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By A. H. Duane, A. E. Miller

The high-temperature allotropy of some heavy rare-earth metals and their alloying behavior with magnesium in the 0 to 50 at. pct Mg region was studied by thermal, microscopic, and X-ray methods. Examination of a hcc phase retained upon quenching alloys of different magnesium content confirmed the existence of a bcc high-temperature allotrope in pure gadolinium, terbium, dysprosium, holmium, erbium, thulium, and lutetium. The lattice constants of the pure metals were determined from a Vegard's Law extrapolation and .found to be 4.05, 4.02, 3.98, 3.96, 3.94, 3.92, and 3.90 + 0.02 A, respectively. In all of the systems studied, the high-temperature bcc phase decomposed eutec-toidally, when slowly cooled, into a hexagonal rare earth-Mg solid solution and a simple-cubic peritec-tic AB-type compound. In 1956, Spedding et al.' observed high-temperature resistivity anomalies in the light rare-earth metals and made several unsuccessful attempts to retain the high-temperature form of these materials at room temperature by quenching the pure metals from temperatures near their melting points. High-temperature X-ray techniques were used by Spedding et a1.' in 1959, to investigate the high-temperature allotropy of the rare-earth metals. This study showed that lanthanum, cerium, praseodymium, neodymium, ytterbium, and possibly gadolinium are bcc at temperatures near their melting points. Discontinuous changes in resistivity at elevated temperatures were also observed for pure gadolinium, terbium, dysprosium, holmium, and lutetium, thus indicating the possible existence of a high-temperature crystalline transformation in these metals. However, due to experimental difficulties encountered in the high-temperature X-ray analysis of these metals, their allotropic form was not identified. Spedding et a~.~ in 1960 observed that yttrium displayed a continuous solid solubility with lanthanum at elevated temperatures, thus showing the high-temperature structure of yttrium to be the same as that of lanthanum, i.e., bcc. Similarly, the high-temperature alloying behavior of gadolinium with yttrium showed gadolinium to be bcc at elevated temperatures. The bcc nature of the high-temperature form of yttrium was again recognized in 1960 by Eash and carlson4 in their study of the alloying behavior of yttrium with thorium. Gibson and Carlson, in a similar study of the alloying behavior of yttrium with magnesium, found that by quenching Y-Mg alloys from within the 0-solid solution region, Fig. l, they were able to retain the allotropic form of yttrium. It was the present authors' intention to use this method to show the existence of a bcc high-temperature form of the heavy rare-earth metals gadolinium, terbium, dysprosium, holmium, erbium, thulium, and lutetium. Simultaneous with the present work, Beaudry and Daane' have shown the bcc nature of the high-temperature form of scandium. EXPERIMENTAL PROCEDURES Materials. The rare-earth metals used in this study were prepared by the calcium reduction of the fluoride and were further purified by vacuum distillation. The magnesium was obtained from the New England Lime Co. and was also purified by distillation prior to its use in the preparation of the rare earth-Mg alloys. The results of chemical and spec-

Jan 1, 1964

By A. G. Jordan, W. Jeitschko, Paul A. Beck

The occurrence qf the V phase structure /Zr,Co,Ge, type) in ternary syste7ns (titanium, zivconium, niobium, lanta1urn) -(nickel, cobalt, iron)-(silicon, germanium) was incestigated. Nine V silicides and four V gertrlanides were found and their lattice constants are reporled. The lattice constants of twenty-one preri-ously identified E phases (TiNiSi type) are given. The average atomic volumes of these phases are discussed in relation to similar binary phases. ThE occurrence of a phase Ti4Ni4Si7 was first reported by Westbrook. DiCerbo, and peat' who gave it the name "V phase". They also reported the existence of an E phase TiNiSi. Subsequently a systematic study was undertaken in this laboratory to explore the occurrence of E' and V phases3 in related ternary systems. In the meantime the crystal structure of the E phase TiNiSi 4 and of the V phase Zr4CO4Ge 75,6 was determined. In the present paper the details of the V phase investigation and the lattice constants of the E and V phases are presented. V PHASES Alloy specimens of approximately 10 to 15 g were prepared by arc melting under argon (99.996 pct Ar) atmosphere. The starting materials were all of purity higher than 99.9 pct, with the exception of cobalt. which contained 0.14 pct Fe as the only major impurity. The weight losses were in all cases less than 2 pct, in most cases less than 1 pct. The samples were encapsulated in fused silica tubes with sufficient argon to yield about 1 atm pressure at the annealing temperature. After the homogenization anneal. Table I. the specimens were water-quenched. A representative portion of each specimen was then examined metallographically (etchant: 20 pct HNO,. 10 pct HF. 25 pct glycerine, 45 pct H20). Only minor amounts of second- and third-phase particles were observed in the specimens listed in Table I, with the exception of alloys Zr4Fe4Si7 and Ta,Fe,Si,. which contained an estimated 10 pct by volume of foreign phases. X-ray powder photographs were taken with a Seeman-Bohlin type focusing camera and Fe-KO radiation. Of the thirty possible combinations of elements in the ternary systems (titanium, zirconium. vanadium. niobium. tantalum)-(iron. cobalt, nickel)-(silicon. germanium) thirteen V phases could be identified. In the remaining seventeen ternary systems and also in the systems Cr-Ni-Si and (M0.W)-(Ni.Co)-Si no V phase was found at the composition 4:4:7 after annealing at temperatures between 900" and 1200'C. For the determination of the lattice constants of the V phases Debye-Scherrer photographs were taken using the asymmetric film arrangement and CrKcr radiation (ka1, = 2.28962A). Using the positional parameters, as determined6 for Zr,Co,Ge,. Table 11. intensity calculations were carried out for each of the V phases with the aid of a computer program.: Thus unequivocal indexing of the diffraction patterns was greatly facilitated. The lattice constants. Table I. were then computed by a least-squares fit of the high-angle lines with f (0) = cos2 Q as extrapolation function. Only few. if any. very weak impurity lines were observed, with the exception of the three iron alloys Zr,Fe,Si7. Zr4Fe,Ge7. and Ta,Fe,Si7. The agreement

