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By W. C. Smith, P. J. Hickey

After a short historical background of the process evolution, this article descvibes present-day plant facilities and operating techniques utilized for high-purity bismuth production. The plant is one of the world's largest, with an annual output of some one million pounds of refined bismutlz. PREVIOUS papers1 written by staff members of Cerro de Pasco Corp. have referred briefly to the production of refined bismuth. Since the Corporation is one of the world's foremost producers of high-purity bismuth, a detailed description of the process for extracting the metal may be of general interest. Following a short historical background of the development of the actual process, this presentation will trace the progress of bismuth from its entry into the primary smelting circuits to its concentration in electrolytic lead cell slimes. Our facilities for the treatment of anode muds will be described and the extractive methods given in some detail, with particular emphasis on the techniques which result in the production of refined metal. HISTORICAL BACKGROUND Shortly after Cerro de Pasco began smelting operations at Oroya, Peru in 1922, it became apparent that the dust carried by copper converter gas contained appreciable amounts of bismuth. Although dust collection efficiency was poor prior to building of the 550-ft stack and installation of the central cottrells in 1938, a large stock of dust was accumulated during the intervening years, having the following approximate composition: Oz. per ton Ag - 11.0 Pct Sn — 0.5 Pct Pb - 49.0 Pct Zn - 6.5 Pct Bi - 2.0 Pct Insol. - 1.5 Pct Cu - 0.7 Pct Fe - 2.3 Pct Sb - 3.0 Pct S - 10.0 Pct As - 7.5 In the mid-1920's, experimental crucible melts of this dust with carbon indicated that most of the bismuth and silver, and some of the lead, could be reduced to a fairly clean bullion. Other products were a small amount of leady copper matte and a slag high in zinc, arsenic, antimony, and lead; this slag contained some tin but only small quantities of silver, bismuth, and copper. After the laboratory results had been confirmed by operation of a small reverberatory, a dust reduction furnace was constructed. The ±10 pct Bi-Pb bullion produced from this operation was stocked until 1930, when an Oroya-designed converter type furnace3 was installed for the elimination of arsenic, antimony, and some lead from the bullion. This process concentrated the bismuth from 10 to about 60 pct. By means of the bismuth process developed4 by W. C. Smith at East Chicago (1909-1914) and the discovery of a method5 for separation of lead from bismuth with chlorine gas in 1929, it became possible to begin production of refined bismuth. Unfortunately, bismuth deleaded with chlorine always contained residual chlorides, and the removal of the chlorides by caustic soda left a lead content of 0.02 to 0.04 pct. This final problem was solved6 by substitution of air-blowing for the caustic treatment, which effectively removed all excess chlorine and gave bismuth which was practically lead-free. In 1934, a pilot electrolytic lead refinery began operations at Oroya. Lead smelting was resumed in 1935 and two years later a 100-ton-per-day lead refinery was put into service. In conjunction with the latter, the present-day Anode Residue Plant was constructed. Until 1940, the plant treated both lead anode slimes and dust reduction bullion. The dust reduction furnace was shut down in that year, and all cottrell dusts (with the exception of the product from the arsenic cottrell) were mixed with pyrite and treated in a Wedge roaster to eliminate all possible arsenic. Calcine from this operation joined the sinter plant feed; hence the bismuth from the copper and lead circuits was collected in the lead bullion and subsequently in lead anode slimes from the electrolytic lead refinery. The latter source has been the only bismuth-bearing material of any consequence entering the Anode Residue Plant from late 1940 to the present. A copper refinery began operating in 1948, and the cell mud from this plant is mixed with lead slimes and processed through the same circuit, though only a small quantity of bismuth is present in electrolytic copper cell residues. BISMUTH INTAKE Present-day routes which are followed by the new bismuth feed from its entry into the primary smelting circuits to its arrival at the Anode Residue Plant are traced schematically in Fig. 1. As illus-

Jan 1, 1962

By D. Harker, E. Epremian

The constitution of the nickel-tungsten system has been studied by a number of investigators, the most recent of which are Ellinger and Sykes.1 On the basis of metallography, electrical resistivity and hardness measurements and some X ray diffraction work, they constructed a consitution diagram (Fig 1). Ellinger and Sykes report a0 for the alpha face-centered cubic phase (nickel saturated with tungsten) as 3.66?.‡ The gamma phase (tungsten saturated with nickel) is given as body-centered cubic, but no value of a. is recorded. At 43 pct tungsten by weight (approximately 20 at. pct) a beta phase is reported, but structure and lattice parameter are not known. Primarily on the basis of metallographic evidence, they conclude that beta is a new phase and rule out the possibility of formation of a superlattice since they- observe a new phase in the microstructure. Grube and Schlecht2 report an ordering reaction in a system similar to the Ni-W (Ni-Mo) and Harker3 has shown that NirMo forms a superlattice upon the pre-existing face-centered cubic lattice of the alpha phase. Elliniger arid Sykes observed a change in the diffraction pattern of a 4.3 pct W alloy upon aging and attributed it to the formation of a new phase. Thus, there appears to be some question as to the character of the beta phase reported by Ellinger and Sykes. The purpose of the present work is to determine precisely the structure and nature of the beta phase in the Ni-w system of X ray diffraction methods. Experimental Procedure One inch diameter ingots of 43.66 pct, 40.15 pct and 34.06 pct .tungsten by weight (19.8, 17.6 and 14.1 at. pct respectively) were melted and cast under vacuum from electrolytic nickel and pure wire filament grade tungsten. The ingots were soaked for 16 hr at 1300°C in a hydrogen atmosphere furnace, then swaged at this temperature and finally drawn to 0.020 in. diam wire. Some of the bar stock was retained in 1/2 in. diam rod for hardness and metallographic studies. Wire samples for diffraction work were sealed in evacuated quartz tubes and subjected to the various solution and aging heat treatments in a hydrogen furnace. X ray photograms were taken in a Debeye-Slierrer camera using copper K radiation filtered by nickel foil. Results X RAY DIFFRACTION The lattice parameters of the alpha and gamma phases at saturation were determined by an X ray photogram of the 19.8 at. pct W alloy after solution heat treatment at a temperature well within the alpha-gamma range above the peritectoid temperature (17 hr at 1150°C—oil quenched). The alpha phase was found to be face-centeted cubic with a. of 3.594 ± 0.001?, while the gamma phase was determined as body-centered cubic with a. of 3.158 ± 0.001?. Exactly the same phases and parameters were ohtained with the 17.6 at. pct W alloy for the same solution heat treatment. Thorough analysis was made of an X ray photogram of a 19.8 at. pct alloy sample in the quenched and aged condition (solution treated 1T hr at

Jan 1, 1950

By Bauer. Larry G.

