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By E. M. Wise

The practice of adding moderate quantities of nickel to a variety of bronzes has been employed by foundrymen for many years with several objects in view. In some instances it was desired to harden the alloy; in others it was to increase the fluidity or to improve the solidity of the castings, or to refine their grain. These important matters have been considered in detail by Pilling and Kihlgrenl and by numerous other workers cited by them, and with the exception of the first will not be considered in the present communication. The possibility of reducing the cost of bronze by replacing a portion of the tin with nickel received attention some years ago by Burgess and Woodward12 and, as will be shown later, offers attractive savings in cost under present conditions. The age-hardening characteristics of the nickel bronzes of appropriate compositions have been known for some time and were mentioned by Price, Grant and Phillips3 and discussed by Wise4 in connection with their paper. These matters are further considered in recent patents15 and are becoming of commercial importance in the production of high-strength castings. The equilibrium relations existing in the high-copper region of the copper-nickel-tin system have been carefully studied by Eash and Upthegrove,6 and in somewhat less detail by Veszelka.7 The observa-

Jan 1, 1934

By T. Vasilos, J. T. Smith

THE mechanism of pressure sintering, or hot pressing, for ceramic materials, has been investigated by several researchers.1-8 Plastic flow has been suggested as the rate-determining mech-anism1,2 while grain boundary sliding3,4 and fragmentation processess have been found controlling in other studies. Vasilos and Spriggs5,6 have reported that pressure sintering occurs by a diffusion-controlled mechanism. For the pressure sintering of metals, investigations with lead7 and with tin6 have not identified the operative mechanism during consolidation of these powders. This note reports the results of a pressure sintering study initiated to determine the mechanism controlling the densification of spherical copper powder. Temperatures of 300°, 400°, 500°, and 600°C at 2500, 5000, 7500, and 10,000 psi pressures were investigated. The copper powder for this study was obtained from Metals Disintegrating Co., Elizabeth, N.J. The minimum purity was reported to be 99.9 pct. The powder size was -325 mesh and a lineal analysis showed the average size to be less than 1 p. An alumina die body and punches were employed. Graphite spacers were placed between the copper powder and the punches before pressing. It was expected that the graphite would form carbon monoxide with any entrapped air and form a reducing atmosphere within the die cavity. This condition was generally realized during pressing although a minor amount of oxidation occurred at 500" and 600°C. The oxide particles were located randomly in the pressed samples and were not considered to influence the densification process. Calibration tests showed the temperature of the copper pellet to be about 20°C less than the die wall temperature, probably resulting from heat losses through the punches. This difference was compensated during the experimental pressing operations. The hot pressing equipment employed for this work has been described by Spriggs et a1.9 and was calibrated with a Baldwin-Lima-Hamilton load cell. Travel of the punches was monitored with a dial indicator showing increments of travel to 0.0005 in. Relative density was calculated at selected time intervals for a known copper weight, punch travel, and die diameter. The accuracy of this calculation was *1 pct. Average grain size after hot pressing was obtained by lineal analysis. Typical densification curves are presented in Fig. 1 and Fig. 2 where relative density is plotted vs log time as a function of applied pressure for the 300" and 600°C pressure sintering temperatures, respectively. The curves for 400" and 500°C were similar to those at 300°C and consequently are not shown. The curves at 300°C as well as 400" and 500°C do not show an end-point or limiting density for a particular applied pressure. At 600°C, a density in excess of 95 pct of theoretical has been reached such that further densification is extremely slow for the 5000, 7500, and 10,000 psi pressures. It is suggested that further densification at these pressure levels may be retarded or prevented by discontinuous grain growth, by entrapped gases, and by other microstructural limitations as described by Cob1e.10 The curve for 2500 psi hot pressing pressure is a straight line over the time interval although a slight change in slope may be occurring at the last time intervals. The plastic flow models,1,2 derived for hot pressing, predict the existence of an end-point (or limiting) density dependent on the yield point of the material at the temperature of interest. The yield stress of copper at a 0.005 strain level has been

Jan 1, 1965

By Theodore Nagel

Fuel-oil, natural gas and coke oven gas, producing the higher temperatures of open-hearth current practice, have been gradually displacing producer gas the lowest cost fuel for open hearth operations. The lower temperatures of combustion products from producer gas is caused by nitrogen dilution. Practical Application of Combustion Thermochemistry One pound of carbon burned to CO produces 3,960 B.T.U. and one pound of carbon burned to C02 produces 14,140 B.T.U. The second unit of oxygen uniting-with gasified car-bon (-CO) produces (14,140 - 3,960) 10,180 B.T.U. which is;(10,180 - 3,960) 6,220 B.T.U. more heat than produced by the first, unit of oxygen forming CO by uniting with solid carbon. A review of the relative combustion heating values of commercial gaseous fuels reveals CO requires a minimum of air for combustion, and because of minimum nitrogen dilution and the high thermal release from CO higher temperature combustion products are produced from CO than from natural gas or from coke-oven gas under similar combustion conditions. Inert nitrogen diluent lowers the calorific value of fuel gas and its diluting effect is cumulative in lowering the temperature of the products of total, combustion. It is not only logical but, practical in partial combustion, converting bituminous coal to gas, to generate the gas, with reduced nitrogen dilution.