Jan 1, 1970

By G. A. Deitz, J. Halpren

The kinetics of dissolution of silver in cyanide solutions under oxygen pressure have been investigated over a wide range of conditions with a view to establishing the reactions involved and the factors which influence the rate. The results indicate that the rate is determined principally by the transport of reactants in solution to the silver surface. The thermodynamic features of the reaction with particular reference to the influence of pH and CN- are also discussed and summarized in the form of potential-pH diagrams. METALLIC silver is readily attacked and dissolved by cyanide solutions in the presence of oxygen. This reaction has long been recognized and extensively applied1 in the well-known cyanide process for the extraction of silver from its ores. While this process has been subjected in the past to a number of investigations2,3 both of a practical and fundamental nature, some features relating to the chemistry of the reactions involved, the role of oxygen, the nature of the rate-controlling step, and the effects of pH and certain reagents such as lime, are still not fully understood. It was felt that this situation justified a further investigation of the reaction, made with a view to obtaining a better understanding of its kinetics and mechanism. In the present investigation rate curves for the dissolution of silver were determined over an extensive range of carefully controlled reaction conditions. By carrying out the reactions in a pressure vessel, the partial pressure of oxygen, and hence its concentration, could be varied widely. The influence on the reaction of other variables including temperature, pH, and the concentrations of cyanide, peroxide, and other salts was also examined. The results of these kinetic studies are presented and discussed in this paper, together with a summary of available thermodynamic information relating to the possible reactions which can accompany the attack on silver by aqueous solutions of cyanide and oxygen. Chemistry and Thermodynamics of the Reaction The chemistry of the reactions of gold and silver with aqueous cyanide solutions has been the subject of several recent reviews.'." It has been proposed' that the following reaction occurs when silver dissolves in cyanide solutions in the presence of oxygen: 4Ag + 8CN- + 0, + 2H.0 -t 4Ag(CN); + 40H- [la] An equation of this form, for the corresponding dissolution of gold, was first suggested by Elsner." Bodlaender5 proposed a similar overall reaction, but suggested that it took place in two steps, 2Ag + 4CN- + O2 + 2H2O ? 2Ag(CN),- + 2OH- + H2O2 [2a] followed by 2Ag + 4CN- + H2O2? 2Ag(CN); + 20H- [3a] On the other hand, Janin- suggested that the dissolution of gold can occur with the liberation of hydrogen, rather than by reduction of oxygen. The corresponding equation for the dissolution of silver is 2Ag + 4CN- + 2H20 -t 2Ag(CN); + 20H + H2 [4a] All these reactions represent oxidation-reduction processes and may be resolved into the corresponding separate oxidation and reduction components. The oxidation step involves the formation of the argentocyanide ion and is the same for all the reactions, i.e., Ag + 2CN? Ag(CN)2 + e [51 However, reactions la, 2a, 3a, and 4a differ in the nature of the reduction steps which are, respectively, O2 + 2H2O + 4e ? 4OH- [lb] O2 + 2H2O + 2e ? H2O2 + 2OH- [2b] H2O2 + 2e ? 2OH- [3b] 2H2O + 2e? 20H- + H2 [4b]

Jan 1, 1954

By R. G. Jones, W. L. Kinney, R. E. Schilson, R. S. Wilson, G. A. Clark, H. Suralo

