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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 E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By G. Sandoz, D. A. Meyn

The fracture surfaces of specimens of titanium a1loys which exhibited susceptibility to subcritical crack growth in a wide variety of environments, including aqueous solutions, alcohols, hydrocarbon gases, carbm tetrachloride, and dry air, were examined. The dominant and characteristic fracture mode was cleavage. which became mixed with an increasing porportion of ductile fracture modes (dimples. and so forth) as the applied KI was increased. The cleavage plane in all the alloys was oriented at 15 deg from (0001) of the a phase. No indices could be assigned to the 15 deg cleavage Plane because of uncertainty as to which zone it belonged to. SLOW crack growth and delayed fracture take place in certain titanium alloys at stress intensity (KI) lower than the critical values for complete fracture (KIc) found in short-time tests for plane strain fracture toughness.' Such crack growth may take place in very dry air on sustained loading if the alloy contains a sufficient amount of hydrogen and if the stress intensity factor is higher than a threshold value designated KIH.2 Similarly, a number of environments such as water, alcohols, and hydrocarbons may cause slow crack growth provided the stress intensity factor exceeds the threshold value KISCC. In this paper it is intended to examine some fracto-graphic and crystallographic details of this subcritical crack propagation process as related to alloy composition, environment, and stress intensity. It has been previously reported that subcritical crack growth takes place in titanium alloys in aqueous environments by cleavage.2"6 The observations to be described here indicate that in the alloys investigated the mode of subcritical crack propagation is more dependent on the stress intensity during cracking than on the environment. The fracture mode is illustrated with photographs of the fracture surfaces at a wide range of magnifications. The crystallographic character of the cleavage mode is also presented and the results discussed. EXPERIMENTAL APPROACH The studies were made on four titanium alloys— Ti-8A1-1Mo-lV, Ti-5A1-2.5Sn, Ti-7Al-1Mo-lV, and Ti-0.350. Of these four alloys the first two were mill annealed and fine grained. The latter two were noncommercial and coarse grained, having been prepared for other experimental purposes. The crystallographic studies required a large-grain size. Consequently the fine-grained alloys were an- nealed in a vacuum at 1950°F and furnace cooled to produce samples for these studies. This treatment did not alter the microstructure significantly except for grain size. All the aluminum-containing alloys showed primary a with a network of ß-phase particles within the a grains; Figs. 1 and 2 show this microstructure for the specific case of fine-grained Ti-8A1-1Mo-1V. The cracks in the figures will be discussed later. Fractographic studies were made on all the alloys, but the electron fractographs displayed herein are from the Ti-8A1-1Mo-1V alloy in the fine-grained condition. Emphasis was placed on this commercial alloy because considerable information was available on the stress-corrosion cracking characteristics in a variety of environments. Sufficient supplementary studies of the alloy after the anneal to produce large grains were conducted to establish that the stress-corrosion cracking susceptibility and fractographic characteristics were not changed significantly. Thus it could be inferred that the crystallographic data obtained exclusively on large-grained specimens would apply also to fine-grained specimens. Fracture surfaces for study were obtained using precracked cantilever beam specimens loaded as described by Brown. The precracked section of a specimen was immersed in the environment of interest. Values of initial stress intensity factor Kli were chosen slightly higher than KISCC in order to obtain a fairly extensive region of slow crack growth. Fracture surfaces representative of a variety of stress intensity levels could then be examined because in the cantilever beam test KI increases as the crack propagates.

Jan 1, 1970

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 M. A. Grossman

The harden ability of most steels can be predicted within 10 to I5 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In the method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a "pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain size may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter", namely, the diameter of bar, in inches, that will just harden all the way through (absence of un-hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test The data bring out certain features rather clearly. For example: i. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals,,) are known; thus an "incidental,, chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybdenum when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful, as would appear to be common experience; observe that an increase from no manaanese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added "20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the fist small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using I.o per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost 10 per cent in hardenability (in these units); this, however, does not apply to certain It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome-molybdenum and chrome-vanadium steels, un-dissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum Passible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the

Jan 1, 1942

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 M. A. Grossman

The harden ability of most steels can be predicted within 10 to I5 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In the method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a "pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain size may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter", namely, the diameter of bar, in inches, that will just harden all the way through (absence of un-hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test The data bring out certain features rather clearly. For example: i. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals,,) are known; thus an "incidental,, chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybdenum when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful, as would appear to be common experience; observe that an increase from no manaanese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added "20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the fist small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using I.o per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost 10 per cent in hardenability (in these units); this, however, does not apply to certain It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome-molybdenum and chrome-vanadium steels, un-dissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum Passible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the

