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By E. A. Gulbransen, K. F. Andrew

Thermodynamic information on the solubility of hydrogen in exothermic metals is limited. Thus, the overall solubility decreased as the temperature rose, which suggests the heat of solution of hydrogen in the metal is negative; yet the terminal solubility in the metal phase increased, which suggests an endothermic reaction. A thermodynamic analysis, therefore, was made of the several equilibria involved when hydrogen dissolved in the metal. Equations were derived expressing the solubility, terminal solubility, and decomposition pressures of hydrogen in terms of the heat, entropy, and free energy of solution of hydrogen in the given phase. The relations between the thermodynamic functions for the a-zirconium and 8-hydride phase were developed. The thermodynamic quantities were determined experimentally by the measurement of the decomposition pressures over a broad composition and temperature range. Two new methods of analyzing the experimental data were developed for determination of the terminal solubility. STUDIES', ' of the impact strength of zirconium at room temperature indicated that small quantities of hydrogen, of the order of 10 parts per million, embrittles the metal. Micrographic' and X-ray diffraction' studies showed this embrittlement to result from the precipitation of a second phase upon slow cooling. These studies suggested that the terminal solubility of hydrogen in the metal phase increased with increase of temperature. This behavior appeared to contradict the effect of temperature on exothermic hydrogen occluders such as zirconium. For these metals, the solubility of hydrogen should decrease with increase of temperature. Before these facts could be understood, a thorough analysis of the several equilibria was essential. It was the purpose of this paper to consider the several equilibria involved when hydrogen was reacted with zirconium from both the theoretical and experimental points of view. Since the overall solubility of hydrogen in the metal has been considered by a number of workers, it was proposed to study the composition range 0 to 6 atomic pct H in detail. Literature Schwartz and Mallett' determined the terminal solubilities of hydrogen in the metallic phase from diffusion studies. They extrapolated concentration-penetration curves to the boundary between the solid solution phase and the hydride phase at the surface. Their results showed values of 2.6 atomic pct at 400°C and 5.2 atomic pct at 500°C. Extrapolations of the data to room temperature suggested very low values for the terminal solubilities. This study confirmed the hydrogen embrittlement results and indicated that the terminal solubilities increased as the temperature was raised. The solution of hydrogen in zirconium over the complete concentration range was studied by Hall, Martin, and Rees3 and by others. The results showed that hydrogen was absorbed up to a maximum composition of 66 atomic pct or ZrH This composition represented the t-hydride phase. The maximum amount of hydrogen absorbed increased with pressure and decreased with temperature. Due to this temperature behavior, zirconium was classed as an exothermic occluder." In 1930 Hägg studied the crystal structures of the Zr-H alloys over a broad composition range. Four hydride phases were found. However, the range of homogeneity of the several phases was not studied. Gulbransen and Andrew" recently studied the phase diagram of this system by X-ray diffraction methods and by a thermodynamic method based on decomposition pressure measurements. The results showed that only two hydride phases existed for low temperatures, the 6 and the .-phases of Hagg.' Both phases had broad regions of homogeneity. The lower limit of the two-phase region of a and d-phases suggested a terminal solubility of 4 atomic pct at 500°C. This value was in agreement with the results of Schwartz and Mallett.' To avoid hydrogen embrittlement at low temperatures, it was necessary to heat the metal in high vacuum at elevated temperatures. To choose the conditions of temperature and high vacuum, it was

Jan 1, 1956

By R. W. Armstrong, D. H. Feisel

Self-diffusion in pure crystalline solids has been described through extension of the Cohen and Tum-hull volume -fluctuation model originally proposed for diffusion in simple liquids. It is shown, for a number of crystalline solids, that the self-diffusion coefficient, D, obeys the relationship where a is the lattice spacing, v the Debye frequency, Z' the lattice-volume fluctuation per atom required for a diffusion jump, and (?V/Vo) the relative increase in the lattice volume resulting from thermal expansion between O°K and the temperature under consideration. The calculated value of Z' is dependent upon the difiusion mechanism and the lattice geometry. ThE need for an increased understanding of mass-transport processes in crystalline solids has resulted in much research to determine rates of self-diffusion.' For several metals (e.g., copper, silver, and iron), the experimental values of the self-diffusion coefficient, D, have been determined over a large interval of temperature and the accuracy of D has been investigated through repeated experiments. Also, a number of empirical and theoretical diffusion studies have established a rational basis for understanding the D values for the different elements.2"6 The empirical diffusion analysis by Sherby and simnad6 supplied the main stimulus for the present study. Sherby and Simnad, reviewing the self-diffusion data for a substantial number of pure crystalline solids, suggested that sufficient data were available to establish with some certainty the apparent intrinsic material properties which influence D. Without explicit regard for any mechanism of diffusion, these investigators obtained an empirical relationship for D which correlated the self- diffusion coefficient for each element with the melting temperature, crystal structure, and valence of the particular element. Their analysis is only unsatisfactory in that the effect on D of crystal structure is not very clear and the valence to be assigned to an element is not always straightforward. The present study is an attempt, from a very different viewpoint from that of Sherby and Simnad, to establish a basis for understanding the self-diffusion coefficients for crystalline solids. This analysis was undertaken for the purpose of developing a general expression for D which would explicitly depend on the mechanism of diffusion. The main result of the study is that diffusion in crystalline solids may be described in terms of a volume-fluctuation model which was originally proposed by Cohen and Turnbull7 to describe diffusion in simple liquids. The model appears to be useful for predicting self-diffusion coefficients in crystals. The following sections describe the volume-fluctuation model for diffusion, the application of this model to crystals, and the resultant agreement with experimental data. 1) THE VOLUME-FLUCTUATION MODEL FOR DIFFUSION Cohen and Turnbull7'8 developed their model for liquid self-diffusivity for the purpose of describing certain properties of liquids, glasses, and the liquid-glass transition. A hard-sphere model for the liquid structure is used. In this model, the size of a spherical molecule or atom is fixed for all temperatures by the interatomic spacing at the absolute zero of temperature. At any temperature above O°K, the atom is viewed as being contained within a larger spherical cage defined by the interatomic spacing of the atoms at that temperature. A random distribution of varying cage sizes is assumed to exist in the liquid. An individual diffusion jump occurs when the free volume of an atom (the volume of the cage containing the atom minus the volume of the atom) is large enough for the atom to jump out of its cage. With this physical picture of diffusion in liquids, Cohen and Turnbull derive the following equation for self-diffusivity: D=Doe-yv*/vf [1] where Do is the product of three factors which are the diffusion-path geometry, the diffusion-jump distance, and the velocity of the diffusing atom, v*