This paper discusses the results of the Fry conventional or cocurrent in situ combustion test, which was conduct-ed in a 3.3-acre inverted five-spot. The depth of the formation was between 880 and 936 ft; the oil had a specific gravity of 28.6° APl and a viscosity of about 40 cp at the reservoir temperature of 65°F. Preceding the combustion test, air injection tests were conducted which, in conjunction with geological studies, were used to evaluate the characteristics of the reservoir. Combustion was initiated on Oct. 13, 1961, with ignition being accomplished by a 40 kw electrical heater. The test phase of the project ended on Oct. 1, 1963. During the test, the average air injection rate was 1,520.-000 scf/D. Throughout the test, production of all fluids— gas, oil, and water—was monitored. Cumulative oil production credited to the project was 100,586 bbl. The cumulative air-oil ratio was 11,500 scf/bbl oil, and the oxygen uti1ization efficiency was 87 per cent. INTRODUCTION The Marathon Oil Co. conducted a successful in situ combustion test, beginning Aug. 22, 1961, at the Fry unit, Crawford County, 111. The purpose of the project was to test the feasibility of cocurrent in situ combustion as a means of oil recovery in the Fry type reservoir. Interest in in situ combulstion as an oil recovery tool has been stimulated mostly by the existence of large reserves of heavy viscous crudes with low expected recovery, usually less than 10 per cent. These are the so-called unrecoverable reserves, and most combustion tests to date have been conducted in this type of reservoir.1-4 In contrast, the Fry combustion test was conducted in a reservoir with a relatively high gravity oil having a relatively low viscosity. This paper discusses the performance of the test. The geology of the reservoir and the field operations are discussed in separate papers.5 TEST SITE The Fry combustion test was carried out in a 3.3-acre inverted five-spot portion of a lenticular body of Robinson sandstone. Net sand was 50 ft thick, porosity averaged 19.7 per cent, oil saturation was 68 per cent of pore volume, and water saturation was 20 per cent of pore volume. The oil in place was estimated at 1,040 bbl/acre-foot, or 171,600 bbl within the 3.3-acre pattern. The water in place was 326 bbl/acre-foot, or 53,800 bbl. The oil has a specific gravity of 28.7° API and a viscosity of 40 cp at the reservoir temperature of 65°F. AIR INJECTION PERFORMANCE Air injection took place in two phases, the phases separated by ignition of the reservoir. In the pre-ignition phase, air injection tests were conducted in the summers of 1960 and 1961. These indicated that the Fry reservoir was confined, and a high return rate of injected air could be expected. This proved to be an outstanding characteristic of the project, as cumulative gas production was 95.3 per cent of the air injected. The difference between the cumulative air injected and the total gas produced can be largely accounted for by the quantity of air stored in the reservoir. An estimated 16 X 10 cf of air remained in the burned-out portion of the reservoir and an indeterminate amount of gas was stored in the unburned but pressurized reservoir. Hence, a complete material balance of gases would account for nearly 100 per cent of the air injected. At times during the test, the daily gas production rate was 98 per cent of the daily air injection rate. Fig. 1 presents the air injection history of the Fry com-

Jan 1, 1966

By J. B. Newkirk, A. H. Geisler

The alloy Cu4Pd has a disordered face-centered-cubic structure when quenched from temperatures between 478ºC and the melting point (about 1100°C). Below 478ºC an ordered phase is stable. The results of a Debye-Scherrer X-ray analysis indicate that the ordered phase has a tetragonal unit cell described by the space group C24h — P42/mt with 2 Cu in 2a, 2 Cu in 2f, 4 Cu in 4j (x = 0.2, y = 0.6), 4Pd in 4j (x = 0.4, y = 0.2), and 8 Cu in 8k (x = 0.1, y = 0.3). The orientation relationship between the face-centered-cubic phase and the ordered tetragonal phase is given by: [100],,. // [130]al,. COO1Ia.d.//COO1I,,.. • The behavior of Cu,Pd is typical of ordering alloys except that the transformation is very sluggish. The increase in hardness and the microstructural and X-ray diffraction effects are interpreted in terms of coherency strains caused by the ordering. AN anomalous construction in the Cu-Pd phase diagram (Fig. 1) was reported in 1939 and has been allowed to stand without further published attention since that time. The odd figuration about the composition 10 to 27 atomic pct Pd is derived mostly from the work of Jones and Sykes.1 Evidently several features of this binary system require further study if the constitutional forms are to be well understood. The present paper includes a study of one of these features, that is, the crystal structure of a single ordered alloy containing nominally 20 atomic pct Pd. This choice of composition was suggested by the work of Harker and associates who determined the structure of Ni4Mo2 and Ni4W.3 The nature of the ordering process in Cu4Pd was studied also by observing the hardness, microstructure, and Debye-Scherrer patterns of specimens which had been aged at various temperatures after quenching from an initial disordering treatment. Experimental Methods A 20 gram ingot of Cu4Pd was made by melting spectrographically standardized copper from Johnson, Matthey, and Co., and commercially pure (99.5 + ) palladium in an argon-filled quartz tube. Chemical analysis showed that the ingot contained 80.0 atomic pct Cu. The ingot was rolled about 60 pct to a strip 0.060 in. thick and was homogenized for 16 hr at 950°C in low pressure argon. Rods cut from the rolled strip were worked into wire 0.015 in. in diameter, and specimens for hardness and microscopic examination were cut from the remaining strip. All specimens, with the exception of some of the wire, were given an initial disordering treatment by heating for 16 hr at 950°C, followed by water quenching. A 10 cm length of as-drawn wire was water quenched after being held in a temperature-gradient furnace4 for 89 days. Room-temperature Debye-Scherrer photograms were then made at points along the wire to determine the temperature below which the ordered phase was stable. Although the accuracy of temperature determination in the gradient was only about ±10 °C, the temperature gradient was sufficiently gradual that the sensitivity was much better and locations which had differed by as little as 1°C could be distinguished. An analysis of the crystal structure of the well ordered alloy was made by X-ray diffraction using a specimen cut from this wire. The change of Debye-Scherrer pattern as ordering progressed was studied by using isothermally aged samples of initially disordered wires. The wires were sealed under low-pressure argon in small quartz tubes for heat treatment. After the aging treatment, the tubes were quenched in water and photograms were made at room temperature in a 10 cm diam camera using filtered Cu kX. (A = 1.540511) Hardness was measured on a Vickers hardness tester using a 10 kg load and 2/3 in. objective lens. Reported values are the average of at least three impressions made on flat specimens 0.060 in. thick. After the hardness of a heat-treated sample had been measured, it was resealed in low-pressure argon and returned to the furnace for continued aging at the same temperature. In this way, two samples served for all aging times at each temperature. Hardness specimens which had been aged 500 hr or more were used for metallographic examination after the final aging treatment. A dilute potassium-dichromate etching solution was used.