The vast coal reserves in the Wyoming, Montana, North and South Dakota region are sufficient to supply the total energy needs of the United States for several hundred years. Not only is there an abundance of this sub-bituminous and lignite coal available, but it is easily obtainable by strip-mining . The overburden varies from several feet to several hundred feet. This western coal has yet another asset, namely, a low sulfur content. Whereas eastern and midwestern coal has a sulfur content of 2.5%, the upper Great Plains coal contains sulfur in the 0.5% range. The importance of the sulfur content of the coal is a direct result of federal government emission standards for sulfur dioxide (SO2). Hand (1) points out that "sub-bituminous coals and lignites have a propensity for retaining this sulfur in the ash under certain conditions which is not evident in higher rank coals." This would tend to reduce further the SO2 concentration in the combustion gases of boilers. Western coal is no panacea, however, in that it is far removed from most population and industrial centers. Furthermore, the moisture content of the coal varies from 20 to 40%. This moisture is almost exclusively inherent, that is, it is chemically and physically bound to the organic matter of the coal. It is believed that the water forms a part of the coal structure perhaps as water of hydration of organic salts or organic acids, perhaps by hydrogen bonding, or perhaps by simple adsorption (2). The primary market for this coal is the electric power industry. Lesser markets will be as coke for the steel industry and possible as a raw material for coal gasification and coal liquefaction plants.

Jan 1, 1983

By Paul Weir

BLEACHING clays have been used extensively in the oil-refining industries for a number of years. Their use in water purification is relatively recent and less extensive. They are frequently classified as (1) those naturally active and (2) those active after artificial activation with acid. Fuller's earths fall within the general group of bleaching clays and gradually the commercial term "fuller's earth" has been applied to natural clays originating, for the most part, in the south-eastern section of the United States. Bentonitic clays are usually classed as activable and are prevalent in the southwestern section of the United States.1 Bleaching clays vary considerably in chemical and physical properties throughout the country, or even in different parts of one deposit (Table 1). TABLE 1.-Physical and Chemical Composition of Different Types of Clays Composition, Per Cent Constituents and Properties Bentonite Fuller's Mud Clay (Wyoming) Earth (P Peak)' (Alluvial) Silica (SiO2) 60.0 69.6 61.67 Alumina (Al203) 19.0 14.3 20.34 Ferric oxide (Fe203) 2.8 3.90 7.70 Titanium oxide (Ti02) 0.13 0.70 1.01 Lime (CaO) 0.5 0.80 0.00 Magnesia (MgO) 2.0 1.00 0.24 Soda (Na2O) 2.4 0.40 0.31 Ignition loss 4.7 6.77 8.51 Moisture content 8.0 10.0 20.0 Isoelectric point, pH 9.2 9.2 6.5 Average swelling volume 15.0 0.0 0.0 Weight per cubic foot, lb 55.0 40.0 65.0 Material passing 200-mesh sieve, per cent 90.0 85.0 50.0

Jan 1, 1939

By William R. Webster

An investigation has been made of 500 samples of universal and sheared plates of basic Bessemer and basic open-hearth steel manufactured by the Pottstown Iron Company, the carbon-limits being 0.07 to 0.18 per cent. Through the courtesy of Mr. W. H. Morris, President, I am able to lag before the Institute the results of these tests. The samples tested were all taken from the finished material, and the chemical determinations were made on drillings from the broken test-pieces, which were sent to the chemist without giving him the heat-numbers. The results are such as to encourage me to keep on with the work, and, if possible, to have it carried out on other steels. It is kith this view that I now offer my tables in their incomplete form. My first table mas constructed by grouping the tests according to chemical analysis in various. ways, and making a rough tabulated statement, from which the ultimate strengths were worked out and carefully compared with the actual results of the tension-tests. From data thus obtained, one table after another was worked out, and by this method of "cutting and trying" I finally arrived at the results which I now present in Table I. (p. 771). I do not claim absolute accuracy, but my approximations have proved to be so close that the figures are practical data for current use at the works. The indications are that a pure iron, without carbon, phosphorus, manganese, or silicon, if it could be obtained, would give 38,000 pounds ultimate strength. This is assumed as a base, and to it is added the effect of each of the above elements, as explained below. The upper part of Table I. gives the ultimate strength due to carbon and phosphorus, and is the same for both basic Bessemer and basic open-hearth steels. The lower part gives the increase in ultimate strength due to manganese. By adding this to the amount obtained from the upper part, we have the ultimate strength of basic Bessemer