Jan 1, 1964

By F. Gordon Smith

ALTHOUGH several geological indicators of the critical type are known, including quartz inversions and decomposition of hydrous minerals such as serpentine, there are very few of the general type. Solid solutions are excepted, but the limitations of use are very restricted and interpretations are sometimes ambiguous. General methods for determining temperature and pressure conditions during the crystallization of minerals would have considerable scientific and economic value. It is not the purpose of this paper .to, discuss the various methods of geological thermometry and barometry, but to present one general method, applicable to all minerals, and to describe what progress has been made in the methods of measurement. The general method, in. brief, is a study of the stress conditions in and around various types of foreign inclusions which are trapped in minerals during growth. The method depends upon the fact that any homogeneous gas, liquid, or solid will in general have coefficients of thermal expansion and volume compressibility different from those of any given mineral. Therefore stress must develop in and around all types of inclusions in minerals if the temperature or the pressure, or both, are changed from the conditions which prevailed during the growth of the mineral. The methods of measurement consist of determinations of the temperature-pressure conditions of fit of the inclusions in the host mineral. The types of inclusions in minerals are: 1-gas, or liquid plus vapor, when observed at room temperature, due to crystallization under pneumatolytic conditions; 2-liquid, or liquid plus vapor when observed at room temperature, due to crystallization under hydrothermal conditions; 3-glassy solid, or devitrified glass, due to crystallization under magmatic or high temperature metamorphic conditions, in a siliceous liquid; and 4-crystals, due to overgrowth of other minerals crystallizing simultaneously or of other minerals which crystallized previously. A survey of the literature shows that much valuable earlier work on inclusions, especially that carried out in England in the last century, has dropped out of current knowledge. The following is a brief summary of the significant, contributions to the problem up to the present day. Davy in 1822 asserted that fluid inclusions in minerals consist of an aqueous solution of salts and a gas bubble, the whole being either at lower or higher pressure than atmospheric.1 At intervals from 1823 to 1862, Brewster contributed information concerning other types of inclusion consisting of 1-aqueous solution, a much more expansible liquid, and a gas; 2-aqueous solution, salt crystals, and a gas; and 3-the very expansible liquid and a gas. The very expansible liquid fills the gas space between 20° and 30°C. Compression strain effects were seen around inclusions in diamond, topaz, and other minerals.2-6 Sorby in 1858 and 1869 further advanced the study begun by Davy, stating that fluid inclusions represent a sample of the mother liquor of crystallization and that the degree of filling of aqueous inclusions at room temperature defines the temperature-pressure relations during formation of the host. The degree of filling may be measured by determining the minimum temperature of filling of the inclusion by the liquid phase. The very expansible liquid in some fluid inclusions is liquid. carbon dioxide. The temperature at which salt crystals in fluid inclusions completely dissolve in the fluid is the minimum temperature of formation. Inclusions of glass or devitrified glass indicate crystallization from a melt. Inclusions of crystals in minerals are often centers of strain, which may be seen by optical effects or by radial tension cracks. Sorby realized that an analysis of stress-strain relations about inclusions could be used to provide precise data on the temperature of crystallization, but the matter was never pursued.7,8 Hartley (1876, 1877),9,10 Hawes (1881),11 Wright (1881),12 Johnsen (1920),13 and Holden (1925)14