Jan 1, 1955

By E. A. G. Colls

IN all branches of the chemical industry, corrosion plays a very costly part unless it is suitably com-batted, and as a result it is probably correct that chemical and design engineers are more corrosion conscious in the field of chemical industry than in others. Most metals occur in nature in combination with other elements. The refined or reduced state to which man converts them for his use, by removing the combining elements, leaves them in an unstable condition. Therefore in most of the media to which the metals are exposed they are constantly combining with the constituents of their environment, or in other words they are continually being corroded. Similarly, nonmetallic materials are corroded by undergoing chemical change. The rate at which corrosion takes place varies widely from metal to metal and medium to medium. In practically all cases the corrosion of metals in solutions (electrolytes) is electrolytic in nature and the rate of corrosion is dependent on many factors such as temperature, pressure, internal stresses, galvanic action, metal-ion concentration, and so on. In the chemical industry substances must be handled which are particularly corrosive to materials of construction. At the chemical plants of The Consolidated Mining and Smelting Co. of Canada, Ltd. (otherwise known as Cominco), situated at Trail, B. C., Canada, the following are some of the materials that have to be handled: Gases. Sulphur dioxide, sulphur trioxide, carbon dioxide, carbon monoxide, oxygen, hydrogen fluoride, ammonia, hydrogen sulphide, and oxides of nitrogen. Liquids. Solutions of ammonium sulphate, ammonium sulphite, ammonium nitrate, caustic soda and potash, sulphuric acid, nitric acid, hydrofluo-silicic acid, hydrofluoric acid, phosphoric acid, aqua ammonia, and formic acid. Solids. Gypsum (containing phosphoric acid), ammonium sulphate, ammonium nitrate, phosphate rock, caustic soda, potash, and phosphate fertilizers.

Jan 1, 1951

By E. A. G. Colls

IN all branches of the chemical industry, corrosion plays a very costly part unless it is suitably com-batted, and as a result it is probably correct that chemical and design engineers are more corrosion conscious in the field of chemical industry than in others. Most metals occur in nature in combination with other elements. The refined or reduced state to which man converts them for his use, by removing the combining elements, leaves them in an unstable condition. Therefore in most of the media to which the metals are exposed they are constantly combining with the constituents of their environment, or in other words they are continually being corroded. Similarly, nonmetallic materials are corroded by undergoing chemical change. The rate at which corrosion takes place varies widely from metal to metal and medium to medium. In practically all cases the corrosion of metals in solutions (electrolytes) is electrolytic in nature and the rate of corrosion is dependent on many factors such as temperature, pressure, internal stresses, galvanic action, metal-ion concentration, and so on. In the chemical industry substances must be handled which are particularly corrosive to materials of construction. At the chemical plants of The Consolidated Mining and Smelting Co. of Canada, Ltd. (otherwise known as Cominco), situated at Trail, B. C., Canada, the following are some of the materials that have to be handled: Gases. Sulphur dioxide, sulphur trioxide, carbon dioxide, carbon monoxide, oxygen, hydrogen fluoride, ammonia, hydrogen sulphide, and oxides of nitrogen. Liquids. Solutions of ammonium sulphate, ammonium sulphite, ammonium nitrate, caustic soda and potash, sulphuric acid, nitric acid, hydrofluo-silicic acid, hydrofluoric acid, phosphoric acid, aqua ammonia, and formic acid. Solids. Gypsum (containing phosphoric acid), ammonium sulphate, ammonium nitrate, phosphate rock, caustic soda, potash, and phosphate fertilizers.