Jan 1, 1936

By Harrison Schmidt

Since the U. S. Geological Survey published the data on the Central Mining District collected by Lindgren and Gratonl and by Paige2 much new information has been obtained by development and mapping, but none of it had been published until recently when Kniffin3 published on Fierro, Lasky4 on the Ground Hog mine, Thorne5 on Santa Rita and Landon6 filed a thesis on the Fierro-Hanover-Santa Rita area at the University of Chicago. During the years 1927-1930 much of the writer's time was spent in mapping the geology and ore deposits of this district, particularly in the area of the zinc deposits at Hanover. Some of the data collected are presented here. Previous publications have been freely drawn upon and additional data used that were generously supplied by L. M. Kniffin, Wilfred Wright and Gerald Ballmer. Thanks are due Augustus Locke, Samuel G. Lasky, Kniffin, Wright and Ballmer for suggestions and critical readings of the manuscript, and to the Empire Zinc Co. (a subsidiary of the New Jersey Zinc Co.) for the privilege of publishing material compiled largely at its expense. The relation of the Central or the Santa Rita-Hanover-Fierro district to the Silver City district is shown on Paige's geologic map in the Silver City folio.7 Granodiorite porphyry and quartz-monzonite porphyry

Jan 1, 1935

By Harrison Schmidt

Since the U. S. Geological Survey published the data on the Central Mining District collected by Lindgren and Gratonl and by Paige2 much new information has been obtained by development and mapping, but none of it had been published until recently when Kniffin3 published on Fierro, Lasky4 on the Ground Hog mine, Thorne5 on Santa Rita and Landon6 filed a thesis on the Fierro-Hanover-Santa Rita area at the University of Chicago. During the years 1927-1930 much of the writer's time was spent in mapping the geology and ore deposits of this district, particularly in the area of the zinc deposits at Hanover. Some of the data collected are presented here. Previous publications have been freely drawn upon and additional data used that were generously supplied by L. M. Kniffin, Wilfred Wright and Gerald Ballmer. Thanks are due Augustus Locke, Samuel G. Lasky, Kniffin, Wright and Ballmer for suggestions and critical readings of the manuscript, and to the Empire Zinc Co. (a subsidiary of the New Jersey Zinc Co.) for the privilege of publishing material compiled largely at its expense. The relation of the Central or the Santa Rita-Hanover-Fierro district to the Silver City district is shown on Paige's geologic map in the Silver City folio.7 Granodiorite porphyry and quartz-monzonite porphyry

Jan 1, 1935

Since the U. S. Geological Survey published the data on the Central Mining District collected by Lindgren and Gratonl and by Paige2 much new information has been obtained by development and mapping, but none of it had been published until recently when Kniffin3 published on Fierro, Lasky4 on the Ground Hog mine, Thorne5 on Santa Rita and Landon6 filed a thesis on the Fierro-Hanover-Santa Rita area at the University of Chicago. During the years 1927-1930 much of the writer's time was spent in mapping the geology and ore deposits of this district, particularly in the area of the zinc deposits at Hanover. Some of the data collected are presented here. Previous publications have been freely drawn upon and additional data used that were generously supplied by L. M. Kniffin, Wilfred Wright and Gerald Ballmer. Thanks are due Augustus Locke, Samuel G. Lasky, Kniffin, Wright and Ballmer for suggestions and critical readings of the manuscript, and to the Empire Zinc Co. (a subsidiary of the New Jersey Zinc Co.) for the privilege of publishing material compiled largely at its expense. The relation of the Central or the Santa Rita-Hanover-Fierro district to the Silver City district is shown on Paige's geologic map in the Silver City folio.7 Granodiorite porphyry and quartz-monzonite porphyry

Jan 1, 1935

By Harrison Schmidt

Since the U. S. Geological Survey published the data on the Central Mining District collected by Lindgren and Gratonl and by Paige2 much new information has been obtained by development and mapping, but none of it had been published until recently when Kniffin3 published on Fierro, Lasky4 on the Ground Hog mine, Thorne5 on Santa Rita and Landon6 filed a thesis on the Fierro-Hanover-Santa Rita area at the University of Chicago. During the years 1927-1930 much of the writer's time was spent in mapping the geology and ore deposits of this district, particularly in the area of the zinc deposits at Hanover. Some of the data collected are presented here. Previous publications have been freely drawn upon and additional data used that were generously supplied by L. M. Kniffin, Wilfred Wright and Gerald Ballmer. Thanks are due Augustus Locke, Samuel G. Lasky, Kniffin, Wright and Ballmer for suggestions and critical readings of the manuscript, and to the Empire Zinc Co. (a subsidiary of the New Jersey Zinc Co.) for the privilege of publishing material compiled largely at its expense. The relation of the Central or the Santa Rita-Hanover-Fierro district to the Silver City district is shown on Paige's geologic map in the Silver City folio.7 Granodiorite porphyry and quartz-monzonite porphyry