Jan 1, 1952

By C. O. Lee, R. H. Feierabend, Z. W. Bartlett

DESPITE the fact that American brimstone production has increased 2 times since the prewar period 1935-1939, the demand for sulphur exceeds the supply. To alleviate this situation efforts are being made to increase the production of sulphur and bring the shortage to an end. The most important developments are being undertaken on the Gulf Coast. One new brimstone mine has been put into operation and three others are being developed. These projects are expected to account for a large part of the additional sulphur production now anticipated for the free world.'.' Except for a small amount of byproduct sulphur from sour natural gas and refinery gases, American brimstone is produced by the same process devised by Frasch 60 years ago, consisting essentially of the injection of superheated water at about 325°F into sulphur-bearing formations through wells which are drilled from the surface by standard oilfield methods. Sulphur deposits vary in depth from a few hundred feet to 2500 ft from the surface; in a typical deposit the sulphur occurs as crystalline aggregates in porous limestone and gypsum in concentrations varying from 5 to 40 pct, the thickness of the formation ranging from a few feet to several hundred.3 The deposits are usually surrounded by formations impermeable to the flow of hot water, the top and sides being enclosed by impermeable sediments and the bottom by dense impermeable anhydrite. As the hot water leaves the well bore, it percolates through the formation and transmits its heat to the rock and sulphur. When the sulphur reaches 240°F it melts, separates from the rock, and flows through the hot channels downward to the bottom of the well. Here it is freed from incoming water and from formation water, which saturates the porous rock, by gravity separation, liquid sulphur being 1.8 times as heavy as water. It then is pumped to the surface in a relatively pure state, 99.5 pct or better. Chief contaminants are organic impurities, such as petroleum residues, which are soluble in sulphur and tend to discolor it.' Sixteen deposits of commercial magnitude have been discovered in the Gulf Coast area. Five of these deposits have been depleted and abandoned with production totalling more than 26,886,000 tons. Eight properties are operating and have produced 65,875,-000 tons to Jan. 1, 1952, for a total Frasch-type production of 92,761,000 tons. Three new deposits are under development. Aforementioned deposits are listed in Table I. Each of these deposits has been found in the cap-rock overlying shallow intrusive salt plugs or domes and buried in several hundred to as much as 2500 ft of sediments. All salt domes do .not contain sulphur; only 16 sulphur deposits have been found in a total of 231 salt domes which are known to exist in the Gulf Coastal states of Texas, Louisiana, Mississippi, and Alabama. Ten of the salt domes lie in the Gulf of Mexico offshore from the Texas and Louisiana coasts. Additional offshore domes may be found, but their value as a sulphur potential is questionable owing to the great hazard and high cost that can be visualized at these exposed locations where depths of water reach 50 ft. Marsh operations of Freeport Sulphur Co. are in the southeast section of Louisiana. In general, the country is low, flat, relatively uninhabited marshland broken by many shallow lakes and bayous which extend for irregular distances inland. Geologically, the coastal area is of sedimentary origin, having been built up gradually under the sea by deposition of material carried down by large streams to their deltas. Offshore bars were formed enclosing

Jan 1, 1953

By C. O. Lee, Z. W. Bartlett, R. H. Feierabend

DESPITE the fact that American brimstone production has increased 2 times since the prewar period 1935-1939, the demand for sulphur exceeds the supply. To alleviate this situation efforts are being made to increase the production of sulphur and bring the shortage to an end. The most important developments are being undertaken on the Gulf Coast. One new brimstone mine has been put into operation and three others are being developed. These projects are expected to account for a large part of the additional sulphur production now anticipated for the free world.'.' Except for a small amount of byproduct sulphur from sour natural gas and refinery gases, American brimstone is produced by the same process devised by Frasch 60 years ago, consisting essentially of the injection of superheated water at about 325°F into sulphur-bearing formations through wells which are drilled from the surface by standard oilfield methods. Sulphur deposits vary in depth from a few hundred feet to 2500 ft from the surface; in a typical deposit the sulphur occurs as crystalline aggregates in porous limestone and gypsum in concentrations varying from 5 to 40 pct, the thickness of the formation ranging from a few feet to several hundred.3 The deposits are usually surrounded by formations impermeable to the flow of hot water, the top and sides being enclosed by impermeable sediments and the bottom by dense impermeable anhydrite. As the hot water leaves the well bore, it percolates through the formation and transmits its heat to the rock and sulphur. When the sulphur reaches 240°F it melts, separates from the rock, and flows through the hot channels downward to the bottom of the well. Here it is freed from incoming water and from formation water, which saturates the porous rock, by gravity separation, liquid sulphur being 1.8 times as heavy as water. It then is pumped to the surface in a relatively pure state, 99.5 pct or better. Chief contaminants are organic impurities, such as petroleum residues, which are soluble in sulphur and tend to discolor it.' Sixteen deposits of commercial magnitude have been discovered in the Gulf Coast area. Five of these deposits have been depleted and abandoned with production totalling more than 26,886,000 tons. Eight properties are operating and have produced 65,875,-000 tons to Jan. 1, 1952, for a total Frasch-type production of 92,761,000 tons. Three new deposits are under development. Aforementioned deposits are listed in Table I. Each of these deposits has been found in the cap-rock overlying shallow intrusive salt plugs or domes and buried in several hundred to as much as 2500 ft of sediments. All salt domes do .not contain sulphur; only 16 sulphur deposits have been found in a total of 231 salt domes which are known to exist in the Gulf Coastal states of Texas, Louisiana, Mississippi, and Alabama. Ten of the salt domes lie in the Gulf of Mexico offshore from the Texas and Louisiana coasts. Additional offshore domes may be found, but their value as a sulphur potential is questionable owing to the great hazard and high cost that can be visualized at these exposed locations where depths of water reach 50 ft. Marsh operations of Freeport Sulphur Co. are in the southeast section of Louisiana. In general, the country is low, flat, relatively uninhabited marshland broken by many shallow lakes and bayous which extend for irregular distances inland. Geologically, the coastal area is of sedimentary origin, having been built up gradually under the sea by deposition of material carried down by large streams to their deltas. Offshore bars were formed enclosing