Jan 1, 1893

By S. Feuerstein

THE influence of environment on the mechanical properties of metals has been extensively studied and documented.' Most investigations have dealt with an interaction between a particular environment and a specific metal surface and the concomitant change in bulk mechanical behavior. Typical contributing media are oxide and metal film:;, electrolytes, and other surface-active agents. In the last category fall controlled gaseous environs (i.e., pressure or vacuum). Most vacuum exposure experiments prior to 1963 were conducted at pressures s>10-6 torr and elevated temperatures, or in such a manner as to prolong the exposure (e.g., by stress-rupture, creep, and fatigue). Little attention has been given to vacuum environment effects on the mechanical behavior of metals subjected to simple uniaxial deformation at room temperature. Test times and temperatures were assumed too ineffective as far as bulk changes were concerned. Further, the contribution of surface effects to the bulk mechanical behavior of metals was considered minimal. Under vacuums of the order of 1.0- 8torr and higher, molecular densities and, consequently, the rate of monolayer formation are such that exposures from seconds to days would be required for complete gas coverage. Thus, atomically clean surfaces created under ultra-high vacuum could conceivably maintain their cleanliness for time intervals orders of magnitude greater than at higher pressures. The influence of this unusual type of environmental surface phenomenon on the short-term bulk mechanical behavior of aluminum was first observed by Krame and Podlaseck in 1963.' kin equivalent effect was reported for magnesium by Williams and Nelson.3 It was concluded from these studies2,3 that vacuum and, consequently, the monolayer formation rate of the oxide, were responsible for the described changes in flow behavior. The presence of an oxide layer impedes dis- I) EXPERIMENTAL DATA: MOLYBDENUM The tensile behavior of molybdenum was investigated by the author4-6 at ambient temperature over a range of pressures from 760 to 10-10 torr. These studies revealed that the flow behavior of the bulk specimens (0.200 in. diam by 2 in. gage length) was independent of pressure on sintered (0.062 mm grain size) and arc-cast polycrystals (0.012 to 0.149 mm grain sizes) and single crystals. Since the specimens were relatively large in size, it was assumed that any flow behavior effect would be surface-limited because of the short-term deformation procedure. Strain-rate-change experiments performed to determine the activation volumes for individual specimens at 760 to 10- 10 torr further indicated that the surface flow contribution was either minimal or zero, contrary to the findings of Shen el a1.7 on aluminum. Although the flow behaviors did not change, specimen ductility did change. For the sintered material at a strain rate of 4.2 x 10-4, specimen ductility was -9 pct higher at l0- 10 torr than at atmospheric pressure (dry nitrogen). A more comprehensive investigations on this same material revealed a distinct pressure dependence, Fig. 1. Intermediate and atmospheric pressure tests were obtained by backfilling the system from l0- 10 torr with extra dry, prepurified nitrogen. Other environments (air and purified argon) were also utilized for the 760 torr experiments; the results were essentially the same as those for dry nitrogen atmospheres. Departure from the fracture strain values obtained at 760 torr takes place in the vicinity of l0-6 torr, as indicated by the scatter band; a noticeable ductility increase is apparent at l0-8 and 10-10 torr.

Jan 1, 1970

By N. A. D. Parlee, I. D. Shah

The solubilities of oxygen in liquid Ag-Au, Ag-Pt, and Ag-Pd alloys have been determined in the range of 940° to 1200°C at 1 atm pressure of oxygen using an improved Sieverts technique. The additions of gold (0 to 57 pct), platinum (0 to 27 pct), and palladium (0 to 22 pct) to liquid silver continuously decrease the solubility of oxygen in liquid silver. Activity coefficients and interaction coefficients of oxygen in these alloys and have been calculated. The interaction coefficientscan be described by the following equations: Approximate second-order interaction coefficients (pM have been calculated. The contribution of the product, pMxNM, to In yo only becomes significant at high alloy concentrations. RECENTLY several investigators1"3 have redeter-mined the solubility of oxygen in liquid silver. In general the recent findings1" for Po, = 1 atm are in good agreement with the equation:4 log %O = 695.4/T + 1.086 [1] It is established1, 2 that the solubility of oxygen follows Sieverts' law reasonably well, at least up to 1 atm partial pressure of oxygen. It should be noted that a very slight deviation from Sieverts' law has been reported by Lupis and Elliott.3 Only recently has the solubility of oxygen in Ag-X binary liquid systems received much attention, and only the Ag-Cu, Ag-Au, Ag-Pt, and Ag-Pd systems have been studied. Par lee, Sacris, and zoellners reported that the solubility of oxygen in liquid silver increases progressively with the small additions of copper (0 to 0.5 pct) up to the point where the copper oxide phase appears. Lupis and ~lliott~ have reported that the solubilities of oxygen in liquid silver decrease progressively with the additions of gold, platinum, and palladium. However, their investigation was limited to 0 to 5 pct of these alloying elements, a range too limited to satisfy the requirements of the research program of this laboratory, where the solubilities of oxygen in the range of 0 to 30 pct were required for the calculation of chemical diffusion coefficients of oxygen in these alloys. The present paper deals only with the solubilities of oxygen in these alloys while another paper will deal with the diffusion of oxygen in these alloys. EXPERIMENTAL METHOD A Sieverts technique was employed which involved an improved design of the reaction tube, Fig. 1, as described briefly in a previous communication.4 Liquid melts (70 to 100 g) were held in Norton Alun-dum crucibles. The induction furnace used had a maximum output of 2.5 kw with very fine control. This induction system had excellent stability and the final equilibrium temperatures measured by calibrated Pt-Pt, 10 pct Rh thermocouples are believed to be within ±2C. These thermocouples were checked against the melting point of pure gold wire, and the results agreed with standard tables (±l°C). Each run involved a careful sequence of operations. The sample was heated to and held at about 900°C in vacuum for 3 to 4 hr with the thermocouple in a retracted position. After melting, the melts were usually exposed to a small amount of oxygen (0.5 to 2.0 cu cm) and then degassed slowly for 1 to 2 min to remove any oxidizable volatile impurities such as carbon and sulfur as CO, CO2, SO2, and SO forth. Argon gas was then allowed to enter the system. The protection tube containing the thermocouple was then