Jan 1, 1951

By Allan E. Martin, Harold M. Feder, Irving Johnson

The cadmium-uranium system was studied by thermal, metallographic, X-7-ay and sampling techniques; special emphasis was placed on the establishment of the liquidus lines, The single inter metallic phase, identified as the compound UCd11 melts peritectically at 473°C to form a-umnium and melt containing 2.5 wt pct uranium. The cadmium-rich eutectic (0.07 wt pct uranium) freezes at 320.6°C. Solid solubilities in uraizium and cadmium appear to be negligible. Between 473°C and 600°C the liquidus line is retograde. NO publication relating to the cadmium-uranium phase diagram was found in the literature. The establishment of this diagram was of considerable interest to us because of a possible application of the system to the pyrometallurgical reprocessing of nuclear fuels. Analysis of liquid samples, metallographic examination, thermal analysis, and X-ray diffraction analysis were used to establish the phase diagram from about 300° to 670°C. Particular emphasis was placed on the establishment of the liquidus lines. The same system was concurrently studied in this laboratory by the galvanic cell method.' Both studies benefited from a continual interchange of information. MATERIALS AND EXPERIMENTAL PROCEDURES Stick cadmium (99.95 pct Cd, American Smelting and Refining Co.) contained 140 ppm lead as the major impurity. Reactor grade uranium (99.9 pct U, National Lead Co.) was most often used in the form of 20-meshspheres. This form was particularly suitable because it does not oxidize as readily as finer powder. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The liquid sampling technique is described elsewhere2 alumina crucibles (Morganite Triangle RR), tantalum stirring rods, tantalum thermocouple protecthecadmiumtion tubes, Vycor or Pyrex sampling tubes, and grades 60 or 80 porous graphite filters were used. Uranium dissolves in liquid cadmium rather slowly. In order to achieve saturation of the melts it was necessary to modify the procedure of Ref. 2 by the use of more vigorous stirring and longer holding periods (at least 3 hr) at each sampling temperature. The samples were analyzed for uranium by spectro-photometry (dibenzoyl methane method) or by polar- ography. The analyses are estimated to be accurate to 2 pct. Thermal analysis was performed on alloys contained in Morganite alumina crucibles in helium atmospheres. Standard techniques were employed; heating and cooling rates were about 1°C per min. For the determination of the peritectic temperature, Cd-10 pct U charges were first held for at least 50 hr at temperatures in the range 435° to 460°C to form substantial amounts of the intermediate phase. For the determination of the effect of cadmium on the a-p transformation temperature of uranium, charges of Cd-25 pct U (-140+100 mesh uranium spheres) were first held near the transformation temperature, with stirring, to promote solution of cadmium in the solid uranium. The holding times and temperatures for these treatments were 18 hr at 680°C for the cooling run and 28 hr at 630°C for the heating run. Alloy specimens for X-ray diffraction and metallographic examination of the intermediate phase were prepared in sealed, helium-filled Vycor or Pyrex tubes. Ingots from solubility runs and thermal analysis experiments also were examined metallographically. Crystals of the intermediate phase were recovered from certain cadmium-rich alloys by selective dissolution of the matrix in 20 pct ammonium nitrate solution at room temperature. Temperatures were measured with calibrated Pt/Pt-10 pct Rh thermocouples to an estimated accuracy of 0.3°C. However, the depression of the freezing point of cadmium at the eutectic is estimated to be accurate to 0.05°C because a special calibration of the thermocouple was made in place in the equipment with pure cadmium just prior to the measurement. EXPERIMENTAL RESULTS The results of this study were used to construct the cadmium-uranium phase diagram shown in Fig. 1. This diagram is relatively simple; it is characterized by a single intermediate phase, 6 (UCd11), which decomposes peritectically, and which forms a eutectic system with cadmium. The solid solubilities in the terminal phases appear to be negligible. An unusual feature of the diagram is the retrograde slope of the liquidus line above the peritectic temperature. The Liquidus Lines. The liquidus lines above and below the peritectic temperature are based on three separate solubility experiments. The data are shown in Fig. 1 and are given in Table I. It is apparent from the figure that the solubility data obtained by the approach to saturation from higher temperatures fall on substantially the same lines as those obtained

Jan 1, 1962

By Noel S. Christensen

COBALT is a silvery white metal with a slight bluish cast, strongly resembling nickel in its appearance and properties, notably its resistance to corrosion, although its alloys with other metals differ quite decidedly in their properties from those of nickel. The name cobalt was derived from the German "Kobold" meaning goblin and this came to be applied to the cobalt minerals which, although they resembled ores, did not readily yield metal when smelted by the primitive processes available in the Middle Ages. Cobalt minerals were used as pigments by potters and glass workers before the Christian era. Cobalt blue glass was found in the tombs of the Egyptians and in the ruins of Troy, and many colors used by the ancient Greeks and Romans contained cobalt. The ancients were entirely unaware that the colors they used were caused by cobalt and the metal itself was only isolated about the middle of the eighteenth century by Brandt although the preparation of cobalt compounds had been carried on in a small way ever since the opening of the silver-cobalt deposits at Schneeberg, Germany, in 1470. The metal is fairly hard, with a density when pure of 8.81 in the cast state and 8.92 after working. The commercial grade of cobalt has a density of about 8.75 in the cast state. The atomic weight is 58.97. The Brinell hardness of the pure metal is 124; that of the commercial grade varies from as low as 100 to as high as 138, depend¬ing upon the impurities present. Pure cobalt has a sharp melting point at 1478°C. The tensile strength of the pure metal in the cast condition is said to be higher than that of any other pure metal. Kalmus gives it as 34,400 lb. per sq. in. for cast unannealed metal; the effect of annealing at 850 to 900°C. is to raise the strength slightly. The yield point is close to the ultimate strength and the reduction in area and elongation are both low. Mechanical working raises the tensile strength of pure cobalt rapidly and in the form of wire it will be over 100,000 lb. per sq. in. The presence of small quantities of carbon in the commercial metal raises the tensile strength to as high as 61,000 lb. per sq. in., the reduction in area and elongation being raised at the same time to approximately 20 per cent.