Jan 1, 1935

By W. R. Phibbs

The blast furnace of the Columbia Steel Corpn., at Ironton, Utah, was put in blast April 30, 1024, and its operation has presented some interesting problems. The coke for the furnace is furnished by 33 Koppers Becker type ovens of 15 tons capacity each. The coal is shipped from the company's mine at Columbia, Utah, which is approximately 123 miles from Ironton, and is probably the highest volatile coal that is being coked for blast furnace use in this country. The analysis of the coal is: PeR Cent. Moisture................................................. 3.90 Volatile.................................................. 39.00 Fixed carbon............................................ 51.10 Ash............................................... 6.00 Sulfur................................................. 1.07 The analysis of the coke is: PeR Cent. Volatile.................................................. 0.55 Fixed carbon............................................. 89.70 Ash...................................................... 9.75 Sulfur................................................... 1.05 The coke is light and of a fingery construction, but is very fast burning. A screen test of the coke as loaded into the skip tubs at the furnace shows the following: Per Cent. On 2 in.................................................. 17.90 On 11/2 in................................................ 41.78 On 1 in.................................................. 27.80 Through 1 in............................................. 12.52 The by-product yields are as follows: Gas................................. 11,000 cu. ft. per ton of coal Sulfate............................... 30 Ib. per ton of coal Tar.................................. 12.65 gal. per ton of coal Motor fuel........................... 3.00 gal. per ton of coal Average B. t. u. in gas................. 567

By Theodore Nagel

Fuel-oil, natural gas and coke oven gas, producing the higher temperatures of open-hearth current practice, have been gradually displacing producer gas the lowest cost fuel for open hearth operations. The lower temperatures of combusts on products from producer gas is caused by nitrogen dilution. Practical Application of Combustion Thermochemistry One pound of carbon burned to CO produces 3,960 B.T.U. and one pound of carbon burned to C02 produces 14,140 B.T.U. The second unit of oxygen uniting with gasified carbon (CO) produces (14,140 - 3,960) 10,180 B.T.U. which is (10,180 - 3,960) 6,220 B.T.U. more heat than produced by the first unit of oxygen forming CO by uniting with solid carbon. A review of the relative combustion heating values of commercial gaseous fuels reveals CO requires a minimum of air for combustion and because of minimum nitrogen dilution and the high thermal release from CO higher temperature combustion products are produced from CO than from natural gas or from coke-oven gas under similar combustion conditions. Inert nitrogen diluent lowers the calorific value of fuel gas and its diluting effect is cumulative in lowering the temperature of the products of total combustion. It is not only logical but practical in partial combustion, converting bituminous coal to gas, to generate the gas with reduced nitrogen dilution.

Jan 1, 1936

By T. J. Hudson, P. B. Queneau, J. D. Prater

The process parameters for effective utilization of nitric acid as an oxidant for copper-iron sulfides have been developed. Leaching variables found to be important were acid concentration, temperature, time, atmosphere, pressure, mineral type, particle size, and percent solids. Particular attention was devoted to analysis and control of fumes evolving during the oxidation. Data were recorded on metal extraction, elemental sulfur formation and oxidation, product gas composition and evolution rate, reagent consumption, and residue flotation response. The study was concluded by laboratory testing a flowsheet based on the foregoing observations. Ninety-eight percent of the copper contained in a chalcopyrite-bornite concentrate was recovered, requiring 1.6 lb of nitric acid to be regenerated externally per pound of copper extracted. Iron remained in the leach residue as hydrogen jarosite and was ultimately rejected from the system by froth flotation. Sixty percent of the sulfur contained in the copper concentrate reported in the elemental form; the remainder was oxidized to sulfate and eliminated with the hydrogen jarosite in the flotation tails or by neutralization of the solvent extraction raffinate with lime. Nitrogen was evolved primarily as NO and NOD; up to 3% N2O also was present. Gases containing sulfur were absent except when pyrrhotite was solubilized in the absence of soluble copper. In this case, HAS was evolved.

Jan 1, 1974

By James Malcolmson

(New York Meeting, February, 1913.) THE Tigre Mining Co. of Mexico, owned by the Lucky Tiger Combination Gold Mining Co. of Kansas City, decided early in 1910 to enlarge its mill, which consisted of a concentrator milling 3,000 tons of ore per month. The enlarged plant was designed to crush and concentrate 6,000 of ore and to cyanide 7,500 tons per mouth. The extra tonnage cyanided was to be obtained from tailings which were stored below the old mill. Power was supplied to the old mill from four boilers; a 150-h-p.. Corliss engine and two Weber 60-h-p. gas-engines using producer-gas made from charcoal. The total horse-power required, including 60 h-p. used for machine-drills in the mine, was approximately 275. Cord-wood cost $4.32 per cord, 8 by 4 by 3 ft., and charcoal $15 per ton. The fuel supply in the surrounding country was approaching exhaustion; more than 150 mules and 50 men were engaged in cutting and transporting this fuel, and the unsettled political, conditions in Sonora were such that it would be practically impossible to keep an organization of this kind together. The price of fuel was steadily rising and at times it became almost impossible to get sufficient fuel to operate.