Jan 1, 1969

By J. W. Putman, N. J. Grant, D. S. Bloom

SEVERAL recent determinations of the melting S point of pure chromium have been reported which give values of 1845°C1; 1895°C,² 1930°C,³ 1860°C,' and 1890°C.5 because of this wide spread of values, it appeared desirable to make one additional attempt to obtain a more accurate, reliable figure. bloom and Grantx recently reported a phase transformation in chromium:.--- it was desired to check this, too, in the course of checking the melting point. To accomplish this, a much higher purity chromium was required. Electrolytic chromium containing about 0.5 pct 0 was crushed to a finer size and was then annealed in highly purified, dried hydrogen at 1375°C for 100 hr. This treatment produced chromium with about 0.008 pct 0, 0.002 pct N, and negligible carbon. The balance of the impurities was 0.3 pct Fe, 0.03 pct Si, 0.004 pct S, and less than 0.001 pct Mo. This chromium was melted in a stabilized zirconia crucible under pre-purified argon, using induction heating. Temperature measurements were made with annealed wolfram-molybdenum thermocouples and a Leeds and Northrup Speedomax Recording Potentiometer. The thermocouples were annealed for 1 min in hydrogen at a temperature of about 2400°C. Each leg of the thermocouple was immersed in an ice-water mixture using mechanical connectors to the lead wires. The thermocouple tip was immersed in the molten chromium in a zirconia protection tube which introduces an error of about 3°C as a temperature drop through the walls of the tube. The weight of chromium was about 183 g. The dimensions of the melt in the crucible were about 1.25 in. diam x 2 in. high. The tip of the thermocouple was held about ½ in. from the bottom of the crucible. Two new thermocouples were used with the above set-up giving the results shown in Table I. Since this chromium is purer than that used by Greenaway, Johnstone and McQuillan,' by Carlile et al.,4 and other investigators,²,3 it is believed to be the more accurate. Thermocouple aging effects which are believed responsible for the high value of 1930°C³ were avoided in this work. This value of 1903°C is correct to about ±10°C. The right hand column lists the temperature of the a ? ß transformation on heating and the ß ? a on cooling.3 A sample curve is shown in Fig. 1. The value so determined is 1840°C + 15°C. Fig. 1 gives adequate evidence that there is a transformation in chromium at high temperatures.' References 'H. T. Greenaway, S. T. M. Johnstone, and M. K. McQuillan: High Temperature Thermal Analysis USing the Tungsten-Molybdenum Thermocouple. Journal Inst. Metals (November 1951) 19, p. 109. ²J. W. Putman, R. D. Potter, and N. J. Grant: The Ternary System Chromium-Molybdenum-Iron. Trans. A.S.M. (1951) 43, p. 824. ³D. S. Bloom and N. J. Grant: Chromium-Nickel Phase Diagram. Trans. AIME (1951) 191, p. 1009; Journal of Metals (November 1951). ' S. J. Carlile, J. W. Christian, and W. Hume-Rothery: The Equilibrium Diagram of the System Chromium-Manganese. Journal Inst. Metals (1949) 76, p. 169. 5G. Grube and R. Knabe: Ztsch. Elektrochemie (1936) 42, p. 793.

Jan 1, 1953

By T. E. Scott, R. P. Zerwekh

The charactevistics of the deformatiotz of fcc thorium were examined between 78 and 473 K. Activation energy, actiuation volume, and the temperature dependence of the flow stress were determined and conlpared uith several theories for the rate-controlling mechnnistn of the tempemture-dependent component of the flou~ stress. It was established that the Cottrell-Stokes law does not hold, even approximately, for thorium. Through consideration of the above factors and other parameters, it was concluded that the vandom solute barrier theory proposed by Friedel demonstrates the best agreement with experimental observations of the deformation of thorium below ambient temperature. THORIUM, the first metal in the actinide series of rare-earth elements, is interesting and important from two points of view. In the more practical vein, it is a potential reactor fuel. As such, it is important to know its properties. Of specific interest here are the mechanical properties of thorium. Second, no detailed information concerning the deformation characteristics of the actinide elements has been gathered to date. In view of the interesting physical and chemical properties of these metals, their mechanical behavior might reveal characteristics which could improve our understanding of the mechanisms controlling deformation of the more common metals. For example, it has been shown1 that thorium exhibits a yield point which is greatly enhanced by interstitial solute elements such as carbon. This is not a normal occurrence in fcc metals. The goal of this investigation, therefore, was to characterize the deformation of polycrystalline thorium. MATERIAL AND PROCEDURES Thorium, made by the magnesium intermediate alloy process described by Peterson et al.,2 was rolled and swaged to 0.065-in.-diam wire. The metal analysis is given in Table I. After preparation, the oxygen and nitrogen contents had risen to 308 and 60 ppm, respectively. The 0.065-in.-diam wires were cut into 2-in. lengths and annealed in a vacuum of lo-' Torr at 750°C for 1 hr, producing a grain size of 2735 grains per sq mm. The ends of the 2-in. sections were masked off so that a 1-in. gage length could be electropolished. Specimens were polished at 35 v in a solution of 6 pct perchloric acid in methanol which was maintained at 0°C . The gage diameters after polishing were about 0.0625 in. The tests were run on a screw-driven tensile machine at a constant crosshead speed corresponding to a strain rate of 0.005 min-'. The strain rate was changed rapidly after each 0.01-in. extension between 0.005 min-' and one of three higher strain rates which were selected in order to achieve strain-rate ratios of 5, 10, and 20. Tests were run at several temperatures from 78" to 473°K; most were tested at 423", 300°, 215", and 78°K. EXPERIMENTAL RESULTS Flow Stress vs Strain and Temperature. Typical true stress-true strain curves for thorium are shown in Fig. 1 for several temperatures over the range 473" to 78°K. The curves for 78", 215", 300") and 423°K were obtained from strain-rate change tests using the lower (0.005 min-') or base strain-rate values of stress. Additional tests, using the same base strain rate at different strain-rate ratios, gave curves which virtually superposed on those shown, indicating that strain-rate changes did not materially influence the work-hardening characteristics at the base strain rate. The curves for 273") 373") and 473°K were standard tensile tests at 0.005 min-'. The behavior of the flow stress with temperature is

