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By V. F. Leferrer

A new process for the treatment of silver crusts from desilverization of lead has been developed by Societe de Penarroya. The zinc contained in the crusts is recuperated by vacuum distillation at low temperature. The use of special retort crucibles is avoided. AT Noyelles-Godault the Parkes process (zinc addition to a silver-bearing lead melt) is used to desilverize lead bullion from the blast furnace. The crust which rises to the surface of the bath is removed and pressed by a well-known process in a press of the Howard type. The pressed crust, called zinc crust or silver crust, contains 10 pct Ag, 30 pct Zn, and 60 pct Pb. It is melted under a salt bed in a small, narrow, and deep kettle heated only in its upper part. A liquid concentrated alloy is obtained which is called T.A.C. in France (triple alliage concentr6) analyzing approximately 25 pct Ag, 65 pct Zn, 8 to 10 pct Pb, and 1 to 1.5 pct Cu. This T.A.C. is a real metallic alloy, completely deoxidized, and can be stored indefinitely. The process used at Noyelles-Godault consists in distilling this alloy in a tight furnace, under low vacuum and at low temperature, so that only the zinc distills and is condensed into liquid form. The residual silver-bearing lead is almost entirely free from zinc and oxidized dross. The vacuum dezincing equipment, see Figs. 1 and 2, consists of: 1) A furnace, constituted of a casing of steel plate lined with refractory bricks, heated internally by means of graphite resistors. The temperature of the furnace is measured by a thermocouple device and controlled by an automatic temperature regulator which acts upon the flow of the current passing through the resistors. Two doors, numbered 1 and 2 in Fig. 2, are provided for, one for charging the T.A.C., the other for tapping the high silver-bearing lead. 2) A condenser, and an ordinary room lined with good heat conductor refractory material. This condenser is provided with a graphite resistor which serves to bring to temperature when starting the furnace. A thermocouple records the temperature of the zinc melt and controls the temperature in the furnace, that is, the flow of current through the resistors, by means of the above mentioned regulator, so that the distillation rate in the furnace does not exceed that of the condensation. The condenser is connected to the vacuum pump by a filter. The whole equipment should, of course, be fluid-tight. The operation is carried out under a vacuum of about 10 mm Hg.

Jan 1, 1958

The Telfer Project, one of the world's newest gold mines, is located about 300 km (190 miles) northeast of the Mt. Newman iron ore project in the northern part of Western Australia. The first mineral claims were staked in 1972; and by mid-1975 ore reserves of 3. 8 million mt (4. 19 million st) of 9.6 g per mt (0. 28 oz per st) ore had been indicated. It is interesting to note that Newmont spent more than 10 years and A$10 million in Australia for extensive mineral exploration before finding the Telfer deposit, and then spent approximately A$3 million in exploration and feasibility engineering on Telfer. Including this A$3 million, a total of A$27 million was spent to complete construction of the mine, village, gold treatment plant and associated roads, airport, water and services. Over 50% of the capital cost is in the metallurgical facility, or approximately A$10, 000 per ton per day. All economically significant gold mineralization at Telfer occurs in a series of layered quartz-limonite reefs in which the former pyrite has been oxidized to limonite to a depth of 100 m (330 ft). The most important gold reef occurs at the base of the siltstone-shale horizon within the enclosing sandstone dome -like structure. At the Main Dome structure the dipping ore horizons will be mined to a vertical depth of about 60 m (200 ft) by open-cut methods. The waste-to-ore ratio is approximately 12:1. Eventually 44 million mt (48. 5 million st) of ore and waste will be mined. Mining of the waste is by contract; however, the ore and a thin layer of waste is company-mined. Dilution from mining the geological ore reserve is about 10%. The ore is completely oxidized and the gold occurs free within the reef, material as discrete particles of varying but mainly fine grain size. Most of the gold is "free milling"; that is, over 50% of the gold is coarse enough to be recoverable by gravity concentration. Two duplex mineral jigs receive the two cyclone underflows from the grinding circuit. The rougher jig concentrate is up-graded on a continuous strake from which the concentrate is tabled to produce a final free gold product. Jig tailings are returned to the ball mill and the concentrates are amalgamated. Gold amalgam is pressed, retorted, and melted into gold bars. The gravity gold recovery circuit is the same as was used in many of the gold mills in California in the 1930s.

Jan 1, 1981

By J. J. Kramer, W. A. Tiller, G. F. Bolling

THE axial orientations of columnar crystals in unidirectionally solidified ingots of zone-refined zinc and tin have been examined using the techniques recently described by us.' Both metals had an initial purity of 99.999+ pct before zone refining and satisfied all qualitative guides for very high purity after zone refining. Fig. 1 presents the orientations of the columnar crystals for tin and zinc, respectively. For tin, there is a preference for grains growing in the [I101 direction, i.e., the dendrite direction.' For zinc, a weak preference for the [0001] direction is seen (a random population in the unit triangle would give equal density on either side of the 60-deg circle centered on [0001]).' There was no apparent evidence for dendritic growth in either metal. These results, and those previously reported,' confirm the recent investigation by Hellawell and Herbert of casting textures observed for zone-refined lead, zinc, and tin.4 The preferred casting orientations for these metals in both the impure and zone-refined states are given in Table I. In the experiments on zone-refined lead,' it was shown that two separate textures existed: a preferred (111) nucleation texture existed at the chill surface and a preferred (111) texture developed during solidification. Either effect is sufficient to produce the result recorded in Table I. Similarly the results recorded for tin and zinc may be attributable to either a preferred nucleation or a preferred growth phenomenon and additional experiments are required to separate these two possible explanations. Hellawell and Herbert' attribute their results to a preferred growth process and account for it on the basis of a "layer-growth" model proposed much earlier by one of the present authors.5 An equally satisfactory growth model would be that based upon anisotropic surface energies. However, both of these growth models would indicate that the preferred growth direction for very pure metals should be normal to the plane of closest packing in the metal. This is consistent for zinc but, contrary to the conclusion of Hellawell and Herbert, it is not consistent for tin since here the (100) is expected to exhibit a greater density of packing than the (110). Although tin is expected to exhibit an anisotropy of thermal conductivity, we would expect the thermal conductivity to be the same in the [1101 as the [l00]

Jan 1, 1963

By Herbert H. Kouns, Harlan W. Nelson, Bruce O. Buckland

GASIFICATION of coal under pressure produces a gas that may be used as the fuel in a gas turbine. The pressure produced by a gas-turbine compressor (5 to 9 atm) should allow the use of high firing rates without unreasonably high solid carry-over rates. Hot make-gas with the tars contained in it in the vapor form can be used in a gas turbine. Most of the ash can be removed through a grate, and only a small portion of the ash and any of the solid combustible material carried over by the make-gas requires separation. The gas stream from which separation is required is a small portion of the total flow of a gas-turbine plant and hence the separator size will be small. The gas stream is reducing and will not, therefore, allow separator fires to occur. The response of the producer to rapid load changes is satisfactory. Only the air rate must change substantially in synchronism with the load. The coal feed, the steam addition to the blast, and the ash-removal rate can follow the load changes with time lags in the order of minutes. The necessary control equipment is simplified by these producer characteristics. With these possibilities in mind, the Steam Turbine Division of the General Electric Co. made arrangements with Battelle Memorial Institute in January 1945 to investigate the problems of the gasification process. A number of tests were made during this investigation on an updraft producer with a grate area of 1 sq ft. The equipment used has been described and the results of the tests made between 1946 and 1950 have been reported.1 The testing with this small producer was recently completed. The concluding tests were run to determine the effectiveness of a clinker-grinding grate and the effect of the operating conditions on the amount and character of the solid carry-over. The present paper describes the producer as modified, and gives the results of the tests using three coals. Another method of using coal in gas turbines is to pulverize it and burn it directly in the combustion chambers. This plan is being tried by the Loco- motive Development Committee of the Bituminous Coal Research, Inc., whose investigation has reached the stage of tests of full-sized equipment.