Jan 1, 1933

By AIME AIME

THE luncheon of the Milling Methods Committee in the Engineers' Club, on Feb. 16, was distinctly a social affair, although several matters of a non-milling nature were fruitfully discussed. The session* on Milling Methods, the same afternoon, attracted a gathering which overtaxed the capacity of the Board Room on the fifteenth floor. Galen H. Clevenger presided, with the moral reinforcement of Charles Butters. As all papers were available in printed form, and since synopses have appeared in MINING & METALLURGY, it is unnecessary to cover the contents of each in detail here. The first paper (T. P. 410), by Leaver and Woolf, on the "Flotation of Minor Gold in Large-scale Copper "Concentrators," was excellently summarized by R. S. Dean of the U. S. Bureau of Mines, who stressed the -very definite action of lime as a depressant of gold, and showed how the authors had worked out the best conditions of alkalinity, pH concentration and reagents for -optimum recovery of gold along with base metals, especially where lime had to be used to depress pyrite. No discussion was evoked.

Jan 1, 1931

For the year ending February, 1919 PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. PAST PRESIDENTS L. D. RICKETTS, NEW YORK, N. Y. PHILIP N. MOORE ST -Louis, Mo FIRST VICE-PRESIDENT C. W. GOODALE, BUTTE, MONT.. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y.

Jan 6, 1918

By F. W. Schroeder

AT the annual meeting of the Institute 2 years ago, a paper,1 " Requirements of Refractories for Open Hearths," was presented by F. W. Davis and G. A. Bole of the U. S. Bureau of Mines. In a brief foreword, D. A. Lyon stated that the paper was not to report the results obtained but rather to present an outline to serve as a basis for discussion. The essential parts of an open-hearth furnace were described and the conditions under which they operate. Some constructive discussion followed the reading of the paper. One of the first fellowship investigations undertaken by the Bureau of Mines in 1924 under the cooperative agreement with Carnegie Institute of Technology, through the Metallurgical Advisory Board, was to determine service conditions of open-hearth refractories. The present paper gives the results of this work which was done in the Pittsburgh district and was in charge of the authors. Material contributions in the form of data were contributed by E. N. Bauer, J. W. Campbell, G. H. Pfeiffer and A. Grodner, Carnegie Institute of Technology research fellows. The study covered 18 mos.

Jan 7, 1926

By J. Norman Bulkley

As electrical power is used to a greater extent on the Rand than in any other mining center, it is thought that a short description of the methods used and results obtained may be of interest. In comparing Rand practice with that on other fields, several general factors should be borne in mind: First, the mines are all working on large tonnages of low-grade ore (average. $6.50). The annual crushing rate is about 27,000,000 tons. Second, the mines are all grouped udder the financial and engineering control of mining houses, so that the results of a group, rather than an individual mine, are open for study, and practice follows more uniform lines. Third, coal of fair quality (about 12,000 B.t.u.) can be obtained for $2 to $3 per ton., Good supplies of condensing water are, however, scarce, and have to be carefully stored. Power Supply Power is supplied by the Victoria Falls & Transvaal Power Co., Ltd., and its subsidiary, the Rand Mines Power Supply Co. Both companies, which are practically one from an engineering point of view, operate the following stations, all feeding into the same system.

Jan 2, 1916

By H. H. Stout

In the early fall of 1925, the writer was conducting, in the Ledoux and Co. laboratory, New York, experiments directed toward ascertaining the effect on its impurity content when cathode copper was subjected to a current of various gases at an elevated temperature below the melting point. The apparatus consisted of a vertical I-in. dia. silica tube about 12 in. long, heated on the outside. The cathodes were broken to pass 3/8-in. mesh, and a current of various different gases was passed up through a 4-in. long column of these loose cathode particles in the vertical tube furnace. Temperature was maintained to 1500º to 1600ºF. and the gas treatments lasted from 3 to 6 hr. The writer observed that whenever reducing gas (H2 or CO) was used, these cathode particles stuck together at points of contact with each other. The cohesion was so marked and tenacious that an examination was made of the fractured surfaces, when cathode particles were broken from the cluster. Crystal growth was always found to have taken place across the surfaces where separate particles were in contact, but only after all oxides, sulphates, etc., had been completely removed. The idea of a possible new process was then conceived and was disclosed to A. M. Smoot (V. P. Ledoux and Co.) with intent to obtain his views. The first conception as given Smoot was "to gas-clean broken cathodes, put them in an extrusion press, solidify and extrude them at around 1500ºF." Smoot's reaction, after a few moments considera- tion, was, "It looks perfectly all right to me.'' The writer and his assistants, W. H. Osborn and H. H. Stout, Jr., after conferring as to ways and means, decided to go ahead with preliminary laboratory experiments, which, it was thought, would move the new process from the possible to the probable. This program followed a course indicated by three basic considerations: 1. Since brittle cathodes were often unintentionally produced, it seemed probable that the laws controlling this type of deposition could be ascertained. 2. We had already proved the gas-cleaning feature. 3. There remained to prove: whether a sound, homogeneous metal billet could be produced with crystal growth established over the entire surface of each individual particle in the billet; and, if so, what would be the physical properties? Osborn arranged with Columbia University for conducting experiments in its research laboratory to prove or disprove the third item; Columbia assigned C. A. Phillipi, Jr. to assist in the project. A press with a cylinder 2 in. high and of I-in. dia. was used. It was surrouilded and heated by a resistance coil 01 Nichrome wire. Broken tough cathodes were used. Experimental Procedure The first run took place March 18, 1926. The resistance wire gave out when temperature of 1000ºF. was obtained. Pressure was immediately applied: perceptible ram movement stopped when 39,000 lb. per sq. in. on the copper was reached, with a maxi-