Jan 1, 1968

By J. A. M. van Liempt

SINCE the discovery of von Laue, that a crystal forms a natural grating for X-rays, our knowledge of the structure of solids has gone forward with rapid strides. This progress is not only of purely scientific interest, but has also yielded direct technological results. One of the most valuable results is the broadening of our knowledge of the structure of pure metals and alloys. To promote these studies it is often desirable to have at our disposal pieces of metal consisting of one single crystal. As is so often the case in the natural sciences, we obtain the best results by making our earliest experiments on pure, simple materials and avoiding unnecessary complications. The Cryogen Laboratory at Leyden followed this method with much success, because the work was done at such low temperatures that the heat movement of the atoms was almost absent. Similarly we can simplify the studies of metals by leaving out of consideration the influence of the grain boundaries and the mutual influence of the crystals by using unicrystalline instead of polycrystalline metal. Methods of making single crystals have been scientifically studied during the past few years. Some methods were already known in the arts, but these have been improved and new methods have been developed. The methods for making metallic single crystals may be divided into the following groups: A. From the liquid state B. From the gaseous state C. Electrolytically D. By recrystallization in the solid state METHOD A 1. Tammann's Method. 1-Tammann succeeded in making bismuth single crystals of a maximum length of 20 cm. by undercooling the molten metal 0.1 to 0.3° G. below its melting point in glass tubes of a maximum

Jan 1, 1928

By J. A. M. van Liempt

Since the discovery of von Laue, that a crystal forms a natural grating for X-rays, our knowledge of the structure of solids has gone forward with rapid strides. This progress is not only of purely scientific interest, but has also yielded direct technological results. One of the most valuable results is the broadening of our knowledge of the structure of pure metals and alloys. To promote these studies it is often desirable to have at our disposal pieces of metal consisting of one single crystal. As is so often the case in the natural sciences, we obtain the best results by making our earliest experiments on pure, simple materials and avoiding unnecessary complications. The Cryogen Laboratory at Leyden followed this method with much success, because the work was done at such low temperatures that the heat movement of the atoms was almost absent. Similarly we can simplify the studies of metals by leaving out of consideration the influence of the grain boundaries and the mutual influence of the crystals by using unicrystalline instead of polycrystal-line metal. Methods of making single crystals have been scientifically studied during the past few years. Some methods were already known in the arts, but these have been improved and new methods have been developed. The methods for making metallic single crystals may be divided into the following groups: A. From the liquid state B. From the gaseous state C. Electrolytically D. By recrystallization in the solid state Method A 1. Tamwmnn's Method1—Tammann succeeded in making bismuth single crystals of a maximum length of 20 cm. by undercooling the molten metal 0.1 to 0.3' G. below its melting point in glass tubes of a maximum

By W. E. Horst

Flotation feed was hell constant for batch laboratory tests and continuous pilot and commercial plant tests on a spodumene ore to determine the relation.ship between flotation behavior and the size and type of flotation machine. Results. showed that additional retention time would be needed in the plant flotation circuit to duplicate laboratory or pilot plant performance when operating Dariables of the. plant flotation machines remained unchanged. During the past few years of operation at Kings Mountain, N. C., full-scale flotation has generally yielded poorer metallurgical results than those obtained in the laboratory or pilot plant. After 2 min in each size of Denver flotation machine in the spodumene rougher circuit, pilot recovery (41.7 pct) was almost three times that of the plant (13.6 pct) and about twice that of the laboratory (21.0 pct). Pilot and commercial plant data are based on continuous operation, and laboratory results on batch testing of rougher performance. The ore is a pegmatite containing spodumene, feldspar, quartz, mica, and amphibolite. Data were accumulated to evaluate the scale-up relationships between laboratory, pilot plant, and plant flotation cells. Flotation rate constants and dimensional analysis were used to define the relationship existing between flotation behavior and scale of operation. Measuring Flotation Rates: Efficiency of the rougher stage was measured by flotation rate, defined as the recovery that can be attained within a given time." • The problem of measuring flotation rates has been studied by many investigators, whose methods have varied. Published studies an flotation kinetics have been summarized recently by Gaudin.l When comparing flotation rates, it is more satisfactory to compare straight line relationships between recovery and flotation time than exponential curves resulting from plotting cumulative recovery vs cumulative flotation time. To convert the exponential curves into straight line relationships, rate equations were applied similar to those used in chemical kinetics to study the velocity of chemical reactions. Two rate equations have been used in this investigation to measure efficiency of the various cells: 1.5 order Rate Equation dR/dt=k (A-R)1.0 [Eq.1] Second Order Rate Equation dR ---- - K(A - R)2 [Eq. 2] dt Upon integration Eq. 1 becomes 1/(A-R)1/2=k/2 t+1/A1/2 [Eq. 3] and Eq 2 becomes: or fEq. 4] t/R=1/A2K+t/A [Eq. 4] where R = cumulative recovery [percent recovery of total value (spodumene) in flotation feed]. A = initial concentration, pct (100 pct of mineral to be separated). t = flotation time (minutes). k = flotation rate constant for 1.5 order rate equation [units: 1/(percent) 0.5 (min)1. K = flotation rate constant for second order rate equation [units: 1/(percent) (min) 1.