Jan 1, 1953

By Eugene S. Perry

The most outstanding event in oil and gas development in Montana during 1936 was the discovery of oil in the Baker-Glendive gas field, in the extreme eastern part of the state. Other notable achievements were small extensions in the Cut Bank oil field; continued favorable results of acidization in the Kevin-Sunburst oil field; and the discovery of oil and gas in commercial quantities about 20 miles southwest of Billings, on what is known as the Mosser dome. Several wildcat wells were drilled. For the coming year of 1937, it is anticipated that the main activities will be confined to drilling in or near known fields. During 1936 Montana had seven fields producing oil, but over 95 per cent of oil production came from four fields, which in order of importance are: Cut Bank, Kevin-Sunburst, Cat Creek and Pondera. Total production for the state was 5,850,893 bbl., which is 1,251,761 bbl. more than the total for 1935. Natural gas was produced and marketed from eight fields, most important being Cut Bank, Baker-Glendive, Kevin-Sunburst and Dry Creek. These four fields accounted for over 85 per cent of total state gas production, which is slightly greater than the 1935 production of nearly 18 billion cubic feet. Increase in gas consumption is due in part to increase in smelter operation. More detailed information pertaining to the various fields is given in Table 1. In the Baker-Glendive field a test 8186 ft. deep, 15 miles southeast of Baker, was completed by the Montana-Dakota Utilities Co. in 1936. The first gas-bearing sandstone (Judith Hiver horizon, Upper Cretaceous) was found at a depth of 528 ft., and a second sand at 1167 ft. Sandstones of the Dakota formation, in which occurred water, were found from 3724 to 3853 ft. White sandstone correlated with the Tensleep (Minnelusa) formation of Pennsylvanian age was found from 5631 to 5751 ft. deep. The lower 1900 ft. of the well (below 6278 ft.) was essentially in limestone and dolomite, and information on correlation of formations in this mass of sediments is not available at this time. The upper portion of this part of the well contained much anhydrite. Cherty and dolomitic limestone below 7000 ft. may be equivalent to limestones of the Madison formation. The thickness of strata beneath the Dakota formation was

Jan 1, 1937

By W. M. Small

Austria.—Austria produced some 430 cisterns of 10,000 kg. each of crude oil of a 0.9428 sp. gr. during 1934. Gosting II well near Zis-tersdorf was placed on the pump in August and at the end of the year was still producing about three cisterns daily. This well is owned by the Erdöl-Produktionsgesellschaft while Gösting I is owned by Raky-Danubia. Only five wells were completed in the republic during the year. These accounted for 1783.5 meters of the 2225 meters drilled. The only producer completed was Gosting 11. At the close of the year, four rigs were in operation and one rigging up. At least 8 or 10 new wells are planned in Lower Austria for 1935. The European Gas & Electric Co. put its 6-km. gas line into operation in May and has sold 12,301,550 cu. m. of gas to the Vienna City Electric Works. A 2-km. pipe line was built from Gösting II to the railway loading rack near Zistersdorf. Hungary.—No oil or gas was produced except a small amount of gas trapped from flowing artesian wells. The Government completed and abandoned a 1500-m. hole at Tisztaberek in northeastern Hungary and is drilling at 967 m. near Bogáes, 120 km. northeast of Budapest. It is unofficially reported it plans to drill two new wells in 1935. The European Gas & Electric Co. has a rig up for a test at Mihalyi in Transdanubia. Czechoslovakia.—In Gbely (Egbell) there were produced 1283 cisterns of 10,000 kg. of 0.935 sp. gr. oil and a small amount of gas used for fuel. This field is operated by the Government; 17 shallow producing wells and three dry holes were drilled, with a total of 3351 m. of hole completed. In Hodonin (Goding) there were produced approximately 1300 cisterns of 10,000 kg. each of 0.91 sp. gr. oil and a small amount of gas used for fuel. The field is operated by the Apollo, which drilled four producing wells averaging 460 m. in depth, one small gas well of 550 m., one small gas well 260, and one dry hole 230 m. Two wells were deepened a total of 80 meters. The Government is drilling below 800 m. in a wildcat test in eastern Czechoslovakia near the Rumanian frontier.

Jan 1, 1935

By Andrew Allen

WHEN a mine is changed from hand, to me-chanical loading, the character of the coal dumped at the tipple is changed in many ways. Selective mining is not so easy with mechanical load-ers, and where much picking is done at the face it is apt to be wasteful anyway. Much recoverable coal is apt to be lost by too free gobbing and, in my opinion, picking at the face should be confined to removal of heavy rock, such as pieces of roof or bottom or sulfur balls. and to such clearly defined and persistent bands as can be readily recognized and segregated. With mechanical loaders of the shovel type, even this amount of gobbing is almost impossible. When coal is shoveled into a conveyor there should be no difficulty in doing as much picking as now by hand loading. The size of lumps may be greatly increased, on ac-count of the ease of handling them with a shovel, as the miners will not break them up in order to lift them into cars. Fines may be increased. This is, of course, not universally true, yet it is my opinion that a shovel breaks the coal more, as a rule, than hand loading. This might not be true with all types of shovels and is cer-tainly not true with a conveyor, either with or without the "duck-bill." The average car load will be greatly reduced in fields such as Illinois and Indiana, in which it is the practice to build up the coal above the sides. Where "level full" regulations prevail there should be no material change. When the coal comes to the tipple these differences usually result in the discovery, that many changes are necessary in the preparation plant. The increase in the percentage of fine sizes will probably not bother the screen, but may overload the conveying apparatus. The larger size lump may clog the chute, but as a rule the efficiency of the sizing screens is not greatly affected. In one completely mechanized mine the proportions of 6-in. lump and 2-in. screenings, when loading by hand, were 16.9 and 51.3 per cent respectively. When loading mechanically, these proportions changed to 15 per cent lump and 53.5 per cent screenings. The picking force on the tipple has been increased from 14 on hand loading to 33 men on mechanically-loaded coal. This is for an output of about 5000 tons.