Jan 1, 1953

By C. O. Lee, Z. W. Bartlett, R. H. Feierabend

DESPITE the fact that American brimstone production has increased 2 ½ times since the prewar period 1935-1939, the demand for sulphur exceeds the supply. To alleviate this situation efforts are being made to increase the production of sulphur and bring the shortage to an end. The most important developments are being undertaken on the Gulf Coast. One new brimstone mine has been put into operation and three others are being developed. These projects are expected to account for a large part of the additional sulphur production now anticipated for the free world.1,2 Except for a small amount of byproduct sulphur from sour natural gas and refinery gases, American brimstone is produced by the same process devised by Frasch 60 years ago, consisting essentially of the injection of superheated water at about 325°F into sulphur-bearing formations through wells which are drilled from the surface by standard oilfield methods. Sulphur deposits vary in depth from a few hundred feet to 2500 ft from the surface; in a typical deposit the sulphur occurs as crystalline aggregates in porous limestone and gypsum in concentrations varying from 5 to 40 pct, the thickness of the formation ranging from a few feet to several hundred.3 The deposits are usually surrounded by formations impermeable to the flow of hot water, the top and sides being enclosed by impermeable sediments and the bottom by dense impermeable anhydrite. As the hot water leaves the well bore, it percolates through the formation and transmits its heat to the rock and sulphur. When the sulphur reaches 240°F it melts, separates from the rock, and flows through the hot channels downward to the bottom of the well. Here it is freed from incoming water and from formation water, which saturates the porous rock, by gravity separation, liquid sulphur being 1.8 times as heavy as water. It then is pumped to the surface in a relatively pure state, 99.5 pct or better. Chief contaminants are organic impurities, such as petroleum residues, which are soluble in sulphur and tend to discolor it.4 Sixteen deposits of commercial magnitude have been discovered in the Gulf Coast area. Five of these deposits have been depleted and abandoned with production totalling more than 26,886,000 tons. Eight properties are operating and have produced 65,875,000 tons to Jan. 1, 1952, for a total Frasch-type production of 92,761,000 tons. Three new deposits are under development. Aforementioned deposits are listed in Table I. Each of these deposits has been found in the caprock overlying shallow intrusive salt plugs or domes and buried in several hundred to as much as 2500 ft of sediments. All salt domes do not contain sulphur; only 16 sulphur deposits have been found in a total of 231 salt domes which are known to exist in the Gulf Coastal states of Texas, Louisiana, Mississippi, and Alabama. Ten of the salt domes lie in the Gulf of Mexico offshore from the Texas and Louisiana coasts. Additional offshore domes may be found, but their value as a sulphur potential is questionable owing to the great hazard and high cost that can be visualized at these exposed locations where depths of water reach 50 ft. Marsh operations of Freeport Sulphur Co. are in the southeast section of Louisiana. In general, the country is low, flat, relatively uninhabited marshland broken by many shallow lakes and bayous which extend for irregular distances inland. Geologically, the coastal area is of sedimentary origin, having been built up gradually under the sea by deposition of material carried down by large streams to their deltas. Offshore bars were formed enclosing

Jan 1, 1952

By Nestor Torres-Acuña, Fathi Habashi

Metallic copper of purity equal to commercial electrolytic copper is deposited during the anodic dissolution of technically available white metal, Cu2S, in m acidic solution of' copper(II) sulfate as electrolyte and copper sheets as cathodes. The process may be applied on commercial scale since it has the advantage of by passing the converting and poling steps, decreasing pollution problems due to SO, and recovering the sulfur of the white metal in the elemental form. The anodic dissolution is believed to take place in three steps: The working conditions that lead to 98 pct cathodic current efficiency are: 30 gpl Cu2+ and 100 gpl H2SO4 in electrolyte, current density 1.0 amp per sq dm, and tetnperature of bath 40°C'. DURING the smelting of copper, nickel, lead, and zinc sulfide ores, large amounts of sulfur dioxide are produced. Because the release of this gas in the atmosphere causes pollution problems, many attempts were made in the past for its recovery either in liquified form or processed to sulfuric acid. Although these two forms of sulfur are the usual forms that are consumed by the chemical and metallurgical industries, their storage and transport usually raise economic problems. It was realized, long ago, that a process by which sulfur can be recovered directly in the elemental form would be most attractive. Elemental sulfur is easily stored and transported, and is readily converted to SO2, H2S, or H2SO4 when needed. Processes aimed to recover the metals from their sulfide ores, and at the same time by-product sulfur in the elemental form, were recently reviewed.' As early as 1882, Marchese2 patented a process in which a matte having the composition: Cu 15, Pb 14, Fe 41, and S 25 pct was electrolyzed. According to cohen3 the process was applied on a pilot scale by the Aktiengesellschaft fur Bergbau-, Blei-, und Zinkhiitten-betriebe at Stolberg, Rheinland, Germany. The process was unsuccessful, however, owing to the contamination of the electrolyte during electrolysis. Studies in this field were reported by Bernfeld4 and Egli.5 Borchers et a1.6-8 developed the process further by using white metal (Cu 78.2 pct, S 19.6 pct) instead of the matte, and a pilot plant was operated by the Mansfeldschen Kupferschiefer Co. at Eisleben, German~.~ It appears, however, that the process never went into commercial operation. Further studies in this direction were carried out by Russian workers.10-23 The International Nickel Co. of Canada erected a pilot plant at Port Colborne in 1951 to apply the process to nickel matte which is essentially pure nickel sulfide."'- 26 Full-scale plant went into operation at the Thompson Refinery in Manitoba in 1964.27 In this method nickel sulfide matte is melted and cast into anodes analyzing 76 pct Ni and 20 pct S with small amounts of copper, cobalt, and iron. These anodes are then electrolyzed in an aqueous solution of NiS04 at pH 4. Further work on this method was reported in the literature.28-31 In this paper, experiments on the anodic dissolution of white metal in aqueous copper sulfate solution are reported. EXPERIMENTAL White metal, Table I, obtained from The Anaconda Co., was cast in form of anodes 10 by 7.5 by 1 cm, Fig. 1. The anodes are mechanically strong and do not break easily; when polished they gave a shiny gray metallic appearance. From the chemical composition shown in Table I, it can be seen that the atomic ratio Cu:S corresponds approximately to the formula CU2.06S. The copper in excess to the formula Cu2S is most probably present as a separate phase since metallic copper could be seen under the microscope, Fig. 2. Fig. 3 shows the X-ray diffraction pattern of white metal which matches fairly well with that of reagent-grade Cu2S.