Jan 1, 1959

By Marsh S. Watson, Robert A. Howard

The effect of depth of formation penetration by casing perforations has been studied by means of an electrolytic model. It is found that the relative productivity of perforated casing is profoundly affected by the depth to which the formation is penetrated. The first in. of penetration i: of especial importance. A scaling equation which was shown to agree with experimental results at zero penetration is used to calculate the relative productivity of a waled down casing with scaled down perforations. INTRODUCTION In an earlier piper' the authors showed that the point sink representation of casing perforations is inade- quate. It was Pointed out at that time that while the electrolytic model results were a marked improvement over point-sink calculations, they still left a great deal to be desired in that the electrolytic model represented a case not realizable in practice, namely, a clean hole through the casing but undisturbed formation on the other side of the casing. Obviously, to be effective, the perforation must penetrate a finite distance into the producing formation. It was the purpose of the present investigation to find how the relative productivity of perforated casing varies with depth of penetration. The term "depth of penetration" as used in this paper refers to the distance which the perforation penetrates the producing formation. The amount of casing and cement penetrated is not taken into account, a fact which is discussed more fully later. The "casing radius," therefore, is to be interpreted as the radius of the boundary between cement and formation wall. in cases where the casing is not in contact with the formation wall. APPARATUS The electrolytic model experimental setup was identical with that described in the previous paper' except that the platinum electrodes were now allowed to project from the lucite cylinder by varying amounts. When fewer than eight electrodes were used, the unused ones were covered with a coat of insulating material to minimize disturbances to the current flow-lines. Comparison runs made with the unused electrodes uninsulated, however, showed that the values of Q/Q0 so obtained did not vary by more than the experimental error from the values obtained with the unused electrodes insulated RESULTS The variation of relative productivity* with perforation density is shown for various penetration depths from 0 to 4.03 in. in Fig. 1. It will be seen that even one in. of penetration into the formation results in a huge increase in the relative productivity. Moreover, as-the depth of penetration increases, it becomes less and less advantageous to use large perforation densities, 80 pel. cent of open hole productivity being obtained with only three 0.5-in. diameter holes per foot when the penetration is 4.03 in.

Jan 1, 1950

By Hsun Hu, R. S. Cline

The effect of rate of deformation on texture formatiotz has been studied with cube-oriented single crystals of 3 pct Si-Fe, compressed 80 pct at two widely different rates. Compression at a low rate (crosshead speed, 0.1 ipm) produces large orienta-tional changes and coarse deformation bands, whereas little change in orientation is observed, particularly at the surface of the crystal, when compressed at a high rate (impact velocity, -500 ips). Thin plates of mechanical twins are produced at the high rate, but their contribution to the deformation texture is practically negligible. The crystal deformed at a high rate has a lower hardness and a more uniform dislocation structure and is morc resistant to recrystallization. There is also a dilference in the recrystallization texture between the slowly and rapidly compressed crystals. These results indicate that plastic flow is less "turbulent" at high strain rates than at low strain ratcs. THE behavior of metals under high-speed deformation has been the subject of wide study in the past decade. Most of these works were concerned with mechanical properties during testing at high rates of loading, the resulting structures, and the theoretical aspects of the observed phenomena. The present status of knowledge and research activities in this field has been documented in recent publications.17' There is, however, very little information available in the literature concerning the effect of high-speed deformation on the texture formation in metals. The possibility of an effect of rate of deformation on texture is suggested by the microstructural differences observed between normally and very rapidly deformed samples. Aside from the strong tendency for twinning (and phase transformation in certain metals) in high-speed deformation, the slip-line patterns and the dislocation configurations show marked differences as a result of large differences in the strain rates. For instance, in mild steel in static and dynamic compression, Campbell and co-worker3,4 observed that coarse slip occurred on several systems in specimens deformed at normal strain rates, whereas specimens deformed rapidly showed only fine slip on fewer systems, the slip-line pattern being very similar to that in specimens deformed at low temperatures and at normal strain rates. The absence of multiple slip was also noticed by Dieter5 in shock-loaded nickel. The dislocation configuration in an iron shock loaded at 70 kbar pressure was shown by Leslie et al.6 to be similar to that produced by light rolling at low temperature—the dislocation lines were mostly straight and uniformly distributed. These observations suggest that the mode of deformation at high strain rates is notably different from that at low strain rates. Consequently, the nature and the extent of lattice reori-entation during deformation should also be different. This investigation was undertaken to test this idea. MATERIAL AND METHOD The remaining part of a single-crystal ingot of a 3 pct Si-Fe alloy,* prepared for an earlier investi- gation,1 was used in the present studies. Specimens 9/16 in. square and 0.365 in. thick were cut from this ingot with (001) planes parallel to the square surfaces, and the [loo] and 1010] directions parallel to the edges of the specimen, within ±1 deg. These machined crystals were etched to remove distorted metal, and annealed at 1300°C for 24 hr in a purified helium atmosphere. The annealed crystals had a hardness of 161 Dph. The crystal orientation was rechecked with X-ray back-reflection techniques. In high-strain rate experiments the crystal was compressed in a Dynapak machine to approximately 80 pct reduction in thickness (from 0.360 to 0.070 in. with an impact velocity of -500 ips). Thus, the duration of loading was approximately 6x 10-4 sec, and the average strain rate was about 103 sec-1. As a result of this rapid, severe deformation, the specimen became a roughly circular thin disc. The original shape of the crystal, however, could still be recognized by a diffusely outlined square area in the center of the disc. For compression at a low speed, the crystal was deformed in a universal testing machine at a rate of crosshead movement of 0.1 ipm. Compared with