Jan 4, 1927

By John W. Burd

A system is described for the simultaneous deposition of epitaxial layers on as many as eight substrates. A high degree of uniformity of both physical and electrical characteristics is achieved in the films. Variation of film thicknesses is consistently less than ±10pct within a wafer and from wafer to wafer within a run with the variation typically on the order of 55 pct. Composition variation of GaAs1-x PX layers within a wafer and from wafer to wafer within a run is consistently less than 51 pct. Electrical evaluation of the films by several techniques indicates excellent doping uniformity within a wafer and from wafer to wafer within a run. Mobilities for lightly doped GaAs films at 300°K are consistently >6000 cm2 v-1 sec-1 and mobilities > 7000 cm2 v- 1 sec-1 are regularly attainable. Techniques for the preparation of material with carrier concentrations from 1 x 1015cm-3 to 1 x 1019 cm-3 n-type and 5 x 1016 to 5 x 1018 cm-3 p-type are discussed. METHODS for the preparation of 111-V compounds by vapor phase reactions have been extensively reported in the literature.1-6 Almost all of the apparatus described for these various methods are suitable for processing one or at the most a very limited number of wafers simultaneously. With the recent rapid advances in the use of vapor grown GaAs for microwave oscillators and GaAs1-xPx as visible light emitters the requirements for these materials are steadily increasing. In order to satisfy these requirements it is necessary to move from a laboratory scale apparatus to one which is capable of processing a large number of wafers simultaneously. Desirable features would be a high degree of uniformity among the wafers and good reproducibility from run to run. The apparatus to be described fulfills these requirements very well. DISCUSSION The various methods reported in the literature can be classified under three headings: 1) closed tube, 2) open tube, and 3) the close-spaced method. Of these three the open-tube method is the most amenable for scale-up to a manufacturing process. It is the most versatile and the various operating conditions can be more precisely controlled than with the other two methods. A number of chemical reactions may be used to achieve vapor-phase growth of 111-V compounds. Sev-era1 of the more generally used reactions are shown in Fig. 1. All of these reactions have the following points in common: 1) generation of a volatile group III(Ga) species by the reaction of the transport agent (halide or HC1) with either Ga or GaAs, 2) introduction of the Group V(As and/or PI component, 3) a method of adding dopant, if desired, and 4) a region in which deposition from the vapor will occur and form as a single crystal epitaxial film on the substrates. The laboratory scale reactors permit the hot re-actant gases to flow into the relatively cooler deposition zone and pass successively over the several substrates which are arrayed along the long axis of the tube parallel to the gas flow. With this arrangement the composition of the reactant stream is continually changing as solid material is deposited on each successive substrate. As a result of this changing gas composition the reaction driving force also changes from substrate to substrate and the degree of uniformity of layer thickness, doping level, and so forth, is poor. This effect can be partially overcome by imposing a controlled temperature gradient along the deposition region to compensate for change in gas composition. However, even when this is done variations in layer thickness on the order of 30 to 40 pct are common and as high as 50 pct are frequently experienced between adjacent wafers in the tube. To expand this arrangement to a large number of wafers would only increase the nonuniformity from the first to last wafer in the line. From the above discussion the two undesirable features of changing gas composition and temperature gradient become evident. A reactor system which eliminates or minimizes these undesirable features is one in which the apparatus is mounted vertically as shown schematically in Fig. 2. The vertical mounting permits the disposition of a number of substrates on a suitable support so that all wafers are at the same vertical height in the furnace and hence at essentially the same temperature. By using only a single row of wafers the reactant gas mixture passes over only one substrate in its path through the reactor. Thus the two undesirable features of changing gas composition and temperature gradient are minimized. An additional design feature which further minimizes temperature variations is rotation of the substrate holder. Rotation serves to integrate any radial temperature gradient existing around the resistance heated furnace. A photograph of a reactor assembly at the completion of a run is shown in Fig. 3. MATERIAL PREPARATION Apparatus. Although any of the several chemical systems shown in Fig. 1 are adaptable for use in this apparatus the one generally used is System 2, the hydride synthesis system. This system has been de-

Jan 1, 1970

By W. V. Green

Creep of tantalum was measured at temperatures from 0.6 to 0.89 of the absolute melting temperature. The creep curves include first, second, and third stages. Steady-state creep rate depends on the fourth power of stress. The activation energy for creep throughout this temperature range is approximately 114 kcal per mole, measured by the aT technique. Subgrain formation occurs as a result of creep strain, and pile-up dislocation arrays are observed in etch-pit patterns. BECAUSE of its high melting point-which is exceeded only by those of rhenium and tungsten—and its high room-temperature ductility compared to most of the other high-melting-point metals, tantalum will undoubtedly be utilized in an increasing number of high-temperature applications. Alloying studies directed toward increased high-temperature strength must use data on tantalum itself as a base line in order to evaluate the effectiveness of the alloying additions. However, to date, no systematic study of creep of tantalum at temperatures above one-half of its melting point has been reported in the literature. Conway, Salyards, McCullough, and Flagella1 have measured linear creep rate of tantalum sheet as a function of stress, but at only one temperature, 2600°C. This paper describes a relatively thorough study of the high-temperature creep of tantalum. METHOD Material Tested. The commercially supplied, l/2-innch-diameter tantalum rod used for this work was electron-beam-melted, cold-forged, rolled, swaged, cleaned chemically, and vacuum-annealed for 1 hr at 1000°C, all by its manufacturer. The vendor's analysis included 60 to 170 ppm C, 3.4 to 4.2 ppm H, 60 to 80 ppm 0, 15 ppm N, and a hardness ranging from 66 to 81 Bhn and averaging 76 Bhn. Creep eimens Used. Two creep-tested specimens are shown in Fig. 1. The 1/4 in.-diameter gage section was 3/4 to 1 in. long, and terminated either at shoulders 5 mils high or at 20-mil-diameter tantalum wires spot-welded to the circumference of the gage section. Both kinds of shoulders served equally well as fiducial marks for optical strain measurements. The spot welding did not alter the creep behavior in any detectable way; the 5-mil- high sharp shoulders did not result in any detectable localized effect on the strain. Before testing, each tensile bar was first mechanically polished -id then electrochemically polished according to the method referred to by Forgeng2 as the "Thompson Ramo Woolridge" method, which was suitable for tantalum after small adjustments of technique were made. Two tensile bars tested at low stresses had 1/8-in.-diameter gage sections and utilized only the weight of the bottom grip for the applied load. Although these diameters were smaller than were desired for other reasons, applied loads were known with high precision in the tests in which they were used. Testing Procedure. Two different constant-load creep-testing machines were employed, one of which has been described by Smith, Olson, and Brown.3 In both, the tensile bar is held vertically on the axis of a cylindrical tungsten tube or screen heater by threaded tungsten grips. The tensile bars and associated grips are heated by radiation from the incandescent heaters, which are heated by their own electrical resistance. Both testing machines use pins to hold the bottom grips in place. The load is applied to a tensile bar through hanging weights, a constant force-multiplication lever, a pull rod sealed to the chamber lid, and a top grip threaded to the pull rod at one end and to the tensile bar at the other. In one machine, the vacuum seal is a bellows with a low spring constant; in the other, the seal involves a rotating "0 ring". With the latter, rotation is converted to translation with a crank shaft, so that elongation of the tensile bar is accommodated with no change of tensile load. The incandescent tensile bar is viewed by an external optical system through slots in the radiation shields and heater, and an enlarged image is projected on a ground-glass screen. Gage-length measurements are made on this image with cathetometers on traveling microscopes. With regard to creep-test results, the two machines were identical. Thorium oxide coatings were applied to the threaded ends of the tensile bars, to prevent diffusion welding of the tensile bars to the grips during testing. Specimen temperatures were measured with an L. & N. optical pyrometer which had been calibrated against a standard carbon arc, and were corrected fir window absorption by calculation from the measured spectral transmittance of the quartz observation windows. Longitudinal temperature gradients in the tensile-bar gage length and temperature drifts during testing were detectable but small, and were estimated to be 10°C or less. Accuracy of temperature measurement was confirmed by comparing the temperature measured on the surface of a special