Jan 1, 1969

By Douglas J. Harvey

The surface tension of lead-tellurium alloys (in the range 0 to 6.70 at. pct Te) ad lead-arsenic alloys (in the range 0 to 10.53 at. pct As) has been examined by the maximum bubble pressure method. The surface tension of high purity lead can be expressed over a range of temperatures (M.P. to 750°C) by the relationship = 512 — 0.133t. Arsenic and lellurium were both found to be surface active in lead. The surface excess concentration at 700°C was .found to be constant at 0.74 x 10-10 moles per sq cm for tellurium. The surface excess of arsenic at 700°C varied between 0.26 x 10-10 moles per sq cm at 0.16 at. pct to 1.5 x 10-10 moles per sq cm at 8.3 at. pet. The surface tension of lead has been investigated sporadically over the last 90 years. The first recorded study was made by Quincke1 who used a rather crude application of the drop-weight method. Hogness2 obtained the first reliable value for the surface tension of lead by measuring the pressure necessary to force the liquid metal from the end of a small capillary of known radius. Hogness gives the empirical formula: ?(surface tension)= 444 - 0.077 (l-327) which describes the relationship between surface tension and temperature ("C); This work was followed by that of Bircumshaw3 who applied the two-capillar maximum bubble pressure method of Sugden.4 The values published by Bircumshaw are in good agreement with those found by Hogness. Matuyama5 examined the surface tension of lead by the drop weight method. However, the values found are somewhat higher than those previously reported. More recent investigations by Greenaway6 and by Melford and oar' have resulted in data which are not in close agreement, but which are well within the expected range at most temperature levels. The study of the surface tension of lead alloys began with Drath and sauerwald8 who examined the lead-bismuth system. They found that the surface tension values of the alloys in this system deviated only slightly from the ideal mixture rule. Matuyarna5 examined the lead-antimony system. Bircumshaw the lead-tin, and the lead-indium system was studied by Hoar and Me1ford.10 The results of these investi- gations are summarized in Fig. 1. It may be seen that the data vary only slightly from the ideal mixture rule. As none of the metals studied and reported in the literature has a very interesting effect on the surface tension of lead,*the next logical step might be to examine the effect of metals of low solubility or nonmetals having some liquid solubility. Baes, and Kellogg11 have pointed out that the elements most likely to be surface active in liquid metals are ones of limited solubility in the liquid state and possessing weak intermolecular bonding forces in the solid state. Therefore, Group V, VI and VII nonmetals are most likely to be surface active. It was decided to examine the effect of a borderline metal, arsenic, and a nonmetal tellurium. Arsenic forms a eutectic with lead having a melting point of 290°C and a composition of 6.9 at. pct As.13 Pure arsenic sublimes when heated above 610°C. Even though alloying with lead lowers the vapor pressure, fumes containing arsenic are evolved at a very noticeable rate when lead-arsenic alloys are heated above 650°C. Tellurium raises the liquidus temperature of lead sharply to 904°C,14 the melting point of PbTe (lead-telluride). The solid solubility of tellurium in lead was determined by Greenwood and worner15 to be 0.0007 at. pct at room temperature. EXPERIMENTAL METHOD Surface Tension Measurement—The two capillary maximum bubble pressure method for measuring surface tension developed by Sugden,4 and used later