Jan 4, 1913

By J. A. Hren, G. Thomas

A high-temperature stage has been used to study precipitation and dissolution in thin foils of Al-20pct Ag alloy directly in the electron microscope. The results show that the aging characteristics are similar to those observed for bulk materials, and in addition, direct evidence is presented for clustering at the solid solution temperature. The limit of solubility of G. P. zones is-350°C. The heterogeneous precipitation, the growth and dissolution of ?&apos;have been studied in detail. Growth of ?&apos; parallel to the basal planes, occurs by continuous motion of inter -facial partial dislocations. Growth stops at intersecting particles due to formation of sessile a/6 <110> interfacial dislocations. Growth normal to the habit plane occurs by the spontaneous nucleation of partial dislocations on alternate (111) planes and the thickening rate is --10-3= times the lengthening rate. The precipitates dissolve in layers and the final product is a whole a/2 <110> dislocation . The nucleation -growth -dissolution processes are thus completely reversible. Kinetic data obtained from the dissolution rates of ?&apos;particles enable the diffusion coefficient to be determined and the activation energy is found to be 37.5(±4) kcal mol-1, which is that expected for dzffusion of silver in aluminum. The velocity of the interfacial dislocations is thus dependent solely on the rate of diffusion of silver atoms. RECENTLY it was demonstrated that a high-temperature stage could be effectively used in the electron microscope to follow directly the processes of precipitation and dissolution in thin foils of A1-4 pct Cu alloy.&apos; These experiments also provided kinetic data which enabled the diffusion coefficient to be estimated. This new development of electron metallography opens up many fruitful areas of research and it was decided to investigate the aging behavior in thin foils of A1-20 pct Ag alloy, particularly the mechanism of heterogeneous precipitation (i.e., precipitation on lattice defects). This system was chosen because the aging characteristics of bulk specimens are now well known,2"7 and because we wished to obtain more details of the role played by partial dislocations and stacking faults in the nucleation growth and dissolution of the hcp ?&apos; phase. This is of interest for the general case of fcc-- hcp transformations. Part of the A1-Ag phase diagram is shown in Fig. 1. The use of a high-temperature stage also enables a study to be made of the clustering process (formation of G. P. zones) and to determine the structure of the solid solution prior to the usual quenching and aging procedures. It is also possible to obtain kinetic data from measurements of the rates of dissolution of precipitate particles. Unlike the results of previous experiments on A1-4 pct CU 1 where much of the initial precipitation occurred on the foil surfaces, the results on the A1-20 pct A1 alloy were identical to those reported for bulk specimens6,7 and no surface precipitation was ever observed. Thus, it was possible to follow the aging sequence: G.P. zones — ?&apos; — ? directly in the thin foils. This paper is concerned with the formation and dissolution of zones and the ?&apos; phase, and no attempt has been made so far to follow the mode of discontinuous precipitation of ?. I) EXPERIMENTAL DETAILS The high-purity A1-20 pct Ag alloy was prepared by the Aluminum Co. of America in the form of 0.001-in.-thick sheets. These were cold rolled with intermediate anneals to a thickness of 0.0004 in.,