Jan 1, 1965

By R. Bakish, M. A. Badiali, N. W. Kirshenbaum

One pound of ultra pul-e molybdenum has been produced containing both metallic and nonmetallic impuvities close to or less than the limits of detection. various purification methods were investigated; althouglz the use of move than one purification step was consideved, it was found that a single, caefully-controlled sublimation of MoCl5 yielded a highly puvified product without prior treatment or recourse to repeated sublimation. Hydrogen reduction of MoC1, to metal was attempted at atmospheric pressure; however, reduced pressure was necessary to obtain substantial yields. The tubular deposits of metal were consolidated into bulk fovm by electron beam melting undev high vacuum yielding a very low gas content. Boblems involved in monitoring the puvity of these materials and analytical results obtained are also presented. THE pronounced effect of even trace amounts of impurities upon fundamental properties of materials is well known to metallurgists and solid-state physicists. Consequently, groups interested in basic studies of metals have in recent years immensely stimulated the preparation and production of numerous ultra-pure metals. Increased demand by scientists for these high purity materials has necessitated development of facilities to prepare them in significant quantities; the procedures reported here were devised to produce significant quantities of ultra-pure molybdenum. Previous work performed in the field of vapor phase purification and hydrogen reduction of several other refractory metal chlorides had demonstrated valuable techniques applicable to molybdenum.' Various purification and reduction steps were individually investigated. Those procedures which showed the most favorable results with respect both to attainment of high purity and to ease of operation were then incorporated in the process utilized to produce the metal.' STARTING MATERIALS It is well known that because of differences in volatility, chlorides may be separated by fractional distillation. It was presumed that distillation of molybdenum pentachloride offered a simple and straightforward method of purification due to its relatively low boiling point. Alternatively, sublimation of the solid chloride also appeared feasible since MoC15 has both a reasonably narrow temperature range in which it exists as a liquid (a property typical of refractory metal chlorides) and a low enthalpy of sublimation. Pertinent thermochemical data of MoC15 are given in Table I. It should be noted that this compound must be handled with care as it is extremely hygroscopic. Anhydrous MoC15 was obtained from the A Metal Climax Co. METHODS OF PURIFYING MOLYBDENUM PENTACHLORIDE Distillation. It was expected that distillation methods, while affording an efficient purification, would prove simple to control and would have a higher production rate than sublimation processes. Also considered was the possibility of effecting a high degree of purification by using both these volatilization methods in conjunction—possibly a distillation followed by sublimation of the solidified condensate. Distillation of MoC15 was investigated using a single stage distillation column packed with chemically resistant glass beads. Heating coils were wound around the column and collection tube (condenser). As-received MoCl5 was charged into a flask connected with the column using a side loading arm under an argon flow. After the column and condenser were brought to about 270" and 210°C, respectively, the apparatus was lowered until the flask was fully immersed in a constant temperature fused salt bath maintained at about 285 °C. Distillation was continued for about 10 or 15 min until 50 to 70 g of distillate had been collected. Analyses of these distillations indicated that several elements, e.g., Cu, Fe, Ni, Cr, and Mg, were lowered in quantity although not all were removed to the same extent. The occurrence of Na, B, Si, and A1 in the distillates appeared to be due to contamination, possibly from corrosion of the pyrex glass. An improved distillation system of larger capacity and longer distilling column was built. Improvements were effected in lowering the amounts of such impurities as B, Mn, Ni, Na, Mg, Cr, Cu, and Fe. These studies were pursued concomitantly with efforts to purify by sublimation; it was subsequently found that although improvements in purity were obtained by distillation, sublimation processes were simpler to control and effected a high degree of purity.

Jan 1, 1963

By J. E. Drury, W. M. Byers, E. J. Lynch

Measurements made with starch ~~~~s indicate that the Presence of starch serves to depress the streaming potential of a clay mud system. Measurements with pure starch slurries show that the addition of NaCl or CaO reduces the streaming potential significantly. The addition of NaOH, however, causes only a minor reduction in potential even when there are large changes in mud resistivity. INTRODUCTION In their excellent study of the streaming potential, Hill and Anderson' proposed that the presence of conductive solids within the filter medium will reduce the generated potential. This theory was demonstrated with measurements on shaly sandstone cores having various "b" factors; the cores with the higher negative b factors showed markedly lower potentials. (The factor b was originally defined by Hill and Milburn2 in an expression relating the resistivity of a shaly sandstone to the resistivity of the interstitial water: log F, = log F,, + b (log 100R,)'. 'he factor b, therefore, is a measure of the contribution of the conductive solids to the total conductivity of the sample. It has been found experimentally to be directly related to the amount of chemically exchangeable ion per unit pore volume.) In the logical extension of this hypothesis to the streaming potential created by filtration through mud cakes, they suggested that the presence of nonconductive starch in a drilling mud would have the opposite effect; i.e., it would cause the streaming POtential to be increased. The high streaming potentials that they observed with lime muds were attributed to this cause. A cross-plot of some of their results which are relevant to this discussion is given in Fig. 1. The lime-mud curves and untreated-mud curve are taken from curves given in their paper. The gyp-mud line was estimated from their statement that the measured streaming potential for gyp muds in the range of 1.5 to 2.0 ohm-m was approximately 18 mv/1,000 psi. These gyp-mud potentials were the lowest that they reported for any of the bentonitic-clay muds, and were the only ones which were less than the untreated-mud potentials. This very low streaming potential of gyp muds has also been observed in field studies.' By way of comparison, a U. of Texas publication4 gives the approxi-ate compositions for lime and gyp muds shown in Table 1. These materials are added to a bentonitic-clay mud base. It can be seen that both of these muds contain significant amounts of calcium salts and that the gyp mud has the higher concentration of starch. It would appear from this and from the data shown in Fig. 1 that starch may well be the cause of a streaming-potential reduction, rather than a potential increase. EXPERIMENTAL A series of streaming-potential experiments has been performed using a cell of a design similar to that reported by Wyllie.5 Calomel electrodes were used in both the mud slurry and the filtrate. Pressure in the cell was generated with high-pressure nitrogen. The primary objective of the investigation was to determine the effect of starch on the potential. Five different slurries were made which ranged in composition from untreated ben-tonitic mud (Baroid Aquagel) to a pure starch suspension (Baroid Im-permex). The intermediate slurries were prepared by mixing together a 9-lb/bbl clay mud with a 12-lb/bbl starch suspension in the ratios 1:3, 1:1 and 3:1. When starch was used alone, it was necessary to use an 18-Ib/bbl mixture, since leaner mixtures would not form a suitable filter cake. The clay mud used in the experiments was aged for three months before use. In addition to this series of measurements on the starch-clay mud mixtures, other experiments were performed to determine the effect on the potential of the absolute starch and Aquagel concentration, and the effect of adding various chemicals. RESULTS The effect of starch on the streaming potential is shown clcarly in Fig 2. Increasing percentages of starch resulted in n continually decreasing