Jan 1, 1965

By G. L. F. Powell, L. M. Hogan

Samples of silver and Ag-O alloy, 0.12 wl pet, have been undercooled to a maximum of 250°C by melting in a slag of commercial soda-lime glass. Grain refinement occurred in undercooled silver samples whet the degree of undercooling exceeded a critical value which varied from 153° to 175°C, depending on the melting conditions. In under cooled Ag-0 samples, the grain structure was fine and equiaxed at degrees of undercooling larger than 50oC. The grain refinement in both silver and Ag-0 alloy samples was the result of recrystallization during or immediately following freezing. When the oxygen content was increased, the degree of undercooling at which recrys-tallization occurred decreased. INVESTIGATIONS of the grain structure of strongly undercooled melts of nickel and cobalt1-4 have revealed a change in room-temperature grain size as a function of undercooling. At large degrees of undercooling the grain size was fine, but samples undercooled by smaller amounts exhibited a much coarser grain structure. The reported undercooling at which this grain size transition occurred in nickel varied between 140° and 175'C undercooling. Walker1 attributed this grain size change to an enhanced nuclea-tion rate. Cavitation at a melt-solid interface was con sidered to generate a high-pressure wave. This, in turn, produced nucleation in the liquid as a result of an elevated freezing point increasing the undercooling in the melt. A similar grain size transition was observed in undercooled silver between 133° and 153°C undercooling.5 The grain size transition in undercooled silver was found to be dependent on oxygen con tent. More recently, the authors5 showed that a simila transition occurred in an undercooled Cu-O alloy, =0.08 pet, but not in oxygen-free copper undercooled more than 200°C. The transition was attributed to recrystallization of the solidified grains after freezing; the greater the degree of undercooling, the more complete the recrystallization. In view of this effect of oxygen content on grain size transition, additional undercooling experiments were carried out with silver. This paper reports the results of these studies on silver and Ag-O alloys undercooled more than 50°C EXPERIMENTAL 1) Materials. The silver was supplied by Matthey Garrett Pty., Ltd., as fine granulate, silver mini' mum 99.9 pet, and contained the trace impurities shown in Table I. The silver originated from two different refineries resulting in the difference in impurity content shown in Table I. However, the variation in composition had no discernible effect on the undercooling behavior. Samples of the silver were melted in an open-ended, vertical, cylindrical resistance furnace, wound with Kantha] wire, the temperature of which was adjusted by means of a variable transformer, 2) Melting and Undercooling. Bulk samples of silver were undercooled by preoxidation and removal of oxidized impurities in a glass slag, as previously described,5 but special precautions were necessary to allow comparison between oxygen-free silver and a Ag-O alloy. Samples free of oxygen were prepared by first melting weights of granulate varying from 200 to 400 g in clean vitreous silica crucibles in air for approximately 15 min. A sample was frozen and a complete glass cover formed over the top surface by adding granulated glass rod. The sample was then melted and frozen several times until no oxygen bubbles appeared in the glass slag. Subsequent thermal analysis indicated that the oxygen content was negligible. The glass acted as an efficient barrier to absorption of oxygen from the air. Ag-O alloys were prepared by melting silver in silica crucibles with only a partial cover of glass, so that the top surface of the melt was in contact with air. The silver was held molten in air for several hours at 1000° to 1050°C, in the expectation that the oxygen in solution would reach equilibrium with atmospheric oxygen. At T - 1000°C the equilibrium oxygen content was calculated as 0.12 wt pet O, using Sieverts law and Eq, [l], derived by Mizikar et a!.7 from the data of Sieverts and Hagenacker8 for 1 atm of oxygen:

Jan 1, 1970

By C. S. Yust, Lida K. Barrett

The change in shape of the void in a sirzterir~g copper mass has been investigated as a juntction of' density. A serial sectioning' technique was used to eoaltrate the irregular shape of the void at two levels qf density. A measure of the void size and configuration, the proximity number, is defined and used to describe the progress of void removal. The process of. void removal deduced front the observations of this study contrasts with current sintering models in that it takes into account the irregularity of structure of a sintering mass and demonstrates that isolated Porosity does not occur first as spherical pores, but as large, definitely nonspherical sections of the void void volume. The process of sintering, about which there is much practical and theoretical knowledge, has evaded a direct and thorough analysis despite the intensity with which it has been studied for 60 years or so. This is due, of course, to the complex structure of a sintering mass and the inability to observe directly the development of a fully dense solid from the initial particulate arrangement. Extensive theoretical analyses have been based on the adoption of one or another of several model systems, that is, by visualization and analysis of some sort of regular assembly or arrangement of geometric "particles" approximating the conditions of a sintering mass. It seems appropriate at this time to try to examine experimentally in some detail the extent to which a sintering mass of irregular particles dlffers from these models. Many models deal with neck growth and the initial stage of sintering and follow the direction established by ~ucz~nski' in 1949 for the sintering of spheres to flat plates. Recently Johnson and cutler2 have adapted these models to sintering of powder masses. coble3 has presented a mathematical model for sintering that applies to the middle and final stages of the process. These papers, without exception, assume a regular geometry, generally spheres in contact in a regular array. Rhines~ and coworkers, however, are studying the sintering process by applying a model based on the topological concept of genus which permits them to consider an irregular structure. whites has described the various models with the exception of that of Rhines et al., and the assumptions on which they are based and their shortcomings. The present paper examines the geometric changes that occur in the powder mass during sintering by examination of the void. The method is to analyze a series of partially sintered structures and to propose from this analysis the sequence of events which occur in the removal of the void space as a sintering mass progresses from a collection of individual particles to a solid body. The irregular nature of the stacking of particles and of the particles themselves will be taken into account. The significant points derived from this study are: first, accurate reconstructions of the irregular void shapes are presented; second, it is clearly established that closed porosity occurs first as widespread volumes of interconnected porosity, definitely nonspherical in shape; and third, a new factor, the proximity number, is defined, which serves in this paper as a tool for describing the void shape changes observed, and which will be used in a later paper as part of the basis of a mathematical model for sintering. While the specific material studied is copper, the observations are thought to be relatively general as indicated by comparison of the results with partially sintered structures in other materials presented in the literature, both metallic and nonmetallic. EXPERIMENTAL PROCEDURE Four series of specimens representing progressive stages of the sintering process were prepared by sintering high-purity copper powder for various time periods. A relatively large particle size was used so that the void-solid interface could be readily distinguished at low magnification. In three series of specimens a loose stacking of particles was obtained by pouring powder into an alumina mold and lightly tapping the mold. The green density of such compacts was approximately 40 pct of theoretical density. Two of these three series utilized irregularly shaped particles in the size range -230 +325 mesh, one series sintered in vacuum and one in hydrogen at 950°C. The third series of loosely stacked particles consisted of spherical particles in the size range -270 +325 mesh, sintered in hydrogen at 950°C. A fourth series was prepared from compacted irregular particles sintered in hydrogen at 950°C. The specimens for this series were formed by lightly pressing the irregularly shaped particles in a steel die; the green density of the pressed pellets was approximately 60 pct. The irregularly shaped particles used in this study are shown in Fig. 1. The density of these particles, measured by a toluene picnometer technique, is 98.2 pct of theoretical density. Each particle is highly convoluted, and in some instances appears in cross section to contain internal porosity. The density measurement, however, indicates that completely enclosed porosity is very small so that the individual particles have a highly irregular surface but are essentially fully dense copper. Therefore, most of the void space that appears in two dimensions to be isolated within the particle is actually at the particle surface and connected to the external void in the dimension not included in the plane of the cross section. The void space that appears as void surrounded by the par -ticle or within folds in the particle w~ll be r~fc\r?

