in the early eighties, and, except for four years, have been steady producers of iron ore. Their location, on a hill overlooking the general offices of the company on the one side and the city of Ishpeming on the other, has made the shaft houses landmarks. In the spring of 1919, as the old wooden shaft houses had become shaky and out of line, and would soon be unsafe, it was necessary to replace them with the least possible delay. Three plans of construction were, therefore, considered: To replace the old shaft houses by somewhat similar structures made of wood; to use steel and radically change the design; or to build reinforced-concrete shaft houses outside of the wooden structures, completely enclosing them. The first plan was disapproved, because it is anticipated that the mine will have a long life and the proximity of other buildings makes the danger from fire rather great. Delay in receiving material, and the necessity for closing the shafts during erection, were other factors in the situation. The second plan was disapproved on account of the high cost of steel, slow delivery, and interference with hoisting during the period of erection. The presence near one of the shafts of a large bed of hard gravel suitable for concrete made, the cost of the third plan considerably less than the second, and little, if any, delay in hoisting was expected. Our expectations in this regard' were fully realized. Furthermore, the work could be done by unskilled labor, which was plentiful, and the erection could be quickly started. When the proposition was submitted to Mr. W. G. Mather, president of the company, he recommended that, on account of the prominence of the buildings due to their location, an effort should be made to combine in the design as far as practicable something of architectural beauty. Following his recommendation, the original plans were submitted to the

Jan 8, 1920

By W. N. Logan

WHAT is mineral wool? This question is frequently asked by those unacquainted with its manufacture. The word "mineral" suggests that it is of mineral origin; the word "wool" suggests that it is of animal origin; but the only similarities it has to wool are its fibrous character and its white fleecyness. Mineral wool is a fiber produced by melting rock to a glasslike condition and blowing the glass into fine white, wool-like threads. A -number of the products fabricated from-mineral wool are used for some form of insulation, but mineral wool is adaptable to many other uses. It is used in the manufacture-of pipe covering designed to with; stand the high temperatures produced in steam pipes. In a similar form of insulation it is used to cover boilers and furnaces. It is used in ,the fabrication of upholstery tow for sofas and car seats: In acoustics it has many uses, such as acoustifibroblock, which is used in floors to destroy sound and vibration, and acoustic mat, which is used under carpets to destroy sound. In the insulation of houses, loose wool and granulated wool are used beneath attic floors and between the studding in frame buildings to prevent the escape of heat in winter and the entrance of heat in summer. Mineral wool is used also in fabrication of linofelt, which is a quilted form of insulation; in fibrofelt, which is an insulating board; in the fabrication of lith, which is an insulating block; in anti-fibroblock ,which is used in insulation and refrigeration; in flexfelt; in loose wool; in pressed block; in heavy oiled wool; in dark oiled block; and for many other purposes. The materials used in the manufacture of mineral wool are of two kinds. The first is a rock which contains silt, clay and silica, with smaller amounts of lime and magnesia. The second is a more highly calcareous rock which may carry a small amount of magnesia. The latter is used as flux to assist in the melting of the former. The relative proportion of the alumina-iron-silica content to the lime-magnesia content is normally as fifty to fifty but a considerable range is possible.

Jan 1, 1932

By John Gillie

Prior to the year 1902 electricity was used in the Butte district only for lighting, for the tramming of ores on the surface, and for the electrolytic refining of copper. In that year the Canyon Ferry hydro-electric plant on the Missouri river, with a transmission line to Butte and Anaconda, was completed, and enabled the mining operators to purchase electric current in large quantities at reasonable rates, and its application and use in the various mining operations and reduction works proceeded rapidly. The principal applications. of electric current in metal mining may be listed as follows: Compressing air for hoisting. Compressing air for rock drills and pneumatic tools. Pumping. Ventilating. Lighting. Tramming. Compressing air for blast furnaces and converters Running shop and miscellaneous motors.