By R. A. Greenkorn

This project originated in a practical problem—we needed five tracers that could be used together to locate flow paths in a pilot flood. While tracers for subsurface liquids have been used since the turn of the century,1-15 none of those reported in the literature appeared to be either consistent or quantitative enough for our purposes. Most were used in field systems without controlled experiments to determine the accuracy and precision of analysis, and many were tracers that could not be used collectively. The ideal tracer, of course, would follow the fiuid of interest exactly, traveling at the same velocity as the fluid front. But the ideal is impractical to attain because adsorption-desorption effects cause the tracer to lag behind the front; these effects, plus diffusion-dispersion effects, cause the tracer front to spread more than the fluid front. Thus, our objective was not to locate a tracer that would be ideal for all circumstances but rather, to find one that would approximately follow the fluid, or one that under controlled conditions could be corrected to calculate the movement of the fluid front. We considered tracers satisfactory—(1) if they were easy to analyze; (2) if their breakthrough-elution curves were not too different from those for the chloride ion, a tracer believed to follow the fluid front closely; and (3) if we could calculate from the curves a material balance, at 1.25-PV (pore volume) injected, within 5 per cent of that calculated from chloride curves. Of a possible 35 materials, we selected 13 tracers that could be quickly and easily identified and whose analysis was claimed to be accurate within 5 per cent. Only one of these, tritiated water, was a radioactive tracer. Radioactive tracers are easy to detect even in small quantities, but they require special handling and special equipment. Also, those that can be used together are limited because special equipment is required to separate emissions from the various tracers. Two of the original 13 tracers were eliminated in static tests to determine how accurately and precisely they could be analyzed, and to check on gross adsorption. The remaining 11 were flowed through a 9-ft linear sandstone model, and breakthrough-elution curves were obtained. Finally, three tracers were field-tested as breakthrough tracers. These tests are described in the following sections. The 13 tracers considered in these experiments were EDTA (ethylene diamine tetra acetic acid), fluo-rescein, picric acid, salicylic acid and ammonium, boron (as borate), bromide, dichromate, iodide, nitrate and thiocyanate ions, plus chloride ion and tritiated water. All but the chloride ion and tritiated water were subjected to static sand tests to eliminate the tracers that could not be analyzed quickly and accurately and to eliminate those that showed excessive adsorption. All but two of the tracers, EDTA and salicylic acid, qualified for flow tests on this basis. The procedures used in the static tests (see Appendix A for analytical details) were as follows. Each tracer (in the amount shown in Table 1) was dissolved in 1,000 ml of water. Then, 800 ml of this solution was added to 500 gm of sand, and the remaining 200 ml was reserved as a control standard. The sand-tracer mixture was agitated once a day over a 10-week period, and during this period we analyzed five duplicate samples from this mixture, along with five duplicate samples from the control solution. From the control-sample analyses, we constructed a control chart on which the sand-tracer analysis results were plotted. The control chart, and its use to determine accuracy and precision of analytical results, as well as the amount of adsorption, is described in Appendix B. The results of the static tests are summarized in Table 1, which lists the concentration c (concentration at time t) divided by c, (initial concentration). If there was no adsorption, c/c, = 1. The acceptable deviation from this value varied from tracer to tracer, depending upon the limits of analytical precision established for the different tracers. The best results were obtained with boron, bromide and dichromate, with all values falling within limits of accuracy and precision. Ammonium, iodide, nitrate and picric acid also were satisfactory, although the ammonium results were erratic. Flourescein and thiocyanate were unsatisfactory ini-

By K. E. Manchester, A. H. Clark

Hall measurements have been made on three groups of silicon samples, which were implanted with boron, aluininunz, and phosphorus ions. Boron and phosphorus implants show essentially bulk properties when annealed under previously determined conditions, i.e., 15 min at 80O°C for boron and 10 mirz at 600°C for phosphorus. Bulk properties were also observed in alu?rrilzum-implanted samples when ion concentrations were below 1015 cm-'; however, strange low- terrzperalure behavior and a falloff in cavrier concenlralion was observed for sarnples with ion concenlration abozle loL5 ern-'. This can be attributed to solid-solubility effects since the average bulk concentration f0.r the sample exhibiting bulk properties was below the reported solubility limit for aluminum, while the other samples were above the limit. A detailed study of the annealirzg process indicates that mobilities reach bulk c~alues in phosphorus implants at 250DC, in alutninurn ivnplanls a1 500°C, and in boron implants at 700°C. A simple rnodel has been proposed to fit the annealing data. THE technique of semiconductor doping by direct injection of energetic ions is being actively investigated at this Center. Previously published results from this laboratory have been concerned with the investigation of implanted profiles in silicon and the electrical properties of the resultant p-n structures.1'2 Diode properties have been reported for junctions produced by implantation of boron ions and aluminum ions in n-type silicon and phosphorus ions in p-type silicon. Reverse current characteristics, as well as electron diffraction data, have indicated that the damage to the structure produced by the energetic ions during the stopping process can be minimized by a gentle anneal. The time-temperature conditions for this process have been determined by sheet resistivity studies.3 Electrical profiles of implanted phosphorus ions which have been determined by a differential sheet conductivity technique are based on the assumption that the carrier mobilities and activation energies for ionization are the same as in bulk silicon. These assumptions have been substantiated experimentally by measurement of Hall constants and resistivities of these implanted structures and the results are presented herein. After establishing the bulk property equivalence of the annealed layers, a more detailed examination of the annealing process was undertaken. The sheet resistivity technique initially used to determine anneal conditions has been broadened to include Hall constants and mobility behavior with anneal conditions. PROCEDURE The three groups of samples prepared for Hall measurements were implanted with mass-separated beams of boron, aluminum, and phosphorus ions. Ion concentrations are equivalent surface concentration and they have been determined from beam current measurements during implantation. Implant conditions for the samples are shown in Table I. In all cases, the samples had previously been angle-lapped on one edge and the junction delineated with an HF-copper sulfate solution. The surfaces of the implanted regions of the samples were exposed to the delineating solution and in the case of the "n"-type phosphorus-implanted areas it was later discovered that a finite amount of surface could be etched by this solution. This is discussed in the section on results. The implanted samples were ultrasonically cut into the conventional six-probe configuration shown in Fig. l.* In the annealing studies, for which the meas- urements were taken at room temperature, the sample holder was a Bakelite jig incorporating tungsten mechanical probes. The other measurements were taken using a conventional liquid-nitrogen cryostat, in which the temperature could be varied from 77" to about 400°K. For these measurements, 10-mil aluminum dots were evaporated onto the samples and alloyed with the silicon at 530°C for 15 min. The samples were then mounted in flat-packs, and gold wires were bonded to the aluminum dots. The electrical measurements were made with either a Leeds & Northrup K-5 Potentiometer, a Keithley 147 Nanovolt Null Detector, or a Keithley 601 Electrometer. No external bias was applied to the substrate. There is an inherent self-biasing arrangement at one or the other of the current contacts (depending upon the polarity), and this suffices to limit the current flow to the implanted layer. The magnetic field was generated by an A. D. Little electromagnet. Except for occasional checks of linearity of the Hall voltage with