Jan 1, 1968

By Donald Barton

THIS paper outlines a time-saving graphical method of calculation for application to the interpretation of observations with the Eötvös torsion balance. Preliminary to the treatment of this short cut method which has been found practicable, the principal formu-las by which the student of interpretation can calculate the gradient and differential curvature produced by different types of bodies in different types of situa-tions are presented and discussed. It is necessary to split most geologic bodies into a series of simpler ones for which not too complicated formulas are avail-able. The gradient and differential curvature effects are calculated for each of the simple bodies and then summed to the total effect for the whole body. The calculations are considerable in number and, though more tedious than difficult, should be' entrusted to an experienced calculator. Considerable facility in qualitative interpretation can be acquired by the geophysicist from experience and from a thorough study of the types of gradient and differential curvature anomalies produced by the dif-ferent types of possible structural situations. How-ever, semi-quantitative calculations' of the probable structure bring out many relations that are not evident in a simple inspection of torsion balance results ; it throws out as impossible or improbable certain of the alternative structural possibilities that may seem equally probable under simple inspection of the results; it will determine more accurately the position of the crest of the structure; and reduce considerably the un-certainty in the interpretation and it is necessary to intelligent interpretations. The calculation of such cross-sections consists of a trial-and-error calculation of a body that will give gradient and differential curvature effects as closely as possible the same as those observed. From his knowledge of the gradient and differential curvature produced by different types of bodies, the geophysicist sketches a tentative cross-section of the structure as indicated-to him-by the observed results of the torsion balance survey, and the calculator then splits the struc-ture into blocks, and calculates the gradient and differ-ential curvature block by block. If, as rather usual, the calculated .gradient and differential curvature pro-files diverge considerably from, the respective observed ones, it is necessary to add and subtract blocks from the cross-section until a close agreement is obtained .between the calculated and observed profiles. The com-plete calculations have to be gone through for each block that is added or subtracted.

Jan 9, 1928

By PAUL DYER MERICA

PAUL DYER MERICA, who has been awarded the James Douglas Gold Medal for his achievements in non-ferrous metallurgy, is a Hoosier, having been born at Warsaw, Ind., in 1889. His father, a clergyman and educator, was president of the University of Wyoming from 1908 to 1913. After graduating from the University of Wisconsin in 1908, young Merica (not yet twenty years of age) went to China, where he was professor of chemistry in Chekiang Provincial College, Hangchow, until 1911. He then went to Germany to s t u d y and was fortunate enough to receive his Ph.D. from the University of Berlin just a few months before the outbreak of the World War in 1914. Returning to America, his first position was as special investigator at the En¬gineering Experiment Station of the University of Illinois, but before the year was out he joined the staff of the U. S. Bureau of Standards as associate physicist. Since 1918, he has been superintendent of research for the International Nickel Co. His work during those years is excellently summarized in the following quotation from the statement of Zay Jeffries recommending him for the award.

Jan 1, 1929

By Walter Harvey Weed

CONTENTS. [ ] INTRODUCTION. THIS paper deals with certain ore-deposits whose structural features or mineral contents (or both) result, directly or indirectly, from igneous intrusions and their after-effects. It is largely a discussion of contact metamorphic ore-deposits based upon the physical changes in rocks due to contact action. It involves a classification of ore-deposits only so far as is abso-

Jan 1, 1913

By Frederick N. Rhines, William A. Anderson

The investigations of Wymanl have demonstrated that copper deoxidized with several of the commonly used agents that confer immunily to ordinary hydrogen em-brittlement can still be embrittled if it is annealed alternately under oxidizing and reducing conditions. During the oxidizing cycle, oxygen diffuses into the copper and frequently deposits a subscale composed of the oxide of the residual deoxidizing agent. Upon subsequent reduction with hot hydrogen, the copper becomes ruptured along the grain boundaries to a depth sharply limited by the previous penetration of oxygen as delineated by the inner boundary of the subscale. Obviously the sensitivity to this kind of hydrogen embrittlement is engendered by the introduction of oxygen during the oxidizing anneal, but beyond this the mechanism of the process, and hence the controlling factors, remain obscure. There are several possibilities: (I) oxygen dissolved in the copper matrix of the subscale may, upon cooling prior to the hydrogen anneal, precipitate as cuprous oxide which is subsequently reduced by hydrogen as in the familiar case of hydrogen embrittlement; (2) oxygen in solid solution in copper may itself confer susceptibility to embrittlement by hydrogen; (3) the normally refractory oxides such as those of aluminum, silicon and titanium may themselves be reduced by hydrogen when in contact with copper; or (4) the precipitated oxides of the subscale may be complex compounds such, perhaps, as SiO2.Cu2O, which are partially reduced by hydrogen. These possibilities have been examined, and it has been concluded that the first three and possibly the fourth are operative collectively or individually under more or less predictable conditions. Effect OF Precipitated Cuprous Oxide and Dissolved Oxygen The literature provides no definite proof that oxygen in solid solution in copper can confer susceptibility to hydrogen embrittlement; indeed, the research of Leiter2 seemed to indicate the opposite—that to produce the effect, cuprous oxide must be present in massive form and in a more or less continuous network along the grain boundaries. To test this point, pure copper has been annealed in hydrogen under conditions designed to ensure the presence in various samples of: (I) precipitated cuprous oxide, (2) dissolved oxygen only, and (3) no oxygen in any form. Very pure copper" said to contain no oxygen and no spectro-scopically detectable traces of any other element (that is, no individual detectable impurity in quantity greater than 0.0001 per cent) was used. Strips of this material cold.-rolled 75 per cent to 1/8 in. in thickness were subjected to the following treatments, the results of which are noted:

Jan 1, 1941