Jan 1, 1942

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

By N. Parlee, V. C. Kashyap

The solubilities of nitrogen in liquid iron and liquid Fe-Ni, Fe-Mo, Fe-V, and Fe-Mo-V alloys were measured by the Sieverts method. Measurements were made at 1600° to 1800°C on binary alloys up to 20 pet Ni, 10 pet V, 10 pet Mo; and on ternary alloys containing 0 to 3 pet V with 0 to 5 pet Mo. The results on liquid iron confirm that Sieverts' law is obeyed in the range 50 to 750 mm pressure. The measured solubilities and their temperature coefficients are in general agreement with other modern authors. The logarithms of the activity coefficients of nitrogen in the binaries are approximately linear functions of the pet of alloying element. A method suggested by Wagner, Chipman, and others for predicting gas solubilities in complex alloys from solubility data on binaries was applied to the Fe-Mo-V alloys. Reasonably good agreement was obtained between calculated and experimental solubilities. NITROGEN'S solubility in liquid iron has been studied by a number of investigators. It is reasonably well established that the solubility of nitrogen follows Sieverts' law at least up to 1 atm partial pressure and that the solubility increases gradually with temperature. The solubility of nitrogen in Fe-X binary liquid systems has been investigated in only a few cases. Only the systems Fe-Cr,3-5, 7 Fe-V,3 Fe-Mn,3, 5 Fe-Ni,3, 5 Fe-Si,B, H Fe-C, L, H and Fe-P4 appear to have received any study. The only work on liquid Fe-V was done by Brick and Creevy.3 This was limited to 13.5 pet and 26.5 pet V, but no exact temperatures were recorded. No work whatsoever appears to have been done on liquid Fe-Mo alloys and even work on Fe-Ni alloys is rather scant. The work on liquid ternary systems is still more limited, and the only publication available appears to be that of Wentrup and Reif,7 who studied the Fe-Cr-Mn and Fe-Cr-Ni alloys. Rassbach, Saunders, and Harbrecht17 have reported work on the solubility of nitrogen in stainless steel but this was not a systematic study of any particular system. Commercial alloys usually contain several alloying elements. Thus, it often becomes important to be able to predict the nitrogen solubility in systems containing two or more added elements without the necessity of making measurements. Wagner,14 Chipman," Darken and Gurry," and Morris and Buehl 14 have suggested means by which this may be accomplished, and Langenberg14 has recently applied one of these methods to nitrogen solubility in complex liquid alloys. This paper reports the results of nitrogen solubility determinations on Fe-Ni, Fe-Mo, Fe-V, and Fe-Mo-V alloys and compares calculated and experimental solubilities in the ternary alloy. Attempted measurements on Fe-Cr alloys were not successful by the experimental method employed. Experimental Method The general method of solubility measurement was that of Sieverts.' The apparatus and procedure were essentially the same as used by Liang, Bever, and Floe."' The equipment consisted of a small vacuum furnace heated by a 6 kw induction unit, gas measuring apparatus, and a gas purification train. The crucibles used were Norton Alundum with alumina sand around them for insulation. The crucibles were charged with 100 to 200 g of material, about 180 g or nearly filling the crucible being found most satisfactory. Hot volumes were determined with argon and ranged from 95 to 130 cu cm (stp). Temperature measurements were made with a Leeds and Northrup optical pyrometer which was calibrated periodically against the melting point of iron in the same apparatus."-'* Good quality nitrogen, hydrogen, and argon gases were further purified and dried in standard purification trains. The sources of the high purity iron and other alloying elements used were as follows:

Jan 1, 1959

By F. N. Rhines, A. S. Nemy

The mode of high-temperature tertiary creep of 523-0 aluminum alloy was found to be strongly stress dependent. The occurrence of necking and/or fissures during tertiary creep exhibited a sequence with varying stress, wherein fissures with no necking occur at a minimum stress and necking with no fissures occur at a maximum stress. At an intermediate stress, tertiary creep begins without necking but with fissures in a region just beneath the external surface, followed by necking and the development of fissures along the axis of the specimen. The results are interpreted in terms of grain boundary gliding and the hydrostatic stresses produced by restraints to grain boundary gliding. THERE appear to be two possible reasons for the existence of a period of accelerating elongation prior to rupture during high-temperature creep in metals; namely, 1) a change in the structure of the metal itself, leading to a change in its response to loading, and 2) a reduction in the cross section of the metal resulting in a higher unit loading. Howe,' by annealing and retesting broken low-temperature creep specimens, found that irreparable damage is done once a metal is subjected to creep. Andrade2 first pointed out the association between the reduction in cross section and the increase in creep rate. The present research was designed to investigate both of these factors by retesting specimens machined from material which had been subjected to high-temperature creep testing short of rupture. EXPERIMENTAL METHOD An aluminum alloy, 52s-0, was selected for these studies because it is constitutionally simple, is strong enough to be relatively insensitive to mechanical damage during machining,3 and undergoes accelerating creep in a convenient temperature range. This alloy is hardened by 2.6 wt pct Mg in solid solution and is not subject to overaging effects; it has a very small quantity of an insoluble impurity phase, Mg2Si, finely dispersed throughout its micro-structure. Creep specimens, similar in design to ASTM 0.252-in. tensile specimens, were machined from 3/4-in. round stock and the surfaces were electro-polished. A 24-hr anneal at 500°C was then applied to stabilize the grain size to an average diameier of 0.27 mm. Subsequent heating for as long as 700 hr at the intended test temperatures produced no change in the tensile properties, indicating a well-stabilized state of the material. Corresponding to each of the typical testing conditions listed in Table I, one creep specimen was tested to destruction and this test was employed as a guide in the selection of times for subsequent tests. Duplicate creep tests were then run to various points along the creep curve to produce specimens which were used to determine changes in mechanical properties and microstructures. The latter were examined at the midsections of the specimens. Other specimens were tested to various stages of tertiary creep, after which they were remachined to new cylindrical test specimens, electropolished and re-tested in creep. RESULTS The major findings of this investigation may be illustrated by a comparison of the results of three sets of creep tests. These were run at 400°C at three stress levels, namely 750, 1000, and 1500 psi. In presenting these results in Figs. 1, 5, and 8, the creep curves are given in pairs: That curve of each pair which is drawn through filled circles corresponds to the initial test, and the curve drawn through open circles (and designated by - R) represents the result of retesting the same specimen after machining to a new cylindrical surface. The load was readjusted to the original unit stress at the beginning of each retest.

Jan 1, 1960

By W. F. Domis, F. von Gemmingen, F. Garofalo

The effect of rain size on the creep behavior of an austenitic iron-base alloy has been studied at 1300° F under conditions of constant stress. The average grain diameter varied between 9 and 190 p (ASTM 10.7-2). The subgrain size and apparent activation energy for creep were not found to depend in any systematic manner on gain size. Grain hozmdary serrations were observed in all specimens tested. The variation of the secondary-creep rate, 2,, with the pain diameter, 1, is given by: es = K(213m + 1 )/l.]; 1, is the grain diameter zohere is reaches a minimum. Results in the literature shoujthat 1,increases as the temperature increases. At low creep temperatures is is therefore proportional to 12, at intermediate temperatures <, exhibits a minimum, and at high creep temperatures is is proportional to 1/1. The dependence ofis on the stress, u, is given by: t, = A" (sinh acrln, a and n show little variation with 1. The dependence of A" on 1 is given by: A" = KA[(21k + 13)/1]. For 1 » >>lmn = 4, and at constant values 01- isat lozu stress levels, the steady-state stress is given by the Hall-Petch relation. The variation of c, with grain size is believed to he associated particularly with grain boundary generation of dislocations which becomes more important with increasing temperatures. SEEMINGLY inconsistent experimental findings have led to a certain amount of confusion concerning the effect of grain size on creep behavior. The confusion is attributed to a lack of test results obtained over sufficiently wide ranges in grain size, stress, and temperature. Experimental results presented in this paper and results available in the literature1-5 show a consistent behavior and lead to a unified concept for the dependence of secondary-or steady-state creep rate on grain size. In accordance with this concept, which is substantiated experimentally, secondary-creep rate should increase with increasing grain diameter at low creep temperatures, leading to greater creep strengths for fine-grained materials. At intermediate temperatures the secondary-creep rate should decrease to a minimum and then increase as the grain size is increased. At high creep temperatures the secondary-creep rate should decrease with increasing grain size, leading to greater creep strengths for coarse-grained materials. Whether a temperature is high or low for creep in a metal or alloy depends primarily on its melting temperature. MATERIAL AND TEST PROCEDURES The material tested was an austenitic iron-base alloy of the following composition (wt pct): C, 0.005; N, 0.017; Mn, 1.26; Ni, 14.21; and Cr, 17.18. Two 15 -lb ingots were forged and hot-rolled to 5/8-in.-diam bars which were then cold-rolled and cold-swaged to a diameter of 0.49 in. These were sectioned into 3-in.-long blanks and heat-treated at various temperatures to obtain different grain sizes. The procedures employed and the results obtained are summarized in Table I. The secondary treatment at 1400° F followed the primary treatment without intermediate cooling to room temperature. This final treatment was employed to minimize various effects arising from heating to different temperatures during the primary treatment, particularly differences in intragranular dislocation structure, segregation of interstitial atoms at grain boundaries, and density of grain boundary ledges. The intragranular dislocation structure was examined by electron transmission metallography after each of the treatments described in Table I. Isolated dislocations and a few tangles were observed but no evidence of subgrains was found after any of the treatments. No grain-size effect was evident on the density and distribution of dislocations. Stabilization of grain boundary structure is particularly important because, as will be discussed later, grain boundaries influence high-temperature creep behavior. Magnetic-permeability measurements after each treatment and