Jan 1, 1969

By I. Fatt

Relative permeability and relative electrical resistivity curves are obtained for networks of tubes with a tube radius distribution by means of a network of resistors used as an analog model. These curves are similar to those obtained from real porous media. The effects of pore size distribution and network structure on relative permeability and resistivity are demonstrated. INTRODUCTION Study of the dynamic properties of networks of single size tubes in paper IT' of this series has shown that the network model has flow properties similar to those observed on real porous media. The comparison of properties of single size tube networks with those of real porous media cannot be carried far because very few porous media have uniform size pores. The capillary pressure curve from most porous materials such as soil, sandstone, and sintered glass indicate that these materials have pore size distribution similar to those shown in Figs. 5-1, 9-1, and 10-I.† To properly test the network model, it is therefore necessary to compare the dynamic properties of real porous media with those of networks of tubes in which the tube radii are distributed accord- ing to the distributions in the aforementioned figures. A network in which the tube sizes are distributed cannot be treated in the same manner as a network of single size tubes. In the single size tube network, the relation between tube geometry, flow resistance, and tube volume did not have to be known if the assumption was made that whatever relation did exist was the same for all tubes in a particular network. In a network of distributed tube size, the relation between tube geometry and flow resistance must be known or assumed in order to replace the tubes by equivalent electrical resistors. Relation of Tube Geometry to Flow Resistance The interchangeability of tubes and electrical resistors in the network model is possible because of the analogy between Poiseuille's law and Ohm's law. Poiseuille's law for a cylinder is q= pr4/8µl ?P.........(1) where q is the volumetric rate of flow, µ is the viscosity, ?P is the pressure gradient, r is the tube radius, and 1 is the tube length. Ohm's law is I=1/R?E..........(2) where I is the flux and is equivalent to the volumetric rate in Poiseuille's law, R is the resistance, and ?E is the voltage gradient. Both laws give the flux as a function of the potential drop and the resistance of the medium. By analogy then, 1/R=pr4/8µl ?P...........(3)

Jan 1, 1957

By R. A. Wattenbarger, H. J. Ramey

A systematic study has been made of the application of the real gas pseudo-pressure m(p) to short-time gas well testing. The m(p) function can be used in real gas flow problems to account for the variation of viscosity and z-factor with pressure. A mathematical model was solved numerically to generate solutions of various real gas flow problems. The effects of turbulence, formation damage and wellbore storage were included in the model. The analysis of simulated well tests showed that the interpretation methods normally used for liquid flow are generally accurate when the m(p) is used. For practical rates without turbulence, the solutions are not rate-sensifive, and the flow capacity.. kh and skin effect can be determined accurately from either a buildup or a drawdown test. However, the kh calculated from a drawdown test can be significantly low when turbulence is present. A case was simulated in which this error wa.s 36 percent. Turbulence does not affect the determination of kh from buildup tests. The proper determination of kh from p and pa buildup and drawdown plots is developed by analyzing their relationship to the m(p) method. A simple equation is given that can be used for long-range gas well performance forecasting. This expression is compared with a method pre-sended by Russell et al." Introduction The formation flow capacity and wellbore damage condition can be determined for liquid-producing tests by means of buildup and drawdown tests. These tests make use of short-time pressure transient data rather than stabilized flow tests that are often used for gas well testing. Tracy' presented a method of gas well testing that was based on ideal gas equations and utilized p2 buildup plots. This method was shown to be good for low pressure wells. MatthewsZ suggested plotting p and using an average slope and average gas properties. This method was more successful on high pressure wells. Al-Hussainy, Ramey and Crawfordh howed that variation in gas properties could be simplified by using the real gas pseu do-pressure m(p). Some cases showed that the use of the m(p) function Original manuscript received in Society of Petroleum Engineers office Aug. 8. 1967. Revised manuscript received June 11, 1968. Paper (SPE 1835) was presented at SPE 42nd Annual Fall Meeting held in Houston Tex., Oct. 1-4. 1967, and at SPE 4th Annual Eastern Regional ~eetin$ held in Pittsburgh. Pa., Nov. 2-3. 1967. 0 Copyright 1968 American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. 'References given at end of paper. provided an accurate method of interpreting buildup and drawdown tests. Because the work of Al-Hussainy et al. included only a few actual cases, there was a need to explore the use of the m(p) method for a greater variety of flow conditions. The occurrence of turbulent flow around the wellbore often is an important factor in gas well testing. Swift and Kiel,' and Carter et a1.' treated turbulence in gas well testing, but did not consider the variation of viscosity and z-factor with pressure. This paper presents the results of an investigation of the application of the m(p) method to buildup and drawdown testing. Vhe investigation included the effects of turbulence, formation damage and wellbore storage. Gas Flow Equations To formulate the mathematical model, many of the assumptions usually used in well testing theory are applied. The system has radial geometry with a closed outer boundary and is composed of a horizontal porous formation that has uniform and isotropic rock properties and uniform thickness. Allowance is made, however, for a radial region of reduced permeability near the wellbore. This region represents formation damage. The geometry of the system is shown in Fig. 1. Darcy's law does not always apply to gas flow. A more general expression is needed for non-Darcy, or "turbulent" REGION OF DAMAGED PERMEABILITY SEALED BOUNDARIES ClRCULAR WELL BORE Fig. 1—Radial flow model. AUGUST, BT7

Jan 1, 1969

By D. A. Elgillani, M. C. Fuerstenau

In this paper, oxidation potentials measured in the presence of various concentrations of cyanide, ferro-cyanide, and ferricyanide and ethyl xanthate at various values of pH are related to flotation response. Eh-pH diagrams are presented to show that the formation of surface ferric ferrocyanide is probably responsible for depression when cyanide is added. The influence of cyanide on the depression of pyrite with xanthates as collector has been the subject of a number of investigations,'-6 and several theories on the mechanism of depression have evolved from these studies. Wark and Cox7 and Gaudin8 have suggested that the depressing effect is due to a competition of cyanide ion with xanthate ion for the surface. Cook and his colleagues9-11 have explained this phenomenon in terms of competition between hydrocyanic acid and xanthic acid. Sutherland 12 has shown that although both of these theories accurately describe the relation between pH value and cyanide addition at constant collector addition, they fail to describe the relation between pH value and the amount of collector required to cause flotation. Taggart 13 suggested that depression in these systems is due to the formation of a reaction product between ferric ion at the pyrite surface and ferrocyanide ion derived from solution. Majumdar4,6 has attempted to prove this hypothesis by measuring the contact angles of pyrite in the presence of 25 mg per liter ethyl xanthate and different concentrations of potassium ferrocyanide and ferricyanide. In all cases the contact angles were quite high up to pH 10. These results indicate that pyrite should not be depressed by either potassium ferrocyanide or ferricyanide. In view of these facts, Majumdar has assumed that the compound Fe(CN)2 forms at the surface. Gründer and Bornl4 have stated that depression may be due to the formation of the compound K2Fe(II)Fe(CN)6 at the pyrite-solution interface. This compound is thought to be an interaction product between the K2Fe(CN)6-2 ion from solution and the Fe++ ion at the pyrite surface and, accordingly, K4Fe(CN)6 should depress pyrite at least as effectively as KCN. This was proven experimentally, but there was no simple relation between the depression of pyrite and the concentration of either KCN or K4Fe(CN)6 in solution. In view of the many mechanisms that have been proposed for pyrite depression by cyanide, it is apparent that a clear understanding of the phenomena occurring in these systems is lacking. One reason for this may be the fact that the species responsible for pyrite flotation in the presence of xanthate is not the xan-thate ion but rather dixanthogen.15 Since the oxidation of xanthate to dixanthogen is dependent on the oxidation potential of the solution, it would seem that knowledge of these potentials would be a requisite to understanding the pyrite-xanthate-cyanide system. It is the object of this paper to measure both the oxidation potential and pH of the pyrite systems in the presence of various concentrations of cyanide, ferrocyanide, and ferricyanide and xanthate and to relate these values to flotation response. EXPERIMENTAL MATERIALS AND 'TECHNIQUES In the experiments discussed here, pure potassium ethyl xanthate was used as collector, and reagent grade potassium cyanide, potassium ferrocyanide, and potassium ferricyanide were used as depressants. Reagent grade HC1 and KOH were added for pH adjustment. Conductivity water, made by passing distilled water through an ion exchange column, was used in all experimental work. Two natural samples of pyrite were used in the investigation. Sample preparation for flotation included dry grinding with a mortar and pestle and sizing the product to 100 x 200 mesh. Prior to flotation, a 0.75-gm sample of pyrite was added to a solution containing a known amount of depressant at the desired pH value, and the system was conditioned for 4 min. Following this, a known amount of collector was added and the system was conditioned for another 4 min. The pH — termed flotation pH - was measured; the pulp was transferred to a Hallimond cell, and flo-