Jan 1, 1941

By George W. Crawford, W. P. Aycock, E. W. Hough

Forty oilfield brines have been examined so far by a polarographic technique new in petroleum engineering called the "tensatnmetric method" by the team of biochemists who perfected its use in their field. Samples of brine were obtained from various oil fields in which the wells were known to be producing fluid from oil productive zones in well-known geologic formations. Most of the reservoirs from which the samples were obtained are believed to have an active water drive under the prevailing conditions of operation. The 40 samples represent brines produced front 16 different formations of various geologic ages. Graphs have been prepared of the data obtained in the testing of each sample, and the distinctive waife-like curves so obtained are characterized by reproducible profiles, called "response curves." Careful comparison of the response curves of salt water coming from different fields producing from the same geologic formation reveals that the curves are similar. The response curves of salt water coming from productive zones of different geologic formations are characteristically different. Preliminary work offers the further hope that response curves of an oilfield brine indigenous to a particular oil-bearing formation and hence representative of a particular geologic environment, such as deposit-ional and all subsequent morphological conditions, may be of value in reservoir engineering in the interpretation of surface and interfacial phenomena. For example, the wettability of the rock matrix and more specifically, the classification of productive oil-bearing strata as hydrophyllic or hydrophobic may be determinable. However, many more brines must be examined and the resulting response curves analyzed in comparison to known causal phenornena before this objective is achieved. INTRODUCTION One of the perennial moot questions in the literature of petroleum engineering is whether the reservoir rock is oil- or water-wet. Possibly an answer to this question could come from a careful examination of oilfield brines. None of the conventional methods of examining brines (chemical analysis, pH and electrical conductivity measurements, and the like) answer the question. Careful analysis of reservoir behavior observed in the exploitation of oil fields, particularly in the application of fluid injection, has been fruitful to the extent that a few reservoirs are believed to be properly classified. Physical chemistry suggests the behavior of reservoir brine and rock may be due to something in the brine in small amount. The ever increasing development and modification of theory in the general field of surface and interfacial chemistry has, and is, contributing to a better understanding of the problem, particularly as theory is verified by data. The work herein reported was begun in 1953 by Hough and Roebuck 1,2 who employed a new form of alternating current polarography, i.e., tensammetry, developed by Breyer, et a13,4 and who studied eight oilfield brines in adapting tensammetry to petroleum engineering needs. THEORY AND DEFINITIONS Tensammetry is a new technique of inquiry into surface phenomena. Specifically, a weak alternating current voltage is superimposed upon the direct current voltage applied to a dropping mercury electrode in contact with an electrolyte containing a small amount of a surfactant. The resultant alternating current can be measured and provides the experimental data for this new area of research. Under the influence of the direct current voltage, polar molecules arrange themselves in a double layer at the electrode. This double layer may be compared to a variable condenser, the capacitance of which is a function of the imposed direct current voltage. The direct current voltage determines the degree of adsorption of the surface active molecule on the electrode. Whenever the molecules are strongly adsorbed on the electrode, the capacitance of the double layer is low and the alternating current through the cell is low. Desorption occurs at some values of the direct current voltage, and at these voltages the capacitance of the double layer is high, resulting in an increase in the alternating current through the cell. The direct current

Jan 1, 1958

By Henry W. Edwards

Concrete is not a new, nor even a modern substance. Important structures built by the old Romans before the commencement of the Christian Era are to-day sound and solid— for example, the dome of the Pantheon in Rome, 142 ft. in diameter. I do not propose, therefore, to discuss the durability of the material, as in the mining and metallurgical business, structures, as a rule, are not calculated to endure for two thousand years. I do wish to urge, however, that much of the stone masonry around mines and smelters would have given better results if concrete had been used in place of stone. Concrete looks better; is stronger, cheaper, more durable, more quickly built, and above all requires no skilled labor, except that of the carpenter, who, like the poor, is always with us. Well proportioned concrete, that is to say, having well proportioned ingredients, may be safely relied upon to withstand a compressive or crushing strength of 50 tons per square foot. In most American cities, however, the building laws limit it to the absurdly low figure of 16 tons. This restriction is probably due to the political influence of the building-trades unions, which object strongly to its too free use, undoubtedly owing to its not requiring the services of skilled workmen. I hope to show that quite important construction work may be' undertaken without the aid of the gentleman with the trowel. In some of the isolated districts of the West and Southwest this is no mean advantage. The weight of good concrete, dry, is from 130 to 160 lb. per cubic foot. Ingredients of Concrete. Concrete is composed of four ingredients; viz., 1. Crushed Stone; 2. Sand; 3. Cement; and 4. Water.