Jan 1, 1964

By D. L. McCain

In considering slurry transportation for Consolidation Coal Company&apos;s Loveridge Mine in Northern West Virginia, many things were taken into account. The advantages of slurry transportation in comparison to shuttle car, belt and rail transport have been given in previous publications." These include increased safety and the potential for increased productivity. In addition to these considerations, the slurry transport system installed in an existing mine provides an alternate or additional transportation mode to the one already existing. In the Loveridge Mine, this is rail haulage. Since the rail system is a single track system and the distances involved are several kilometers, it is not always possible to provide for haulage of loaded cars, return of empties, supplies and maintenance in an efficient manner. Slurry transport of the coal from the production faces to the preparation plant allows the rail system to fulfill the remaining transportation needs in an efficient manner. Consol initiated development work in slurry transportation in the early fifties leading to the construction and operation of the 174-km (108-mile) Cadiz-to-Cleveland pipeline which carried 1,200,000 metric t/y (1,300,000 t/y) from 1957 to 1963. Development work on coarse coal slurry transportation for underground mines started in 1970 with feasibility tests on coarse coal at Conoco&apos;s Ponca City, Oklahoma, slurry test facility. A series of tests were conducted in several locations as development work proceeded on the various subsystems, mechanical equipment and controls required to produce a working system to follow a continuous miner in a room-and-pillar type mine, then to combine the coal production from several mine faces for mainline transportation to the preparation plant. The face system, including the crusher-pump vehicle, hose hauler vehicle, slurry booster pump units, return water unit and 900 to 1,200 m (3,000 to 4,000 feet) of pipeline was brought together for the first time and tested as a system at Consol&apos;s Robinson Run Mine in northern West Virginia in 1975. A pipeline wear test at the Loveridge Mine where 300,000 tonnes (330,000 tons) of minus 127-mm (5-inch) run-of-mine coal were pumped from the raw coal bin into the preparation plant and a large scale test in Ponca City on a multiple feed sump where several slurry flows could be combined to provide surge capacity and a constant reclaim rate for mainline transportation completed the preliminary testing for a complete system. A decision was made to commit the system to a mine, and the south half of the Loveridge Mine was chosen. This site required the transporting of coal from one longwall and two continuous miner development faces. To prevent startup and unexpected problems in the slurry system from shutting down production of coal from the longwall face, the rail car loading point from the main section belt was chosen as the feed point for the slurry system and the design would allow for rapidly switching from one transport mode to the other. Scheduling of required development entry work and the developmental nature of the system led to a decision to install only one continuous miner face slurry transport system rather than two for this first system. The type of continuous miner in use at the mine for the foreseeable future was the Joy 2BT6 twin boring machine. This machine cuts a stable, arch-shaped entry and was therefore allowed to mine about 26 m (85 feet) of entry before roof bolting was re¬quired. Since peak production from this type of machine was not high, a smaller transport system could be used with it.