Jan 1, 1969

By L. W. Holm, G. G. Bernard

Laboratory experiments were conducted to determine the effect of foam on gas flow in porous media. Previous studies have indicated that foam may be applicable as a restrictive agent in influencing underground gas flow. Foam was found to be exceedingly effective in reducing the permeability of porous media to gas. Consolidated and unconsolidated sands with specific permeabilities of 100 to 146,000 md had, in the presence of foam, gas permeabilities that were less than 1 per cent of the specific permeability; in many cases the gas permeability was practically zero. Foam reduced the gas permeability of loose sand to a much greater degree than that of a tight sand. For example, the permeability of a 125,000-md sand was reduced to 3 md while the permeability of a 4,000-md sand was reduced to 7 md. This effect should cause, to some degree, selective plugging of high permeability channels in various oil displacement processes. The presence of oil in a porous medium decreased the effectiveness of foam in reducing gas permeability; apparently oil acts as a foam depressant. However, it was found that certain foaming agents were very effective in reducing permeability even. in the presence of oil. Also, continuous injection of other foaming agents increased their effectiveness, when oil was present. The effect of foam on permeability of porous media to gas was studied as a function of foaming agent concentration and injection rate, absolute permeability, total pressure, pressure gadient, length of porous system, brine concentration and time. INTRODUCTION The use of surface active agents in flood water to increase the recovery of oil has been studied in the laboratory and in the field for decades, with rather limited success. In recent years a new approach to the problem was proposed. Instead of using an aqueous solution of surfactant as an oil recovery agent, Bond and Holbrook2 proposed that the oil recovery agent be a mixture of surfactant solution and gas. In their method, a water-soluble surface active agent with foam-producing characteristics is injected into an underground formation as an aqueous slug. This slug is followed by gas to produce a foam within the rock. Foams are defined as "agglomerations of gas bubbles separated from each other by thin liquid films'! A foam is fundamentally an unstable system. The foam process for oil recovery has since been studied by other investigators. Fried 1 has shown that foam can displace from porous structures oil that normally is unrecoverable by conventional water or gas drives. This superior oil displacing action is believed to be the result of several factors: (1) foam introduces into the reservoir many resilient interfaces of various sizes and curvatures, which increase the probability that a proper combination of forces for oil displacement will be created; (2) foam has appreciable viscosity which improves mobility ratio and contact efficiency; (3) foam accentuates the trapped gas effect because high gas saturations are possible without producing high gas/oil ratios. Deming4 studied the effect of various foam properties on the displacement of liquid. He found that (1) high foaming ability favors high displacement efficiency; (2) high foam stability is not necessary for high displacement efficiency; (3) displacement efficiency decreases with increase in plasticity of foam and (4) displacement efficiency is unaffected by surface tension of foaming agent solution. One of the important aspects of this oil recovery process is the effect of foam on gas permeability. The simultaneous flow of gas and liquid in porous media has been studied by numerous investigators and a large amount of literature exists on the subject. In this previous work, gas and liquid have generally been considered as essentially independent phases, whose flow characteristics are related through the saturation parameter. Foam, however, is a material with properties that are considerably different from those of its components; for example, the viscosity of a foam is greater than either of its components. Gas flow in a porous medium in the presence of foam should be considerably different

Jan 1, 1965

By Elton A. Youngberg

The Holden mine operated by the Chelan Division of the Howe Sound Co. is on the east slope of the Cascade Range in north central Washington on the south slope of Railroad Creek valley at an elevation of 3500 ft. The mine may be reached by a 40 mile boat trip from the town of Chelan which is at the southern tip of Lake Chelan, to Lucerne at the mouth of Railroad Creek and an 11. mile bus ride up Railroad Creek to Holden. A11 freight and concentrate is moved over this route to Chelan Falls on the Columbia River which is on the railroad four miles below the town of Chelan. The mine is now producing 2000 tons of gold, copper, and zinc ore per day which is treated in the Holden mill. Gold-copper and zinc concentrates are made, the first of which is shipped to Tacoma, Wash., and the latter to Kellogg, Idaho, for smelting. Ore is broken by long-hole blasting using the Noranda system which has been modified to meet local conditions. Until recently, blastholes have been drilled by diamond drills. Now a partial substitution of percussion drill holes, drilled with tungsten carbide insert bits, is being made. Geology The ore body occurs as a replacement deposit in a highly metamorphosed series of sedimentary rocks, mainly gneiss and schists, in a shear zone several hundred feet in width and of undetermined length. Commercial ore has been found in mineable widths of 25 to 100 ft for approximately 2500 ft along its strike. The commercial minerals are chalcopyrite, sphalerite, and gold. During the period of mineralization considerable silicifica-tion took place giving the ore an abrasive drilling characteristic. Following the period of mineralization, numerous dikes were introduced into the ore body. The earlier ones were of granite composition having a width of a few inches up to 80 ft. These were followed by much younger, fine grained basic dikes which usually do not exceed 2 ft in width. Development of Percussion Blasthole Drilling Equipment Test work with the 1½-in. tungsten carbide bit was carried on in development headings for several months early in 1947. The short life of the bits, because of gauge loss caused by the abrasive nature of the rock, prevented its adoption for this use. However fast drilling speed and ability to drill a long uniform hole suggested its use for drilling blastholes in competition with diamond drills as diamond costs were steadily increasing and exper-ienced drillers were difficult to obtain. The 1½-in. bit was the largest available at the time initial test work was started with sectional steel. The 1½-in. hole limited the diameter of the steel thread and coupling which could be used. Type F couplings were first used but because of the small thread section excessive breakage of the steel was experienced. Type H couplings were tried next. In order to use this coupling which is 15/8 in. in outside diameter, it was reduced to 1 3/8 in. giving 1/8 in. clearance between the coupling and the hole. Rod breakage at the thread was substantially reduced but some coupling breakage was experienced, however the overall performance was considered satisfactory (see Fig 1 for illustration of coupling and thread). Early test work with the 1½ in. bit indicated machines of piston diameters larger than 255 in. would cause inserts to loosen or break. It was found however that the additional weight of the sectional steel cushioned the blow enough to prevent bit failures when 3-in. Leyners were used. Rods used with the 1½-in. bits were 7/8 in. q. o. for sectional steel and 1 in. q. o. for all chuck pieces. In May 1948, 2-in. tungsten carbide bits became available and test work was immediately started. The 2-in. hole approximated the AX (1 15/16 in.) diamond drill hole which was being used exclusively for blastholes and permitted their substitution for diamond drill holes in a ring without alteration of pattern, burden, or explosives. The 2-in. bit also gave room in the hole for larger couplings and permitted the use of heavier rods and 3½-in. machines, increasing the