Jan 1, 1963

By J. W. Downey, J. B. Darby, L. J. Norton

THE only previous investigation of the phase equilibria in the Ta-Pd system was reported by Greenfield and Beck.1 Their work (actually a portion of a much broader survey) was limited to the composition range 50 to 75 at. pct Ta and to a single temperature, 1000°C. The results indicated that no intermediate phases were present at this temperature. They pointed out that this was an unexpected result in view of the fact that niobium, which belongs to the same group in the periodic table as tantalum and has essentially the same atomic size, forms a o phase with palladium.&apos; Also, tantalum in combination with rhodium,&apos; iridium,&apos; or platinum&apos; stabilizes the s phase. By analogy, the Ta-Pd system would also be expected to contain a s phase. The present investigation was therefore undertaken to explore more fully the phase relationships in this system. Alloys were prepared by arc melting on a water-cooled copper hearth in an argon-helium atmosphere. The purity of the starting materials was greater than 99.9 pct. The weight losses on melting were less than 1 pct and therefore the alloys were not analyzed chemically. Specimens were wrapped in molybdenum foil, encapsulated in quartz capsules under a vacuum of at least 1 x 10-5 mm of Hg, annealed as indicated in Table I, and water quenched. Optical and X-ray metallography were used for identifying the phases present in the annealed and quenched alloys. The alloys were resistant to attack by several acids; however, a sodium cyanide electroetch and an immersion etch containing 1 part HF, 1 part HNO3, 2 parts H2SO4, and 5 parts H2O by volume were found satisfactory. The X-ray diffraction patterns were taken with a Straumanis-type Debye-Scherrer camera and filtered copper or chromium radiation. A summary of the phases found in this investigation is presented in Table I. No attempt was made to determine the composition limits of the various phases. The present results indicate that this system consists of two terminal solid solutions separated by at least four intermediate phases at the approximate compositions Ta3Pd, -TaPd, TaPd,, and TaPd3. The Ta-rich solid solution, containing less than 10 at. pct Pd at 1150°C, is in equilibrium with a o phase which is stable in the vicinity of 25 at. pct Pd. The latter phase is also in equilibrium with a bct phase at the equiatomic composition. At high temperatures it appears that the Pd-rich solid solution extends to at least 66.6 at. pct Pd and is in equilibrium with the bct phase. When annealed at 900°C, a sample containing 66.6 at. pct Pd transformed to an unidentified phase designated as X. An X-ray diffraction pattern of this phase contained sharp low-angle lines while the high-angle lines were characteristically diffuse. The observed d-spacings and relative intensities for lines in the low-angle region are presented in Table 11. In the vicinity of 70 at. pct Pd an intermediate phase having the TiA13-type structure is formed. It is stable to at least 1100°C, and presumably dissolves congruently into the ter-

Jan 1, 1963

By N. Pessall, A. D. McQuillan

The phase relalionsllips in an isothernzal section of the Ti-Zr-H system at 750°Chave been investigated by measurement of hydrogen equilibrium pressures. The resulting diagram indicates that the hydride phase has an anomalously wide range of homogencity extending from 66.6 to 30 at. pct H in alloys containing about 15 al. pet Zr. Measurement of the heat of solution of hydrogen as a function of alloy composition in ß-phase alloys indicates no anomalous behavior in the region of 15 at. pet Zr, and suggests that the extensive range of homogeneity in the hydride phase at about this composition must he attributed to an enhanced stability of the, hydride phase. THE manner in which titanium and zirconium react with hydrogen and the constitutional diagrams of the two metal-hydrogen systems are qualitatively very similar,&apos;-6 as can be seen from Fig. 1 which shows the constitutional diagrams of the two systems. Quantitatively, however, there are some differences. For example, the exothermic heat of solution of hydrogen in ß titanium is smaller than that in ß zirconium, and consequently the equilibrium hydrogen pressure of a Ti-H alloy is higher than a Zr-H alloy at the same temperature and hydrogen concentration. Other differences manifest themselves in the hydride phases which exist at high hydrogen concentrations. In the Ti-H system, above room temperature, there exists only a single hydride phase in which the metal atoms are arranged on a fee lattice, but in the zirconium system there are two hydrides, and whereas the hydride of lower hydrogen concentration has a fee structure, the higher hydride has a face-centered tetragonal structure. The tetragonal hydride retains its stability up to temperatures in excess of 450oC.7 From the foregoing, it would be expected that the constitutional diagram of the ternary Ti-Zr-H system would have a very simple form, especially as titanium and zirconium are completely miscible in both the a and ß forms.8 The present work, which consists of a study of an isothermal section of the ternary system, was carried out in order to check the assumption frequently made that the electronic structure of the two metals and the mechanism by which hydrogen is held in solution in the metals is the same for each. Although this proved largely to be true, certain inter esting and unexpected features of the ternary system emerged which must be explained before we can really say that the reactions of titanium and zirconium with hydrogen are fully understood. EXPERIMENTAL PROCEDURE The most convenient method of studying hydrogen-metal systems is by the measurement of the hydrogen pressure in equilibrium with the hydrogen dissolved in the metal as a function of hydrogen concentration and temperature. In binary systems, the results are easily interpreted in terms of alloy constitution, since two-phase regions can be recognized by the fact that the hydrogen pressure at constant temperature does not vary with the hydrogen concentration in the alloy when it is in the two-phase condition. This criterion does not apply in ternary systems, but there is usually a marked change of slope in the isothermal pressure-composition curves when a phase boundary is crossed, and with care, and a knowledge of the limiting binary systems, the phase structure of the alloys can usually be deduced. In the