Jan 1, 1981

By S. A. McGhee

Introduction ASARCO&apos;s Ray Operations include an open-pit copper mine in the Mineral Creek Mining District of Pinel County. The district is located in east central Arizona, 132 km (82 miles) southeast of Phoenix, AZ, and 126 km (78 miles) north of Tucson, AZ. The mine lies 8 km (5 miles) north of the Gila River in Mineral Creek Valley, between the Tortilla Mountains to the west and the Dripping Springs Range to the east. The rich copper deposits of the Mineral Creek mining district were first noted by a US Army Officer in 1847. The Ray Copper Company was the first major operation in the area. The company was named after the Ray mining claim, which was one of the earliest recorded claims. After decades of sporadic and unsuccessful mining ventures, the Ray Consolidated Mining Company was formed in 1910. The company introduced one of the first successful block caving operations in the world. In 1933, the Kennecott Copper Corporation acquired the Ray Consolidated Mining Company and continued operation of the mine under the same name until 1943, when the property was renamed the Ray Mines Division of Kennecott. Underground mining continued until 1955, when the mine was converted to an open pit operation. In November 1986, ASARCO Inc. purchased the Ray Mines Division and related facilities from Kennecott. The purchase also included the Hayden concentrator and the Ray Smelter, located approximately 32 km (20 miles) from the Ray Mine. This paper summarizes the 54,400 tpd (60,000 stpd) in-pit crusher and overland-conveying system and the 24,200 tpd (30.000 stpd) copper SAG concentrator and tailings disposal system constructed at ASARCO&apos;s Ray Complex - Ray Operations. General description of facilities The Ray concentrator includes a sulfide SAG concentrator, a "relocatable" in-pit primary-crushing plant and overland-conveyor system, a concentrator tailings-disposal system and plant ancillary facilities, The major elements of the project include: • A relocatable Fuller-Traylor in-pit 1524-mm (60-in) x 2261-mm (89-in) primary gyratory crusher at the 442 m (1450 ft) mine elevation. The crushing plant has a nominal capacity of 54,400 tpd (60,000 stpd) of sulfide ore. • A 1524-mm (60-in) wide x 1253-m (4110-ft) long overland belt conveyor, which runs from the in-pit crushing facility to a transfer station serving both the Ray Concentrator and the existing Hayden concentrator railroad load-out facility. • A 1524-mm (60-in) wide x 152-m (500-ft) long stackerbelt conveyor, which delivers a nominal 27,200 tpd (30,000 stpd) of ore from the transfer station to a 23,600 t (26,000 st) live-capacity coarse-ore stockpile serving the Ray Concentrator. • A nominal 27,200-tpd (30,000-stpd) concentrator, including semiautogenous grinding, flotation, copper concentrate filtration and associated plant ancillary facilities. • A tailings disposal system. Flotation tailings are pumped from the Ray Concentrator to a 122-m (400-ft) diam. thickener, located 4.8 km (3 miles) southeast of the Ray Concentrator site. The thickener overflow is pumped to two 76.2-m (250-ft.) diam. concrete process-water reservoirs. The thickener underflow, at 45% solids, is pumped to a new tailings disposal site located at Elder Gulch. • An HDPE-lined temporary-containment area to collect material from Ray Concentrator plant upsets and local storm-water run-off from a 100-year, 24-hour rain event. •A reclaim-water system from the Elder Gulch tailing pond area to the Ray Concentrator. • A 610-mm (24-in.) diam. x 31.9-km (19.2 mile) long fresh-water pipeline from the Hayden fresh-water-well field system to the Ray Concentrator. The overall process design criteria for the new Ray Concentrator is based on a nominal throughput of 27,200 tpd (30,000 stpd) of ore at 90% plant availability. However, based on the maximum performance capacity of the installed grinding equipment, it may be possible to achieve a sustained operating level in excess of 36,300 tpd (40,000 stpd) when processing soft ores. The balance of this paper will cover the major process systems including:

Jan 1, 1995

By L Baumgardner, A. V. Castelli

Barite In 1987, United States mine production of barite increased 15.870, consumption (sold or used by grinding plants) increased by 6.97, and imports are estimated to have fallen by 19.57. World mine production decreased by 137, according to the US Bureau of Mines. The value of US produced barite, fob mine, decreased 1.4%, according to the Bureau. The declared value for cif US port of all imported unground barite during the first 10 months of 1987 decreased from $39.02/t ($35.40 per st) to $37.16/t ($33.71 per st), the Bureau stated. Nevada continued to be the leading US producer of&apos; barite with 637r of the total. It is followed by Georgia, Missouri, California, Tennessee, and Montana. The Bureau of Mines estimates 657 of the US mine production was used as a weighting agent in drilling fluids. The remaining 35°/r was used in barium chemicals, glass or as a filler. Most of the production from Missouri, Georgia, and Tennessee was used in the non-oilfield sector. This sector continued to increase. Of the total consumption (used by grinding plants and chemical manufacturers), it is estimated that 8070 was used in drilling fluids and 2017( in the non-oilfield sector - barium chemicals and fillers in paper, plastics, and glass. The tonnage consumed in the drilling fluids market increased slightly. But the average number of rotary rigs operating decreased from 964 in 1986 to 936 in 1987. This is the lowest number of operating rigs reported since 1949. The increase in consumption in this sector is due to an increase of rigs operating in the US Gulf and other higher consumption areas over 1986. Crude barite imports were estimated to be down by 19.5% in 1987. Still, they accounted for 637 of the barite consumed in the US. During the first 10 months, China continued to be the leading exporter to the US with 86.970, followed by Mexico with 10.997, and Morocco 2.107(. About 5Y of the imported ore was used in the nonoilfield sector. Ground barite imports dropped from 19.8 kt to 8.8 kt (21,800 st to 9800 st) in 1987. Of this amount, 1.4 kt (1598 st) was used in drilling muds and the remainder of the non-oilfield use. During 1987, a few more grinding plants that supplied the drilling fluid market were closed. Along the US Gulf Coast, there are 13 operating plants versus a high of 31 in 1981. Cameron Offshore reopened its grinding plant at Cameron, LA. New Riverside Ochre Co. of Cartersville, GA, purchased a jigging-washing plant in Missouri and plans to place it in operation this year on a new deposit near Cartersville, GA. Milpark purchased Hughes Drilling Fluid in 1987 and operates under Milpark. US mine production will probably stay about the same as 1987. Price increases in the 10 % range for imported ore are expected due to water freight and the weak dollar. Baker Hughes estimates the average number of operating rotary rigs at 1070. A slight increase is expected in the non-drilling fluid market (chemicals, glass, and filler). Bauxite and alumina L. Baumgardner, US Bureau of Mines Domestic bauxite production in 1987, expressed as dried equivalent, was 581 kt (640,400 st), a 14% increase over 1986. US mine production amounted to less than 170 of total world production. Virtually none of the domestic bauxite was consumed in the production of primary alumina metal. About 30% of the bauxite produced by US mines was calcined to produce 117 kt (128,970 st) for use in abrasives, catalysts, chemicals, proppants, and refractories. Most of the uncalcined bauxite was refined to specialty aluminum oxide (alumina) forms. Metallurgical grade bauxite was imported from 10 countries in 1987. Principal suppliers of the 9.8 Mt (10.8 million st) were Guinea (4270), Jamaica (3501,), Australia (127), and Brazil (57). The average value, delivered U.S. ports, cif, as reported to US Customs Service, was $29.50/t ($26.76 per st). Calcined refractory grade baux-