Jan 9, 1913

By M. E. Nicholson

The effect of boron on the austenitic transformation rate of iron is smaller than on low carbon steels. The influence of austenitizing temperature on B-Fe is the reverse of its influence on steels. THERE have been many studies made of the influence of boron on the hardenability of steel, but apparently none has been made of its influence on the y-a transformation of pure iron. There are several facts suggesting that boron should have a pronounced effect on the transformation rate of iron. First, Simcoe et a1.l indicated that boron reduces the nucleation rate of ferrite and bainite. Second, they showed, along with others,', " that the lower the carbon content of steel the greater the influence of boron on hardenability. If this trend extends to pure iron, the influence on rate of ferrite formation should be considerably greater for iron than for medium carbon steels. According to Rahrer and Armstrong," the multiplying factor for boron in pure iron should be about 2.40, compared with 1.50 in a 0.35 pet C steel. According to an extrapolation made by Grange and Mitchell,' the effect should be even greater, and the multiplying factor should be about 3.5 in iron. Many investigations of the boron influence'.7, 2, 5 indicated that boron is effective only when in solid solution. On the other hand, Chandler and Bredig" suggested that boron increases hardenability by combining with nitrogen, thereby preventing formation of AlN, which catalyzes the decomposition of austenite. If their hypothesis is valid, boron should have no effect on an alloy free from nitrogen. Digges et al." showed that so far as low nitrogen high purity Fe-C alloys are concerned this is not the case. No experiments, however, have been made on low nitrogen iron. To determine whether or not boron has an effect on low nitrogen iron and, if an effect exists, to determine whether it is as large as predicted from the investigations of boron treated steels, the following work was performed. Because of the rapidity with which iron transforms from austenite to ferrite at even a moderate degree of supercooling, it was decided to study the influence of boron on the transformation rate of iron by determining the effect of quenching rate on the temperature of the beginning of transformation. The technique, essentially that used by Greninger' and Duwez,H consisted of heating small specimens, 0.1 in. sq and 0.010 in. thick, in an atmosphere of purified helium with a resistance heater coil, and then quenching the sample in a jet of helium gas. At the time the jet was applied, the heating coil was removed from around the sample. The sample was suspended in the furnace on 30 gage chrome1 and alumel wires, one welded to each side of the specimen, which also served as a thermocouple for measuring the specimen temperature. Specimens were prepared from vacuum-melted iron obtained from the National Research Corp. which was rolled to a thickness of 0.060 in. and then decarburized in wet hydrogen for 51/2 hr at 700°C. This treatment also removed any boron present in the iron. The resulting iron contained 0.001 pet C. 0.0002 pet N, and 0.005 pet 0. One half of the piece was then boronized by surrounding it with 325 mesh boron powder and heating it for about 2 hr at 900°C in H,. The boronized iron was then homogenized at 1100°C for 24 hr. The iron boride case formed by boronizing was removed by grinding 0.010 in. from each side of the plate, and the piece was finally rolled to a thickness of 0.010 in. The resulting alloy contained

Jan 1, 1957

By F. W. Jessen, H. Kazemi

A washing technique has been developed to form a spherical cavity in massive salt. The technique is, basically, a process of controlling the fluid motion in the cavity, the concentration distribution of brine, the rate of dissolution at the walls of the cavity, and the particular settings of the wash pipe, or pipes (inlet and outlet pipe) employed. For a particular arrangement of tubing and casing, fresh water enters from the casing annulus at a position above the bottom of the tubing, and the dissolved material leaves the cavity through the tubing near the bottom of the projected hole. The initial configuration of the cavity is cylindrical, representing the drilled hole situated at the axis of the projected cavity. As washing progresses the original hole is enlarged radially (any direction perpendicular to the axis of the hole). An inert fluid (generally a hydrocarbon, natural gas, or air) which serves as a blanket is injected through the annular space between the original hole and the casing. The controlled downward motion of this blanket maintains the upper edge of the brine region that is expanding on the surface of the projected sphere. A large spherical glass container and a radial model were used to investigate the flow patterns and the concentration distribution of brine occurring during the progress of solution of the salt. Aluminum flakes and dye were injected and flow patterns were observed and recorded on motion picture film. Based on the results of these model studies and other work carried out in this laboratory, the controlled washing technique was formulated. INTRODUCTION Underground cavities leached in salt beds and salt domes have been used extensively for storing hydrocarbons. Little attention has been focused on the shape of the cavities as long as large volumes were obtained and the cavities were structurally stable. The general process involves circulating fresh water and removing brine. Two distinctly different circulating systems can be employed, each of which yields characteristically different shapes. By far the most generally accepted method of washing storage caverns in salt domes is the direct circulation system. Water is introduced through the innermost pipe of a concentric pipe system, and brine is withdrawn through the annulus. In the reverse-circulation method, water enters through the annulus and is discharged through the smallesc tubing string. The size of the operation, and hence the size of tubing and casing used, depends on such factors as cavity volume, length of hole, availability of water, disposal of brine and power requirements. Underground caverns are from 100 to 1,000 ft or more in length, and when completed vary from 40 to 100 ft in diameter, providing storage of 100,000 bbl or more. The volumes of water required per volume of salt removed vary from 6 to 7 for the reverse circulation method to 10 to 11 for the direct circulation method. Up to 80,000 BWPD are often circulated. In the direct circulation method, because water enters near the bottom of the projected cavity, solution of salt is greatest at this point, particularly in view of the fact that when the washing is begun turbulent flow undoubtedly exists in the immediate vicinity of the discharge of the inlet water. As the diameter of the hole increases, flow rates also are increased, so perhaps the condition of fluid turbulence is maintained for some time. During the later stages of leaching, when capacity of equipment may be the limiting factor in maintaining flow rates, there may still exist some turbulence adjacent to the point of influx; however, for the most part laminar flow conditions prevail. There appears, therefore, rather good evidence to indicate that the state of fluid motion is responsible for the typically shaped cavity which results from such washing — namely a cylindrical form, generally somewhat larger at the bottom than at the top. Depending on the number of so-called stages which might be employed, the walls or surfaces of the salt diminish rather uniformly from bottom to