Jan 1, 1962

By Robert G. Johnson, Richard J. Prosen

THE present work was done in connection with a program for investigating metal-to-ceramic braze techniques using the well-known reactivity of titanium with certain ceramic oxides. The investigation extended over the range of 0 to 30 pct Ti. The indium was obtained from the Indium Corp. of America and was specified to be 99.97 pct pure. The titanium was supplied by Metals Disintegrating Co. and was stated to be 99.5 pct pure. Each 2 to 4 g quantity of the alloy compositions studied was prepared using a mixture of 300 mesh powders pressed into pellet form. The pellets were heated in thin-walled molybdenum crucibles using a resistance-wound furnace in a vacuum less than 10-4 mm of Hg. Little reaction occurred between the molten alloy and the crucibles at the temperatures and short time intervals used. Only slight spectroscopic traces of molybdenum were found in the melt after a typical period of heating. The points shown on the phase diagram of Fig. 1 represent thermal arrest measurements. The phase boundaries shown are consistent with the thermal arrest and X-ray data obtained. The temperatures were determined using a Pt-Pt 10 pct Rh thermocouple with the junction spot-welded to a short molybdenum rod. The rod was almost completely immersed in the liquid metal, so that good thermal contact with the melt was achieved. The small mass of the crucible and its contents made it possible to obtain many heating and cooling curves in a few minutes time, an advantage which helped to minimize the effects of indium evaporation at the higher temperatures. A Brown strip chart recorder was used to display the thermal arrest curves. To check the technique, the melting point of 99.999 pure Al was measured and found to be within 1 of 660.2c, the accepted melting point. The upper limit of temperature with this technique was about 900°C beyond which the evaporation rate of indium became great enough to alter appreciably the alloy composition during the runs. A peritectic transition was found at 796°+ 5°C from 1.5 to 30 wt pct Ti. It was not found at 0.5 or 1.0 pct. A small super-cooling effect was observed. The melting-point transition to the B + L phase was found up to 20 pct Ti but not at 25 pct. Within the 1 deg accuracy of the measurement, the transition temperature was that of pure indium, 156°C. The liquidus line to the left of the 1.5 titanium point was located only approximately. The two crossed circle points at 1.0 and 0.5 pct Ti place a lower limit on the liquidus line and were determined by observing visually the cessation of vibrations in the melt caused by the damping effect as B-phase crystals were formed during cooling. The B-phase boundary was found at 23.8 pct Ti by X-ray analyses of small single crystals of the B phase isolated from 2 pct Ti melts. The compound was found to be Jetragonal with lattice dimensions of c = 3.052A and a = 10.094W. From the unit cell dimensions and the measured density of 6.42 i 0.05 g per cc, the compound was determined to be In4Ti3 which has 23.8 pct Ti. The calculated density of 6.44 g per cc is obtained assuming 2 mol

Jan 1, 1962

By N. T. Cotman, C. H. Pickering, P. B. Crawford

A beat-conduction model has been developed to study the flow of fluids in a stratified oil reservoir which is being subjected to unsteady-state depletion. To simulate stratification, plates of different metals were joined together so that cross flow could occur between strata. A description of the model, plate construction and necessary instruments is included. The data indicate that stratified oil reservoirs experiencing cross flow may be treated as a single, homogeneous, producing sand having properties intermediate between those of the layers making up the system. A technique for averaging core-analysis data to arrive at the proper average value of rock permeability and porosity is presented INTRODUCTION Although oil has been produced from reservoirs for 100 years and reservoir injection processes have been undertaken for 40 years, the industry is still inadequately informed on the problem of reservoir inhomogeneities. Stratification is perhaps the best-known type of reservoir heterogeneity. Urenl discussed the possible significance of this nonuniformity in his 1927 paper on the theoretical aspects of water flooding. Since this time the problem of vertical permeability variations has been the subject of much discussion and numerous papers. Levorsen2 simply describes the origin of layered beds in his Geology of Petroleum. Some beds are field-wide and may be traced from well to well, while others apparently pinch-out and become discontinuous. In addition, the physical characteristics of a layer may vary from place to place. For these reasons, a stratified system is not easily defined. In calculations involving oil reservoirs in which permeabi1ities vary, methods presently used contain many simplifying assumptions. The reservoir frequently is considered as consisting of permeable layers, each of uniform vertical and lateral permeability and each behaving as if separated from adjacent layers by thin impermeable layers. Other assumptions frequently made in reservoir calculations are steady-state flow conditions, unit mobility ratio, linear geometry, average or homogeneous porosity, and negligible capillary-pressure and gravity effects. Muskat3 has. developed solutions to the stratification problem for mobility ratios other than unity for both linear and exponential permeability distributions. He assumes lateral uniformity and continuity of all productive strata and does not consider porosity. This study will take into account transient effects, cross flow and varying porosity, as well as the variations in permeability, by means of a heat analogy. Muskat5 has shown the similarity of the equations which describe the flow of fluids in a porous medium to the flow of heat through a solid. Landrum, et al,6 made an analogy between the flow of fluid in an unsymmetrical reservoir and the conduction of heat in a similarly shaped metal plate. This analogy is summarized briefly as follows. If fluid is produced from an oil reservoir above the bubble point, the resulting pressure distribution will be identical to the temperature which would result in a metal or heat-conducting plate if heat were similarly removed. This means that a study of heat flow in stratified thermal models will behave like fluid flow in stratified oil reservoirs. For mathematical correspondencies, set- Ref. 6. The fluid mobility k/p is proportional to the thermal conductivity, and the porosity-times-compressibility product is proportional to the density times specific heat of the thermal plate. EXPERIMENTAL EQUIPMENT AND PROCEDURE The stratified reservoir model used in this study is illustrated schematically in Fig. 1. A Leeds and Northrup Speedomax Type G temperature recorder