Jan 1, 1950

By P. Greenfield, P. A. Beck

The phase is a hard and extremely brittle material with a tetragonal crystal structure, containing 30 atoms per unit cell' It occurs in many binary and ternary alloys of the transition elements. The existence of twelve a phases has been reported in binary alloys of metals from the group vanadium, chromium, molybdenum, and tungsten with metals from the group manganese, iron, cobalt, and nickel. It is a characteristic fact that the composition of the o- phases in the various binary systems is not the same. Rather, there is a gradual shift in composition, for instance in the series of chromium a phases, approximately as follows: CrMn,, FeCr, Cr3Co,. In recent years several ideas have been put forward to account for this variability of composition. SullyZ proposed that a was a type of electron compound, characterized by 1.7 electrons per atom in excess of the number required to fill the Pauling atomic orbitals. These excess electrons were supposed to just fill the first Brillouin zone of the u structure. However, later work indicated that the phase is ferromagnetic at low temperatures, so that a- is unlikely to be a full zone compound.~ Another proposal,* which is also based on the structure of the transition elements advanced by Pauling, and in fact leads to essentially the same a compositions as Sully's theory, suggests that the u phase is characterized by a constant number of electron vacancies per atom. The electron vacancy numbers N,. used were originally the same as those in the Pauling theory, but were later modified empirically vn order to bring about better agreement with data for the p phase in certain ternary systems. For alloys, N,, was calculated on the assumption of simple additivity from the electron vacancy numbers of the components, as follows: N,. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2 (Fe) + 1.71 (Co) + 1.6 (Ni). On this basis a reasonably constant value of N, = 3.4 was obtained for all of the binary u phases and a fairly constant value of N,, = 3.1 for the various p phases. More recently, Bloom and Granta pointed out that a similar correlation with the total number of 3d and 4s electrons per atom is also fairly well fulfilled and concluded that no reference need be made to the Pauling theory. This proposal does not lead to the same binary a compositions as the one described above, so that the relative merits of the two proposals may be determined on the basis of direct comparison with experimental composition data. The purpose of the present paper is to provide such a comparison. Since the experimental data for the composition ranges of several of the known u phases were rather incomplete, it was decided to carry out new experimental determinations for many of the binary systems. Experimental Procedure The alloys were prepared by induction melting in recrystallized alumina crucibles, either in vacuum or in helium atmospheres. Some aluminum was picked up from the crucibles in the alloys of high vanadium content, but this was minimized by keeping the alloys in the molten state for as short a time as possible. The maximum aluminum impurity was 0.13 wt pct by chemical analysis, in an alloy containing over 50 wt pct V. In general, the as-melted compositions agreed accurately with those obtained by chemical analysis. In the case of manganese, however, losses inevitably occurred; consequently all manganese alloys were analyzed. Specimens of all alloys were annealed at temperatures ranging from 1000" to 1300°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. All manganese alloys were sealed in quartz tubes under vacuum before annealing. The specimens were held at temperature for between four and eight days before being quenched into cold water. Alloys were prepared for microscopic examination by mechanical polishing, usually followed by electrolytic etching. X-ray diffraction specimens were prepared by crushing the homogenized alloys, and by reanneal-ing the obtained powders in evacuated quartz tubes for a few hours at the temperature of the lump anneal. X-ray diffraction patterns were made with unfiltered chromium radiation, using an asymmetrical focusing camera of high dispersion. Using microscopic and X-ray techniques jointly, the accuracy

Jan 1, 1955

By J. T. Norton, H. Blumenthal, S. J. Sindeband

The interstitial phases formed by the transition elements with carbon, nitrogen and boron constitute a unique class of substances which are of considerable technical interest because of their well developed metallic properties and their high hardness and melting points. They are also of interest from the point of view of structure. It was pointed out by Hagg1 some years ago that the principal factor determining these structures was the relative sizes of metal and metalloid atoms. He predicted that if the ratio of the radii of metalloid to metal atoms was less than 0.59, the metal atoms would be arranged in a close-packed fashion of relatively simple type. This prediction has been amply confirmed. It appears, however, that this specification applies most generally to those structures in which the metalloid atoms occupy isolated positions in the lattice and there is no tendency for strong binding between the metalloid atoms themselves. The series of borides of the type MeB2 formed from the transition elements of the fourth (Ti, Zr) and fifth (V, Cb, Ta) groups of the periodic table provide an opportunity to investigate this situation further. If one takes as a basis the radius of 0.87 A for the boron radius and the Goldschmidt values for the metal atoms in 12 coordination, then the radius ratio varies from 0.54 for zirconium to 0.64 for vanadium, which latter is considerably greater than Hagg's limit of 0.59. It was of interest, therefore, to see if these five elements would form borides of the MeB2 type and have simple isomorphous structures. When this investigation was initiated, relatively little information had been published on the structure of this group of borides. McKenna2 reported the preparation of ZrB2 by a carbon reduction process. Its structure was hexagonal and the approximate lattice constants were given as a = 3.15 A, c = 3.53 A. Ehrlich3 reported the structure of TiB2 as being of the C 32 type with a = 3.02, c = 3.21 and c/a = 1.06 A. Recently, Kiessling4 published the results on ZrB2, showing it to be one in which the metal atoms are arranged in a simple hexagonal lattice with the boron atoms in flat sheets, midway between the layers of metal atoms. The structure is C 32 type with a = 3.169, c = 3.530 and an axial ratio =1.11 A. He also states that CbB2 and TaB2 are isomorphous with ZrB2. Preparation of Borides The borides of titanium, zirconium, columbium and tantalum were made by the electrolysis of fused salt baths after the method described by Andrieux.5 The bath, totalling about 6500 g in each case had the following general composition: Metal Oxide + B2O3 + CaO + CaF2. The actual proportions of the ingredients were determined for each individual case. Although Andrieux reports the preparation of vanadium boride by the same electrolytic method, several attempts proved unsuccessful. However, it was possible to prepare VB2 by the carbon reduction method used by McKenna to produce ZrB2. The mixture consisted of V2O5 + 6B2O3 + 11C and the reduction was carried out in an induction heated graphite crucible. This method proved satisfactory for ZrB2 and TiB2 and undoubtedly the others could be made in the same way. The borides, which were all in the form of fine gray metallic crystals from the electrolytic bath or gray powders from the reduction process, were carefully separated from other constituents and analyzed chemically for metal and boron content. The densities of the boride powders were measured using a standard 10 cc pyenometer at 18°C and ethyl benzene proved to be the most satisfactory liquid for this purpose. X Ray Technique The boride crystals, as prepared, were too small for single crystal examination so that powder techniques were employed. Patterns of the finely ground borides were prepared, using the Norelco recording X ray spectrometer. The lines on these patterns were indexed with the aid of Hull-Davy charts and the approximate dimensions

Jan 1, 1950