Jan 1, 1965

By J. C. Sarace, S. M. Sze, C. R. Crowell

Thin films of tungsten 077 n-type germanium, silicon, and gallium arsenide were obtained by reacting tungsten hexafluoride with the semiconductor surface in an argom atmosplrere at temperatures between 325° and 400° C. Capacity-voltage, current-iloltage, and photoelectric measurements were used to investigate the characteristics of the tungsten -semiconductor diodes thus Produced. The junctions are shown to he very close to ideal Schottky barlp/ers with barrier heights measured with respect to the Fermi energy of 0.18, 0.65, and 0.78 1.1 jar W-Ge, W-Si, and W-GaAs, respectively. The electrical properties of the W-Si interface show no deterioration when heated to 1000°C in dry forming gas for 5 min. A theoretical value of the Richardson constant, A, appropriate to the semiconductor-hand structure has been used in evaluating the current-voltage characteristics. ThE W-Si surface-barrier diode was initially proposed for investigation because the eutectic temperature with silicon (1400°C) is much higher than that in the Si-Au system 1370°C).1 This would permit more flexibility in heat treatment and possibly provide greater reliability at elevated temperatures. The lower work function of tungsten (4.54 ev)2 compared with that of gold (4.78 ev)3 also suggested that a lower barrier height would be obtained with tungsten and hence a lower forward bias and lower minority carrier injection ratio for a given current density. The investigation was extended to include the characterization of W-Ge md W-GaAs surface-barrier diodes. The tungsten films have been produced by reacting WF6 with germanium, silicon, and GaAs surfaces in an argon atmosphere at temperatures from 300° to 500°C.4 This process is a very satisfactory alternative to the relatively difficult process of evaporating tungsten films in vacuo. To ensure an adequate electrical characterization of the tungsten-semiconductor interface, three types of barrier-height measurements have been performed. The mutually consistent results obtained lead to the conclusion that the tungsten-semiconductor junctions are indeed of the Schottky type. EXPERIMENTAL PROCEDURE The apparatus used for producing tungsten films is shown schematically in Fig. 1. It consists of an argon carrier gas line to which metered amounts of tungsten hexafluoride can be rapidly added. The mixture passes through a heated reaction tube containing the semiconductor slices and is exhausted to a hood. The argon is purified by passage through a 6-in. column of titanium turnings maintained at 800°C. The tungsten hexafluoride dispensing arrangement was designed by V. C. Garbarini and W. R. Bracht.4 A measured amount of liquid tungsten hexafluoride is injected into the argon stream and vaporizes. The mixture passes through a sodium fluoride absorption cell to remove traces of hydrogen fluoride, then into the nickel reaction tube. The tube is 12 in. long with an inside diameter of 1/2 in. The center section is heated by a furnace of the self-supporting wire-filament type. It was chosen for its rapid heatup and cooling. The wall thickness is 10 mils except for a 3-in. hot zone which is 30 mils thick to reduce thermal gradients along the length. The samples to be coated are placed on a sapphire plate and centered in this section. The tungsten is deposited with the following sequential steps: the loaded reaction tube is flushed with argon at a rate of 500 cu cm per min and heated to 370°C. Then 0.45 g of liquid tungsten hexafluoride is injected into the argon stream. The samples are held at this temperature for 2 min. The tube and samples are then cooled to room temperature and the samples removed. Tungsten films were grown on (111) faces of silicon and germanium polished with Linde A abrasive and lightly etched with HF-HNO3. The GaAs surfaces were (100) faces chemically polished with a H2SO4-H2O2 solution. The films have typical sheet resistances of 0.2, 8, and 15 52/0 when grown on germanium, silicon, and GaAs, respectively. After the tungsten deposition, ohmic contacts were alloyed on the back surfaces of the wafers. Ohmic contacts to the germanium and silicon were obtained by alloying Au-Sb at 370°C, ohmic con-