Jan 1, 1962

By S. A. Bradford

Internal-oxide precipitates in decarburized a iron alloys were studied by microscopic and X-ray methods. Diffusion of oxygen is primarily trans-granular, although large amounts of manganese or PhosPhorus cause preferred grain boundary dimsion at temperatures below 1450OF. Transgvanular internal oxidation follows the parabolic rate law with an apparent activation energy of 60 kcal per g-atom for decarburized rimmed steel and around 50 kcal per g-atom for higher alloy contents. The internal oxide is (Fe,Mn)0. Evidence was found for a miscibility gap in the FeO-MnO system. UNTIL very recently, the internal oxidation of metals was studied primarily as a scientific curiosity or, in a few cases, as a means of strengthening alloys by precipitation hardening. However, with the recent development of low-carbon enameling sheet steel, internal oxidation has become a problem of practical importance to the steel industry. For example, in 1961 it was reported1 that internal oxidation of steel can occur during decar-burization by open-coil annealing and will reduce the notch ductility of the sheet unless the process is carefully controlled. The present study was therefore undertaken to learn more about the rates and mechanism of oxygen diffusion and oxide formation in iron alloys. BACKGROUND The process of internal oxidation has been well-defined in the literature:',' oxygen dissolves in an alloy, diffuses inward from the surface of the metal, and reacts to form a precipitate with the alloying element that will provide the most stable oxide. he growth of the finely divided so-called subscale, i.e., the internal-oxidation zone, depends on the diffusion rates of both the oxygen and the reactive element.4 Investigators have generally found that increasing the temperature increases the size of the oxide particles, the rate of subscale growth, and the tendency to transgranular diffusion. With very few exceptions, the square of the thickness of the internal oxide layer is directly proportional to the reaction time. Given two conditions easily satisfied for iron systems— a) an oxygen solubility much less than the concentration of the alloying metal and b) an oxygen-diffusion rate to the oxide boundary much faster than that of the alloying element—then the general expression developed by Rhines and co-workers5 for the parabolic growth rate of the internal-oxide zone can be simplified to the following form: where Co and CM are, respectively, the solubility of oxygen and the concentration of the alloying element, DO is the diffusion coefficient of oxygen, O/M is the weight ratio of oxygen to metal in the precipitated oxide, and x is the thickness of the internal-oxide zone after an annealing time t. Both the oxygen solubility and diffusion coefficient can be approximately expressed as functions of temperature by Arrhenius-type equations: in which H and Q are, respectively, the heat of solution and the activation energy of diffusion. Consequently, the apparent activation energies calculated from Arrhenius plots are the sum of the heat of solution of oxygen in iron and the activation energy for diffusion of oxygen. The data, if not the interpretation, of Schenck et al.8 bear out the fact that oxygen diffuses in the atomic form. The general rate law for atomic diffusion is: the reaction rate being proportional to the square root of the pressure at low pressures. Benard and Moreau8 studied both the surface oxidation of Fe-Ni alloys and the gradual penetration of oxygen into the metal. They observed that oxide particles first form along grain boundaries and then grow to form continuous films that eventually envelop the grains. The parabolic rate law does not usually apply in these cases, especially at the higher temperatures. The oxide formed is wustite which gradually transforms into Fe3O4 and finally into Kennedy and coauthors8 examined Fe-Ni alloys with 26, 75, and 84 pct Ni oxidized at 800°C and

Jan 1, 1964

By R. F. Burdyn

The inadequate use of centrifugation to economically recover solids from weighted drilling fluids reflects the need for better equipment and techniques for this putpose. Laboratory studies in the development of an improved separator are described in which an operating equation is derived and tested. Results show that the concentric cylinder geometry employed effectively separates bnrite from a suspension and that the operating equation provides a good approxinmtion for scale-up. INTRODUCTION Our current drilling technology frequently requires a high-density drilling fluid obtained by addition of barite. In the course of drilling, formation solids which are too fine to be removed either by screening or settling become suspended in the drilling fluid and gradually the volume of solids in the mud increases. The volume fraction of solids must be limited (if a satisfactory set of rheological parameters are to be maintained). A centrifugal separatorprovidesan economical way of accomplishing this. The barite recovery process can be considered as a separation of two solids. One, the light solids, composed of formation and added solids, has a specific gravity of 2.6 to 2.7; the other, barite, has a specific gravity of 4.2 to 4.3. This density difference, plus the fact that the average light-solids particle size is much smaller than the average barite particle size, permits separation by a centrifuge. In drilling fluids some of the coarse particles of the light-solids-range will settle faster than fine particles of the barite-particle range. As a result a complete separation of the two species is not possible. since the object of the process is not merely recovering the maximum amount of barite but includes as well removing the maximum amount of light solids, an optimum barite recovery efficiency exists. From a practical standpoint this optimum cannot be determined in the field for each drilling fluid system, and in practice the separation is less than optimum, with some sacrifice of barite. Drilling technology has included centrifugal separators for barite recovery for more than a decade. Results have been reported by a number of investigators indicating that the process is practical and economica1. l-4 The decision to use a centrifuge is based on economics in which direct cost savings and the indirect benefits in rig time derived from improvement of the drilling fluid are important factors. One would expect that centrifugal separation of barite from drilling fluids would significantly affect barite consumption; however, this is not the case. The Minerals Yearbook shows an annual domestic barite consumption in the drilling industry of nearly 1 million tons.5 By rough estimate there are perhaps 80 separators presently in field use. Assuming half of these in use at any one time, operating an average of four hours per day, at recovery rates averaging 3,000 Ib of barite per hour, total annual recovery is about 90,000 tons. This is less than 10 per cent of he total barite used. I conservatively estimate that barite consumption in drilling operations can be reduced by 30 per cent through greater utilization of centrifugal separators. To encourage more widespread acceptance of centrifugal separators in the drilling industry, improved equipment and techniques would be very desirable. The present paper, covering theory and results obtained from a laboratory model, is the first in a series on he development of an improved mud separator for field use. THE CONCENTRIC CYLINDER GEOMETRY AS A SEPARATING DEVICE Consider the geometry shown in Fig. 1, consisting of two concentric cylinders separated by an annular space. These are arranged so that the outer cylinder is fixed and the inner one can be rotated about its axis on shafts sealed against the ends of the outer cylinder. If the outer cylinder is fitted with openings at either end, the inner