By B. D. Smith, K. H. Coats

Experiments in which calcium chloride displaced sodium chloride from four cores showed the extent of asymmetry in the resulting effluent concentration profiles. These results provided a check on how validly the mixing process is modeled by a differential (i.e., not finite-stage) capacitance mathematical model. The effluent concentration profile from two consolidated cores exhibited considerable asymmetry, while two unconsolidated cores yielded nearly symmetrical profiles. All runs resulted in breakthrough of the 50 per cent concentration significantly before one pore volume was injected. In addition, velocity appreciably affected the effluent concentration profile from a Torpedo sandstone core. The differential capacitance model matched the data significantly better than a simple diffusion model. The capacitance model allows determination of the amount of dead-end pore space in a porous matrix and the effect of velocity on the rate of diffusion into this space. An experimental program yielding insight into the physical validity of the capacitance effect is described. INTRODUCTION Axial dispersion — the mixing accompanying the flow of miscible fluids through porous media — has been the subject of many relativeiy recent studiesl-13 and a comprehensive review of the topic has been given by Perkins and Johnston.14 This dispersion is of practical interest in studies of the miscible displacement process, fixed-bed chemical reactors, and the adsorption of solutes from a flowing stream onto the surface of a porous medium. In the latter case, the effect of dispersion must be considered when adsorption parameters are determined from the nature of concentration profiles. In general, early studies of dispersion assumed applicability of a simple diffusion equation and were concerned with correlation of the experimentallv determined "effective" diffusion coefficient with system properties over a large range of the latter. Recent have been concerned with the deviations between the asymmetrical effluent concentration profiles observed and the symmetrical ones predicted by the diffusion model. In the present study, effluent concentration profiles were obtained from consolidated and unconsolidated cores. These profiles were compared with those predicted by a differential (i.e., not finite-stage) capacitance model. Solutions to the simple diffusion model, for three sets of boundary conditions, were compared with one another and with the experimental profiles. SUMMARY OF PREVIOUS WORK The reader is referred to Perkins and johnston14 for an extensive review of studies of dispersion in porous media. Many investigators have employed the simple diffusion model characterized by Eq. 1 below: The dispersion coefficient D for unconsolidated systems is correlated by u is interstitial velocity and dp is particle diameter. Since heterogeneity of the sand pack affects the mixing, this equation is also expressed as where a is proportional to the degree of heterogeneity and is about 3.5 for random packs of unconsolidated sand.l4 Eq. 3 holds for 2 For a Do homogeneous (regular) type of packing, should be 1 or less.6 Aris and Amundson6 and Carberry and Bretton consider o to be the number of particle lengths per mixing cell in the finite-stage model. Data from consolidated cores indicate dp to be about 0.36 cm for outcrop rocks, Torpedo sandstone having a reported value of 0.17 cm.15 For v /Do less than about 2, the effect of molecular diffusion must be considered and the total dispersion coeffi-

Jan 1, 1965

By T. R. Ingraham

When aluminum sulfate was decomposed in an evacuated apparatus and the sample cooled, Q alumina was found. The thermodynamics of the decomposition reaction were resolved by measurements of the total pressure of SO3, SO2, and O2 generated over the sample at various temperatures. The results were correlated with other published data to calculate the rmges of thermodynamic stability of the various compounds involved. The thermal decomposition of aluminum sulfate was studied by Wijhler, Pluddeman, and Wöhler1 and by Warner and Ingraham.2 The results of both studies were critically reviewed by Kellogg,3 who observed that "each set of data shows considerable scatter and strong curvature on a plot of log pso3 vs 1/T".3 He agreed with Warner and Ingraham2 that both the discrepancy in the two sets of results and their curvature may arise from the indefinite properties of the particular form of A12O3 which is formed during the decomposition. While studying the thermal stability of other sulfate systems, we had noted the presence of nonequilibrium oxide properties in both the cobalt4 and manganese5 systems, but neither had shown any appreciable curvature on a logPSO, vs 1/T relationship, and the data from both systems agreed reasonably well with prior work. It therefore seemed reasonable to reexamine the technique which had been used in our earlier work on aluminum sulfate.2 The principal difference was that a tightly compacted pellet had been used for the earlier aluminum sulfate work, whereas a loose powder, contained in a platinum boat, was used for our work on other sulfate systems. In addition, a better technique had been developed for dehydrating the samples. From work done on the nickel system,6 we had become aware of the highly protective nature of some sulfate layers on their oxjdes, and hence of the necessity of providing a large surface area of P3e sample when equilibrium was to be attained in a reasonable time. That observation suggested that perhaps a steady state, rather than equilibrium, had been reached in the earlier work on aluminum sulfate. This paper reports a repetition of the experimental work with large, finely divided samples of anhydrous aluminum sulfate. APPARATUS AND PROCEDURE The apparatus used in the experimental work was described in earlier papers.2,7 The source material was Anachemia reagent-grade Al2(sO4)3 - 18H2O which was first partly dehydrated by heating at 400°C for 48 hr and then completely dehydrated by repeated baking of an aluminum sulfate-oleum slush to dryness at 450°C. ? Alas was prepared by decomposing some of the sulfate in a muffle furnace at 800° C overnight. Approximately equal amounts of the 7) alumina and aluminum sulfate were used in the experiments. The finely divided samples were handled under dry box conditions, and in addition some of the aluminum sulfate was decomposed in the apparatus while it was under vacuum, to ensure its complete dehydration prior to sealing the apparatus. The samples were heated to a series of constant temperatures on both increasing- and decreasing-tem-perature programs. Two to three days were required to obtain steady readings of the total decomposition pressure on an increasing-temperature program, and 5 to 6 days on a decreasing-temperature program. Three samples were examined on both programs. Within experimental error, the results for each sample and each program could not be distinguished.