Jan 1, 1965

By T. P. Floridis, J. H. Young

The need for close control of the phosphorus content of steels has led to numerous investigations on the equilibria of the dephosphorization reactions. Winkler and chipman1 have established the general conditions for effective dephosphorization of steel. They are high slag basicity, high oxygen potential, and low temperature. Other investigators have made additional contributions to the understanding of the dephosphorization process. The current status of the understanding of the dephosphorization of steel is concisely presented by Bodsworth2 and by Ward. The investigation reported in this communication was undertaken with the purpose of establishing the effect of additions of barium oxide and calcium fluoride on the dephosphorizing capacity of slags. Esin and Gel'd4 proposed that barium oxide, being more basic than calcium oxide, should cause an increase in dephosphorizing capacity when added to steelmaking slags, or when used as a substitute for calcium oxide. Derge5 has also proposed that in the future conventional slags might be replaced by BaO-Al2O3 slags. There is, however, no experimental evidence confirming the effect of barium oxide on the dephosphorizing capacity of slags. The effect of calcium fluoride on the dephosphorization of steel is not clearly understood. It is generally recognized that additions of calcium fluoride are beneficial. It is not clear, however, whether calcium fluoride affects the equilibrium of the dephosphorization reaction, or whether it simply causes an increase in the fluidity of the slag and, consequently, faster approach to equilibrium. The experimental procedure consisted in equilibrating synthetic molten slags with liquid copper at 1550°C under a gas stream containing argon, hydrogen, and water vapor. In all experiments the argon to hydrogen ratio was approximately 4:1, and the hydrogen to water ratio was 5.42:l. Molybdenum crucibles were used as containers for the slag and metal. Under the above-described conditions of temperature and composition of atmosphere, there was no observable attack of the crucibles by the metal, slag, or atmosphere. Copper was used instead of iron, because iron attacks molybdenum. The equilibration was made in a tubular furnace consisting of a recrystallized alumina tube. The alumina tube was heated by electrical resistance. A Pt-40 pct Rh wire winding was used for most runs. A silicon carbide tubular resistor was also used for some runs. Temperatures were measured with a Pt-Pt-Rh (10 pct Rh) thermocouple and kept constant within ±5°C. Equilibrium was approached from both sides, i.e., by adding the phosphorus either as oxide in the slag or as a phosphorus-rich alloy of phosphorus and copper. The holding time at the equilibrium temperature was 6 hr. At the end of each run the crucibles were rapidly cooled and removed from the furnace. The slag and metal were separated and analyzed. The experimental results are shown in Table I. The phosphorus content of the slag is expressed both as percent phosphorus pentoxide and as percent phosphorus. The basicity ratio is computed by dividing the number of moles of basic oxides-oxides of barium, calcium, magnesium, and sodium—by the number of moles of acidic oxides- oxides of aluminum, phosphorus, and silicon. Calcium fluoride is not included in the computation of the basicity ratio; i.e., calcium fluoride is assumed to be neither basic nor acidic. The distribution ratio of phosphorus—percentage of phosphorus in the slag divided by the percentage of phosphorus in the metal- is plotted in Fig. 1 against the basicity ratio. The results indicate that slags containing barium oxide have greater dephosphorizing capacity than slags containing calcium oxide. The high dephosphorizing capacity of slags containing sodium oxide and the low dephosphorizing capacity of magnesia-containing slags which already have been reported in the literature2 are confirmed by the results of this investigation. It appears that calcium fluoride has a beneficial effect on the distribution of phosphorus between slag and metal in acid slags only. Although the obtained distribution ratios between the phosphorus contents of slag and copper are not directly applicable to the dephosphorization of steel, they are sufficient for evaluating the effect of slag additions on the dephosphorizing capacity of slags in general. An increase in the ratio of distribution of phosphorus between slag and metal indicates lowering

Jan 1, 1968

By Richard D. Call

Data obtained from development drilling provide the basic input for open pit mine planning and design. Development drilling is defined as delineation of the size, mineral content, and disposition of an ore body by drilling boreholes (Thrush, 1968). The objectives of development drilling are: ( 1 ) determining the geometry of the mineralization, ( 2 ) determining the grade and tonnage, , ( 3 ) obtaining samples for metallurgical testing, and ( 4 ) obtaining geotechnical data for mine design. To accomplish these objectives, an appropriate drilling plan must include the number of holes, the spacing and orientation of the holes, and a suitable data collection program. The data collection program covers sample collection, hole logging, and data presentation. This chapter will present some guidelines for development drilling and data collection techniques. The operational aspects of drilling will be covered in an- other chapter.