Jan 1, 1966

P. H. ARGALL, Magdalena, N. Mex. (written discussion *).-The Chilean mill has generally been considered a fine-crushing machine and as such has had many advocates; it has also. had quite a number of denouncers; hence, the action of the Portland engineers in using the Chilean mill for the preparatory work usually accomplished in, rolls or rock breakers and adding a ball mill to do the fine grinding is novel, though of doubtful utility in the long run, even though a fair efficiency is obtained for the combination machines, as measured by Chilean mill practice. In order to follow the development of Chilean mill practice on Cripple Creek ores, I might say that two 6-ft., Chilean mills were placed in operation in Stratton's Independence mill in April, 1908, treating ore crushed by rolls to pass Y4 in. screen aperture. Screening was, however, found to be an unnecessary refinement, as was also the use of plows in the mills; both screening and plowing were abandoned before the Portland engineers finished the experiments in stamp milling upon which they were then engaged. Two additional 6-ft. Chilean mills were added in the spring of 1911, three of them giving the required 10,000 tons per month capacity, one being always in reserve. The Portland company began using Chilean mills in June, 1910, at its Victor mill, and the same company purchased the Stratton's Independence mill in June, 1915, and remodeled it; it is now known as the Independence mill. A description of Stratton's Independence milling practice, is given in the November, 191.1, issue of Mining Majazine (London). These Chilean mills were used as fine grinders and that they accomplished their purpose is shown by the screen analyses, in which 62 per cent. of the pulp passed 150-mesh screens. To make coarse crushers of these Chilean mills, the Portland engineers have increased the speed, substituted steel in various parts for cast iron, provided new and enlarged thrust bearings to take care of the centrifugal force incident to higher speed, and have, thereby, greatly increased the cost of the machines. They have also reduced the width of the tires and dies from 8 in., as used in the original mill, to 7 in., a reduction of 12 ½ per cent. in the crushing surfaces, to say nothing of the loss of abrasion or attrition incident to the larger surface. At the same time, they have apparently increased the weight of the rollers by using tires 5 7/8 in. thick as against tires varying between 3 and 4 in. on the original mills, thereby increasing

Jan 4, 1920

By M. A. Scheil

Austenitic stainless alloys are susceptible to stress-corrosion cracking which may occur under certain corrosion environments irrespective of their susceptibility to intergranular corrosion. Test samples are described for investigating stress-corrosion susceptibility of alloys for industrial equipment. A laboratory test using a solution of magnesium chloride boiling at 309 F. was found to produce transgranular cracks in several alloys investigated and in types 347 and 316 stainless steel tubing a residual stress of the order of 10,000 psi. was observed to initiate cracking. The susceptibility to stress-corrosion cracking as judged by the boiling magnesium chloride test indicates that alloys may be selected which will withstand a high stress in service Stressed specimens of stainless alloys included in a corrosion testing program will aid in determining the acceptibility of these fabricated alloys, when stressed, to the service conditions.

Jan 1, 1945

By C. C. Furnas

IT is well known that particles of different sizes are not distributed evenly throughout the average charge in an iron blast furnace. Just how great the disparity in particle size in different parts of a single plane in a furnace may be is indicated by the results of some recent investigations1 conducted by the Bureau of Mines on a furnace operating on Lake ores. The wide variations found in gas velocity, gas composition, and temperature from the periphery to the center of the upper charge column were caused by the great variation in particle size of the raw materials used and were also greatly influenced by the methods of charging. This paper summarizes the results of an investigation of the influence of different methods of charging and of the treatment of raw materials upon the size distribution of the solid particles in the blast furnace. A more complete report will appear later as a Bureau of Mines technical paper.

Jan 1, 1929

Jan 1, 1951

By AIME AIME

The Bulletin. The Bulletin of the Institute will be issued hereafter monthly instead of bi-monthly as heretofore. Among other reasons for this change, it is desired to effect thereby the earlier transmission to members of important papers, lists of candidates tin? membership, and other items of timely information. The New Haven Meeting. As already announced in special circular, the XCVIth meeting of the institute for the reading and discussion of papers will be held at New Haven, Conn., beginning Feb. 23, 1909. The Secretary of the Local Committee is Prof. J. D. Irving, Box D, Yale Station, New Haven. The program embraces visits to many interesting works in New Haven, Ansonia, Bridgeport, etc. The leading topics for discussion at the sessions will lie: The Conservation of Natural Resources; A Sea-Level Canal at Panama; and The Technical Education of Mining Engineers. But papers on other subjects also are announced. Lt is probable that a supplementary session of this meeting, will be held in New York City, at some time during March, 1909, as a joint session with other national engineering societies, for the farther discussion of the subject of The Conservation of Natural Resources. A Pacific Coast Meeting. It is now reasonably certain that the XCVIIth meeting will be held oil the Pacific Coast, including a. visit to the Exposition at Seattle, and various other points en. route going or coming, depending upon the route and program finally adopted. (lore definite information will be announced at the New Haven Meeting, or at the earliest possible date thereafter.

Jan 1, 1909

By H. M. St. John

MAINTAINING a satisfactory structure in brass and bronze castings has always been a foundry problem of great practical importance. While metallurgists and scientific investigators have not entirely ignored this matter, it has received less of their attention than has been given to iron, steel and the wrought copper and aluminum alloys. Investigation in this field has probably been discouraged to some extent by the complicated nature of the alloys involved. Hundreds of alloys are in more or less common use, most of them containing copper, zinc, lead and tin in-widely varying proportions. They also contain appreciable percentages of iron and antimony as impurities, and often phosphorus, which has been added as a deoxidizer and fluidifier. Small amounts of sulfur are usually present. It is not uncommon to find nickel, sometimes in rather substantial quantities. Traces of other metals are frequently present. So complicated and variable a mixture obviously offers difficulties in. any investigation of the various factors that influence the structure and other properties of the casting.