Jan 1, 1905

F. E. BASH, Philadelphia, Pa.-In order to make a definite check on the emissivity of crucible steel under works conditions, a test was planned and executed by the plant of the Midvale Steel Co., by a Sub-committee, as follows: Five crucibles were put in a crucible furnace with-the normal charge and were treated in the same manner as a number of others that were charged at the same time; the only difference was that the five cur-cibles had lids with.2-in. holes in the center. It was thought that after the crucibles were removed from the furnace a reading could be made through the hole in the lid with the optical pyrometer and that such a reading would give the true temperature of the steel as black-body con-ditions should prevail inside the crucible. If after obtaining the true temperature, the crucible lid were removed and the steel poured into the ladle, the apparent temperature could be taken by sighting on the steel stream and the emissivity obtained from the two temperature values. Such a test was carried out with five crucibles. About a third of the crucibles charged into the furnace with the five experimental ones were first drawn from the furnace and poured into the ladle. The experimental crucibles were then drawn and readings of the true temperature were made

Jan 12, 1919

By J. L. Brimhall

Slip-line formation during bending has been studied on neutron-irradiated molybdenum single crystals. For equivalent strains, the slip lines are coarse and distinct in the irradiated molybdenum and not resolvable in the unirradiated molybdenum. The slip lines have been directly correlated with dislocation channels present in the irradiated and deformed thin foils. The heterogeneous distribution of the dislocations during deformation in the irradiated material results from dislocation interaction with the dejects produced during irradiation. Impurities , in the form of' carbides, affected the dislocation channeling Principally by acting as dislocation sources. ALTHOUGH the mechanical behavior of irradiated materials has been studied extensively, the precise mechanism of irradiation hardening has not been established. Some information on the microstructural species responsible for hardening of irradiated materials has been derived from direct and indirect observations. The direct observation of the structure of deformed irradiated metals, particularly by transmission electron microscopy, is a relatively new and unexplored area. Slip-line studies in fcc metals have been restricted primarily to copper.1-3 Very coarse slip lines, representing slip on many closely spaced planes, have been observed in deformed, irradiated copper. Coarse slip lines have also been observed in irradiated aluminum.4 Clear channels in irradiated copper caused by dislocation motion through the defect structure have been seen by transmission electron microscopy and correlated with slip lines.5-6 To date, little work has been reported on the irradiated bcc metals. Eyre described the slip lines around hardness indentations on irradiated iron and found them to be more distinct than lines in unirradiated material.' Mastel et al.' have observed channels in deformed irradiated molybdenum similar to those reported in copper. As part of a program concerned with the effect of neutron irradiation on metals, the slip-line

Jan 1, 1965

By Walter L. Maxson, Fred C. Bond

There is more information contained in a screen analysis than is ordinarily recognized, and there is an increasing need for methods of making this additional information easily available. As more comprehensive studies of crushing and grinding are made, and as the possibilities of decreased expense and increased extraction through a closer control of grinding are explored, methods of interpreting screen analyses assume an importance which they have not had heretofore. The information commonly desired, which can be determined from a complete and carefully made screen analysis, includes: (1) the size distribution of the material passing the finest screen, (2) the presence of a hard grinding fraction, (3) the location of natural grain sizes, (4) the presence of different materials with markedly different grinding characteristics, (5) the presence and amount of finely divided material such as clay, which is merely unlocked in grinding, and (6) the total surface area of the ground product. It is necessary to know the fundamental law of size distribution of a homogeneous material in order to correctly resolve a screen-analysis curve, and to understand the variations and anomalies that a sample may exhibit when compared with the ideal curve. This fundamental law was developed by Gaudin,1 who showed that when the logarithm of the per cent weight retained on any screen and passing the next larger screen in the Tyler standard screen scale was plotted against the logarithm of the screen aperture the resulting curve for the finer sizes of a homogeneous crusher or grinding-mill product would be a straight line. Gross and Zimmerley2 experimentally confirmed Rittinger's law, which states that the useful work done in crushing a homogeneous material is directly proportional to the new surface area produced; and showed that in the larger screen sizes resulting from impact crushing a

Jan 1, 1935

By Guido Del Giudice

THE term "slime-coating" is not new in the art of flotation; the phenomenon has been observed and described by Taggart;(1)? Taggart, Taylor, and Ince;(2) and by Ince.(3) Notwithstanding that flotation was introduced for the treatment of finely crushed ore, the adverse effects of slimes have been recognized since the earliest days of the process, and the Elmore, Delprat, Potter, and other processes actually specified desliming of the ore prior to treatment. The cause of this trouble has been studied and described by Taggart;(1) Taggart, Taylor, and Ince;(2) Ince; 3 Morrow and Griswold;(4) and by Gaudin and Malozemoff.(5) OLD THEORY OF SLIME-COATINGS At present, so far as published work shows, there seems to be but one theory for the mechanism of slime-coatings. Ince(3) states that they are due to attraction between electrostatic charges of opposite sign on the sulfide and, on the slime particles, supporting this theory by migration experiments in the Burton tube. He also used the microscope in conjunction with a glass cell employed by Beans and Eastlack(6) in studying migration, but met with interference from endosmosis. Several attempts have been made in the Department of Mineral Dressing at Columbia University to duplicate Ince's experiments with the Burton tube, but the results have never been convincing. Formation of precipitates which settled through the pulp levels, and evolution of gas at the electrodes, which disturbed the interface between the pulp and the distilled water above it, seriously interfered with observations. However, by use of the migration cell shown in Fig. 1, endosmosis effects and the disturbances due to precipitation and gas evolution were avoided, and distinct and reproducible migrations or absence of migration were observed.

Jan 1, 1934