Jan 1, 1979

By P. A. Young

The historical background of on-strand cooling is given, together with a resume of recent practical developments. Laboratory test procedures are then considered in detail, for both productivity and quality parameters, with particular reference to the design of the Ravenscraig No 3 machine (Scotland). A heat transfer model is presented for a porous sinter with propagating cracks. The influence of cooling/sintering area ratio, sinter strength, granulometry, return fines, coke consumption and FeO levels are examined in relation to economics. A detailed comparison of capital and running costs for two different strands, designed for identical duties, but with off or on-strand cooling, is then given.

Jan 1, 1977

By V. N. Mackiw, D. E. Weir, D. J. I. Evans

The world's largest reserves of nickel are found in lateritic ores. Commercial exploitation has been carried out for almost one hundred years; however, none of the plants currently in operation produce pure nickel but rather ferronickel, matte, impure nickel oxide or mixed sulphide precipitate. Over the past decade Sherritt has studied various processes, including the modified reduction roast-ammonia-ammonium carbonate leach process, for the production of pure nickel powder and briquettes from laterites. Nickel can be reduced to the pure elemental form at elevated temperatures and pressures from impure basic nickel carbonate slurries. Several methods were studied in the development of the process for working up the pregnant leach liquor and basic nickel carbonate to produce feed for the aqueous hydrogen reduction step in which pure nickel powder is produced. This paper is concerned only with the laboratory studies using the basic nickel carbonate slurry reduction procedures.

Jan 1, 1973

By J. H. Schloen, C. W. Clark

Two papers have been written previously concerning operations at the Montreal East plant of Canadian Copper Refiners Limited. The first one,' written in 1932, described silver-refinery operations at the time for producing silver and gold bullion from tankhouse anode slimes; the second,2 published in 1933, consisted of a description of the entire plant. Since publication of these papers the refinery has become the world's largest producer of refined selenium. The first selenium was produced in August 1934. Tellurium production on a commercial scale followed in October 1935. This paper will deal with selenium and tellurium production and also with present operations in the silver refinery. Blister cakes from Hudson Bay Mining and Smelting Co., Flin Flon, Manitoba, and commercial anodes from Noranda Mines Limited, Noranda, Quebec, are refined at Montreal East. Both these bullions have unusually high gold, selenium and tellurium content. The average assay of raw slimes produced from domestic and Noranda anodes is about 40 per cent Cu, 3600 oz. per ton Ag, 800 oz. per ton Au, 22 per cent Se and 3.7 per cent Te. Early Silver-refinery Operations From the start of operations in 1931 until July 1934, the raw slimes were oxidize-roasted at 700" I?. in a Nichols-Herreshoff furnace, acid-leached with tankhouse discarded foul electrolyte (20 per cent H²SO), filtered and charged directly to the doré furnace for refining to doré meta1. This is the customary method for treating tankhouse anode slimes but was not suitable at the Montreal East plant because of the high selenium and tellurium content of our slimes. In the acid-leaching process about 50 per cent of the selenium and tellurium in the roasted slimes was dissolved in the electrolyte. These elements were recovered with the copper as a sludge in a small electrolytic