Jan 1, 1930

Jan 1, 1888

By H. M. Howe

§ 24. Introduction.—This paper discusses the chief existing data as to the temperature, in iron-carbon alloys, of Ae3, the upper limit of the transformation range when in equilibrium, as distinguished from Ac3, the temperature at which the end of the transformation is noted in heating up, and from Ar3, that at which its beginning is noted in cooling down. The former is in fact carried above Ae3 and the latter below Ae3 by lag. I touch incidentally on the influence of manganese on Ae3 (§ 29, p. 614). The sections, tables, and illustrations are numbered consecutively with those in the accompanying papers by Howe and Levy on Determination of the Position of Ae3 in Carbon-Iron Alloys, and by Burgess, Crowe, and Rawdon on Thermal and Microscopical Examination of Professor Howe's Standard Commercial Steels, to which the present paper forms a sequel. § 25. The contradictoriness of our present evidence is shown by grouping it together in Fig. 14. For instance, both Goerens and Meyer (Series 2) and Meuthen (Series 12) used practically stationary temperature, and thus reduced the influence of lag very greatly; yet Ae3 for 0.32 carbon steel according to the former investigators is 894", but according to Meuthen it is at or below 770°, a discrepancy of 124" or more. In view of our ability to measure these high temperatures within a few degrees, the existence of such a discrepancy is as unwelcome as it seems needless. I attack the thankless task of bringing some order out of this chaos. In Part 11. (§§ 29 to 39) I consider the chief causes of error. In Part III. (§§ 40 to 48) I apply certain corrections to some of the existing data, review those data, weight them, and calculate a prob-

Jan 1, 1914

By J. D. Ridge

The geologic setting and mineral relationships of seven European massive sulfide deposits that more or less conform to the bedding of the largely noncal-careous sedimentary rocks and/or bedded volcanics in which they are found are considered here. These orebodies consist largely of massive beds or lenses of sulfides usually surrounded by halos of disseminated sulfides and distorted by tectonic activity. The formations containing these deposits have been metamorphosed in varying degrees at times subsequent to their lithification. The ore-forming process is thought to be essentially volcanic, with the ore constituents being brought to the shallow-water site of deposition through tectonic fissures from magma chambers at depth as gases or relatively concentrated hydrother-mal solutions. Certain European ore deposits of base metal sulfide have previously been considered to be of hydro-thermal or magmatic origin, but today a number of European mining geologists consider them to be syngenetically produced. In an effort to provide American geologists with some idea of the reasons behind this change in thought, the geological settings of seven of these deposits have been studied. These are: Ldkken, Meggen, Rammelsberg, Ergani-Maden, Outokumpu, Boliden and Roros. These deposits lie in bedded rocks that have undergone metamorphism from causes not universally agreed upon; most of the formations were originally shales, and may have been intercalated with limey and occasionally quartzitic beds, volcanic tuff, agglomerate, extrusive lavas and usually basic intrusives. Deposits of the conformable type, however, are not confined to these rock types but may be in calcareous and associated igneous rocks or almost entirely in volcanics. These deposits may be closely associated in space with igneous rocks that, again, are usually basic types. Although the ages of the enclosing rocks range from mid-Precambrian (Boliden and Outokumpu) to Eocene (Ergani-Maden), the bulk of them are Paleozoic, with two (Meggen, and eammelsberg) being upper middle Devonian and two (LØkken and RØros) being Cambro-Ordovician. Geographically, two are in West Germany, four in Scandanavia and one in Turkey. Of the seven deposits, six are mined for copper, with three of these also producing zinc, and two lead; one is mined for zinc and minor lead. In the discussions of the seven conformable deposits that follow, I have attempted to present as uniform a treatment as their varying characters will permit. For each deposit, I have considered the stratigraphy of the area, its major structural characteristics, the form of the orebodies, their mineral content, and the origin of the ore. In the last of these subdivisions, I have presented only the viewpoint of those who believe the ores to have been formed by syngenetic processes, processes that went on at the same time as those which produced the beds that enclose the ores but that are not, in the deposits in question, thought to have been sedimentary in the strict sense of the term. The materials of which these orebodies are composed, it is suggested, did actually collect by falling through sea water to the floor of that portion of the sea in which they accumulated. The ore constituents, however, are believed by a considerable number of European geologists to have been added to the sea water from intratelluric sources, probably igneous magma chambers, as exhalations — hydrothermal solutions or volcanic gases. The effect of the encounter with sea water on these ejected gases or water-rich vapors was to precipitate their potentially solid constituents with great rapidity; they were deposited so quickly, in fact, that the amounj of normally accumulated mechanical or chemical sediment deposited over the same period of time was essentially negligible. The ores formed in this manner, however, are generally interbedded with normal sediments or with lava flows, or with any combination of these two types of rock-forming materials. Such departures as these deposits may have from their original mineral content and attitude are thought to be directly related to the degree of dynamic or static metamorphism that they may have undergone after their accumulation. I have not attempted here to present alternate hypotheses to that of so-called exhalative sedimentation although, of course, such exist and, in my

Jan 1, 1963

Jan 1, 1914