Jan 1, 1969

By J. D. MacKenzie

THE world production of copper for the first eight months of 1927 shows an increase of 3 per cent over the same period in 1926. Since February of this year, however, production has been considerably curtailed. The United States reduction in the last four months has been offset by the increased South Ameri-can and Belgian Congo production. The United States is now producing 58 per cent of the world production, Chile and Peru 17.3 per cent, Belgian Congo 5 per cent. In 1926 the United States produced 54 per cent, Chile and Peru 16.3 per cent, Belgian Congo 6.3 per cent. Production, Tons 1917-largest war year 1,580,000 1925 1,581,000 1926-increase 3 per cent 1,628,000 1927-increase 3 per cent 1,670,000 Copper Producing Countries, 8 mo., 1927: Tons Per Cent United States 644,000 58.0 Chile and Peru 192,000 17.3 Europe 90,000 8.1 Belgian Congo 56,000 5.0 Japan 46,000 4.1 Mexico 30,000 2.7 Canada 23,000 2.1 Figures are not available for Spain and Portugal, which would probably precede Mexico.

Jan 12, 1927

By J. L. Huitt, IM. L. Slusser, E. E. Glenn, M. L. Slusser

This paper is concerned with: (1) an analysis and interpretation of the filtration characteristics of drilling muds on filter paper, and (2) an interpretation of early stage "filtration" on consolidated synthetic porous media, herein referred to as the "surge loss" period. It is shown that water-loss data can be plotted so as to disclose the existence of a surge period, a non-uni-form cake thickness period, and a constant pressure filtration period. The same periods occur during exposure of consolidated porous media to muds. The data on consolidated porous media indicate that: (1) mud particles bridge pores inside porous media during the surge period, and (2) "filter cake" build-up inside porous media occurs during subsequent filtration. The data also show that the surge loss increases with sample permeability and with pressure differential. INTRODUCTION The phenomenon of mud filtrate invasion into porous sands of a drilling well has been recognized for many years.1,2,3,4 Part of API Code 29 is concerned with the filtration testing of a drilling mud to yield data on this subject. In a number of investigations "plastering properties" of muds were studied,5,6,7,8 "plastering" apparently meaning cake forming properties. In such studies the characteristics (thickness, permeability, and toughness) of the cake and the rate at which the liquid phase of the mud was separated from the solids (filtration rate through the cake, commonly referred to as water loss) were measured or at least considered. From the standpoint of its effect on well productivity, filtrate invasion into "clean" water-wet pay sands (i.e., those containing no clay minerals) may not necessarily be a serious problem. An increase in water saturation in the zone immediately around the wellbore would cause loss of oil permeability. However, in such a system, much of this water may be removed by oil production. If filtration occurs into "dirty" sands (i.e., those containing appreciable clay minerals), clay swelling or other mechanisms may cause losses in oil permeability which cannot be overcome by oil production.&apos;.&apos; The phenomenon of mud particle invasion into the pay sand of a drilling well was considered to be a possible serious factor in the early days of rotary drilling. Opinions varied as to whether drilling fluids "mudded up" and "sealed" oil sands. In 1932 Rubel,9 Gill,10 and Parsons," in separate papers, presented differences of opinion together with some laboratory and field data concerning loss of oil production caused by drilling fluid invasion into pay zones. These papers, and the discussions, furnish a large background on this subject and indicate the very clear thinking of many men at a time when petroleum production technology was in its infancy. Jones and Babson,6 and Silent,&apos; experimentally found that the depth to which mud particles invaded water-saturated sand packs was small (no greater than 1/16 in). Arn-quist12 in 1937 observed loss of water permeability due to invasion of mud particles into water-saturated, consolidated, sandstone samples. Williams and Cannon5 studied the filtra-tion properties of drilling muds and mentioned "sludge" which penetrated a short distance into the water-saturated filtering medium (sand pack). Byck5 concluded that formation permeability had no effect on the plas-

Jan 1, 1958