Jan 1, 1943

By C. W. Clark, J. H. Schloen

Two papers have been written previously concerning operations at the Montreal East plant of Canadian Copper Refiners Limited. The first one,' written in 1932, described silver-refinery operations at the time for producing silver and gold bullion from tankhouse anode slimes; the second,2 published in 1933, consisted of a description of the entire plant. Since publication of these papers the refinery has become the world's largest producer of refined selenium. The first selenium was produced in August 1934. Tellurium production on a commercial scale followed in October 1935. This paper will deal with selenium and tellurium production and also with present operations in the silver refinery. Blister cakes from Hudson Bay Mining and Smelting Co., Flin Flon, Manitoba, and commercial anodes from Noranda Mines Limited, Noranda, Quebec, are refined at Montreal East. Both these bullions have unusually high gold, selenium and tellurium content. The average assay of raw slimes produced from domestic and Noranda anodes is about 40 per cent Cu, 3600 oz. per ton Ag, 800 oz. per ton Au, 22 per cent Se and 3.7 per cent Te. Early Silver-refinery Operations From the start of operations in 1931 until July 1934, the raw slimes were oxidize-roasted at 700" I?. in a Nichols-Herreshoff furnace, acid-leached with tankhouse discarded foul electrolyte (20 per cent H²SO), filtered and charged directly to the doré furnace for refining to doré meta1. This is the customary method for treating tankhouse anode slimes but was not suitable at the Montreal East plant because of the high selenium and tellurium content of our slimes. In the acid-leaching process about 50 per cent of the selenium and tellurium in the roasted slimes was dissolved in the electrolyte. These elements were recovered with the copper as a sludge in a small electrolytic

Jan 1, 1943

By W. S. Morris, R. R. Bradenthaler, G. Wade

Petroleum engineers generally are of the opinion that the flow conditions and, therefore, the formulas that apply to the flow of oil and gas in long pipe lines differ in many ways from flow conditions in oil wells. One of the reasons why the formulas in common use for pipe-line flow do not correctly apply to oil wells is that the flow lines are vertical and not horizontal. Another factor to be considered is that the fluid is a mixture of oil and gas and that the physical characteristics of these two components are affected differently by changing conditions of pressure and temperature during upward flour. Realizing the need for accurate data on flow in vertical pipes under conditions caused both by natural flow and the gas-lift, the U. S: Bureau of Mines has installed equipment at the Petroleum Experiment Station, Bartlesville, Okla., for the purpose of studying this problem. In additon a study will be made of the comparative effects of different natural-flow and gas-lift methods of producing oil on ultimate production from reservoir sands. Experimental Equipment The experimental equipment consists of a regular oil-field steel derrick, a large pressure tank installed in a concrete pit beneath the derrick floor, compressors and pumps, gas separators and absorbers, metering and control devices, and the necessary pipe connections. The crown-block level represents the derrick floor at an oil well, and the "producing sand" is the pressure tank below the derrick floor. The difference in elevation between the crown-block level and the tank is 90 ft. Figs. 1, 2 and 3 show the construction and exterior arrangement of the equipment. The success of the experiment will of course depend largely upon the accuracy of the oil and gas measurements and the temperature and pressure determinations. Because extreme accuracy is necessary, all oil and gas measurements will be checked at least twice, and in some

Jan 1, 1929

By Robert T. Howard, Morris Cohen

IT has long been realized among metallurgists that a fast, reliable method for the quantitative determination of the percentage of microconstituents in an alloy would be of great benefit in studies of equilibrium and transformation in the solid state. For example, Polushkin1 has shown that the compositions of two coexisting phases in a a binary system at a given temperature may be calculated very simply with the aid of two alloys lying in the two-phase field if the relative amounts of the two phases in each alloy can be determined. Recently, Grange and Stewart2 have traced the course of the austenite-martensite reaction in a series of commercial steels by making visual estimates of the percentage of martensite formed as a function of cooling temperature. The correlation of mechanical properties with structure, a subject of wide-spread current interest, is likewise dependent upon quantitative microanalysis.3 Yet, there are very few investigations described in the metallurgical literature, wherein methods of quantitative microscopy are employed. Usually, the relative amounts of the microconstituents are estimated in a qualitative or semiquantitative way. The authors were faced with this problem some time ago in studying the kinetics of austenite decomposition. Several aspects of, this research could not be treated satisfactorily by other quantitative tools, such as specific volume,4 magnetic,5 dilatometric,6 electrical resistance7 or x-ray measurements.8 It became necessary to find an impersonal quantitative method that could be applied to microstructures. Fortunately, it was noted that geologists and petrographers had coped with quantitative microscopy to a considerable degree in their attempts to evaluate the mineral contents of rocks. A number of excellent articles were found on this subject, and since they appear to be unknown generally to many metallurgists, the first part of the present paper is concerned with a review of the literature in some detail. With this survey as a background, the authors have adapted the so-called methods of point-counting and lineal analysis to metallography, as described in the second part of the paper. Austenite-martensite structures were selected for illustration not only because they are important in many ways, but because such fine intermixtures are notoriously difficult to estimate visually. LITERATURE SURVEY Perhaps the earliest work on quantitative microscopic analysis goes back to Delesse9 (1848) who proved mathemati-

Jan 1, 1947