Jan 6, 1988

By B. J. Vorster

Introduction The South African Iron and Steel Co. Ltd., in Sishen, operates a large iron ore mine in the Cape Province of the Republic of South Africa. The mine is about 600 km (370 miles) west of Johannesburg. Its annual capacity is 100 Mt (110 million st) of ore and waste. Present production is 60 Mt/a (66 million stpy). The mine operates continuously six days a week. Primary equipment includes 55 154 t (170 st) Wabco and Unit Rig trucks and 14 P&H shovels. During 1979, a feasibility study into the application of a trolley assist system was launched. This was due to the escalation in diesel fuel costs and the appeal by the South African government to reduce the use of fossil fuels. Tests and economic evaluations proved the system technically feasible. The estimated discounted cash flow return exceeded 50%. Diesel fuel consumption would be reduced by 120 ML (31.7 million gal) in the next 10 years. The construction of 7.7 km (4.8 miles) of line and the conversion of 66 154 t (170 st) trucks were completed in March 1982. System description The conventional 154 t (170 st) diesel electric rear-dump haul-truck is equipped with two direct current wheelmotors in the rear axle. They drive the rear wheels through planetary gearboxes. A 1.2-MV (1600-hp) diesel engine and an alternator is used to power the wheelmotors. The trolley assist system consists of an overhead power line, a current collector mounted on the truck, and add-on control equipment where external electric power is routed by way of the current collector to the motorized wheels. The diesel engine is used to propel the truck on level sections. On inclines, the wheel-motors of the truck are coupled by way of a current collector to the externally generated electrical power supply for propulsion. The diesel engine, having lower output than the wheelmotors, limits the truck performance. Previously, maximum output was required from an engine on inclines. By supplying the wheelmotors from a virtually unlimited outside electric energy source, the truck performance is enhanced to the extent that speed is increased by 46% and fuel consumption reduced by 75%. System design The unique operational requirements of this mine rendered the already proven trolley pole system useless. Minimum loss in truck mobility and flexibility was required. Overhead lines and substations were required to be relatively light and portable. This enables fast repositioning of a line with no loss in material. These unique specifications set the base for the design of the Sishen system. Steel I-beams, 203 x 203 mm x 52 kg/m (8 x 8 in. x 35 lb per ft) with lengths varying from 8.3 to 11.3 m (27 to 37 ft), mounted on base plates about 4 x 2.6 m (13 x 8.6 ft) were used as masts. The masts were erected at about 50 m (165 ft) and the base plates covered with about 12 t (13 st) of iron ore to keep them absolutely stable. Results from the pilot installations indicated that using single cantilever cross arms for insulator and overhead conductor suspension was not practical. The tension in the overhead varied too much with temperature changes, causing too much sag in the lines. There had to be a positive and negative conductor. It was decided to suspend each polarity on an independent cantilever and keep the conductors under constant tension by weights acting through a two-to-one pulley tensioning arrangement. For each overhead conductor, a standard 160-mm (6.5-sq in.) grooved copper railway conductor was used. To obtain the necessary current carrying capacity, two of these conductors are used in parallel per pole. Insulators are rated at 4 kV and are of the composite type. An 11-kV three-phase line, supported by the pantograph line masts on the opposite side of the dc line, feeds the rectifier stations. The rectifier stations consist of an 11-kV to 860-V, three-phase 1.46 MVA transformer and a three-phase diode bridge rectifier. The output voltage is 1200 V do earthed through a current limiting resistance network so that the line po-

Jan 4, 1986

By E. D. Gardner

FIFTY years ago the Utah Copper enterprise at Bingham was just getting under way. An epic in metal mining was in the making. Throughout the West the bonanza deposits were approaching exhaustion and most ore still went direct to smelter. But concentrators were shortly to be constructed for treating milling grade ores, and most important, the pilot plant for the Utah Copper enterprise was being built that year at the mouth of Bingham Canyon. The same decade was to see development at the Inspiration mine in Arizona of the most important new mining method for 50 years to come—undercut block caving. Although the average grade of ore being mined has been declining for 50 years, and wage rates and prices of supplies have been greatly increased, the mining industry has continued to grow and to prosper. Technology has advanced to a point where minerals can be mined under the most severe conditions. The hardest rock can be drilled and broken and the heaviest ground handled. Large or small, an ore-body can be mined successfully, at any desired rate of production. It is possible to pump great volumes of water and to ventilate the most extensive workings; air conditioning has made practicable the mining of ore where the rock temperatures are beyond those that can be borne by man. Mining today in the U. S. is a huge earth-moving operation. In 1953 nearly 2 billion tons of material were mined for direct use or for processing. Stripping at open-cut mines totaled about 1.7 billion cu yd. Table I gives relative tonnages of the branches of the mineral industry in 1953. In addition to the solid materials moved, 350 million tons of petroleum and 340,000 tons of gas were produced in 1953. Fifteen million tons of salt and 5 million tons of liquid sulphur were pumped from wells. An appreciable amount of copper was recovered by leaching old mine workings and dumps. Total value of minerals produced in 1953 was $14.4 billion: oil and gas $7.6 billion, coal $2.6 billion, nonmetallics $2.4 billion, and metals $1.8 billion. Formidable problems face some branches of the industry today, especially pertaining to increased output tons per manshift. The time has come when these problems should be reappraised. With current wage rates, the industry no longer can afford to pay men to do manual labor. It should be recognized, also, that the miner is a skilled worker; efforts to promote the dignity of his calling and his pride of accomplishment have yielded beneficial results. Mineral deposits occur under widely varying conditions. In most instances the degree of support needed by the roof and walls is the deciding factor in selection of an underground mining method. The degree of support needed, in turn, is governed by natural physical characteristics of the ore and its enclosing rocks. Mine operators, of course, learn to judge ground by observation, and an experienced mine boss generally can anticipate what will happen following any given mining operation. A more scientific approach, however, would be advantageous in most cases. More should be known about the strength of the ore and the enclosing rocks, more about stresses set up in the ground when ore is removed, and more about the mechanics of moving ground. Better understanding would work both ways: first, favorable rock conditions could be fully utilized for more efficient mining, and second, hazards of rock falls could be minimized, loss of ore in mining reduced, and expenses caused by ground pressures and subsidence lowered. In general, mining comprises breaking the ore or rock in place, supporting the mine workings, and transporting the ore to the surface. This latter is a materials handling problem. Ventilation, of course, must be provided, and the mines must be kept free of water. Development work at some places is the most important cost item in extracting ore. Drilling and blasting remain the usual practice for breaking ore or rock from place except, of course, at block-caving mines. The drilling and blasting practice at a mine must fit the mining method. In laying out mining procedures attention is being given to

Jan 1, 1956

By Owen Thornton

Recently equations have been presented by Rose and Bruce&apos; and by Rose², showing how the relative permeability of a reservoir rock may be determined from the capillary character of the rock. In particular, equations were developed to show the relationship between capillary pressure and the effective permeability to the wetting phase in a poly-phase flow system. The equations are as follows (nomenclature the same as in the Rose and Bruce paper) Rose and Bruce assume that the average length of path (L,), which the wetting fluid follows in flowing through a porous media is independent of the saturation to the wetting phase, so that 1 is a constant dependent only on the k rock, and the permeability to the wetting phase is a function of the saturation and of the capillnry pressure: In measuring the flow of ekctric current through partially saturated core samples, it has been observed that the electrical resistance usually is not a simple linear function of saturation. This fact indicates that the average length of path in the flow of electric current is not independent of saturation, but rather that the tortuosity of the path depends upon the average saturation to the conducting fluid as well as upon the characteristics of the rock. itself. Inasmuch as the flow of fluid and the flow of electric current in many respects are analogous, it may be indicated further that the length of path for fluid also may not be independent of saturation. The following relationship can be derived to express the resistance to flow of electric current through a core sample partially saturated with conductive wetting phase, the non-wetting phase being non-conductive: where L is the average length of path followed by the current in flowing through a length L of partially saturated core, where L is the length of current path when the core is fully saturated, and where Rs and R, are the specific resistivities of the partially saturated and saturated core sample, respectively. It will be noted that R., the specific resistivity of the core sample when S, = 1.0, is equal to the "formation resistivity factor"&apos; multiplied by the specific resistivity of the saturating fluid. If it be assumed that the average lengths of path for fluid flow and for the flow of electric current are the same, then equation (5) may be combined with equations (l), (2) and (3) to give the following relationship: The above equation suggests including a correction for tortuosity when calculating the relative permeability of a reservoir rock to a wetting phase. The correction factor may be obtained from the resistivity-saturation relationship. For instance, the following calcu- lations are obtained for the unconsoli-dated sands described by Leverett Kw Kw Sw R°/Rs Pt/Pc¹ (Calc.) (Obs.) 0.30 0.08 0.88 0.02 0.0 0.40 0.16 0.94 0.06 0.04 0.50 0.27 0.97 0.14 0.11 0.60 0.40 0.98 0.26 0.21 0.70 0.53 0.98 0.39 0.35 0.80 0.68 0.99 0.57 0.54 0.90 0.84 0.99 0.77 0.76 1.00 1.00 1.00 1.00 1.00 It will be noted that the agreement between the calculated points and the observed data is rather good. Further investigation of the above method for obtaining relative permeabilities may be merited. For many sands within specified ranges of saturations the following relationship has been found to hold approximately&apos;: — =SW"......(7) Rs The exponent n in the above equation has been found to equal two for many sands so that equation (6) reduces to the following: The writer acknowledges the permission of The Texas Co. to submit this note for publication. 1. Walter Rose and W. A. Bruce—Jnl. of Pet. Tech., Vol. 1, No. 5, p. 127 (1949). 2. Walter Rose—Jnl. of Petr. Tech., Vol. 1, No. 5, p. 111 (1949). 3. G. E. Archie— -Trans. AIME, 146, 54 (1942). 4. M. C. Leverett— Trans. AIME, 142, 152 (1941). 5. M. C. Leverett—Trans. AIME, 132, 149 (1939).

Jan 1, 1949